US20120205645A1 - Heteroleptic carbene complexes and the use thereof in organic electronics - Google Patents

Heteroleptic carbene complexes and the use thereof in organic electronics Download PDF

Info

Publication number
US20120205645A1
US20120205645A1 US13/504,725 US201013504725A US2012205645A1 US 20120205645 A1 US20120205645 A1 US 20120205645A1 US 201013504725 A US201013504725 A US 201013504725A US 2012205645 A1 US2012205645 A1 US 2012205645A1
Authority
US
United States
Prior art keywords
carbon atoms
substituted
heteroatoms
radical
optionally
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US13/504,725
Inventor
Evelyn Fuchs
Oliver Molt
Korinna Dormann
Thomas Gessner
Nicolle Langer
Ingo Muenster
Jianqiang Qu
Christian Lennartz
Christian Schildknecht
Soichi Watanabe
Gerhard Wagenblast
Guenter Schmid
Herbert Friedrich Boerner
Volker Van Elsbergen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Osram Oled GmbH
OLEDworks GmbH
Original Assignee
BASF SE
Osram Opto Semiconductors GmbH
Koninklijke Philips Electronics NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE, Osram Opto Semiconductors GmbH, Koninklijke Philips Electronics NV filed Critical BASF SE
Priority to US13/504,725 priority Critical patent/US20120205645A1/en
Assigned to BASF SE, OSRAM OPTO SEMICONDUCTORS GMBH, KONINKLIJKE PHILIPS ELECTRONICS N.V. reassignment BASF SE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LANGER, NICOLLE, MUENSTER, INGO, WAGENBLAST, GERHARD, WATANABE, SOICHI, DORMANN, KORINNA, GESSNER, THOMAS, MOLT, OLIVER, FUCHS, EVELYN, QU, JIANQIANG, BOERNER, HERBERT FRIEDRICH, VAN ELSBERGEN, VOLKER, SCHMID, GUENTER, LENNARTZ, CHRISTIAN, SCHILDKNECHT, CHRISTIAN
Publication of US20120205645A1 publication Critical patent/US20120205645A1/en
Assigned to OLEDWORKS GMBH reassignment OLEDWORKS GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KONINKLIJKE PHILIPS ELECTRONICS N. V.
Assigned to OSRAM OLED GMBH reassignment OSRAM OLED GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OSRAM OPTO SEMICONDUCTORS GMBH
Abandoned legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0086—Platinum compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Definitions

  • the present invention relates to heteroleptic complexes comprising a phenylimidazole or phenyltriazole unit bonded via a carbene bond to a central metal atom, and phenylimidazole ligands attached via a nitrogen-metal bond to the central atom, to OLEDs which comprise such heteroleptic complexes, to light-emitting layers comprising at least one such heteroleptic complex, to a device selected from the group consisting of illuminating elements, stationary visual display units and mobile visual display units comprising such an OLED, to the use of such a heteroleptic complex in OLEDs, for example as emitter, matrix material, charge transport material and/or charge blocker.
  • OLEDs Organic Light-Emitting Diodes
  • OLEDs exploit the property of materials to emit light when they are excited by electrical current.
  • OLEDs are of particular interest as an alternative to cathode ray tubes and liquid-crystal displays for production of flat visual display units.
  • devices comprising OLEDs are suitable especially for mobile applications, for example for applications in cellphones, laptops, etc.
  • white OLEDs give great advantages over the illumination technologies known to date, especially a particularly high efficiency.
  • the prior art proposes numerous materials, examples of which include heteroleptic complexes with iridium as the central metal atom, which emit light on excitation by electrical current.
  • WO 2006/121811 A1 discloses phosphorescent heteroleptic metal complexes which comprise carbene ligands.
  • Compounds which have imidazolocarbenes (imidazolylidenes) or triazolocarbenes (triazolylidenes) as ligands are not disclosed in WO 2006/121811 A1.
  • WO 2006/067074 A1 likewise discloses electroluminescent heteroleptic metal complexes with carbene ligands.
  • the noncarbene ligands used include arylpyridines, arylpyrazoles and aryltriazoles.
  • Use of 2-phenyl-1H-imidazoles as noncarbene ligands is not disclosed in WO 2006/067074 A1.
  • WO 2007/115981 discloses heteroleptic metal complexes comprising both carbene ligands and heterocyclic noncarbene ligands, a process for preparation thereof, and the use of these compounds in OLEDs.
  • the compounds disclosed by way of example in WO 2007/115981 do not comprise a combination of 2-phenyl-1H-imidazole ligands with an imidazolocarbene (imidazolylidene) ligand or a triazolocarbene (triazolylidene) ligand.
  • JP 2009057505 discloses optoelectronic components which comprise compounds with tunable emission wavelength, high light emission efficiency and long lifetime.
  • the components according to this document comprise metal complexes which, as well as two ligands optionally joined to one another, comprise at least one ligand attached to the metal atom firstly via a carbene bond and secondly via a noncarbene bond.
  • No combination of a 2-phenyl-1H-imidazole ligand with an imidazolocarbene (imidazolylidene) ligand or a triazolocarbene (triazolylidene) ligand is disclosed.
  • electroluminescence is understood to mean both electrofluorescence and electrophosphorescence.
  • M in which M, A 1 , A 2 , n, m, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each defined as follows:
  • aryl radical, unit or group, heteroaryl radical, unit or group, alkyl radical, unit or group and cycloalkyl radical, unit or group are each defined as follows, as long as no different meanings are mentioned:
  • An aryl radical or group is understood to mean a radical with a base skeleton of 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, which is formed from an aromatic ring or a plurality of fused aromatic rings.
  • Suitable base skeletons are, for example, phenyl, benzyl, naphthyl, anthracenyl or phenanthrenyl. This base skeleton may be unsubstituted, which means that all carbon atoms which are substitutable bear hydrogen atoms, or may be substituted at one, more than one or all substitutable positions of the base skeleton.
  • Suitable substituents are, for example, alkyl radicals, preferably alkyl radicals having 1 to 8 carbon atoms, more preferably methyl, ethyl, i-propyl or t-butyl, aryl radicals, preferably C 6 -aryl radicals, which may in turn be substituted or unsubstituted, heteroaryl radicals, preferably heteroaryl radicals which comprise at least one nitrogen atom, more preferably pyridyl radicals, alkenyl radicals, preferably alkenyl radicals which bear one double bond, more preferably alkenyl radicals with one double bond and 1 to 8 carbon atoms, or groups with donor or acceptor action.
  • Groups with donor action are understood to mean groups which have a +I and/or +M effect
  • groups with acceptor action are understood to mean groups which have a ⁇ I and/or ⁇ M effect.
  • Suitable groups with donor or acceptor action are halogen radicals, preferably F, Cl, Br, more preferably F, alkyl radicals, alkoxy radicals, aryloxy radicals, carbonyl radicals, ester radicals, amine radicals, amide radicals, CH 2 F groups, CHF 2 groups, CF 3 groups, CN groups, thio groups or SCN groups.
  • the aryl radicals most preferably bear substituents selected from the group consisting of methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, tert-butyl, aryloxy, amine, thio groups and alkoxy, or the aryl radicals are unsubstituted.
  • the aryl radical or the aryl group is preferably a C 6 -aryl radical optionally substituted by at least one of the aforementioned substituents.
  • the C 6 -aryl radical more preferably has none, one, two or three of the aforementioned substituents.
  • a heteroaryl radical or a heteroaryl group is understood to mean radicals having 5 to 30 carbon atoms and/or heteroatoms, which differ from the aforementioned aryl radicals in that at least one carbon atom in the base skeleton of the aryl radicals is replaced by a heteroatom.
  • Preferred heteroatoms are N, O and S.
  • one or two carbon atoms of the base skeleton of the aryl radicals are replaced by heteroatoms.
  • the base skeleton is especially preferably selected from electron-poor systems such as pyridyl, pyrimidyl, pyrazyl and triazolyl, and five-membered heteroaromatics such as pyrrole, furan, thiophene, imidazole, pyrazole, triazole, oxazole and thiazole.
  • the base skeleton may be substituted at one, more than one or all substitutable positions of the base skeleton. Suitable substituents are the same as have already been specified above for the aryl groups.
  • alkyl radical or an alkyl group is understood to mean a radical having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms.
  • This alkyl radical may be branched or unbranched and may optionally be interrupted by one or more heteroatoms, preferably N, O or S.
  • this alkyl radical may be substituted by one or more of the substituents already specified for the aryl groups. It is likewise possible that the alkyl radical bears one or more aryl groups. All of the aryl groups listed above are suitable.
  • alkyl radicals selected from the group consisting of methyl, ethyl, i-propyl, n-propyl, i-butyl, n-butyl, t-butyl, sec-butyl, i-pentyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl, i-hexyl and sec-hexyl.
  • alkyl radicals selected from the group consisting of methyl, ethyl, i-propyl, n-propyl, i-butyl, n-butyl, t-butyl, sec-butyl, i-pentyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl, i-hexyl and sec-hexyl.
  • methyl, i-propyl, tert-butyl
  • a cycloalkyl radical or a cycloalkyl group is understood to mean a cyclic radical having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms.
  • This cycloalkyl radical may optionally be interrupted by one or more heteroatoms, preferably N, O or S.
  • this cycloalkyl radical may be unsubstituted or substituted, i.e. may be substituted by one or more of the substituents already specified for the aryl groups. It is likewise possible that the cycloalkyl radical bears one or more aryl groups. All of the aryl groups listed above are suitable.
  • aryl, heteroaryl, alkyl and cycloalkyl radicals applies, in accordance with the invention, independently to the radicals mentioned in the present application, especially to the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 radicals, where R 8 and R 9 , in the case that A 1 and/or A 2 is N, are a free electron pair, which means that no substituent selected from the abovementioned group is present on these ring nitrogen atoms. In the case that A 1 and/or A 2 is C, R 8 and R 9 are each independently hydrogen and/or the substituents specified.
  • M, A 1 , A 2 , n, m, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each defined as follows:
  • M is Ir or Pt, preferably Ir.
  • Ir is present in the inventive heteroleptic complexes in the +3 oxidation state.
  • Pt is present in the inventive heteroleptic complexes in the +2 oxidation state.
  • a 1 and A 2 are each independently C or N. Preference is given in accordance with the invention to the following embodiments:
  • R 1 is a linear or branched alkyl radical having 1 to 20 carbon atoms, a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms.
  • R 1 is more preferably a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, most preferably a substituted, especially ortho,ortho′- or ortho,ortho′,para-substituted, or unsubstituted phenyl radical.
  • the substituents are preferably alkyl radicals having 1 to 10, especially 1 to 6, carbon atoms, for example methyl, ethyl, propyl, butyl.
  • Very particularly preferred R 1 radicals are phenyl, 2,6-dimethylphenyl, 2,6-di-iso-propylphenyl or 2,4,6-trimethylphenyl, i.e. mesityl.
  • the present invention therefore relates more particularly to an inventive heteroleptic complex where R 1 is an aryl radical which has 6 to 30 carbon atoms and is substituted in the ortho,ortho′ positions in each case by a linear or branched alkyl radical having 1 to 10 carbon atoms.
  • R 2 , R 3 are each independently hydrogen, a linear or branched alkyl radical having 1 to 20 carbon atoms, a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms.
  • R 4 , R 5 , R 6 , R 7 are each hydrogen or R 4 and R 5 or R 5 and R 6 or R 6 and R 7 , especially R 5 and R 6 or R 6 and R 7 , together form a saturated, unsaturated or aromatic carbon ring optionally interrupted by at least one heteroatom and having a total of 6 to 30 carbon atoms.
  • R 4 and R 5 or R 5 and R 6 or R 6 and R 7 together form a cycle of the general formula (IIa) or (IIb)
  • R 8 , R 9 are each independently a free electron pair if A 1 or A 2 is N, or, if A 1 or A 2 is C, hydrogen or linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms or substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms, most preferably phenyl radical.
  • R 10 is a linear or branched alkyl radical having 1 to 20 carbon atoms, more preferably having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, more preferably having 6 to 10 carbon atoms.
  • particularly preferred alkyl radicals for R 10 are methyl, ethyl, propyl, especially isopropyl, butyl, especially tert-butyl, or pentyl.
  • aryl radicals for R 10 are unsubstituted phenyl or substituted phenyl, preferably substituted in the ortho position, for example by alkyl radicals having 1 to 6 carbon atoms, for example methyl, ethyl or propyl, especially isopropyl.
  • R 11 , R 12 , R 13 , R 14 are each independently hydrogen or a linear or branched alkyl radical having 1 to 20 carbon atoms, more preferably hydrogen.
  • R 1 and R 14 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused.
  • R 1 and R 14 form an unsaturated bridge having two carbon atoms, to which a six-membered aromatic ring is fused, which is either unsubstituted or substituted by one or two alkyl radicals having 1 to 6 carbon atoms, for example methyl or ethyl.
  • R 7 and R 8 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused.
  • R 7 and R 8 form an unsaturated bridge having two carbon atoms, to which a six-membered aromatic ring is fused, which is either unsubstituted or substituted by one or two alkyl radicals having 1 to 6 carbon atoms, for example methyl or ethyl.
  • the present invention more preferably relates to inventive heteroleptic complexes of the general formula (I) where M, A 1 , A 2 , n, m, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each defined as follows:
  • the present invention preferably further relates to inventive heteroleptic complexes of the general formula (I) where M, A 1 , A 2 , n, m, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each defined as follows:
  • the present invention preferably also relates to inventive heteroleptic complexes of the general formula (I) where M, A 1 , A 2 , n, m, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each defined as follows:
  • Very particularly preferred inventive heteroleptic complexes of the general formula (I) have the ligands depicted in table 1, especially preferably in the combinations shown:
  • heteroleptic complexes of the general formula (I) Depending on the coordination number of the metal M present in the inventive heteroleptic complexes of the general formula (I) and the number of carbene ligands and noncarbene ligands used, different isomers of the corresponding heteroleptic metal complexes may be present with the same metal M and the same nature of the carbene ligands and noncarbene ligands used.
  • the S1a/S1b and S2a/S2b isomers are referred to as pseudo-meridional isomers and the S3a/S3b and S4a/S4b isomers as pseudo-facial isomers.
  • the S3 and S4 isomers when used in OLEDs, give particularly good results with regard to efficiency and lifetime when used in diodes.
  • the S3a/S3b and S4a/S4b isomers, i.e. the pseudo-facial isomers, are therefore particularly preferred in accordance with the invention.
  • inventive complexes of the general formula (I) which comprise two noncarbene ligands and one carbene ligand are present as pseudo-facial isomers.
  • the T1a/T1b and T2a/T2b isomers are referred to as pseudo-meridional isomers and the T3a/T3b and T4a/T4b isomers as pseudo-facial isomers.
  • the T3 and T4 isomers when used in OLEDs, usually give particularly good results with regard to efficiency and lifetime when used in diodes.
  • the T3a/T3b and T4a/T4b isomers i.e. the pseudo-facial isomers, are therefore particularly preferred in accordance with the invention.
  • the inventive complexes of the general formula (I) which comprise one noncarbene ligand and two carbene ligands are present as pseudo-facial isomers.
  • the different isomers of the heteroleptic metal complexes of the formula (I) can be separated by processes known to those skilled in the art, for example by chromatography, sublimation or crystallization.
  • the different isomers can generally be interconverted by suitable reaction conditions (e.g. pH), thermally or photochemically.
  • the present invention relates both to the individual isomers or enantiomers of the heteroleptic complexes of the formula (I) and to mixtures of different isomers or enantiomers in any desired mixing ratio.
  • the present invention therefore relates, in a particularly preferred embodiment, to the inventive heteroleptic complexes with the general and preferred definitions specified for M, A 1 , A 2 , n, m, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 , where these have one of the following configurations IIIa, IIIb, IVa or IVb:
  • the present invention additionally also relates to a process for preparing an inventive heteroleptic complex of the general formula (I) by
  • a complex comprising appropriate noncarbene ligands, attached to the appropriate metal M, preferably iridium, and appropriate carbene ligands, preferably in deprotonated form as the free carbene or in the form of a protected carbene, for example as the silver-carbene complex, are contacted.
  • suitable precursor compounds comprise the appropriate substituents R 1 to R 14 which are to be present in the complexes of the general formula (I).
  • these complexes used as precursor compounds may comprise further ligands known to those skilled in the art, for example halides, preferably chloride.
  • Further suitable ligands are, for example 1,5-cyclooctadiene (COD), phosphines, cyanides, alkoxides, pseudohalides and/or alkyl.
  • R 1 , R 2 , R 3 , R 11 , R 12 , R 13 and R 14 where Y may independently be F, Cl, Br, I, methoxy or carboxylate.
  • Particularly preferred precursor compounds for the carbene ligands used in complexes of the general formula (I) correspond, for example, to the general formulae (VII) or (VIII)
  • R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and A where Z may be F, Cl, Br, I, BF 4 , PF 6 , ClO 4 or SbF 6 .
  • the carbene ligand precursors are deprotonated, preferably before the reaction, for example, by basic compounds known to those skilled in the art, for example basic metalates, basic metal acetates, acetylacetonates or alkoxides, or bases such as KO t Bu, NaO t Bu, LiO t Bu, NaH, silylamides, Ag 2 O and phosphazene bases.
  • the carbene can also be released by removing volatile substances, for example lower alcohols such as methanol, ethanol, for example at elevated temperature and/or reduced pressure, from precursor compounds of the carbene ligands. Corresponding processes are known to those skilled in the art.
  • the contacting is preferably effected in a solvent.
  • Suitable solvents are known to those skilled in the art and are preferably selected from the group consisting of aromatic or aliphatic solvents, for example benzene or toluene, cyclic or acyclic ethers, alcohols, esters, amides, ketones, nitriles, halogenated compounds and mixtures thereof.
  • Particularly preferred solvents are toluene, xylenes, dioxane and THF.
  • the molar ratio of metal-noncarbene complex used to carbene ligand precursor used is generally 1:10 to 10:1, preferably 1:1 to 1:5, more preferably 1:2 to 1:4.
  • the contacting is generally effected at a temperature of 20 to 200° C., preferably 50 to 150° C., more preferably 60 to 130° C.
  • the reaction time depends on the desired carbene complex and is generally 0.02 to 50 hours, preferably 0.1 to 24 hours, more preferably 1 to 12 hours.
  • the complexes of the general formula (I) obtained after the reaction can optionally be purified by processes known to those skilled in the art, for example washing, crystallization or chromatography, and optionally isomerized under conditions likewise known to those skilled in the art, for example thermally or photochemically.
  • the aforementioned heteroleptic complexes and mixtures thereof are outstandingly suitable as emitter molecules in organic light-emitting diodes (OLEDs). Variations in the ligands make it possible to provide corresponding complexes which exhibit electroluminescence in the red, green and especially in the blue region of the electromagnetic spectrum.
  • the inventive heteroleptic complexes of the general formula (I) are therefore outstandingly suitable as emitter substances, since they have emission (electroluminescence) in the visible region of the electromagnetic spectrum, for example at 400 to 800 nm, preferably 400 to 600 nm.
  • the inventive heteroleptic complexes make it possible to provide compounds which have electroluminescence in the red, green and especially in the blue region of the electromagnetic spectrum. It is thus possible, with the aid of the inventive heteroleptic complexes as emitter substances, to provide industrially usable OLEDs.
  • inventive heteroleptic complexes of the general formula (I) are suitable as matrix material, charge transport material, especially hole transport material, and/or charge blocker material.
  • the inventive heteroleptic complex of the general formula (I) are preferably suitable as emitter and/or hole transport material, more preferably as emitter.
  • the present application therefore further provides an OLED comprising at least one inventive heteroleptic complex of the general formula (I).
  • inventive heteroleptic complex of the general formula (I) is preferably employed in the OLED as emitter, matrix material, charge transport material, expecially hole transport material, and/or hole blocker, more preferably as emitter and/or hole transport material, particularly preferably as emitter.
  • the present application also provides for the use of the heteroleptic complexes of the general formula (I) as a light-emitting layer in OLEDs, preferably as an emitter, matrix material, charge transport material, especially hole transport material, and/or charge blocker, more preferably as emitter and/or hole transport material, particularly preferably as emitter.
  • Organic light-emitting diodes are in principle formed from a plurality of layers:
  • the OLED does not comprise all of the layers mentioned, an OLED formed from the layers (1) (anode), (3) (light-emitting layer) and (5) (cathode) is for example also useful, wherein the functions of the layers (2) (hole-transport layer) and (4) (electron-transporting layer) are taken over by the adjacent layers.
  • OLEDs comprising the layers (1), (2), (3) and (5) respectively the layers (1), (3), (4) and (5) are also suitable.
  • the heteroleptic complexes of the general formula (I) are preferably used as emitter molecules and/or matrix materials in the light-emitting layer (3).
  • the inventive heteroleptic complexes of the general formula (I) can also be employed—in addition to the application as emitter molecules and/or matrix materials in the light-emitting layer (3) or instead of the application in the light-emitting layer—as charge transport material in the hole-transporting layer (2) or in the electron-transporting layer (4) and/or as charge blocker, wherein the application as charge transport material in the hole-transporting layer (2) (hole-transport material) is preferred.
  • the present application therefore further provides a light-emitting layer comprising at least one of the inventive heteroleptic complexes of the general formula (I), preferably as emitter molecule.
  • a light-emitting layer comprising at least one of the inventive heteroleptic complexes of the general formula (I), preferably as emitter molecule.
  • Preferred heteroleptic complexes of the general formula (I) have already been specified above.
  • heteroleptic complexes of the general formula (I) used in accordance with the invention may be present in the light-emitting layer in substance, i.e. without further additions.
  • further compounds are present in the light-emitting layer.
  • a fluorescent dye may be present in order to alter the emission color of the heteroleptic complex used as the emitter molecule.
  • a diluent material matrix material
  • This diluent material may be a polymer, for example poly(N-vinylcarbazole) or polysilane.
  • the diluent material may, however, likewise be a small molecule, for example 4,4′-N,N′-dicarbazolebiphenyl (CDP) or tertiary aromatic amines.
  • CDP 4,4′-N,N′-dicarbazolebiphenyl
  • the proportion of the inventive heteroleptic complexes of the general formula (I) used in the light-emitting layer is generally less than 40% by weight, preferably 3 to 30% by weight.
  • the inventive heteroleptic complexes of the general formula (I) are preferably used in a matrix.
  • the light-emitting layer thus preferably comprises at least one inventive heteroleptic complex of the general formula (I) and at least one matrix material as diluent material.
  • Suitable matrix materials are—in addition to the aforementioned dilution materials—in principle the materials specified hereinafter as hole and electron transport materials, and also carbene complexes, for example the carbene complexes of the formula (I) or the carbene complexes mentioned in WO 2005/019373.
  • Particularly suitable are carbazole derivatives, for example 4,4′-bis(carbazol-9-yl)-2,2′-dimethylbiphenyl (CDBP), 4,4′-bis(carbazol-9-yl)biphenyl (CBP), 1,3-bis(N-carbazolyl)benzene (mCP), and the matrix materials specified in the following applications: WO2008/034758, WO2009/003919.
  • WO2007108459 H-1 to H-37
  • H-20 to H-22 and H-32 to H-37 most preferably H-20, H-32, H-36, H-37,
  • WO2008035571 A1 Host 1 to Host 6
  • JP2010135467 compounds 1 to 46 and Host-1 to Host-39 and Host-43
  • one or more compounds of the general formula (X) specified hereinafter are used as matrix material.
  • Preferred embodiments of the compounds of the general formula (X) are likewise specified hereinafter.
  • the matrix materials mentioned above as well as the compounds of the general formula (X) mentioned below are not only applicable as matrix material in the light-emitting layer, but also as matrix materials in other layers of an OLED, for example in the electron-transport layer and/or in the hole transport layer. It is also possible, to apply two or more different matrix materials mentioned before and/or compounds of the general formula (X) mentioned below as matrix materials.
  • the HOMO (highest occupied molecular orbital) of the hole-transporting layer should be aligned to the work function of the anode
  • the LUMO (lowest unoccupied molecular orbital) of the electron-transporting layer should be aligned to the work function of the cathode.
  • the present application further provides an OLED comprising at least one inventive light-emitting layer.
  • the further layers in the OLED may be formed from any material which is typically used in such layers and is known to those skilled in the art.
  • Suitable materials for the aforementioned layers are known to those skilled in the art and are specified, for example, in H. Meng, N. Herron, Organic Small Molecule Materials for Organic Light - Emitting Devices in Organic Light - Emitting Materials and Devices , eds: Z. Li, H. Meng, Taylor & Francis, 2007, Chapter 3, pages 295 to 411.
  • the anode is an electrode which provides positive charge carriers. It may be composed, for example, of materials which comprise a metal, a mixture of different metals, a metal alloy, a metal oxide or a mixture of different metal oxides. Alternatively, the anode may be a conductive polymer. Suitable metals comprise the metals of groups 11, 4, 5 and 6 of the Periodic Table of the Elements, and also the transition metals of groups 8 to 10. When the anode is to be transparent, mixed metal oxides of groups 12, 13 and 14 of the Periodic Table of the Elements are generally used, for example indium tin oxide (ITO). It is likewise possible that the anode (1) comprises an organic material, for example polyaniline, as described, for example, in Nature, Vol. 357, pages 477 to 479 (Jun. 11, 1992). At least either the anode or the cathode should be at least partly transparent in order to be able to emit the light formed.
  • ITO indium tin oxide
  • Suitable hole transport materials for layer (2) of the inventive OLED are disclosed, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pages 837 to 860, 1996. Either hole-transporting molecules or polymers may be used as the hole transport material.
  • Customarily used hole-transporting molecules are selected from the group consisting of 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl ( ⁇ -NPD), N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine (TPD), 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine (ETPD), tetrakis(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA), ⁇ -phenyl-4-N,N-diphenylamin
  • Customarily used hole-transporting polymers are selected from the group consisting of polyvinylcarbazoles, (phenylmethyl)polysilanes and polyanilines. It is likewise possible to obtain hole-transporting polymers by doping hole-transporting molecules into polymers such as polystyrene and polycarbonate. Suitable hole-transporting molecules are the molecules already mentioned above.
  • carbene complexes are, for example, the inventive carbene complexes of the general formula (I), carbene complexes as described in WO 2005/019373 A2, WO 2006/056418 A2, WO 2005/113704, WO 2007/115970, WO 2007/115981 and WO 2008/000727.
  • a suitable carbene complex is Ir(DPBIC) 3 with the formula:
  • mixtures in the hole-transporting layer in particular mixtures which lead to electrical p-doping of the hole-transporting layer.
  • p-Doping is achieved by the addition of oxidizing materials.
  • These mixtures may, for example, be the following mixtures: mixtures of the abovementioned hole transport materials with at least one metal oxide, for example MoO 2 , MoO 3 , WO x , ReO 3 , and/or preferably MoO 3 and/or ReO 3 , more preferably ReO 3 or mixtures comprising the aforementioned hole transport materials and one or more compounds selected from V 2 O 5 , 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 -TCNQ), 2,5-bis(2-hydroxyethoxy)-7,7,8,8-tetracyanoquinodimethane, bis(tetra-n-buty
  • oxinoid compounds such as tris(8
  • Layer (4) may serve both to ease the electron transport and as a buffer layer or as a barrier layer in order to prevent quenching of the exciton at the interfaces of the layers of the OLED. Layer (4) preferably improves the mobility of the electrons and reduces quenching of the exciton.
  • mixtures of at least two materials in the electron-transporting layer in which case at least one material is electron-conducting.
  • at least one material is electron-conducting.
  • at least one phenanthroline compound is used in such mixed electron-transporting layers.
  • alkali metal hydroxyquinolate complexes for example Liq.
  • mixtures may, for example, be mixtures of the abovementioned electron transport materials with alkali/alkaline earth metals or alkali/alkaline earth metal salts, for example Li, Cs, Ca, Sr, Cs 2 CO 3 , with alkali metal complexes, for example 8-hydroxyquinolatolithium (Liq), and with Y, Ce, Sm, Gd, Tb, Er, Tm, Yb, Li 3 N, Rb 2 CO 3 , dipotassium phthalate, W(hpp) 4 from EP 1786050, or with compounds as described in EP1837926 B1.
  • alkali/alkaline earth metals or alkali/alkaline earth metal salts for example Li, Cs, Ca, Sr, Cs 2 CO 3
  • alkali metal complexes for example 8-hydroxyquinolatolithium (Liq)
  • the present invention therefore also relates to an inventive OLED which comprises an electron-transporting layer comprising at least two different materials, of which at least one material should be electron-conductive.
  • the present invention relates to an inventive OLED wherein the electron-transporting layer comprises at least one phenanthroline derivative.
  • the invention relates to an inventive OLED wherein the electron-transporting layer comprises at least one phenanthroline derivative and at least one alkali metal hydroxyquinolate complex.
  • the invention relates to an inventive OLED wherein the electron-transporting layer comprises at least one phenanthroline derivative and 8-hydroxyquinolatolithium.
  • hole transport materials and electron-transporting materials can fulfill several functions.
  • some of the electron-transporting materials are simultaneously hole-blocking materials if they have a low-lying HOMO.
  • the charge-transporting layers may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thickness more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device.
  • the hole transport materials may for example be doped with electron acceptors, phthalocyanines respectively arylamines like TPD or TDTA may be for example doped with tetrafluorotetracyano-chinodimethane (F4-TCNQ).
  • Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, No. 1, 1. July 2003 (p-doped organic layers); A.
  • the cathode (5) is an electrode which serves to introduce electrons or negative charge carriers.
  • the cathode may be any metal or nonmetal which has a lower work function than the anode. Suitable materials for the cathode are selected from the group consisting of alkali metals of group 1, for example Li, Cs, alkaline earth metals of group 2, metals of group 12 of the Periodic Table of the Elements, comprising the rare earth metals and the lanthanides and actinides. In addition, metals such as aluminum, indium, calcium, barium, samarium and magnesium, and combinations thereof, may be used.
  • lithium-comprising organometallic compounds such as 8-hydroxyquinolatolithium (Liq) or LiF or at least one of the following compounds (Cs 2 CO 3 , KF, CsF or NaF may be applied between the organic layer and the cathode as an electron injection layer in order to reduce the operating voltage.
  • organometallic compounds such as 8-hydroxyquinolatolithium (Liq) or LiF or at least one of the following compounds (Cs 2 CO 3 , KF, CsF or NaF may be applied between the organic layer and the cathode as an electron injection layer in order to reduce the operating voltage.
  • the OLED of the present invention may additionally comprise further layers which are known to those skilled in the art.
  • a layer which eases the transport of the positive charge and/or matches the band gaps of the layers to one another may be applied between the layer (2) and the light-emitting layer (3).
  • this further layer may serve as a protective layer.
  • additional layers may be present between the light-emitting layer (3) and the layer (4) in order to ease the transport of the negative charge and/or to match the band gaps between the layers to one another.
  • this layer may serve as a protective layer.
  • the inventive OLED in addition to the layers (1) to (5), comprises at least one of the further layers mentioned below:
  • the OLED does not have all of the layers (1) to (5) mentioned; for example, an OLED comprising layers (1) (anode), (3) (light-emitting layer) and (5) (cathode) is likewise suitable, in which case the functions of layers (2) (hole-transporting layer) and (4) (electron-transporting layer) are assumed by the adjoining layers. OLEDs having layers (1), (2), (3) and (5) or layers (1), (3), (4) and (5) are likewise suitable.
  • Suitable materials for the individual layers are known to those skilled in the art and disclosed, for example, in WO 00/70655.
  • the layers (1), (2), (3), (4) and (5) have been surface-treated in order to increase the efficiency of charge carrier transport.
  • the selection of the materials for each of the layers mentioned is preferably determined by obtaining an OLED having a high efficiency.
  • the inventive OLED can be produced by methods known to those skilled in the art.
  • the OLED is produced by successive vapor deposition of the individual layers onto a suitable substrate.
  • Suitable substrates are, for example, glass, inorganic materials like ITO or IZO or polymer films.
  • customary techniques may be used, such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD) and others.
  • the organic layers may be coated from solutions or dispersions in suitable solvents, in which case coating techniques known to those skilled in the art are employed.
  • Suitable coating techniques are, for example, spin-coating, the casting method, the Langmuir-Blodgett (“LB”) method, the inkjet printing method, dip-coating, letterpress printing, screen printing, doctor blade printing, roller printing, reverse roller printing, offset lithography printing, flexographic printing, web printing, spray coating, coating by a brush or pad printing, and the like.
  • LB Langmuir-Blodgett
  • the inkjet printing method dip-coating, letterpress printing, screen printing, doctor blade printing, roller printing, reverse roller printing, offset lithography printing, flexographic printing, web printing, spray coating, coating by a brush or pad printing, and the like.
  • spin-coating the inkjet printing method and the casting method since they are particularly simple and inexpensive to perform.
  • the coating can be obtained using a solution prepared by dissolving the composition in a concentration of 0.0001 to 90% by weight in a suitable organic solvent such as benzene, toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide, acetone, acetonitrile, anisole, dichloromethane, dimethyl sulfoxide, water and mixtures thereof.
  • a suitable organic solvent such as benzene, toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide, acetone, acetonitrile, anisole, dichloromethane, dimethyl sulfoxide, water and mixtures thereof.
  • all layers of the OLED are prepared with the same coating technique. It is further also possible that two or more coating techniques are carried out in the production of the layers of the OLED.
  • the different layers have the following thicknesses: anode (2) 500 to 5000 ⁇ , preferably 1000 to 2000 ⁇ ( ⁇ ngström); hole-transporting layer (3) 50 to 1000 ⁇ , preferably 200 to 800 ⁇ ; light-emitting layer (4) 10 to 1000 ⁇ , preferably 100 to 800 ⁇ ; electron-transporting layer (5) 50 to 1000 ⁇ , preferably 200 to 800 ⁇ ; cathode (6) 200 to 10 000 ⁇ , preferably 300 to 5000 ⁇ .
  • the position of the recombination zone of holes and electrons in the inventive OLED and thus the emission spectrum of the OLED may be influenced by the relative thickness of each layer.
  • the thickness of the electron transport layer should preferably be selected such that the electron/hole recombination zone is within the light-emitting layer.
  • the ratio of the layer thicknesses of the individual layers in the OLED is dependent upon the materials used. The layer thicknesses of any additional layers used are known to those skilled in the art.
  • the present invention also relates to an OLED comprising at least one inventive heteroleptic complex of the general formula (I), and at least one compound of the general formula (X)
  • two units of the general formula (X) are bridged to one another via a linear or branched, saturated or unsaturated bridge optionally interrupted by at least one heteroatom, via a bond or via O.
  • the compounds of the formula (X) have the formula (XI) or (XI*):
  • the compounds of the general formula (X) can be used as a matrix (diluent material), hole/exciton blocker, electron/exciton blocker, electron transport material or hole transport material in combination with the heteroeleptic complexes claimed, which then preferably serve as emitters.
  • Inventive OLEDs which include both at least one compound of the formula (X) and a compound of the formula (I) exhibit particularly good efficiencies and lifetimes. Depending on the function in which the compound of the formula (X) is used, it is present in pure form or in different mixing ratios.
  • one or more compounds of the formula (X) are used as matrix material in the light-emitting layer.
  • aryl radical or group, heteroaryl radical or group, alkyl radical or group, cycloalkyl radical or group, heterocycloalkyl radical or group, alkenyl radical or group, alkynyl radical or group, and groups with donor and/or acceptor action are each defined as follows:
  • An aryl radical is understood to mean a radical having a base skeleton of 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, which is formed from an aromatic ring or a plurality of fused aromatic rings.
  • Suitable base skeletons are, for example, phenyl, naphthyl, anthracenyl or phenanthrenyl, indenyl or fluorenyl.
  • This base skeleton may be unsubstituted (which means that all carbon atoms which are substitutable bear hydrogen atoms), or may be substituted at one, more than one or all substitutable positions of the base skeleton.
  • Suitable substituents are, for example, deuterium, alkoxy radicals, aryloxy radicals, alkylamino groups, arylamino groups, carbazolyl groups, silyl groups, SiR 78 R 79 R 80 , suitable silyl groups SiR 78 R 79 R 80 being specified below, alkyl radicals, preferably alkyl radicals having 1 to 8 carbon atoms, more preferably methyl, ethyl or i-propyl, aryl radicals, preferably C 6 -aryl radicals, which may in turn be substituted or unsubstituted, heteroaryl radicals, preferably heteroaryl radicals which comprise at least one nitrogen atom, more preferably pyridyl radicals and carbazolyl radicals, alkenyl radicals, preferably alkenyl radicals which bear one double bond, more preferably alkenyl radicals having one double bond and 1 to 8 carbon atoms, alkynyl radicals, preferably alkynyl radical
  • the substituted aryl radicals most preferably bear substituents selected from the group consisting of methyl, ethyl, isopropyl, alkoxy, heteroaryl, halogen, pseudohalogen and amino, preferably arylamino.
  • the aryl radical or the aryl group is preferably a C 6 -C 18 -aryl radical, more preferably a C 6 -aryl radical, which is optionally substituted by at least one or more than one of the aforementioned substituents.
  • the C 6 -C 18 -aryl radical, preferably C 6 -aryl radical more preferably has none, one, two, three or four, most preferably none, one or two, of the aforementioned substituents.
  • a heteroaryl radical or a heteroaryl group is understood to mean radicals which differ from the aforementioned aryl radicals in that at least one carbon atom in the base skeleton of the aryl radicals is replaced by a heteroatom, and in that the base skeleton of the heteroaryl radicals preferably has 5 to 18 ring atoms.
  • Preferred heteroatoms are N, O and S.
  • Heteroaryl radicals suitable with particular preference are nitrogen-containing heteroaryl radicals. Most preferably, one or two carbon atoms of the base skeleton are replaced by heteroatoms, preferably nitrogen.
  • the base skeleton is especially preferably selected from systems such as pyridine, pyrimidine and five-membered heteroaromatics such as pyrrole, furan, pyrazole, imidazole, thiophene, oxazole, thiazole, triazole.
  • the heteroaryl radicals may be fused ring systems, for example benzofuryl, benzothienyl, benzopyrrolyl, dibenzofuryl, dibenzothienyl, phenanthrolinyl, carbazolyl radicals, azacarbazolyl radicals or diazacarbazolyl radicals.
  • the base skeleton may be substituted at one, more than one or all substitutable positions of the base skeleton. Suitable substituents are the same as have already been specified for the aryl groups.
  • alkyl radical or an alkyl group is understood to mean a radical having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8, most preferably 1 to 4 carbon atoms.
  • This alkyl radical may be branched or unbranched and optionally be interrupted by one or more heteroatoms, preferably Si, N, O or S, more preferably N, O or S.
  • this alkyl radical may be substituted by one or more of the substituents specified for the aryl groups.
  • the alkyl radicals present in accordance with the invention may have at least one halogen atom, for example F, CI, Br or I, especially F.
  • the alkyl radicals present in accordance with the invention may be fully fluorinated. It is likewise possible that the alkyl radical bears one or more (hetero)aryl groups. In the context of the present application, for example, benzyl radicals are thus substituted alkyl radicals. In this context, all of the (hetero)aryl groups listed above are suitable.
  • the alkyl radicals are more preferably selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl and tert-butyl, very particular preference being given to methyl and ethyl.
  • a cycloalkyl radical or a cycloalkyl group is understood to mean a radical having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms.
  • This base skeleton may be unsubstituted (which means that all carbon atoms which are substitutable bear hydrogen atoms) or substituted at one, more than one or all substitutable positions of the base skeleton.
  • Suitable substituents are the groups already mentioned above for the aryl radicals. It is likewise possible that the cycloalkyl radical bears one or more (hetero)aryl groups. Examples of suitable cycloalkyl radicals are cyclopropyl, cyclopentyl and cyclohexyl.
  • a heterocycloalkyl radical or a heterocycloalkyl group is understood to mean radicals which differ from the aforementioned cycloalkyl radicals in that at least one carbon atom in the base skeleton of the cycloalkyl radicals is replaced by a heteroatom.
  • Preferred heteroatoms are N, O and S.
  • Most preferably, one or two carbon atoms of the base skeleton of the cycloalkyl radicals are replaced by heteroatoms.
  • suitable heterocycloalkyl radicals are radicals derived from pyrrolidine, piperidine, piperazine, tetrahydrofuran, dioxane.
  • alkenyl radical or an alkenyl group is understood to mean a radical which corresponds to the aforementioned alkyl radicals having at least two carbon atoms, with the difference that at least one C—C single bond of the alkyl radical is replaced by a C—C double bond.
  • the alkenyl radical preferably has one or two double bonds.
  • alkynyl radical or an alkynyl group is understood to mean a radical which corresponds to the aforementioned alkyl radicals having at least two carbon atoms, with the difference that at least one C—C single bond of the alkyl radical is replaced by a C—C triple bond.
  • the alkynyl radical preferably has one or two triple bonds.
  • SiR 78 R 79 R 80 group is understood to mean a silyl radical in which
  • R 78 , R 79 and R 80 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or OR 73 .
  • SiR 74 R 75 R 76 group is understood to mean a silyl radical in which
  • R 74 , R 75 and R 76 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or OR 73 .
  • a group or a substituent with donor or acceptor action is understood to mean the following groups:
  • Groups with donor action are understood to mean groups which have a +I and/or +M effect, and groups with acceptor action are understood to mean groups which have a —I and/or -M effect.
  • Preferred suitable groups are selected from C 1 -C 20 -alkoxy, C 6 -C 30 -aryloxy, C 1 -C 20 -alkylthio, C 6 -C 30 -arylthio, SiR 81 R 82 R 83 , OR 73 , halogen radicals, halogenated C 1 -C 20 -alkyl radicals, carbonyl (—CO(R 81 )), carbonylthio (—C ⁇ O(SR 81 )), carbonyloxy (—C ⁇ O(OR 81 )), oxycarbonyl (—OC ⁇ O(R 81 )), thiocarbonyl (—SC ⁇ O(R 81 )), amino (—NR 81 R 82 ), pseudohalogen radicals, amido (—C ⁇
  • R 81 , R 82 and R 83 radicals mentioned in the aforementioned groups with donor or acceptor action are each independently:
  • R 81 , R 82 and R 83 radicals are more preferably C 1 -C 6 -alkyl, e.g. methyl, ethyl or i-propyl, or phenyl.
  • R 81 , R 82 and R 83 are preferably each independently substituted or unsubstituted C 1 -C 20 -alkyl or substituted or unsubstituted aryl, preferably phenyl.
  • Preferred substituents with donor or acceptor action are selected from the group consisting of:
  • CF 3 CH 2 F, CHF 2 or C 2 F 5 ; amino, preferably dimethylamino, diethylamino or diarylamino, more preferably diarylamino; pseudohalogen radicals, preferably CN, —C(O)OC 1 -C 4 -alkyl, preferably —C(O)OMe, P(O)R 2 , preferably P(O)Ph 2 .
  • Very particularly preferred substituents with donor or acceptor action are selected from the group consisting of methoxy, phenyloxy, halogenated C 1 -C 4 -alkyl, preferably CF 3 , CH 2 F, CHF 2 , C 2 F 5 , halogen, preferably F, CN, SiR 81 R 82 R 83 , suitable R 81 , R 82 and R 83 radicals already having been specified, diarylamino (NR 84 R 85 where R 84 , R 85 are each C 6 -C 30 -aryl), —C(O)OC 1 -C 4 -alkyl, preferably —C(O)OMe, P(O)Ph 2 .
  • Halogen groups are preferably understood to mean F, Cl and Br, more preferably F and Cl, most preferably F.
  • Pseudohalogen groups are preferably understood to mean CN, SCN and OCN, more preferably CN.
  • aryl radicals or groups, heteroaryl radicals or groups, alkyl radicals or groups, cycloalkyl radicals or groups, heterocycloalkyl radicals or groups, alkenyl radicals or groups and groups with donor and/or acceptor action may—as mentioned above—be substituted or unsubstituted.
  • an unsubstituted group is understood to mean a group in which the substitutable atoms of the group bear hydrogen atoms.
  • a substituted group is understood to mean a group in which one or more substitutable atom(s) bear(s) a substituent in place of a hydrogen atom at least at one position. Suitable substituents are the substituents specified above for the aryl radicals or groups.
  • radicals having the same numbering occur more than once in the compounds according to the present application, these radicals may each independently have the definitions specified.
  • the T radical in the compounds of the formula (X) is NR 57 , S, O or PR 57 , preferably NR 57 , S or O, more preferably O or S, most preferably O.
  • the R 57 radical is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, preferably aryl, heteroaryl or alkyl, more preferably aryl, where the aforementioned radicals may be unsubstituted or substituted. Suitable substituents have been specified above.
  • R 65 is more preferably phenyl which may be substituted by the aforementioned substituents or unsubstituted.
  • R 57 is most preferably unsubstituted phenyl.
  • the Q′ group in the compounds of the formula (X) is —NR 58 R 59 , —P(O)R 60 R 61 , —PR 62 R 63 , —S(O) 2 R 64 , —S(O)R 65 , —SR 66 or —OR 67 ; preferably NR 58 R 59 , —P(O)R 60 R 61 or —OR 67 , more preferably —NR 58 R 59 .
  • R 58 to R 67 and R 74 to R 76 radicals are each defined as follows:
  • T is NPh, S or O.
  • —NR 58 R 59 groups suitable with preference are selected from the group consisting of pyrrolyl, 2,5-dihydro-1-pyrrolyl, pyrrolidinyl, indolyl, indolinyl, isoindolinyl, carbazolyl, azacarbazolyl, diazacarbazolyl, imidazolyl, imidazolinyl, benzimidazolyl, pyrazolyl, indazolyl, 1,2,3-triazolyl, benzotriazolyl, 1,2,4-triazolyl, tetrazolyl, 1,3-oxazolyl, 1,3-thiazolyl, piperidyl, morpholinyl, 9,10-dihydroacridinyl and 1,4-oxazinyl, where the aforementioned groups may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, ary
  • Particularly preferred —NR 58 R 59 groups are:
  • Particularly preferred —P(O)R 60 R 61 groups are:
  • a particularly preferred PR 62 R 63 group is:
  • R 55 , R 56 in the compounds of the formula (X) are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, a further A group or a group with donor or acceptor action; preferably each independently alkyl, aryl, heteroaryl or a group with donor or acceptor action.
  • R 55 or R 56 may each independently be:
  • a′′ R 55 groups and/or b′ R 56 groups may be present, where a′′ and b′ are:
  • a′′ is 0, 1, 2, 3 or 4; preferably independently 0, 1 or 2; b′ is 0, 1, 2 or 3; preferably independently 0, 1 or 2.
  • At least a′′ or b′ is 0, very especially preferably a′′ and b′ are each 0 or a′′ is 1 and b′ is 0.
  • R 73 in the compounds of the general formula (XI) is generally independently SiR 74 R 75 R 76 , aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, optionally substituted by an OR 77 group.
  • R 77 in compounds of the general formula (XI) is generally independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl.
  • OR 77 substituent optionally present may generally be present in the radicals mentioned at all sites which appear suitable to the person skilled in the art.
  • two units of the general formula (XI) and/or (XI*) are bridged to one another via a linear or branched, saturated or unsaturated bridge optionally interrupted by at least one heteroatom or via O, where this bridge in the general formula (XI) and/or (XI*) is in each case attached to the silicon atoms in place of R 71 .
  • This bridge is preferably selected from the group consisting of —CH 2 —, —C 2 H 4 —, —C 4 H 8 —, —C 6 H 12 —, —C 8 H 16 —, —C 9 H 18 —, —CH(C 8 H 17 )CH 2 —, —C 2 H 4 (CF 2 ) 8 C 2 H 4 —, —C ⁇ C—, -1,4-(CH 2 ) 2 -phenyl-(CH 2 ) 2 —, 1,3-(CH 2 ) 2 -phenyl-(CH 2 ) 2 —, -1,4-phenyl-, -1,3-phenyl-, —O—, —O—Si(CH 3 ) 2 —O—, —O—Si(CH 3 ) 2 —O—, —O—Si(CH 3 ) 2 —O—Si(CH 3 ) 2 —O—, —O—.
  • the compounds of the general formula (X) have the general formula (XIa), (XIb), (XIc), (XId) or (XIe), i.e. they are preferred embodiments of the compounds of the general formula (XI) or (XI*):
  • R 70 , R 71 or R 72 in the compounds of the general formula (XI) or (XI*) are aromatic units of the general formulae (XIi) and/or (XIi*)
  • R 55 , R 56 , Q′, T, a′ and b′ are each as defined above.
  • the present invention therefore relates, in one embodiment, to an inventive OLED where R 70 , R 71 or R 72 in the compounds of the general formula (XI) or (XI*) are aromatic units of the general formulae (XIi) and/or (XIi*)
  • R 56 , R 56 , Q′, T, a′ and b′ are each as defined above.
  • the present invention relates to an OLED wherein the compound of the general formula (XI) or (XI*) is selected from the following group:
  • T is O or S, preferably O.
  • R 70 , R 71 , R 72 are each defined as follows:
  • Nr R 70 R 71 R 72 1 methyl methyl ethyl 2 methyl methyl i-propyl 3 methyl methyl n-propyl 4 methyl methyl n-butyl 5 methyl methyl i-butyl 6 methyl methyl t-butyl 7 methyl methyl n-pentyl 8 methyl methyl n-hexyl 9 methyl methyl —CH 2 CH 2 C(CH 3 ) 3 10 methyl methyl n-C 8 H 17 11 methyl methyl i-C 8 H 17 12 methyl methyl n-C 10 H 21 13 methyl methyl n-C 12 H 25 16 methyl methyl n-C 18 H 37 17 methyl methyl n-C 30 H 61 19 methyl methyl cyclohexyl 20 methyl methyl C(CH 3 ) 2 Ph 21 methyl methyl —C(CH 3 ) 2 CH(CH 3 ) 2 22 methyl methyl —CCH 2 CH(CH 3 )(C 2 H
  • R 70 , R 71 , R 72 , R 87 , R 88 and R 89 are each defined as follows:
  • R therein is independently Me, phenyl or R 86 , where at least one R radical is R 86 :
  • the present invention relates to an OLED which, as well as at least one metal-carbene complex of the general formula (I), comprises at least one compound of the general formula (X), in which case the compound of the formula (X) is most preferably at least one of the compounds specified below:
  • T is O or S, preferably O.
  • all T groups have the same definition.
  • crosslinked or polymeric materials comprising repeat units based on the general formula (X) in crosslinked or polymerized form together with at least one heteroeleptic complex of the general formula (I).
  • the latter are preferably used as matrix materials.
  • the crosslinked or polymeric materials have outstanding solubility in organic solvents, excellent film-forming properties and relatively high glass transition temperatures.
  • high charge carrier mobilities, high stabilities of color emission and long operating times of the corresponding components can be observed when crosslinked or polymeric materials according to the present invention are used in organic light-emitting diodes (OLEDs).
  • the crosslinked or polymerized materials are particularly suitable as coatings or in thin films since they are thermally and mechanically stable and relatively defect-free.
  • crosslinked or polymerized materials comprising repeat units based on the general formula (X) can be prepared by a process comprising steps (a) and (a):
  • the crosslinked or polymerized materials may be homopolymers, which means that exclusively units of the general formula (X) are present in crosslinked or polymerized form. They may also be copolymers, which means that further monomers are present in addition to the units of the general formula (X), for example monomers with hole-conducting and/or electron-conducting properties, in crosslinked or polymerized form.
  • inventive OLED comprises an emission layer comprising at least one inventive heteroeleptic complex of the general formula (I), at least one matrix material of the formula (X), and optionally at least one further hole-transporting matrix material.
  • the inventive OLEDs can be used in all devices in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile visual display units and illumination means. The present invention therefore also relates to a device selected from the group consisting of stationary visual display units and mobile visual display units and illumination means, comprising an inventive OLED.
  • Stationary visual display units are, for example, visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations and information panels.
  • Mobile visual display units are, for example, visual display units in cellphones, laptops, digital cameras, mp-3 players, smartphones, vehicles, and destination displays on buses and trains.
  • inventive heteroleptic complexes of the general formula (I) can be used in OLEDs with inverse structure.
  • the inventive complexes are preferably used in turn in these inverse OLEDs in the light-emitting layer.
  • the structure of inverse OLEDs and the materials typically used therein are known to those skilled in the art.
  • a further embodiment of the present invention is a white OLED comprising at least one heteroleptic complex of the general formula (I).
  • the heteroleptic complex of the general formula (I) is employed in the white OLED as emitter material. Preferred embodiments of the heteroleptic complex of the general formula (I) are mentioned before.
  • Beside the at least one heteroleptic complex of the general formula (I) the white OLED may comprise at least one compound of the formula (X).
  • the compound of formula (X) is preferably employed as matrix material. Preferred compounds of the formula (X) are mentioned before.
  • the OLED In order to obtain white light, the OLED must generate light which colors the entire visible range of the spectrum.
  • organic emitters normally emit only in a limited portion of the visible spectrum—i.e. are colored.
  • White light can be generated by the combination of different emitters. Typically, red, green and blue emitters are combined.
  • the prior art also discloses other methods for formation of white OLEDs, for example the triplet harvesting approach. Suitable structures for white OLEDs or methods for formation of white OLEDs are known to those skilled in the art.
  • the present invention also relates to an organic electronic component, preferably an organic light-emitting diode (OLED), organic photovoltaic cell (OPV), organic filed-effect transistor (OFET) or light-emitting electrochemical cell (LEEC), comprising a least one inventive heteroleptic complex of the general formula (I).
  • OLED organic light-emitting diode
  • OPFET organic field-effect transistor
  • LEEC light-emitting electrochemical cell
  • N-(2,6-Diisopropylphenyl)-2-phenylimidazole L1 is synthesized analogously to example 14 in WO2006/121811.
  • the synthesis of 5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole C1 is effected according to D. Enders, K. Breuer, G. Raabe, J. Runsink, J. H. Teles, J.-P. Melder, K. Ebel, S. Brode, Angew. Che—m. 1995, 107, 9, 1119-1122 or D. Enders, K. Breuer, U. Kallank, T. Balensiefer, Synthesis 2003, 8, 1292-1295.
  • 3-(2,6-Dimethylphenyl)-7-methylimidazo[1,2-f]phenanthridine L3 is synthesized analogously to example 10 in WO 2007/095118.
  • the synthesis of the ligand precursor 1-isopropyl-1,2,4-triazolo[4,3-f]phenanthridinium iodide C3 is effected as described in WO 2009/050281.
  • the synthesis of the exciton and hole blocker 2,8-bis(triphenylsilyl)-dibenzofuran LB1 is disclosed in synthesis example 4g in WO 2009/003898.
  • Em1-i corresponds to the configuration IVa or IVb of the pseudo-facial isomer S4a or S4b.
  • Em1-i is present as the racemate; for crystal structure see FIG. 2 , the sample for the x-ray structure analysis is crystallized from cyclohexane/ethyl acetate (cyclohexane still present in the crystals).
  • the photoluminescence quantum yield of the facial isomer Em1-i is 1.36 times the quantum yield of the meridional isomer Em1-s.
  • the cooling bath is removed, and the mixture is allowed to come to room temperature in a water bath within approx. 30 min and stirred for a further two hours. Subsequently, 60 ml of saturated sodium chloride solution are added cautiously (slightly exothermic reaction, temperature rise 1-2° C.). The organic phase is removed and freed of the solvent under reduced pressure. The oily red-brown residue is taken up in 900 ml of dichloromethane and washed successively with 500 ml of HCl solution (1 N) and 400 ml of water. The organic phase is dried over magnesium sulfate and freed of the solvent under reduced pressure.
  • 119.00 g of the first stage (comprise 110.66 g, 447.9 mmol of 4-bromodibenzofuran) are dissolved in 700 ml of dimethylformamide and admixed successively with 37.15 g (545.7 mmol) of imidazole, 15.80 g (83.0 mmol) of copper(I) iodide and 83.20 g (602.0 mmol) of potassium carbonate. The mixture is stirred at 150° C. for 48 h, in the course of which a further 3.75 g (55.1 mmol) of imidazole are added after 24 h and a further 1.93 g (28.3 mmol) after 44 h.
  • Em2-i corresponds to the configuration IVa or IVb of the pseudo-facial isomer S4a or S4b.
  • Em2-1 is present as the racemate; for crystal structure see FIG. 3 , the sample for the x-ray structure analysis was crystallized from tetra hydrofuran/n-hepta ne.
  • the photoluminescence quantum yield of the facial isomer Em2-i is 1.44 times the quantum yield of the isomer Em2-s.
  • ⁇ 0.79 (d, 3H), 0.89 (d, 3H), 0.90 (d, 3H), 0.97 (d, 6H), 1.02 (d, 3H), 1.10 (d, 3H), 1.15 (d, 3H), 1.16 (d, 3H), 1.47 (d, 3H), 2.03 (sept, 1H), 2.47 (sept, 1H), 2.65 (sept, 1H), 2.76 (sept, 1H), 4.47 (sept, 1H), 6.13 (d, 1H), 6.21 (d, 1H), 6.35 (d, 1H), 6.46 (m c , 3H), 6.58 (dd, 2H), 6.65-6.76 (m, 3H), 6.93 (dd, 1H), 7.09 (dd, 1H), 7.15 (d, 1H), 7.25 (dd, 1H), 7.28-7.33 (m, 3H), 7.44-7.52 (m, 2H), 7.58 (dd, 1H), 7.67-7.76 (m, 2H), 8.39 (
  • Em3-s A suspension of 2.1 g of Em3-s in 2000 ml of acetonitrile is irradiated with a moderate-pressure mercury immersion lamp at room temperature for 8 h (TQ150 with Duran sheath). Subsequently, the solvent is removed under reduced pressure. The residue was stirred twice with acetone and filtered. 1.6 g of Em3-i were obtained as a yellow powder (76%).
  • ⁇ 0.68 (d, 3H), 0.75 (d, 3H), 0.82 (d, 3H), 0.96 (d, 3H), 0.99 (d, 3H), 1.05 (d, 3H), 1.13 (d, 3H), 1.20 (d, 3H), 1.24 (d, 3H), 1.60 (d, 3H), 1.79 (sept, 1H), 2.42 (sept, 1H), 2.51 (sept, 1H), 2.76 (sept, 1H), 4.56 (sept, 1H), 6.10 (dd, 2H), 6.30-6.35 (m, 1H), 6.38-6.45 (m, 2H), 6.53 (d, 1H), 6.61 (dd, 1H), 6.68 (d, 1H), 6.73 (d, 1H), 6.74-6.78 (m, 2H), 6.79 (d, 1H), 6.96 (dd, 1H), 7.07-7.15 (m, 1H), 7.19 (d, 1H), 7.22 (d, 1H), 7.27-7.34 (m,
  • the photoluminescence quantum yield of the isomer Em3-i is 1.21 times the quantum yield of the isomer Em3-s.
  • Stage 1 Benzonitrile (51.5 g, 0.50 mol) is admixed with ethanol (anhydrous, 25 ml). Then a constant stream of HCl gas is introduced over 2 h and the mixture is subsequently stirred at room temp. for 48 h, in the course of which a solid forms. The solvent is drawn off from the reaction mixture under reduced pressure (95 g).
  • Stages 2+3 12 g of stage 1 (64.6 mmol) are again dissolved in EtOH (120 ml), and phenylhydrazine (9.4 g, 84 mmol, 1.3 equiv.) is added, in the course of which a solid forms. Triethylamine (22 ml, 162 mmol, 2.5 equiv.) is added and then the mixture is stirred at room temp. for 16 h. The solvent is again removed from the reaction mixture under reduced pressure at room temp., such that the amidrazone formed remains, still moist. After the addition of formic acid (200 ml), the mixture is heated to reflux for 3.5 h.
  • Stage 4 The triazole of the preceding stage (1.5 g, 66 mmol) is dissolved in THF (anhydrous, 40 ml), admixed with MeI (14 ml) and heated to reflux for 5 days. The solid obtained is filtered off, recrystallized repeatedly (CH 2 Cl 2 /n-hexane) and dried (780 mg, 32%).
  • the photoluminescence quantum yield of the isomer Em-4-i has 1.40 times the quantum yield of the isomer Em-4-s.
  • Stage 1 Aq. NaHCO 3 solution (5%, 330 g, 190 mmol, 2.0 equiv.) is added at room temp. to a suspension of o-tolylhydrazine hydrochloride (15 g, 97 mmol) in methyl chloride (450 ml). After stirring for 30 minutes, the biphasic solution is phase-separated. The organic phase is dried over Na 2 SO 4 , freed of the solvent and dried under reduced pressure at 60° C. to isolate tolylhydrazine as a pale yellow solid (7.3 g, 62%).
  • Stage 2 Benzoyl chloride (8.4 g, 60 mmol, 1.0 equiv.) is initially charged in toluene (anhydrous, 60 ml) and cooled to 5° C. Then aniline (5.6 g, 60 mmol, 1.0 equiv.) is added, and the reaction mixture is heated to reflux for 16 h and then stirred at room temp. for a further 48 h. Then the mixture is heated to 80° C., thionyl chloride (21.4 g, 180 mmol, 3.0 equiv.) is added at this temperature and the mixture is stirred for a further 2 h. Then the mixture is cooled to room temp.
  • reaction mixture is admixed with THF (anhydrous, 180 ml) and triethylamine (9.1 g, 90 mmol, 1.5 equiv.) and cooled to 5° C., and then the tolylhydrazine of stage 1 (7.3 g, 60 mmol), dissolved in THF (20 ml), is added. The mixture is stirred at room temperature for 16 h. After the removal of the solvent, the residue is recrystallized from acetic acid (2%, 150 ml), washed with iPrOH (80 ml, 20 ml) and dried (10.3 g, 57%).
  • Stage 3 Triethyl orthoformate (9.0 ml, 8.1 g, 56 mmol, 5.6 equiv.) and 3 g of the hydrazone of stage 2 (10 mmol) are initially charged, ammonium iodide (1.4 g, 10 mmol, 1.0 equiv.) is added and the suspension is heated to reflux for 7 h. After cooling, the solid is filtered off with suction and washed repeatedly with n-hexane and ethyl acetate, from which the iodide salt is obtained as a gray powder (3.2 g, 73%).
  • the photoluminescence quantum yield of the isomerized Em5-i complex mixture has 1.50 times the quantum yield of the Em5-s complex mixture.
  • the synthesis is performed analogously to D1.
  • the precipitate obtained is extracted with dichloromethane. After removing the solvent, D2 is obtained from the extract in a yield of 36%.
  • CEm1 corresponds to compound (N-3) from WO 2006067074
  • complex CEm1 is not suitable as an emitter in OLEDs.
  • CEm2 corresponds to the compound “Compound 3” from WO 2006121811. The synthesis was analogous WO 2006121811.
  • the ITO substrate used as the anode is cleaned first with commercial detergents for LCD production (Deconex® 20NS, and 25ORGAN-ACID® neutralizing agent) and then in an acetone/isopropanol mixture in an ultrasound bath. To eliminate possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for a further 25 minutes. This treatment also improves the hole injection properties of the ITO.
  • the hole injection layer AJ20-1000 from Plexcore respectively PEDT: PSS (CLEVIOS P AR 4083) from H. C. Starck is spun on from solution.
  • the organic materials specified below are applied by vapor deposition to the cleaned substrate at about 10 ⁇ 7 -10 ⁇ 9 mbar at a rate of approx. 0.5-5 nm/min.
  • the hole conductor and exciton blocker applied to the substrate is Ir(DPBIC) 3 with a thickness of 45 nm, of which the first 35 nm are doped with MoO x to improve the conductivity,
  • a mixture of emitter and of the compound Ma1 is applied by vapor deposition with a thickness of 40 nm, the latter compound functioning as a matrix material.
  • the material Ma1 is applied by vapor deposition with a thickness of 10 nm as an exciton and hole blocker.
  • an electron transporter BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) is applied by vapor deposition in a thickness of 20 nm, as are a 0.75 nm-thick lithium fluoride layer and finally a 100 nm-thick Al electrode. All components are adhesive-bonded to a glass lid in an inert nitrogen atmosphere.
  • electroluminescence spectra are recorded at different currents and voltages.
  • the current-voltage characteristic is measured in combination with the light output emitted.
  • the light output can be converted to photometric parameters by calibration with a photometer.
  • the lifetime t 1/2 of the diode is defined by the time taken for the luminance to fall to 50% of its initial value. The lifetime measurement is carried out at a constant current.
  • ITO-40 nm AJ20-1000-35 nm Ir(DPBIC) 3 mixed with MoO x -10 nm Ir(DPBIC) 3 -40 nm Ma1 mixed with 20 wt % Em1-i-5 nm Ma1-40 nm electron conductor-1 nm Liq-100 nm Al.
  • the preparation of the OLED is carried out in analogy to Example 17.
  • Imidazoliumiodide C6 corresponds to a pre-intermediate of the compound “example 1” in WO 2006056418.
  • the synthesis is carried out in analogy to the synthesis of the compound “example 1” in WO 2006056418.
  • ⁇ 0.83 (d, 3H), 0.89-0.96 (m, probably interpreted as 4 ⁇ d, 12H), 1.00 (d, 3H), 1.13 (d, 3H), 1.15 (d, 3H), 1.98 (sept, 1H), 2.31 (sept, 1H), 2.70 (sept, 1H), 2.74 (sept, 1H), 3.21 (s, 3H), 6.10 (dd, 2H), 6.37-6.45 (m, 4H), 6.56-6.65 (m, 4H), 6.70 (dd, 1H), 6.83 (m c , 1H), 6.95 (d, 1H), 7.06 (m c , 1H), 7.19 (m c , 2H), 7.25-7.31 (m, 4H), 7.44-7.50 (m, 3H).
  • ⁇ 0.65 (d, 3H), 0.77 (d, 3H), 0.85 (d, 3H), 0.97 (d, 3H), 0.98 (d, 3H), 1.02 (d, 3H), 1.13 (d, 6H), 1.82 (sept, 1H), 2.33 (sept, 1H), 2.54 (sept, 1H), 2.67 (sept, 1H), 3.04 (s, 3H), 6.09 (dd, 2H), 6.37 (td, 1H), 6.40-6.44 (m, 3H), 6.50 (m, 1H), 6.59 (d, 1H), 6.61 (td, 1H), 6.68 (d, 1H), 6.70 (d, 1H), 6.72 (d, 1H), 6.86 (d, 1H), 6.96 (br.s, 1H), 7.14 (m c , 2H), 7.20-7.23 (m, 1H), 7.23-7.31 (m, 3H), 7.44-7.50 (m, 3H).
  • the photoluminescence quantum efficiency of the isomer Em9-i has the 1.14-fold value of the quantum efficiency of the isomer Em9-s.
  • a solution of 19.50 g (58.7 mmol) 2-anilino-1,2-di-o-tolyl-ethanone in 80 ml of tetrahydrofuran is meaned with 7.80 g (88.1 mmol) acetformylanhydride and stirred for 17 hours at room temperature.
  • the reaction mixture is reduced at a rotarap to a syrup and purified at silica gel with a petrol ether-acetic ester solution as eluent at first in a ratio of 10:1 then 1:1. After removal of the solvent 18.4 g (91%) of a nearly colorless syrup are obtained.
  • Step 4 Preparation of 1,3-diphenyl-4,5-di-o-tolylimidazolium-tetrafluoroborate C7
  • a suspension of 1.61 g (3.30 mmol) 1,3-diphenyl-4,5-di-o-tolyl-imidazolium-tetrafluoroborate in 25 ml of toluene are stirred for 15 min under argon at room temperature and then cooled to 0° C. 12.6 ml (6.29 mmol) 0.5 M potassium-bis(trimethylsilyl)-amide in toluene are added with 1 min.
  • the reaction solution is then stirred for 15 min at 0-12° C., and subsequently, 2.50 g (1.50 mmol) bis(iridium-p-chloro-complex) D1 are added. It is purged with 5 ml of toluene.
  • the orange-yellow suspension is heated under reflux to boiling. After 75 min the reaction solution is cooled to room temperature diluted with 20 ml acetic ester and then extracted two times with 20 ml of phosphate buffer solution (ph 7). The organic phase is separated, dryed over sodium sulfate and then reduced to dryness. The solid is shortly heated in 150 ml of methanol under reflux to boiling. After cooling of the suspension to 50° C. the solid is sucked, washed two times with 10 ml of methanol each and dryed. 2.52 g of a yellow solid are obtained. The filtrate is reduced to 40 ml and stirred overnight at room temperature. The precipitate is sucked, washed with a small amount of methanol and dried. 0.28 g of a yellow solid are obtained, which is combined with the residue.
  • Em10-s 0.50 g (0.42 mmol) of Em10-s are dissolved in 300 ml of acetonitril and irradiated with a mercury pressure dipping lamp TQ 150 (365 nm, 150 W) for 5.5 hours. The solution is freed from the solvent. The residue is dissolved in 30 ml of methanol by heating. After cooling the precipitate is sucked, washed with methanol and dried. The complex isomer Em10-i [0.19 g (38%)] is obtained as yellow powder melting at 316-317° C.
  • Structure B ITO-AJ20-1000-35 nm Ir(DPBIC) 3 mixed with 10 wt.-% MoO 3 -10 nm Ir(DPBIC) 3 -40 nm “MaX” mixed with 15 wt.-% Em1-i-10 nm LB1-20 nm electron conductor BCP-0.70 nm LiF-100 nm Al.
  • the preparation of the diode is carried out in analogy to Example 17.
  • the preparation of the diode is carried out in analogy to Example 17.
  • matrix material Ma10 is described in JP2009046408, compound B, [0039], p. 13.

Abstract

The present invention relates to heteroleptic complexes comprising a phenylimidazole or phenyltriazole unit bonded via a carbene bond to a central metal atom, and phenylimidazole ligands attached via a nitrogen-metal bond to the central atom, to OLEDs which comprise such heteroleptic complexes, to light-emitting layers comprising at least one such heteroleptic complex, to a device selected from the group consisting of illuminating elements, stationary visual display units and mobile visual display units comprising such an OLED, to the use of such a heteroleptic complex in OLEDs, for example as emitter, matrix material, charge transport material and/or charge blocker.

Description

  • The present invention relates to heteroleptic complexes comprising a phenylimidazole or phenyltriazole unit bonded via a carbene bond to a central metal atom, and phenylimidazole ligands attached via a nitrogen-metal bond to the central atom, to OLEDs which comprise such heteroleptic complexes, to light-emitting layers comprising at least one such heteroleptic complex, to a device selected from the group consisting of illuminating elements, stationary visual display units and mobile visual display units comprising such an OLED, to the use of such a heteroleptic complex in OLEDs, for example as emitter, matrix material, charge transport material and/or charge blocker.
  • Organic Light-Emitting Diodes (OLEDs) exploit the property of materials to emit light when they are excited by electrical current. OLEDs are of particular interest as an alternative to cathode ray tubes and liquid-crystal displays for production of flat visual display units. Owing to the very compact design and the intrinsically low power consumption, devices comprising OLEDs are suitable especially for mobile applications, for example for applications in cellphones, laptops, etc. In addition, white OLEDs give great advantages over the illumination technologies known to date, especially a particularly high efficiency.
  • The prior art proposes numerous materials, examples of which include heteroleptic complexes with iridium as the central metal atom, which emit light on excitation by electrical current.
  • WO 2006/121811 A1 discloses phosphorescent heteroleptic metal complexes which comprise carbene ligands. The complexes specified in WO 2006/121811 A1, for example iridium complexes, all have benzimidazolocarbenes (benzimidazolylidenes) as carbene ligands. Compounds which have imidazolocarbenes (imidazolylidenes) or triazolocarbenes (triazolylidenes) as ligands are not disclosed in WO 2006/121811 A1.
  • WO 2006/067074 A1 likewise discloses electroluminescent heteroleptic metal complexes with carbene ligands. The noncarbene ligands used include arylpyridines, arylpyrazoles and aryltriazoles. Use of 2-phenyl-1H-imidazoles as noncarbene ligands is not disclosed in WO 2006/067074 A1.
  • WO 2007/115981 discloses heteroleptic metal complexes comprising both carbene ligands and heterocyclic noncarbene ligands, a process for preparation thereof, and the use of these compounds in OLEDs. The compounds disclosed by way of example in WO 2007/115981 do not comprise a combination of 2-phenyl-1H-imidazole ligands with an imidazolocarbene (imidazolylidene) ligand or a triazolocarbene (triazolylidene) ligand.
  • JP 2009057505 discloses optoelectronic components which comprise compounds with tunable emission wavelength, high light emission efficiency and long lifetime. The components according to this document comprise metal complexes which, as well as two ligands optionally joined to one another, comprise at least one ligand attached to the metal atom firstly via a carbene bond and secondly via a noncarbene bond. No combination of a 2-phenyl-1H-imidazole ligand with an imidazolocarbene (imidazolylidene) ligand or a triazolocarbene (triazolylidene) ligand is disclosed.
  • Even though compounds which exhibit electroluminescence in the visible region, more particularly in the red, green and especially blue region of the electromagnetic spectrum, for example iridium complexes, are already known, the provision of alternative compounds which possess high quantum yields and exhibit long diode lifetimes is desirable. In the context of the present invention, electroluminescence is understood to mean both electrofluorescence and electrophosphorescence.
  • It is therefore an object of the present invention to provide alternative iridium and platinum complexes which are suitable for electroluminescence in the visible region, more particularly in the red, green and especially blue region of the electromagnetic spectrum, which enables the production of full-color displays and white OLEDs. It is a further object of the present invention to provide corresponding complexes which can be used as a mixture with a host compound (matrix material) or in substance, i.e. in the absence of host substances, as a light-emitting layer in OLEDs. It is a further object of the present invention to provide corresponding complexes which have a high quantum yield and a high stability in diodes. The complexes should be usable as emitter, matrix material, charge transport material, especially hole transport material, or charge blocker in OLEDs.
  • These objects are achieved in accordance with the invention by heteroleptic complexes of the general formula (I)
  • Figure US20120205645A1-20120816-C00001
  • in which M, A1, A2, n, m, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are each defined as follows:
    • M is a metal atom selected from the group consisting of Ir and Pt,
    • A1, A2 are each independently N or C,
    • n, m are each independently 1 or 2, where, if M is Pt, the sum of n and m is 2, or, if M is Ir, the sum of n and m is 3,
    • R1 is a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 5 to 18 carbon atoms and/or heteroatoms,
    • R2, R3 are each independently hydrogen, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 5 to 18 carbon atoms and/or heteroatoms,
    • R4, R5,
    • R6, R7 are each independently hydrogen, substituent with donor or acceptor action, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 5 to 18 carbon atoms and/or heteroatoms,
      or
      R4 and R5 or R5 and R6 and/or R6 and R7 together form a saturated, unsaturated or aromatic carbon ring optionally interrupted by at least one heteroatom and having a total of 5 to 30 carbon atoms or heteroatoms,
    • R8, R9 are each independently a free electron pair if A1 or A2 is N, or, if A1 or A2 is C, hydrogen, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 5 to 18 carbon atoms and/or heteroatoms,
    • R10 linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 5 to 18 carbon atoms and/or heteroatoms
    • R11, R12,
    • R13, R14 are each independently hydrogen, substituent with donor or acceptor action, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 5 to 18 carbon atoms and/or heteroatoms,
      or
      R11 and R12 or R12 and R13 and/or R13 and R14 together form a saturated, unsaturated or aromatic carbon ring optionally interrupted by at least one heteroatom and having a total of 5 to 30 carbon atoms and/or heteroatoms
      and/or
      R1 and R14 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused,
      and/or
      if A1 is C, R7 and R8 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused.
  • In the context of the present invention, the terms aryl radical, unit or group, heteroaryl radical, unit or group, alkyl radical, unit or group and cycloalkyl radical, unit or group are each defined as follows, as long as no different meanings are mentioned:
  • An aryl radical or group is understood to mean a radical with a base skeleton of 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, which is formed from an aromatic ring or a plurality of fused aromatic rings. Suitable base skeletons are, for example, phenyl, benzyl, naphthyl, anthracenyl or phenanthrenyl. This base skeleton may be unsubstituted, which means that all carbon atoms which are substitutable bear hydrogen atoms, or may be substituted at one, more than one or all substitutable positions of the base skeleton. Suitable substituents are, for example, alkyl radicals, preferably alkyl radicals having 1 to 8 carbon atoms, more preferably methyl, ethyl, i-propyl or t-butyl, aryl radicals, preferably C6-aryl radicals, which may in turn be substituted or unsubstituted, heteroaryl radicals, preferably heteroaryl radicals which comprise at least one nitrogen atom, more preferably pyridyl radicals, alkenyl radicals, preferably alkenyl radicals which bear one double bond, more preferably alkenyl radicals with one double bond and 1 to 8 carbon atoms, or groups with donor or acceptor action. Groups with donor action are understood to mean groups which have a +I and/or +M effect, and groups with acceptor action are understood to mean groups which have a −I and/or −M effect. Suitable groups with donor or acceptor action are halogen radicals, preferably F, Cl, Br, more preferably F, alkyl radicals, alkoxy radicals, aryloxy radicals, carbonyl radicals, ester radicals, amine radicals, amide radicals, CH2F groups, CHF2 groups, CF3 groups, CN groups, thio groups or SCN groups. The aryl radicals most preferably bear substituents selected from the group consisting of methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, tert-butyl, aryloxy, amine, thio groups and alkoxy, or the aryl radicals are unsubstituted. The aryl radical or the aryl group is preferably a C6-aryl radical optionally substituted by at least one of the aforementioned substituents. The C6-aryl radical more preferably has none, one, two or three of the aforementioned substituents.
  • A heteroaryl radical or a heteroaryl group is understood to mean radicals having 5 to 30 carbon atoms and/or heteroatoms, which differ from the aforementioned aryl radicals in that at least one carbon atom in the base skeleton of the aryl radicals is replaced by a heteroatom. Preferred heteroatoms are N, O and S. Most preferably, one or two carbon atoms of the base skeleton of the aryl radicals are replaced by heteroatoms. The base skeleton is especially preferably selected from electron-poor systems such as pyridyl, pyrimidyl, pyrazyl and triazolyl, and five-membered heteroaromatics such as pyrrole, furan, thiophene, imidazole, pyrazole, triazole, oxazole and thiazole. The base skeleton may be substituted at one, more than one or all substitutable positions of the base skeleton. Suitable substituents are the same as have already been specified above for the aryl groups.
  • An alkyl radical or an alkyl group is understood to mean a radical having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. This alkyl radical may be branched or unbranched and may optionally be interrupted by one or more heteroatoms, preferably N, O or S. In addition, this alkyl radical may be substituted by one or more of the substituents already specified for the aryl groups. It is likewise possible that the alkyl radical bears one or more aryl groups. All of the aryl groups listed above are suitable. Particular preference is given to the alkyl radicals selected from the group consisting of methyl, ethyl, i-propyl, n-propyl, i-butyl, n-butyl, t-butyl, sec-butyl, i-pentyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl, i-hexyl and sec-hexyl. Very particular preference is given to methyl, i-propyl, tert-butyl.
  • A cycloalkyl radical or a cycloalkyl group is understood to mean a cyclic radical having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms. This cycloalkyl radical may optionally be interrupted by one or more heteroatoms, preferably N, O or S. In addition, this cycloalkyl radical may be unsubstituted or substituted, i.e. may be substituted by one or more of the substituents already specified for the aryl groups. It is likewise possible that the cycloalkyl radical bears one or more aryl groups. All of the aryl groups listed above are suitable.
  • The statements made for the aryl, heteroaryl, alkyl and cycloalkyl radicals applies, in accordance with the invention, independently to the radicals mentioned in the present application, especially to the R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 radicals, where R8 and R9, in the case that A1 and/or A2 is N, are a free electron pair, which means that no substituent selected from the abovementioned group is present on these ring nitrogen atoms. In the case that A1 and/or A2 is C, R8 and R9 are each independently hydrogen and/or the substituents specified.
  • In a preferred embodiment, M, A1, A2, n, m, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are each defined as follows:
  • According to the invention, M is Ir or Pt, preferably Ir. Ir is present in the inventive heteroleptic complexes in the +3 oxidation state. Pt is present in the inventive heteroleptic complexes in the +2 oxidation state.
  • According to the invention, A1 and A2 are each independently C or N. Preference is given in accordance with the invention to the following embodiments:
    • 1. Both A1 and A2 are C, i.e. the inventive heteroleptic complexes comprise at least one phenylimidazole unit attached via a metal-carbene bond.
    • 2. In a further preferred embodiment, A1 and A2 are each N or C, where A1=N when A2=C or A1=C when A2 is N, i.e. one of A1 and A2 is N, the other is C. In this embodiment, the inventive heteroleptic complexes comprise at least one phenyltriazole unit attached via a metal-carbene bond.
  • n and m are each independently 1 or 2, where, if M is Pt, the sum of n and m is 2, or, if M is Ir, the sum of n and m is 3. Therefore, if M is Pt, n and m are each 1. If M is Ir, preferably, n=2 and m=1.
  • In a preferred embodiment, R1 is a linear or branched alkyl radical having 1 to 20 carbon atoms, a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms.
  • R1 is more preferably a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, most preferably a substituted, especially ortho,ortho′- or ortho,ortho′,para-substituted, or unsubstituted phenyl radical. The substituents are preferably alkyl radicals having 1 to 10, especially 1 to 6, carbon atoms, for example methyl, ethyl, propyl, butyl. Very particularly preferred R1 radicals are phenyl, 2,6-dimethylphenyl, 2,6-di-iso-propylphenyl or 2,4,6-trimethylphenyl, i.e. mesityl.
  • The present invention therefore relates more particularly to an inventive heteroleptic complex where R1 is an aryl radical which has 6 to 30 carbon atoms and is substituted in the ortho,ortho′ positions in each case by a linear or branched alkyl radical having 1 to 10 carbon atoms.
  • In a preferred embodiment, R2, R3 are each independently hydrogen, a linear or branched alkyl radical having 1 to 20 carbon atoms, a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms.
  • In a preferred embodiment, R4, R5, R6, R7 are each hydrogen or R4 and R5 or R5 and R6 or R6 and R7, especially R5 and R6 or R6 and R7, together form a saturated, unsaturated or aromatic carbon ring optionally interrupted by at least one heteroatom and having a total of 6 to 30 carbon atoms.
  • In a very particularly preferred embodiment of the inventive heteroleptic complex, R4 and R5 or R5 and R6 or R6 and R7 together form a cycle of the general formula (IIa) or (IIb)
  • Figure US20120205645A1-20120816-C00002
  • In a further preferred embodiment, R8, R9 are each independently a free electron pair if A1 or A2 is N, or, if A1 or A2 is C, hydrogen or linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms or substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms, most preferably phenyl radical.
  • In a preferred embodiment, R10 is a linear or branched alkyl radical having 1 to 20 carbon atoms, more preferably having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, more preferably having 6 to 10 carbon atoms. Examples of particularly preferred alkyl radicals for R10 are methyl, ethyl, propyl, especially isopropyl, butyl, especially tert-butyl, or pentyl. Examples of particularly preferred aryl radicals for R10 are unsubstituted phenyl or substituted phenyl, preferably substituted in the ortho position, for example by alkyl radicals having 1 to 6 carbon atoms, for example methyl, ethyl or propyl, especially isopropyl.
  • In a preferred embodiment, R11, R12, R13, R14 are each independently hydrogen or a linear or branched alkyl radical having 1 to 20 carbon atoms, more preferably hydrogen.
  • In a further embodiment of the inventive heteroleptic complexes, R1 and R14 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused. Most preferably, R1 and R14 form an unsaturated bridge having two carbon atoms, to which a six-membered aromatic ring is fused, which is either unsubstituted or substituted by one or two alkyl radicals having 1 to 6 carbon atoms, for example methyl or ethyl.
  • In a further embodiment of the inventive heteroleptic complexes, if A1 is C, R7 and R8 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused. Most preferably, R7 and R8 form an unsaturated bridge having two carbon atoms, to which a six-membered aromatic ring is fused, which is either unsubstituted or substituted by one or two alkyl radicals having 1 to 6 carbon atoms, for example methyl or ethyl.
  • The present invention more preferably relates to inventive heteroleptic complexes of the general formula (I) where M, A1, A2, n, m, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are each defined as follows:
    • M is Ir,
    • A1, A2 is C,
    • n, m are each independently 1 or 2, where the sum of n and m is 3; preferably, n=2 and m=1,
    • R1 is a linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms; preferably R1 is an unsubstituted or substituted aryl radical,
    • R2, R3 are each independently hydrogen, linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms; preferably R2 and R3 are each hydrogen,
    • R4, R5,
    • R6, R7 are each hydrogen
      • or
        R4 and R5 or R5 and R6 or R6 and R7 together form a saturated, unsaturated or aromatic ring optionally interrupted by at least one heteroatom and having a total of 5 to 30 carbon atoms and/or heteroatoms,
    • R8, R9 are each hydrogen,
    • R10 is a linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, and
    • R11, R12,
    • R13, R14 are each independently hydrogen or linear or branched alkyl radical having 1 to 20 carbon atoms,
      and/or
      R1 and R14 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused,
      and/or
      R7 and R8 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused.
  • The abovementioned preferred and particularly preferred embodiments apply correspondingly.
  • The present invention preferably further relates to inventive heteroleptic complexes of the general formula (I) where M, A1, A2, n, m, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are each defined as follows:
    • M is Ir,
    • A1, A2 are each N or C, where A1=N when A2=C and A1=C when A2=N
    • n, m are each independently 1 or 2, where the sum of n and m is 3; preferably n=2 and m=1,
    • R1 is a linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms; preferably R1 is a substituted or unsubstituted aryl radical,
    • R2, R3 are each independently hydrogen, linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms; preferably, R2 and R3 are each hydrogen,
    • R4, R5,
    • R6, R7 are each hydrogen
      or
      R4 and R5 or R5 and R6 or R6 and R7 together form a saturated, unsaturated or aromatic ring optionally interrupted by at least one heteroatom and having a total of 5 to 30 carbon atoms and/or heteroatoms,
    • R8, R9 are each independently a free electron pair if A1 or A2 is N, or, if A1 or A2 is C, hydrogen, linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms,
    • R10 linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, and
    • R11, R12,
    • R13, R14 hydrogen or linear or branched alkyl radical having 1-20 carbon atoms
      and/or
      R1 and R14 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused,
      and/or
      R7 and R8 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused.
  • The abovementioned preferred and particularly preferred embodiments apply correspondingly.
  • The present invention preferably also relates to inventive heteroleptic complexes of the general formula (I) where M, A1, A2, n, m, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are each defined as follows:
    • M is Ir,
    • A1 is C,
    • A2 is N or C,
    • n, m are each independently 1 or 2, where the sum of n and m is 3; preferably n=2 and m=1,
    • R1 is a linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms; preferably, R1 is a substituted or unsubstituted aryl radical,
    • R2, R3 are each independently hydrogen, linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms; preferably R2 and R3 are each hydrogen,
    • R4, R5,
    • R6 are each independently hydrogen, linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms,
    • R7, R8 together form an unsaturated C2 bridge, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, may be fused,
    • R9 is a free electron pair if A2 is N or, if A2 is C, hydrogen, linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms,
    • R10 is a linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, and
    • R11, R12,
    • R13, R14 are each independently hydrogen or linear or branched alkyl radical having 1 to 20 carbon atoms,
      and/or
    • R1 and R14 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused.
  • The latter embodiment corresponds to the following general formula (Ib):
  • Figure US20120205645A1-20120816-C00003
  • Very particularly preferred inventive heteroleptic complexes of the general formula (I) have the ligands depicted in table 1, especially preferably in the combinations shown:
  • TABLE 1
                            Ligands
    Figure US20120205645A1-20120816-C00004
    Figure US20120205645A1-20120816-C00005
    K1 
    Figure US20120205645A1-20120816-C00006
    Figure US20120205645A1-20120816-C00007
    K2 
    Figure US20120205645A1-20120816-C00008
    Figure US20120205645A1-20120816-C00009
    K3 
    Figure US20120205645A1-20120816-C00010
    Figure US20120205645A1-20120816-C00011
    K4 
    Figure US20120205645A1-20120816-C00012
    Figure US20120205645A1-20120816-C00013
    K5 
    Figure US20120205645A1-20120816-C00014
    Figure US20120205645A1-20120816-C00015
    K6 
    Figure US20120205645A1-20120816-C00016
    Figure US20120205645A1-20120816-C00017
    K7 
    Figure US20120205645A1-20120816-C00018
    Figure US20120205645A1-20120816-C00019
    K8 
    Figure US20120205645A1-20120816-C00020
    Figure US20120205645A1-20120816-C00021
    K9 
    Figure US20120205645A1-20120816-C00022
    Figure US20120205645A1-20120816-C00023
    K10
    Figure US20120205645A1-20120816-C00024
    Figure US20120205645A1-20120816-C00025
    K11
    Figure US20120205645A1-20120816-C00026
    Figure US20120205645A1-20120816-C00027
    K12
    Figure US20120205645A1-20120816-C00028
    Figure US20120205645A1-20120816-C00029
    K13
    Figure US20120205645A1-20120816-C00030
    Figure US20120205645A1-20120816-C00031
    K14
    Figure US20120205645A1-20120816-C00032
    Figure US20120205645A1-20120816-C00033
    K15
    Figure US20120205645A1-20120816-C00034
    Figure US20120205645A1-20120816-C00035
    K16
    Figure US20120205645A1-20120816-C00036
    Figure US20120205645A1-20120816-C00037
    K17
    Figure US20120205645A1-20120816-C00038
    Figure US20120205645A1-20120816-C00039
    K18
    Figure US20120205645A1-20120816-C00040
    Figure US20120205645A1-20120816-C00041
    K19
    Figure US20120205645A1-20120816-C00042
    Figure US20120205645A1-20120816-C00043
    K20
    Figure US20120205645A1-20120816-C00044
    Figure US20120205645A1-20120816-C00045
    K21
    Figure US20120205645A1-20120816-C00046
    Figure US20120205645A1-20120816-C00047
    K22
    Figure US20120205645A1-20120816-C00048
    Figure US20120205645A1-20120816-C00049
    K23
    Figure US20120205645A1-20120816-C00050
    Figure US20120205645A1-20120816-C00051
    K24
    Figure US20120205645A1-20120816-C00052
    Figure US20120205645A1-20120816-C00053
    K25
    Figure US20120205645A1-20120816-C00054
    Figure US20120205645A1-20120816-C00055
    K26
    Figure US20120205645A1-20120816-C00056
    Figure US20120205645A1-20120816-C00057
    K27
    Figure US20120205645A1-20120816-C00058
    Figure US20120205645A1-20120816-C00059
    K28
    Figure US20120205645A1-20120816-C00060
    Figure US20120205645A1-20120816-C00061
    K29
    Figure US20120205645A1-20120816-C00062
    Figure US20120205645A1-20120816-C00063
    K30
    Figure US20120205645A1-20120816-C00064
    Figure US20120205645A1-20120816-C00065
    K31
    Figure US20120205645A1-20120816-C00066
    Figure US20120205645A1-20120816-C00067
    K32
    Figure US20120205645A1-20120816-C00068
    Figure US20120205645A1-20120816-C00069
    K33
    Figure US20120205645A1-20120816-C00070
    Figure US20120205645A1-20120816-C00071
    K34
    Figure US20120205645A1-20120816-C00072
    Figure US20120205645A1-20120816-C00073
    K35
    Figure US20120205645A1-20120816-C00074
    Figure US20120205645A1-20120816-C00075
    K36
    Figure US20120205645A1-20120816-C00076
    Figure US20120205645A1-20120816-C00077
    K37
    Figure US20120205645A1-20120816-C00078
    Figure US20120205645A1-20120816-C00079
    K38
    Figure US20120205645A1-20120816-C00080
    Figure US20120205645A1-20120816-C00081
    K39
    Figure US20120205645A1-20120816-C00082
    Figure US20120205645A1-20120816-C00083
    K40
    Figure US20120205645A1-20120816-C00084
    Figure US20120205645A1-20120816-C00085
    K41
    Figure US20120205645A1-20120816-C00086
    Figure US20120205645A1-20120816-C00087
    K42
    Figure US20120205645A1-20120816-C00088
    Figure US20120205645A1-20120816-C00089
    K43
    Figure US20120205645A1-20120816-C00090
    Figure US20120205645A1-20120816-C00091
    K44
    Figure US20120205645A1-20120816-C00092
    Figure US20120205645A1-20120816-C00093
    K45
    Figure US20120205645A1-20120816-C00094
    Figure US20120205645A1-20120816-C00095
    K46
    Figure US20120205645A1-20120816-C00096
    Figure US20120205645A1-20120816-C00097
    K47
    Figure US20120205645A1-20120816-C00098
    Figure US20120205645A1-20120816-C00099
    K48
    Figure US20120205645A1-20120816-C00100
    Figure US20120205645A1-20120816-C00101
    K49
    Figure US20120205645A1-20120816-C00102
    Figure US20120205645A1-20120816-C00103
    K50
    Figure US20120205645A1-20120816-C00104
    Figure US20120205645A1-20120816-C00105
    K51
    Figure US20120205645A1-20120816-C00106
    Figure US20120205645A1-20120816-C00107
    K52
    Figure US20120205645A1-20120816-C00108
    Figure US20120205645A1-20120816-C00109
    K53
    Figure US20120205645A1-20120816-C00110
    Figure US20120205645A1-20120816-C00111
    K54
    Figure US20120205645A1-20120816-C00112
    Figure US20120205645A1-20120816-C00113
    K55
    Figure US20120205645A1-20120816-C00114
    Figure US20120205645A1-20120816-C00115
    K56
    Figure US20120205645A1-20120816-C00116
    Figure US20120205645A1-20120816-C00117
    K57
    Figure US20120205645A1-20120816-C00118
    Figure US20120205645A1-20120816-C00119
    K58
    Figure US20120205645A1-20120816-C00120
    Figure US20120205645A1-20120816-C00121
    K59
    Figure US20120205645A1-20120816-C00122
    Figure US20120205645A1-20120816-C00123
    K60
    Figure US20120205645A1-20120816-C00124
    Figure US20120205645A1-20120816-C00125
    K61
    Figure US20120205645A1-20120816-C00126
    Figure US20120205645A1-20120816-C00127
    K62
    Figure US20120205645A1-20120816-C00128
    Figure US20120205645A1-20120816-C00129
    K63
    Figure US20120205645A1-20120816-C00130
    Figure US20120205645A1-20120816-C00131
    K64
    Figure US20120205645A1-20120816-C00132
    Figure US20120205645A1-20120816-C00133
    K65
    Figure US20120205645A1-20120816-C00134
    Figure US20120205645A1-20120816-C00135
    K66
    Figure US20120205645A1-20120816-C00136
    Figure US20120205645A1-20120816-C00137
    K67
    Figure US20120205645A1-20120816-C00138
    Figure US20120205645A1-20120816-C00139
    K68
    Figure US20120205645A1-20120816-C00140
    Figure US20120205645A1-20120816-C00141
    K69
    Figure US20120205645A1-20120816-C00142
    Figure US20120205645A1-20120816-C00143
    K70
    Figure US20120205645A1-20120816-C00144
    Figure US20120205645A1-20120816-C00145
    K71
    Figure US20120205645A1-20120816-C00146
    Figure US20120205645A1-20120816-C00147
    K72
    Figure US20120205645A1-20120816-C00148
    Figure US20120205645A1-20120816-C00149
    K73
    Figure US20120205645A1-20120816-C00150
    Figure US20120205645A1-20120816-C00151
    K74
    Figure US20120205645A1-20120816-C00152
    Figure US20120205645A1-20120816-C00153
    K75
    Figure US20120205645A1-20120816-C00154
    Figure US20120205645A1-20120816-C00155
    K76
    Figure US20120205645A1-20120816-C00156
    Figure US20120205645A1-20120816-C00157
    K77
    Figure US20120205645A1-20120816-C00158
    Figure US20120205645A1-20120816-C00159
    K78
    Figure US20120205645A1-20120816-C00160
    Figure US20120205645A1-20120816-C00161
    K79
    Figure US20120205645A1-20120816-C00162
    Figure US20120205645A1-20120816-C00163
    K80
    Figure US20120205645A1-20120816-C00164
    Figure US20120205645A1-20120816-C00165
    K81
    Figure US20120205645A1-20120816-C00166
    Figure US20120205645A1-20120816-C00167
    K82
    Figure US20120205645A1-20120816-C00168
    Figure US20120205645A1-20120816-C00169
    K83
    Figure US20120205645A1-20120816-C00170
    Figure US20120205645A1-20120816-C00171
    K84
    Figure US20120205645A1-20120816-C00172
    Figure US20120205645A1-20120816-C00173
    K85
    Figure US20120205645A1-20120816-C00174
    Figure US20120205645A1-20120816-C00175
    K86
    Figure US20120205645A1-20120816-C00176
    Figure US20120205645A1-20120816-C00177
    K87
    Figure US20120205645A1-20120816-C00178
    Figure US20120205645A1-20120816-C00179
    K88
    Figure US20120205645A1-20120816-C00180
    Figure US20120205645A1-20120816-C00181
    K89
    Figure US20120205645A1-20120816-C00182
    Figure US20120205645A1-20120816-C00183
    K90
    Figure US20120205645A1-20120816-C00184
    Figure US20120205645A1-20120816-C00185
    K91
    Figure US20120205645A1-20120816-C00186
    Figure US20120205645A1-20120816-C00187
    K92
    Figure US20120205645A1-20120816-C00188
    Figure US20120205645A1-20120816-C00189
    K93
    Figure US20120205645A1-20120816-C00190
    Figure US20120205645A1-20120816-C00191
    K94
    Figure US20120205645A1-20120816-C00192
    Figure US20120205645A1-20120816-C00193
    K95
    Figure US20120205645A1-20120816-C00194
    Figure US20120205645A1-20120816-C00195
    K96
    Figure US20120205645A1-20120816-C00196
    Figure US20120205645A1-20120816-C00197

    in each case where M=Ir, n=2 and m=1.
  • Depending on the coordination number of the metal M present in the inventive heteroleptic complexes of the general formula (I) and the number of carbene ligands and noncarbene ligands used, different isomers of the corresponding heteroleptic metal complexes may be present with the same metal M and the same nature of the carbene ligands and noncarbene ligands used.
  • For example, for octahedral iridium(III) complexes with two noncarbene ligands and one carbene ligand, the following isomers S1 to S4 are possible, each of which may be present in the form of two enantiomers (a and b):
  • Figure US20120205645A1-20120816-C00198
    Figure US20120205645A1-20120816-C00199
  • In the present application, owing to the arrangement of the two 2-phenyl-1H-imidazole ligands, the S1a/S1b and S2a/S2b isomers are referred to as pseudo-meridional isomers and the S3a/S3b and S4a/S4b isomers as pseudo-facial isomers.
  • It has been found in accordance with the invention that, surprisingly, the S3 and S4 isomers, when used in OLEDs, give particularly good results with regard to efficiency and lifetime when used in diodes. The S3a/S3b and S4a/S4b isomers, i.e. the pseudo-facial isomers, are therefore particularly preferred in accordance with the invention.
  • More preferably, the inventive complexes of the general formula (I) which comprise two noncarbene ligands and one carbene ligand are present as pseudo-facial isomers.
  • For iridium(III) complexes with one noncarbene ligand and two carbene ligands, the following isomers T1 to T4 are possible, each of which may in turn be present in the form of two enantiomers (a and b):
  • Figure US20120205645A1-20120816-C00200
    Figure US20120205645A1-20120816-C00201
  • In the present application, owing to the arrangement of the two phenylcarbene ligands, the T1a/T1b and T2a/T2b isomers are referred to as pseudo-meridional isomers and the T3a/T3b and T4a/T4b isomers as pseudo-facial isomers.
  • It has been found in accordance with the invention that, surprisingly, the T3 and T4 isomers, when used in OLEDs, usually give particularly good results with regard to efficiency and lifetime when used in diodes. The T3a/T3b and T4a/T4b isomers, i.e. the pseudo-facial isomers, are therefore particularly preferred in accordance with the invention. More preferably, the inventive complexes of the general formula (I) which comprise one noncarbene ligand and two carbene ligands are present as pseudo-facial isomers.
  • In the case of square-planar platinum(II) complexes with one carbene ligand and one noncarbene ligand, the two isomers U1 and U2 are possible:
  • Figure US20120205645A1-20120816-C00202
  • In general, the different isomers of the heteroleptic metal complexes of the formula (I) can be separated by processes known to those skilled in the art, for example by chromatography, sublimation or crystallization. The different isomers can generally be interconverted by suitable reaction conditions (e.g. pH), thermally or photochemically.
  • The present invention relates both to the individual isomers or enantiomers of the heteroleptic complexes of the formula (I) and to mixtures of different isomers or enantiomers in any desired mixing ratio.
  • The present invention therefore relates, in a particularly preferred embodiment, to the inventive heteroleptic complexes with the general and preferred definitions specified for M, A1, A2, n, m, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14, where these have one of the following configurations IIIa, IIIb, IVa or IVb:
  • Figure US20120205645A1-20120816-C00203
    Figure US20120205645A1-20120816-C00204
  • The present invention additionally also relates to a process for preparing an inventive heteroleptic complex of the general formula (I) by
  • contacting at least one precursor compound comprising the metal M and the at least one ligand which, in the complexes of the general formula (I), is attached to M via noncarbene bonds with at least one ligand which, in the complexes of the general formula (I), is attached to M via at least one carbene bond, or the ligand precursor thereof, for example a corresponding imidazolium salt,
    or
    by contacting at least one precursor compound comprising the metal M and a ligand which, in the complexes of the general formula (I), is bonded to M via at least one carbene bond with at least one ligand which, in the complexes of the general formula (I), is attached to M via noncarbene bonds.
  • In a preferred embodiment of the process according to the invention, a complex comprising appropriate noncarbene ligands, attached to the appropriate metal M, preferably iridium, and appropriate carbene ligands, preferably in deprotonated form as the free carbene or in the form of a protected carbene, for example as the silver-carbene complex, are contacted. Suitable precursor compounds comprise the appropriate substituents R1 to R14 which are to be present in the complexes of the general formula (I).
  • Appropriate complexes comprising appropriate noncarbene ligands attached to the appropriate metal M, preferably iridium, are known to those skilled in the art. In addition to the noncarbene ligands present in the complex of the general formula (I), these complexes used as precursor compounds may comprise further ligands known to those skilled in the art, for example halides, preferably chloride. Further suitable ligands are, for example 1,5-cyclooctadiene (COD), phosphines, cyanides, alkoxides, pseudohalides and/or alkyl.
  • Particularly preferred complexes comprising appropriate noncarbene ligands, attached to the appropriate metal M, are, for example, compounds of the general formula (VI)
  • Figure US20120205645A1-20120816-C00205
  • with the abovementioned definitions of R1, R2, R3, R11, R12, R13 and R14, where Y may independently be F, Cl, Br, I, methoxy or carboxylate.
  • Particularly preferred precursor compounds for the carbene ligands used in complexes of the general formula (I) correspond, for example, to the general formulae (VII) or (VIII)
  • Figure US20120205645A1-20120816-C00206
  • with the abovementioned definitions of R4, R5, R6, R7, R8, R9, R10 and A, where Z may be F, Cl, Br, I, BF4, PF6, ClO4 or SbF6.
  • The carbene ligand precursors are deprotonated, preferably before the reaction, for example, by basic compounds known to those skilled in the art, for example basic metalates, basic metal acetates, acetylacetonates or alkoxides, or bases such as KOtBu, NaOtBu, LiOtBu, NaH, silylamides, Ag2O and phosphazene bases. In a further preferred embodiment, the carbene can also be released by removing volatile substances, for example lower alcohols such as methanol, ethanol, for example at elevated temperature and/or reduced pressure, from precursor compounds of the carbene ligands. Corresponding processes are known to those skilled in the art.
  • The contacting is preferably effected in a solvent. Suitable solvents are known to those skilled in the art and are preferably selected from the group consisting of aromatic or aliphatic solvents, for example benzene or toluene, cyclic or acyclic ethers, alcohols, esters, amides, ketones, nitriles, halogenated compounds and mixtures thereof. Particularly preferred solvents are toluene, xylenes, dioxane and THF.
  • The molar ratio of metal-noncarbene complex used to carbene ligand precursor used is generally 1:10 to 10:1, preferably 1:1 to 1:5, more preferably 1:2 to 1:4.
  • The contacting is generally effected at a temperature of 20 to 200° C., preferably 50 to 150° C., more preferably 60 to 130° C.
  • The reaction time depends on the desired carbene complex and is generally 0.02 to 50 hours, preferably 0.1 to 24 hours, more preferably 1 to 12 hours.
  • The complexes of the general formula (I) obtained after the reaction can optionally be purified by processes known to those skilled in the art, for example washing, crystallization or chromatography, and optionally isomerized under conditions likewise known to those skilled in the art, for example thermally or photochemically.
  • The aforementioned heteroleptic complexes and mixtures thereof are outstandingly suitable as emitter molecules in organic light-emitting diodes (OLEDs). Variations in the ligands make it possible to provide corresponding complexes which exhibit electroluminescence in the red, green and especially in the blue region of the electromagnetic spectrum. The inventive heteroleptic complexes of the general formula (I) are therefore outstandingly suitable as emitter substances, since they have emission (electroluminescence) in the visible region of the electromagnetic spectrum, for example at 400 to 800 nm, preferably 400 to 600 nm. The inventive heteroleptic complexes make it possible to provide compounds which have electroluminescence in the red, green and especially in the blue region of the electromagnetic spectrum. It is thus possible, with the aid of the inventive heteroleptic complexes as emitter substances, to provide industrially usable OLEDs.
  • Further the inventive heteroleptic complexes of the general formula (I) are suitable as matrix material, charge transport material, especially hole transport material, and/or charge blocker material.
  • The inventive heteroleptic complex of the general formula (I) are preferably suitable as emitter and/or hole transport material, more preferably as emitter.
  • Particular properties of the inventive heteroleptic complexes of the general formula (I) are particularly good efficiencies and lifetimes when used in OLEDs.
  • The present application therefore further provides an OLED comprising at least one inventive heteroleptic complex of the general formula (I). The inventive heteroleptic complex of the general formula (I) is preferably employed in the OLED as emitter, matrix material, charge transport material, expecially hole transport material, and/or hole blocker, more preferably as emitter and/or hole transport material, particularly preferably as emitter.
  • The present application also provides for the use of the heteroleptic complexes of the general formula (I) as a light-emitting layer in OLEDs, preferably as an emitter, matrix material, charge transport material, especially hole transport material, and/or charge blocker, more preferably as emitter and/or hole transport material, particularly preferably as emitter.
  • Organic light-emitting diodes are in principle formed from a plurality of layers:
      • anode (1)
      • hole-transporting layer (2)
      • light-emitting layer (3)
      • electron-transporting layer (4)
      • cathode (5).
  • However, it is also possible, that the OLED does not comprise all of the layers mentioned, an OLED formed from the layers (1) (anode), (3) (light-emitting layer) and (5) (cathode) is for example also useful, wherein the functions of the layers (2) (hole-transport layer) and (4) (electron-transporting layer) are taken over by the adjacent layers. OLEDs comprising the layers (1), (2), (3) and (5) respectively the layers (1), (3), (4) and (5) are also suitable.
  • The heteroleptic complexes of the general formula (I) are preferably used as emitter molecules and/or matrix materials in the light-emitting layer (3). The inventive heteroleptic complexes of the general formula (I) can also be employed—in addition to the application as emitter molecules and/or matrix materials in the light-emitting layer (3) or instead of the application in the light-emitting layer—as charge transport material in the hole-transporting layer (2) or in the electron-transporting layer (4) and/or as charge blocker, wherein the application as charge transport material in the hole-transporting layer (2) (hole-transport material) is preferred.
  • The present application therefore further provides a light-emitting layer comprising at least one of the inventive heteroleptic complexes of the general formula (I), preferably as emitter molecule. Preferred heteroleptic complexes of the general formula (I) have already been specified above.
  • The heteroleptic complexes of the general formula (I) used in accordance with the invention may be present in the light-emitting layer in substance, i.e. without further additions. However, it is also possible that, in addition to the heteroleptic complexes of the general formula (I) used in accordance with the invention, further compounds are present in the light-emitting layer. For example, a fluorescent dye may be present in order to alter the emission color of the heteroleptic complex used as the emitter molecule. In addition, a diluent material (matrix material) may be used. This diluent material may be a polymer, for example poly(N-vinylcarbazole) or polysilane. The diluent material may, however, likewise be a small molecule, for example 4,4′-N,N′-dicarbazolebiphenyl (CDP) or tertiary aromatic amines. When a diluent material is used, the proportion of the inventive heteroleptic complexes of the general formula (I) used in the light-emitting layer is generally less than 40% by weight, preferably 3 to 30% by weight. The inventive heteroleptic complexes of the general formula (I) are preferably used in a matrix. The light-emitting layer thus preferably comprises at least one inventive heteroleptic complex of the general formula (I) and at least one matrix material as diluent material.
  • Suitable matrix materials are—in addition to the aforementioned dilution materials—in principle the materials specified hereinafter as hole and electron transport materials, and also carbene complexes, for example the carbene complexes of the formula (I) or the carbene complexes mentioned in WO 2005/019373. Particularly suitable are carbazole derivatives, for example 4,4′-bis(carbazol-9-yl)-2,2′-dimethylbiphenyl (CDBP), 4,4′-bis(carbazol-9-yl)biphenyl (CBP), 1,3-bis(N-carbazolyl)benzene (mCP), and the matrix materials specified in the following applications: WO2008/034758, WO2009/003919.
  • Further suitable matrix materials, which may be small molecules or (co)polymers of the small molecules mentioned, are specified in the following publications:
  • WO2007108459 (H-1 to H-37), preferably H-20 to H-22 and H-32 to H-37, most preferably H-20, H-32, H-36, H-37, WO2008035571 A1 (Host 1 to Host 6), JP2010135467 (compounds 1 to 46 and Host-1 to Host-39 and Host-43), WO2009008100 compounds No. 1 to No. 67, preferably No. 3, No. 4, No. 7 to No. 12, No. 55, No. 59, No. 63 to No. 67, more preferably No. 4, No. 8 to No. 12, No. 55, No. 59, No. 64, No. 65, and No. 67, WO2009008099 compounds No. 1 to No. 110, WO2008140114 compounds 1-1 to 1-50, WO2008090912 compounds 00-7 to 00-36 and the polymers of Mo-42 to Mo-51, JP2008084913 H-1 to H-70, WO2007077810 compounds 1 to 44, preferably 1, 2, 4-6, 8, 19-22, 26, 28-30, 32, 36, 39-44, WO201001830 the polymers of monomers 1-1 to 1-9, preferably of 1-3, 1-7, and 1-9, WO2008029729 the (polymers of) compounds 1-1 to 1-36, WO20100443342 HS-1 to HS-101 and BH-1 to BH-17, preferably BH-1 to BH-17, JP2009182298 the (co)polymers based on the monomers 1 to 75, JP2009170764, JP2009135183 the (co)polymers based on the monomers 1-14, WO2009063757 preferably the (co)polymers based on the monomers 1-1 to 1-26, WO2008146838 the compounds a-1 to a-43 and 1-1 to 1-46, JP2008207520 the (co)polymers based on the monomers 1-1 to 1-26, JP2008066569 the (co)polymers based on the monomers 1-1 to 1-16, WO2008029652 the (co)polymers based on the monomers 1-1 to 1-52, WO2007114244 the (co)polymers based on the monomers 1-1 to 1-18, JP2010040830 the compounds HA-1 to HA-20, HB-1 to HB-16, HC-1 to HC-23 and the (co)polymers based on the monomers HD-1 to HD-12, JP2009021336, WO2010090077 the compounds 1 to 55, WO2010079678 the compounds H1 to H42, WO2010067746, WO2010044342 the compounds HS-1 to HS-101 and Poly-1 to Poly-4, JP2010114180 the compounds PH-1 to PH-36, US2009284138 the compounds 1 to 111 and H1 to H71, WO2008072596 the compounds 1 to 45, JP2010021336 the compounds H-1 to H-38, preferably H-1, WO2010004877 the compounds H-1 to H-60, JP2009267255 the compounds 1-1 to 1-105, WO2009104488 the compounds 1-1 to 1-38, WO2009086028, US2009153034, US2009134784, WO2009084413 the compounds 2-1 to 2-56, JP2009114369 the compounds 2-1 to 2-40, JP2009114370 the compounds 1 to 67, WO2009060742 the compounds 2-1 to 2-56, WO2009060757 the compounds 1-1 to 1-76, WO2009060780 the compounds 1-1 to 1-70, WO2009060779 the compounds 1-1 to 1-42, WO2008156105 the compounds 1 to 54, JP2009059767 the compounds 1 to 20, JP2008074939 the compounds 1 to 256, JP2008021687 the compounds 1 to 50, WO2007119816 the compounds 1 to 37, WO2010087222 the compounds H-1 to H-31, WO2010095564 the compounds HOST-1 to HOST-61, WO2007108362, WO2009003898, WO2009003919, WO2010040777, US2007224446 and WO06128800.
  • In a particularly preferred embodiment, one or more compounds of the general formula (X) specified hereinafter are used as matrix material. Preferred embodiments of the compounds of the general formula (X) are likewise specified hereinafter.
  • The matrix materials mentioned above as well as the compounds of the general formula (X) mentioned below are not only applicable as matrix material in the light-emitting layer, but also as matrix materials in other layers of an OLED, for example in the electron-transport layer and/or in the hole transport layer. It is also possible, to apply two or more different matrix materials mentioned before and/or compounds of the general formula (X) mentioned below as matrix materials.
  • In order to obtain particularly efficient OLEDs, the HOMO (highest occupied molecular orbital) of the hole-transporting layer should be aligned to the work function of the anode, and the LUMO (lowest unoccupied molecular orbital) of the electron-transporting layer should be aligned to the work function of the cathode.
  • The present application further provides an OLED comprising at least one inventive light-emitting layer. The further layers in the OLED may be formed from any material which is typically used in such layers and is known to those skilled in the art.
  • Suitable materials for the aforementioned layers (anode, cathode, hole and electron injection materials, hole and electron transport materials and hole and electron blocker materials, matrix materials, fluorescence and phosphorescence emitters) are known to those skilled in the art and are specified, for example, in H. Meng, N. Herron, Organic Small Molecule Materials for Organic Light-Emitting Devices in Organic Light-Emitting Materials and Devices, eds: Z. Li, H. Meng, Taylor & Francis, 2007, Chapter 3, pages 295 to 411.
  • The anode is an electrode which provides positive charge carriers. It may be composed, for example, of materials which comprise a metal, a mixture of different metals, a metal alloy, a metal oxide or a mixture of different metal oxides. Alternatively, the anode may be a conductive polymer. Suitable metals comprise the metals of groups 11, 4, 5 and 6 of the Periodic Table of the Elements, and also the transition metals of groups 8 to 10. When the anode is to be transparent, mixed metal oxides of groups 12, 13 and 14 of the Periodic Table of the Elements are generally used, for example indium tin oxide (ITO). It is likewise possible that the anode (1) comprises an organic material, for example polyaniline, as described, for example, in Nature, Vol. 357, pages 477 to 479 (Jun. 11, 1992). At least either the anode or the cathode should be at least partly transparent in order to be able to emit the light formed.
  • Suitable hole transport materials for layer (2) of the inventive OLED are disclosed, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pages 837 to 860, 1996. Either hole-transporting molecules or polymers may be used as the hole transport material. Customarily used hole-transporting molecules are selected from the group consisting of 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (α-NPD), N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine (TPD), 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine (ETPD), tetrakis(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA), α-phenyl-4-N,N-diphenylaminostyrene (TPS), p-(diethylamino)benzaldehyde diphenylhydrazone (DEH), triphenylamine (TPA), bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP), 1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline (PPR or DEASP), 1,2-trans-bis(9H-carbazol-9-yl)-cyclobutane (DCZB), N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB), fluorene compounds such as 2,2′,7,7′-tetra(N,N-di-tolyl)amino-9,9-spirobifluorene (spiro-TTB), N,N′-bis(naphthalene-1-yl)-N,N′-bis(phenyl)-9,9-spirobifluorene (spiro-NPB) and 9,9-bis(4-(N,N-bis-biphenyl-4-yl-amino)phenyl-9H-fluorene, benzidine compounds such as N,N′-bis(naphthalene-1-yl)-N,N′-bis(phenyl)benzidine and porphyrin compounds such as copper phthalocyanines. Customarily used hole-transporting polymers are selected from the group consisting of polyvinylcarbazoles, (phenylmethyl)polysilanes and polyanilines. It is likewise possible to obtain hole-transporting polymers by doping hole-transporting molecules into polymers such as polystyrene and polycarbonate. Suitable hole-transporting molecules are the molecules already mentioned above.
  • In addition—in one embodiment—it is possible to use carbene complexes as hole conductor materials, in which case the band gap of the at least one hole conductor material is generally greater than the band gap of the emitter material used. In the context of the present invention, band gap is understood to mean the triplet energy. Suitable carbene complexes are, for example, the inventive carbene complexes of the general formula (I), carbene complexes as described in WO 2005/019373 A2, WO 2006/056418 A2, WO 2005/113704, WO 2007/115970, WO 2007/115981 and WO 2008/000727. One example of a suitable carbene complex is Ir(DPBIC)3 with the formula:
  • Figure US20120205645A1-20120816-C00207
  • It is likewise possible to use mixtures in the hole-transporting layer, in particular mixtures which lead to electrical p-doping of the hole-transporting layer. p-Doping is achieved by the addition of oxidizing materials. These mixtures may, for example, be the following mixtures: mixtures of the abovementioned hole transport materials with at least one metal oxide, for example MoO2, MoO3, WOx, ReO3, and/or preferably MoO3 and/or ReO3, more preferably ReO3 or mixtures comprising the aforementioned hole transport materials and one or more compounds selected from V2O5, 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), 2,5-bis(2-hydroxyethoxy)-7,7,8,8-tetracyanoquinodimethane, bis(tetra-n-butylammonium)tetracyanodiphenoquino-dimethane, 2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene, 11,11,12,12-tetracyanonaphtho-2,6-quinodimethane, 2-fluoro-7,7,8,8-tetracyanoquino-dimethane, 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane, dicyanomethylene-1,3,4,5,7,8-hexafluoro-6H-naphthalen-2-ylidene)malononitrile (F6-TNAP), Mo(tfd)3 (from Kahn et al., J. Am. Chem. Soc. 2009, 131 (35), 12530-12531), compounds as mentioned in EP 1 988 587 and in EP 2 180 029 and with quinone compounds as mentioned in EP 09153776.1.
  • Suitable electron-transporting materials for layer (4) of the inventive OLEDs comprise metals chelated with oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum (Alq3), compounds based on phenanthroline such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA=BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-phenanthroline (DPA) or phenanthroline derivatives disclosed in EP1786050 or in EP1097981, and azole compounds such as 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) and 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ). Layer (4) may serve both to ease the electron transport and as a buffer layer or as a barrier layer in order to prevent quenching of the exciton at the interfaces of the layers of the OLED. Layer (4) preferably improves the mobility of the electrons and reduces quenching of the exciton.
  • It is likewise possible to use mixtures of at least two materials in the electron-transporting layer, in which case at least one material is electron-conducting. Preferably, in such mixed electron-transporting layers, at least one phenanthroline compound is used. More preferably, in mixed electron-transporting layers, in addition to at least one phenanthroline compound, alkali metal hydroxyquinolate complexes, for example Liq, are used. In addition, it is possible to use mixtures which lead to electrical n-doping of the electron-transporting layer. n-Doping is achieved by the addition of reducing materials. These mixtures may, for example, be mixtures of the abovementioned electron transport materials with alkali/alkaline earth metals or alkali/alkaline earth metal salts, for example Li, Cs, Ca, Sr, Cs2CO3, with alkali metal complexes, for example 8-hydroxyquinolatolithium (Liq), and with Y, Ce, Sm, Gd, Tb, Er, Tm, Yb, Li3N, Rb2CO3, dipotassium phthalate, W(hpp)4 from EP 1786050, or with compounds as described in EP1837926 B1.
  • The present invention therefore also relates to an inventive OLED which comprises an electron-transporting layer comprising at least two different materials, of which at least one material should be electron-conductive.
  • In a preferred embodiment, the present invention relates to an inventive OLED wherein the electron-transporting layer comprises at least one phenanthroline derivative.
  • In a further preferred embodiment, the invention relates to an inventive OLED wherein the electron-transporting layer comprises at least one phenanthroline derivative and at least one alkali metal hydroxyquinolate complex.
  • In a further preferred embodiment, the invention relates to an inventive OLED wherein the electron-transporting layer comprises at least one phenanthroline derivative and 8-hydroxyquinolatolithium.
  • Some of the materials mentioned above as hole transport materials and electron-transporting materials can fulfill several functions. For example, some of the electron-transporting materials are simultaneously hole-blocking materials if they have a low-lying HOMO.
  • The charge-transporting layers may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thickness more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device. The hole transport materials may for example be doped with electron acceptors, phthalocyanines respectively arylamines like TPD or TDTA may be for example doped with tetrafluorotetracyano-chinodimethane (F4-TCNQ). Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, No. 1, 1. July 2003 (p-doped organic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No. 25, 23. June 2003 and Pfeiffer et al., Organic Electronics 2003, 4, 89-103 and K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev. 2007, 107, 1233.
  • The cathode (5) is an electrode which serves to introduce electrons or negative charge carriers. The cathode may be any metal or nonmetal which has a lower work function than the anode. Suitable materials for the cathode are selected from the group consisting of alkali metals of group 1, for example Li, Cs, alkaline earth metals of group 2, metals of group 12 of the Periodic Table of the Elements, comprising the rare earth metals and the lanthanides and actinides. In addition, metals such as aluminum, indium, calcium, barium, samarium and magnesium, and combinations thereof, may be used. In addition, lithium-comprising organometallic compounds such as 8-hydroxyquinolatolithium (Liq) or LiF or at least one of the following compounds (Cs2CO3, KF, CsF or NaF may be applied between the organic layer and the cathode as an electron injection layer in order to reduce the operating voltage.
  • The OLED of the present invention may additionally comprise further layers which are known to those skilled in the art. For example, a layer which eases the transport of the positive charge and/or matches the band gaps of the layers to one another may be applied between the layer (2) and the light-emitting layer (3). Alternatively, this further layer may serve as a protective layer. In an analogous manner, additional layers may be present between the light-emitting layer (3) and the layer (4) in order to ease the transport of the negative charge and/or to match the band gaps between the layers to one another. Alternatively, this layer may serve as a protective layer.
  • In a preferred embodiment, the inventive OLED, in addition to the layers (1) to (5), comprises at least one of the further layers mentioned below:
      • a hole injection layer between the anode (1) and the hole-transporting layer (2);
      • a blocking layer for electrons between the hole-transporting layer (2) and the light-emitting layer (3);
      • a blocking layer for holes between the light-emitting layer (3) and the electron-transporting layer (4);
      • an electron injection layer between the electron-transporting layer (4) and the cathode (5).
  • As already mentioned above, however, it is also possible that the OLED does not have all of the layers (1) to (5) mentioned; for example, an OLED comprising layers (1) (anode), (3) (light-emitting layer) and (5) (cathode) is likewise suitable, in which case the functions of layers (2) (hole-transporting layer) and (4) (electron-transporting layer) are assumed by the adjoining layers. OLEDs having layers (1), (2), (3) and (5) or layers (1), (3), (4) and (5) are likewise suitable.
  • Those skilled in the art know how suitable materials have to be selected (for example on the basis of electrochemical investigations). Suitable materials for the individual layers are known to those skilled in the art and disclosed, for example, in WO 00/70655.
  • In addition, it is possible that some or all of the layers (1), (2), (3), (4) and (5) have been surface-treated in order to increase the efficiency of charge carrier transport. The selection of the materials for each of the layers mentioned is preferably determined by obtaining an OLED having a high efficiency.
  • The inventive OLED can be produced by methods known to those skilled in the art. In general, the OLED is produced by successive vapor deposition of the individual layers onto a suitable substrate. Suitable substrates are, for example, glass, inorganic materials like ITO or IZO or polymer films. For the vapor deposition, customary techniques may be used, such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD) and others.
  • In an alternative process, the organic layers may be coated from solutions or dispersions in suitable solvents, in which case coating techniques known to those skilled in the art are employed.
  • Suitable coating techniques are, for example, spin-coating, the casting method, the Langmuir-Blodgett (“LB”) method, the inkjet printing method, dip-coating, letterpress printing, screen printing, doctor blade printing, roller printing, reverse roller printing, offset lithography printing, flexographic printing, web printing, spray coating, coating by a brush or pad printing, and the like. Among the processes mentioned, in addition to the aforementioned vapor deposition, preference is given to spin-coating, the inkjet printing method and the casting method since they are particularly simple and inexpensive to perform. In the case that layers of the OLED are obtained by the spin-coating method, the casting method or the inkjet printing method, the coating can be obtained using a solution prepared by dissolving the composition in a concentration of 0.0001 to 90% by weight in a suitable organic solvent such as benzene, toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide, acetone, acetonitrile, anisole, dichloromethane, dimethyl sulfoxide, water and mixtures thereof.
  • It is also possible that all layers of the OLED are prepared with the same coating technique. It is further also possible that two or more coating techniques are carried out in the production of the layers of the OLED.
  • In general, the different layers have the following thicknesses: anode (2) 500 to 5000 Å, preferably 1000 to 2000 Å (ångström); hole-transporting layer (3) 50 to 1000 Å, preferably 200 to 800 Å; light-emitting layer (4) 10 to 1000 Å, preferably 100 to 800 Å; electron-transporting layer (5) 50 to 1000 Å, preferably 200 to 800 Å; cathode (6) 200 to 10 000 Å, preferably 300 to 5000 Å. The position of the recombination zone of holes and electrons in the inventive OLED and thus the emission spectrum of the OLED may be influenced by the relative thickness of each layer. This means that the thickness of the electron transport layer should preferably be selected such that the electron/hole recombination zone is within the light-emitting layer. The ratio of the layer thicknesses of the individual layers in the OLED is dependent upon the materials used. The layer thicknesses of any additional layers used are known to those skilled in the art.
  • In a preferred embodiment, the present invention also relates to an OLED comprising at least one inventive heteroleptic complex of the general formula (I), and at least one compound of the general formula (X)
  • Figure US20120205645A1-20120816-C00208
  • in which
    • T is NR57, S, O or PR57, preferably S or O, more preferably O;
    • R57 is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl;
    • Q′ is —NR58R59, —P(O)R60R61, —PR62R63, —S(O)2R64, —S(O)R65, —SR66 or —OR67, preferably —NR58R59; more preferably
  • Figure US20120205645A1-20120816-C00209
      • in which
      • R66, R69 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl; preferably methyl, carbazolyl, dibenzofuryl or dibenzothienyl;
      • y, z are each independently 0, 1, 2, 3 or 4, preferably 0 or 1;
    • R55, R56 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, SiR70R71R72, a Q′ group or a group with donor or acceptor action;
    • a″ is 0, 1, 2, 3 or 4;
    • b′ is 0, 1, 2 or 3;
    • R58, R59 form, together with the nitrogen atom, a cyclic radical which has 3 to 10 ring atoms and may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action, and/or may be fused to one or more further cyclic radicals having 3 to 10 ring atoms, where the fused radicals may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action;
    • R70, R71, R72, R60, R61, R62, R63, R64, R65, R66, R67
      • are each independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl,
    Or
  • two units of the general formula (X) are bridged to one another via a linear or branched, saturated or unsaturated bridge optionally interrupted by at least one heteroatom, via a bond or via O.
  • Preference is given to compounds of the formula (X) in which:
    • T is S or O, preferably O, and
    • Q′ is
  • Figure US20120205645A1-20120816-C00210
      • in which
      • R68, R69 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl; preferably methyl, carbazolyl, dibenzofuryl or dibenzothienyl;
      • y, z are each independently 0, 1, 2, 3 or 4, preferably 0 or 1.
  • Particularly preferred compounds of the formula (X) have the following formula (Xa):
  • Figure US20120205645A1-20120816-C00211
  • in which the symbols and indices Q′, T, R55, R56, a″ and b′ are each as defined above.
  • Very particularly preferred compounds of the formula (X) have the formula (Xaa):
  • Figure US20120205645A1-20120816-C00212
  • in which the symbols and indices R68, R69 y, z, T, R55, R56, a″ and b′ are each as defined above.
  • In a very particularly preferred embodiment, in formula (Xaa):
    • T is O or S, preferably O;
    • a″ is 1;
    • b′ is 0;
    • y, z are each independently 0 or 1; and
    • R68, R69 are each independently methyl, carbazolyl, dibenzofuryl or dibenzothienyl
    • R55 is substituted phenyl, carbazolyl, dibenzofuryl or dibenzothienyl.
  • In a further preferred embodiment, the compounds of the formula (X) have the formula (XI) or (XI*):
  • Figure US20120205645A1-20120816-C00213
    • in which
    • T is NR57, S, O or PR57;
    • R57 is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl;
    • Q′ is —NR58R59, —P(O)R60R61, —PR62R63, —S(O)2R64, —S(O)R65, —SR66 or —OR67;
    • R70, R71, R72 are each independently aryl, heteroaryl, alkyl, cycloalkyl, heterocycloalkyl, where at least one of the R70, R71, R72 radicals comprises at least two carbon atoms, or OR73,
    • R55, R56 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, a Q group or a group with donor or acceptor action;
    • a′, b′ for the compound of the formula (XI): are each independently 0, 1, 2, 3; for the compound of the formula (XI*), a′ is 0, 1, 2 and b′ is 0, 1, 2, 3, 4;
    • R58, R59 form, together with the nitrogen atom, a cyclic radical which has 3 to 10 ring atoms and may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action and/or may be fused to one or more further cyclic radicals having 3 to 10 ring atoms, where the fused radicals may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action;
    • R73 are each independently SiR74R75R76, aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, optionally substituted by an OR77 group,
    • R77 are each independently SiR74R75R76, aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl,
    • R60, R61, R62, R63, R64, R65, R66, R67, R74, R75, R76
      • are each independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl,
        or
        two units of the general formulae (XI) and/or (XI*) are bridged to one another via a linear or branched, saturated or unsaturated bridge optionally interrupted by at least one heteroatom or via O, where this bridge in the general formulae (XI) and/or (XI*) is in each case attached to the silicon atoms in place of R71.
  • The compounds of the general formula (X) can be used as a matrix (diluent material), hole/exciton blocker, electron/exciton blocker, electron transport material or hole transport material in combination with the heteroeleptic complexes claimed, which then preferably serve as emitters. Inventive OLEDs which include both at least one compound of the formula (X) and a compound of the formula (I) exhibit particularly good efficiencies and lifetimes. Depending on the function in which the compound of the formula (X) is used, it is present in pure form or in different mixing ratios. In a particularly preferred embodiment, one or more compounds of the formula (X) are used as matrix material in the light-emitting layer.
  • For the compounds of the general formula (X), especially for the R55 to R77 radicals:
  • The terms aryl radical or group, heteroaryl radical or group, alkyl radical or group, cycloalkyl radical or group, heterocycloalkyl radical or group, alkenyl radical or group, alkynyl radical or group, and groups with donor and/or acceptor action are each defined as follows:
  • An aryl radical (or group) is understood to mean a radical having a base skeleton of 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, which is formed from an aromatic ring or a plurality of fused aromatic rings. Suitable base skeletons are, for example, phenyl, naphthyl, anthracenyl or phenanthrenyl, indenyl or fluorenyl. This base skeleton may be unsubstituted (which means that all carbon atoms which are substitutable bear hydrogen atoms), or may be substituted at one, more than one or all substitutable positions of the base skeleton.
  • Suitable substituents are, for example, deuterium, alkoxy radicals, aryloxy radicals, alkylamino groups, arylamino groups, carbazolyl groups, silyl groups, SiR78R79R80, suitable silyl groups SiR78R79R80 being specified below, alkyl radicals, preferably alkyl radicals having 1 to 8 carbon atoms, more preferably methyl, ethyl or i-propyl, aryl radicals, preferably C6-aryl radicals, which may in turn be substituted or unsubstituted, heteroaryl radicals, preferably heteroaryl radicals which comprise at least one nitrogen atom, more preferably pyridyl radicals and carbazolyl radicals, alkenyl radicals, preferably alkenyl radicals which bear one double bond, more preferably alkenyl radicals having one double bond and 1 to 8 carbon atoms, alkynyl radicals, preferably alkynyl radicals having one triple bond, more preferably alkynyl radicals having one triple bond and 1 to 8 carbon atoms or groups with donor or acceptor action. Suitable groups with donor or acceptor action are specified below. The substituted aryl radicals most preferably bear substituents selected from the group consisting of methyl, ethyl, isopropyl, alkoxy, heteroaryl, halogen, pseudohalogen and amino, preferably arylamino. The aryl radical or the aryl group is preferably a C6-C18-aryl radical, more preferably a C6-aryl radical, which is optionally substituted by at least one or more than one of the aforementioned substituents. The C6-C18-aryl radical, preferably C6-aryl radical, more preferably has none, one, two, three or four, most preferably none, one or two, of the aforementioned substituents.
  • A heteroaryl radical or a heteroaryl group is understood to mean radicals which differ from the aforementioned aryl radicals in that at least one carbon atom in the base skeleton of the aryl radicals is replaced by a heteroatom, and in that the base skeleton of the heteroaryl radicals preferably has 5 to 18 ring atoms. Preferred heteroatoms are N, O and S. Heteroaryl radicals suitable with particular preference are nitrogen-containing heteroaryl radicals. Most preferably, one or two carbon atoms of the base skeleton are replaced by heteroatoms, preferably nitrogen. The base skeleton is especially preferably selected from systems such as pyridine, pyrimidine and five-membered heteroaromatics such as pyrrole, furan, pyrazole, imidazole, thiophene, oxazole, thiazole, triazole. In addition, the heteroaryl radicals may be fused ring systems, for example benzofuryl, benzothienyl, benzopyrrolyl, dibenzofuryl, dibenzothienyl, phenanthrolinyl, carbazolyl radicals, azacarbazolyl radicals or diazacarbazolyl radicals. The base skeleton may be substituted at one, more than one or all substitutable positions of the base skeleton. Suitable substituents are the same as have already been specified for the aryl groups.
  • An alkyl radical or an alkyl group is understood to mean a radical having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8, most preferably 1 to 4 carbon atoms. This alkyl radical may be branched or unbranched and optionally be interrupted by one or more heteroatoms, preferably Si, N, O or S, more preferably N, O or S. In addition, this alkyl radical may be substituted by one or more of the substituents specified for the aryl groups. In addition, the alkyl radicals present in accordance with the invention may have at least one halogen atom, for example F, CI, Br or I, especially F. In a further embodiment, the alkyl radicals present in accordance with the invention may be fully fluorinated. It is likewise possible that the alkyl radical bears one or more (hetero)aryl groups. In the context of the present application, for example, benzyl radicals are thus substituted alkyl radicals. In this context, all of the (hetero)aryl groups listed above are suitable. The alkyl radicals are more preferably selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl and tert-butyl, very particular preference being given to methyl and ethyl.
  • A cycloalkyl radical or a cycloalkyl group is understood to mean a radical having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms. This base skeleton may be unsubstituted (which means that all carbon atoms which are substitutable bear hydrogen atoms) or substituted at one, more than one or all substitutable positions of the base skeleton. Suitable substituents are the groups already mentioned above for the aryl radicals. It is likewise possible that the cycloalkyl radical bears one or more (hetero)aryl groups. Examples of suitable cycloalkyl radicals are cyclopropyl, cyclopentyl and cyclohexyl.
  • A heterocycloalkyl radical or a heterocycloalkyl group is understood to mean radicals which differ from the aforementioned cycloalkyl radicals in that at least one carbon atom in the base skeleton of the cycloalkyl radicals is replaced by a heteroatom. Preferred heteroatoms are N, O and S. Most preferably, one or two carbon atoms of the base skeleton of the cycloalkyl radicals are replaced by heteroatoms. Examples of suitable heterocycloalkyl radicals are radicals derived from pyrrolidine, piperidine, piperazine, tetrahydrofuran, dioxane.
  • An alkenyl radical or an alkenyl group is understood to mean a radical which corresponds to the aforementioned alkyl radicals having at least two carbon atoms, with the difference that at least one C—C single bond of the alkyl radical is replaced by a C—C double bond. The alkenyl radical preferably has one or two double bonds.
  • An alkynyl radical or an alkynyl group is understood to mean a radical which corresponds to the aforementioned alkyl radicals having at least two carbon atoms, with the difference that at least one C—C single bond of the alkyl radical is replaced by a C—C triple bond. The alkynyl radical preferably has one or two triple bonds.
  • An SiR78R79R80 group is understood to mean a silyl radical in which
  • R78, R79 and R80 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or OR73.
  • An SiR74R75R76 group is understood to mean a silyl radical in which
  • R74, R75 and R76 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or OR73.
  • In the context of the present application, a group or a substituent with donor or acceptor action is understood to mean the following groups:
  • Groups with donor action are understood to mean groups which have a +I and/or +M effect, and groups with acceptor action are understood to mean groups which have a —I and/or -M effect. Preferred suitable groups are selected from C1-C20-alkoxy, C6-C30-aryloxy, C1-C20-alkylthio, C6-C30-arylthio, SiR81R82R83, OR73, halogen radicals, halogenated C1-C20-alkyl radicals, carbonyl (—CO(R81)), carbonylthio (—C═O(SR81)), carbonyloxy (—C═O(OR81)), oxycarbonyl (—OC═O(R81)), thiocarbonyl (—SC═O(R81)), amino (—NR81R82), pseudohalogen radicals, amido (—C═O(NR81)), —NR81C═O(R83), phosphonate (—P(O)(OR81)2, phosphate (—OP(O)(OR81)2), phosphine (—PR81R82), phosphine oxide (—P(O)R81 2), sulfate (—OS(O)2OR81), sulfoxide (—S(O)R81), sulfonate (—S(O)2OR81), sulfonyl (—S(O)2R81, sulfonamide (—S(O)2NR81R82), NO2, boronic esters (—OB(OR81)2), imino (—C═NR81R82)), borane radicals, stannane radicals, hydrazine radicals, hydrazone radicals, oxime radicals, nitroso groups, diazo groups, vinyl groups, sulfoximines, alanes, germanes, boroximes and borazines.
  • The R81, R82 and R83 radicals mentioned in the aforementioned groups with donor or acceptor action are each independently:
  • substituted or unsubstituted C1-C20-alkyl or substituted or unsubstituted C6-C30-aryl, or OR76, suitable and preferred alkyl and aryl radicals having been specified above. The R81, R82 and R83 radicals are more preferably C1-C6-alkyl, e.g. methyl, ethyl or i-propyl, or phenyl. In a preferred embodiment—in the case of SiR81R82R83—R81, R82 and R83 are preferably each independently substituted or unsubstituted C1-C20-alkyl or substituted or unsubstituted aryl, preferably phenyl.
  • Preferred substituents with donor or acceptor action are selected from the group consisting of:
  • C1- to C20-alkoxy, preferably C1-C6-alkoxy, more preferably ethoxy or methoxy; C6-C30-aryloxy, preferably C6-C10-aryloxy, more preferably phenyloxy; SiR81R82R83 where R81, R82 and R83 are preferably each independently substituted or unsubstituted alkyl or substituted or unsubstituted aryl, preferably phenyl; more preferably, at least one of the R81, R82 and R83 radicals is substituted or unsubstituted phenyl, suitable substituents having been specified above; halogen radicals, preferably F, Cl, more preferably F, halogenated C1-C20-alkyl radicals, preferably halogenated C1-C6-alkyl radicals, most preferably fluorinated C1-C6-alkyl radicals, e.g. CF3, CH2F, CHF2 or C2F5; amino, preferably dimethylamino, diethylamino or diarylamino, more preferably diarylamino; pseudohalogen radicals, preferably CN, —C(O)OC1-C4-alkyl, preferably —C(O)OMe, P(O)R2, preferably P(O)Ph2.
  • Very particularly preferred substituents with donor or acceptor action are selected from the group consisting of methoxy, phenyloxy, halogenated C1-C4-alkyl, preferably CF3, CH2F, CHF2, C2F5, halogen, preferably F, CN, SiR81R82R83, suitable R81, R82 and R83 radicals already having been specified, diarylamino (NR84R85 where R84, R85 are each C6-C30-aryl), —C(O)OC1-C4-alkyl, preferably —C(O)OMe, P(O)Ph2.
  • Halogen groups are preferably understood to mean F, Cl and Br, more preferably F and Cl, most preferably F.
  • Pseudohalogen groups are preferably understood to mean CN, SCN and OCN, more preferably CN.
  • The aforementioned groups with donor or acceptor action do not rule out the possibility that further radicals and substituents mentioned in the present application, but not included in the above list of groups with donor or acceptor action, have donor or acceptor action.
  • The aryl radicals or groups, heteroaryl radicals or groups, alkyl radicals or groups, cycloalkyl radicals or groups, heterocycloalkyl radicals or groups, alkenyl radicals or groups and groups with donor and/or acceptor action may—as mentioned above—be substituted or unsubstituted. In the context of the present application, an unsubstituted group is understood to mean a group in which the substitutable atoms of the group bear hydrogen atoms. In the context of the present application, a substituted group is understood to mean a group in which one or more substitutable atom(s) bear(s) a substituent in place of a hydrogen atom at least at one position. Suitable substituents are the substituents specified above for the aryl radicals or groups.
  • When radicals having the same numbering occur more than once in the compounds according to the present application, these radicals may each independently have the definitions specified.
  • The T radical in the compounds of the formula (X) is NR57, S, O or PR57, preferably NR57, S or O, more preferably O or S, most preferably O.
  • The R57 radical is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, preferably aryl, heteroaryl or alkyl, more preferably aryl, where the aforementioned radicals may be unsubstituted or substituted. Suitable substituents have been specified above. R65 is more preferably phenyl which may be substituted by the aforementioned substituents or unsubstituted. R57 is most preferably unsubstituted phenyl.
  • The Q′ group in the compounds of the formula (X) is —NR58R59, —P(O)R60R61, —PR62R63, —S(O)2R64, —S(O)R65, —SR66 or —OR67; preferably NR58R59, —P(O)R60R61 or —OR67, more preferably —NR58R59.
  • The R58 to R67 and R74 to R76 radicals are each defined as follows:
    • R58, R59 form, together with the nitrogen atom, a cyclic radical which has 3 to 10 ring atoms and may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action and/or may be fused to one or more further cyclic radicals having 3 to 10 ring atoms, where the fused radicals may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action;
    • R60, R61, R62, R63, R64, R65, R66, R67, R74, R75, R76
      • are each independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, preferably aryl or heteroaryl, where the radicals may be unsubstituted or substituted by one or more of the radicals selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action, more preferably unsubstituted or substituted phenyl, suitable substituents having been specified above, for example tolyl or a group of the formula
  • Figure US20120205645A1-20120816-C00214
      • in which the T group and the R70, R71 and R72 radicals are each independently as defined for the compounds of the formula (XI) or (XI*).
        R69, R61, R62, R63, R64, R65, R66 and R67 are most preferably each independently phenyl, tolyl or a group of the formula
  • Figure US20120205645A1-20120816-C00215
  • in which T is NPh, S or O.
  • Examples of —NR58R59 groups suitable with preference are selected from the group consisting of pyrrolyl, 2,5-dihydro-1-pyrrolyl, pyrrolidinyl, indolyl, indolinyl, isoindolinyl, carbazolyl, azacarbazolyl, diazacarbazolyl, imidazolyl, imidazolinyl, benzimidazolyl, pyrazolyl, indazolyl, 1,2,3-triazolyl, benzotriazolyl, 1,2,4-triazolyl, tetrazolyl, 1,3-oxazolyl, 1,3-thiazolyl, piperidyl, morpholinyl, 9,10-dihydroacridinyl and 1,4-oxazinyl, where the aforementioned groups may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action; the —NR6R7 group is preferably selected from carbazolyl, pyrrolyl, indolyl, imidazolyl, benzimidazolyl, azacarbazolyl and diazacarbazolyl, where the aforementioned groups may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action; the —NR58R59 group is more preferably carbazolyl which may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action.
  • Particularly preferred —NR58R59 groups are:
  • Figure US20120205645A1-20120816-C00216
    • in which
    • R68, R69 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl; preferably methyl, carbazolyl, dibenzofuryl or dibenzothienyl;
    • y, z are each independently 0, 1, 2, 3 or 4, preferably 0 or 1;
      for example:
  • Figure US20120205645A1-20120816-C00217
  • Particularly preferred —P(O)R60R61 groups are:
  • Figure US20120205645A1-20120816-C00218
  • A particularly preferred PR62R63 group is:
  • Figure US20120205645A1-20120816-C00219
  • Particularly preferred groups —S(O)2R64 and —S(O)R65 are:
  • Figure US20120205645A1-20120816-C00220
  • Particularly preferred groups —SR66 and —OR67 are:
  • Figure US20120205645A1-20120816-C00221
  • R55, R56 in the compounds of the formula (X) are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, a further A group or a group with donor or acceptor action; preferably each independently alkyl, aryl, heteroaryl or a group with donor or acceptor action. For example, R55 or R56 may each independently be:
  • Figure US20120205645A1-20120816-C00222
  • In the compounds of the formula (X) a″ R55 groups and/or b′ R56 groups may be present, where a″ and b′ are:
  • a″ is 0, 1, 2, 3 or 4; preferably independently 0, 1 or 2;
    b′ is 0, 1, 2 or 3; preferably independently 0, 1 or 2.
  • Most preferably at least a″ or b′ is 0, very especially preferably a″ and b′ are each 0 or a″ is 1 and b′ is 0.
  • R73 in the compounds of the general formula (XI) is generally independently SiR74R75R76, aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, optionally substituted by an OR77 group.
  • R77 in compounds of the general formula (XI) is generally independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl.
  • The OR77 substituent optionally present may generally be present in the radicals mentioned at all sites which appear suitable to the person skilled in the art.
  • In a further embodiment, two units of the general formula (XI) and/or (XI*) are bridged to one another via a linear or branched, saturated or unsaturated bridge optionally interrupted by at least one heteroatom or via O, where this bridge in the general formula (XI) and/or (XI*) is in each case attached to the silicon atoms in place of R71.
  • This bridge is preferably selected from the group consisting of —CH2—, —C2H4—, —C4H8—, —C6H12—, —C8H16—, —C9H18—, —CH(C8H17)CH2—, —C2H4(CF2)8 C2H4—, —C≡C—, -1,4-(CH2)2-phenyl-(CH2)2—, 1,3-(CH2)2-phenyl-(CH2)2—, -1,4-phenyl-, -1,3-phenyl-, —O—, —O—Si(CH3)2—O—, —O—Si(CH3)2—O—Si(CH3)2—O—, —O—.
  • In a preferred embodiment of the present application, the compounds of the general formula (X) have the general formula (XIa), (XIb), (XIc), (XId) or (XIe), i.e. they are preferred embodiments of the compounds of the general formula (XI) or (XI*):
  • Figure US20120205645A1-20120816-C00223
  • in which the Q′, T, R70, R71, R72, R55, R56 radicals and groups, and a′ and b′, are each as defined above.
  • In another embodiment preferred in accordance with the invention, R70, R71 or R72 in the compounds of the general formula (XI) or (XI*) are aromatic units of the general formulae (XIi) and/or (XIi*)
  • Figure US20120205645A1-20120816-C00224
  • where R55, R56, Q′, T, a′ and b′ are each as defined above.
  • The present invention therefore relates, in one embodiment, to an inventive OLED where R70, R71 or R72 in the compounds of the general formula (XI) or (XI*) are aromatic units of the general formulae (XIi) and/or (XIi*)
  • Figure US20120205645A1-20120816-C00225
  • where R56, R56, Q′, T, a′ and b′ are each as defined above.
  • In a preferred embodiment, the present invention relates to an OLED wherein the compound of the general formula (XI) or (XI*) is selected from the following group:
  • Figure US20120205645A1-20120816-C00226
    Figure US20120205645A1-20120816-C00227
    Figure US20120205645A1-20120816-C00228
    Figure US20120205645A1-20120816-C00229
    Figure US20120205645A1-20120816-C00230
    Figure US20120205645A1-20120816-C00231
    Figure US20120205645A1-20120816-C00232
    Figure US20120205645A1-20120816-C00233
  • In these particularly preferred compounds of the general formula (XI) or (XI*):
    • T is S or O, and
    • R′ is H or CH3; and
    • R70, R71, R72 are each phenyl, carbazolyl, dibenzofuran or dibenzothiophene.
  • Further particularly suitable compounds of the general formula (XI) or (XI*) are:
  • Figure US20120205645A1-20120816-C00234
    Figure US20120205645A1-20120816-C00235
    Figure US20120205645A1-20120816-C00236
    Figure US20120205645A1-20120816-C00237
  • In these particularly preferred compounds of the general formula (XI) or (XI*) too, T is O or S, preferably O.
  • Further inventive compounds of the general formula (XI) or (XI*) correspond to the following formula (XII)
  • Figure US20120205645A1-20120816-C00238
  • In the general formula (XII), R70, R71, R72 are each defined as follows:
  • Nr R70 R71 R72
    1 methyl methyl ethyl
    2 methyl methyl i-propyl
    3 methyl methyl n-propyl
    4 methyl methyl n-butyl
    5 methyl methyl i-butyl
    6 methyl methyl t-butyl
    7 methyl methyl n-pentyl
    8 methyl methyl n-hexyl
    9 methyl methyl —CH2CH2C(CH3)3
    10 methyl methyl n-C8H17
    11 methyl methyl i-C8H17
    12 methyl methyl n-C10H21
    13 methyl methyl n-C12H25
    16 methyl methyl n-C18H37
    17 methyl methyl n-C30H61
    19 methyl methyl cyclohexyl
    20 methyl methyl C(CH3)2Ph
    21 methyl methyl —C(CH3)2CH(CH3)2
    22 methyl methyl —CCH2CH(CH3)(C2H5)
    23 methyl methyl —CH2CH(C10H21)2
    24 methyl methyl —CH2CH(C12H25)2
    25 methyl methyl —CH2CH2(C3F6)CF3
    26 methyl methyl —CH2CH2(C7F14)CF3
    27 methyl methyl —CH2CH2(C5F10)CF3
    29 methyl methyl —CH2CH2CF3
    30 methyl methyl phenyl
    31 methyl methyl 2-biphenyl
    32 methyl methyl p-tolyl
    33 methyl methyl C6F5
    34 methyl methyl 3,5-(cf3)2phenyl
    35 methyl methyl —ch2c(ch3)2phenyl
    36 methyl methyl 9-fluorenyl
    37 methyl methyl 3,6-di(tert-butyl)-9-fluorenyl
    15 methyl methyl R86
    38 methyl methyl —OMe
    39 methyl methyl —OEt
    40 methyl methyl 2,4,6-t-butylphenoxy
    41 methyl methyl —O—tBu (tert-butoxy)
    42 methyl methyl —OSiEt3
    43 methyl ethyl ethyl
    44 methyl ethyl phenyl
    45 methyl ethyl R86
    46 methyl n-propyl n-propyl
    47 methyl n-propyl phenyl
    48 methyl n-propyl R86
    49 methyl i-propyl i-propyl
    50 methyl i-propyl phenyl
    51 methyl i-propyl R86
    52 methyl n-butyl n-butyl
    53 methyl n-butyl phenyl
    54 methyl n-butyl R86
    55 methyl i-butyl i-butyl
    56 methyl i-butyl phenyl
    57 methyl i-butyl R86
    58 methyl t-butyl t-butyl
    59 methyl t-butyl phenyl
    60 methyl t-butyl R86
    61 methyl n-pentyl n-Pentyl
    62 methyl n-pentyl n-hexyl
    63 methyl n-pentyl phenyl
    64 methyl n-pentyl R86
    65 methyl n-hexyl hexyl
    66 methyl n-hexyl phenyl
    67 methyl n-hexyl R86
    68 methyl n-heptyl R86
    69 methyl n-octyl R86
    70 methyl n-decyl R86
    71 methyl n-C12H25 R86
    72 methyl n-C18H37 R86
    73 methyl n-C22H45 R86
    74 methyl n-C30H61 R86
    75 methyl cyclopentyl cyclopentyl
    76 methyl cyclopentyl phenyl
    77 methyl cyclopentyl R86
    78 methyl cyclohexyl cyclohexyl
    79 methyl cyclohexyl phenyl
    80 methyl cyclohexyl R86
    81 methyl —CF2CHF2 R86
    82 methyl —CH2CH2CF3 R86
    83 methyl —CH2CH2(CF2)3CF3 R86
    84 methyl —CH2CH2(CF2)5CF3 R86
    85 methyl —CH2CH2(CF2)7CF3 R86
    86 methyl phenyl phenyl
    87 methyl phenyl p-tolyl
    89 methyl phenyl mesityl
    90 methyl phenyl R86
    91 methyl p-tolyl p-tolyl
    92 methyl p-tolyl R86
    93 methyl mesityl mesityl
    94 methyl mesityl R5
    95 methyl R86 R86
    96 methyl methoxy methoxy
    97 methyl ethoxy ethoxy
    98 methyl —OSiEt3 —OSiEt3
    99 methyl —O—SiMe2—CH2CH2(CF2)4CF3 —O—SiMe2—CH2CH2(CF2)4CF3
    100 ethyl ethyl ethyl
    101 ethyl ethyl n-propyl
    102 ethyl ethyl i-propyl
    103 ethyl ethyl n-butyl
    104 ethyl ethyl i-butyl
    105 ethyl ethyl t-butyl
    106 ethyl ethyl phenyl
    107 ethyl ethyl R5
    108 ethyl phenyl phenyl
    109 ethyl phenyl R86
    110 ethyl R86 R86
    111 ethyl ethoxy ethoxy
    112 n-propyl n-propyl n-propyl
    113 n-propyl n-propyl phenyl
    114 n-propyl n-propyl R86
    115 n-propyl phenyl phenyl
    116 n-propyl phenyl R86
    117 n-propyl R86 R86
    118 i-propyl i-propyl i-propyl
    119 i-propyl i-propyl phenyl
    120 i-propyl i-propyl R86
    121 i-propyl i-propyl 2-biphenyl
    122 i-propyl i-propyl ethoxy
    123 i-propyl phenyl phenyl
    124 i-propyl phenyl R86
    125 i-propyl R86 R86
    126 n-butyl n-butyl n-butyl
    127 n-butyl n-butyl phenyl
    128 n-butyl n-butyl R86
    129 n-butyl n-hexyl R86
    130 n-butyl phenyl phenyl
    131 n-butyl phenyl R86
    132 n-butyl R86 R86
    133 sec-butyl sec-butyl sec-butyl
    134 sec-butyl sec-butyl phenyl
    135 sec-butyl sec-butyl R86
    136 sec-butyl phenyl phenyl
    137 sec-butyl phenyl R86
    138 sec-butyl R86 R86
    139 i-butyl i-butyl i-butyl
    140 i-butyl i-butyl n-C8H17
    141 i-butyl i-butyl n-C18H37
    142 i-butyl i-butyl phenyl
    143 i-butyl i-butyl R86
    144 i-butyl phenyl phenyl
    145 i-butyl phenyl R86
    146 i-butyl R86 R86
    147 t-butyl t-butyl t-butyl
    148 t-butyl t-butyl n-C8H17
    149 t-butyl t-butyl phenyl
    150 t-butyl t-butyl R86
    151 t-butyl phenyl phenyl
    152 t-butyl phenyl R5
    153 t-butyl R86 R86
    154 n-pentyl n-pentyl n-pentyl
    155 n-pentyl n-pentyl phenyl
    156 n-pentyl n-pentyl R86
    157 n-pentyl phenyl phenyl
    158 n-pentyl phenyl R86
    159 n-pentyl R86 R86
    160 cyclopentyl cyclopentyl cyclopentyl
    161 cyclopentyl cyclopentyl phenyl
    162 cyclopentyl cyclopentyl R86
    163 cyclopentyl phenyl phenyl
    164 cyclopentyl phenyl R86
    165 cyclopentyl R86 R86
    166 n-hexyl n-hexyl n-hexyl
    167 n-hexyl n-hexyl phenyl
    168 n-hexyl n-hexyl R86
    169 n-hexyl phenyl phenyl
    170 n-hexyl phenyl R86
    171 n-hexyl R86 R86
    172 —CH2CH2C(CH3)3 —CH2CH2C(CH3)3 —CH2CH2C(CH3)3
    173 —CH2CH2C(CH3)3 —CH2CH2C(CH3)3 R86
    174 —CH2CH2C(CH3)3 R86 R86
    175 t-hexyl t-hexyl t-hexyl
    176 t-hexyl t-hexyl R86
    177 t-hexyl R86 R86
    178 n-heptyl n-heptyl n-heptyl
    179 n-heptyl n-heptyl R86
    180 n-heptyl R86 R86
    181 n-octyl n-octyl n-octyl
    182 n-octyl n-octyl R86
    183 n-octyl R86 R86
    184 i-octyl i-octyl i-octyl
    185 i-octyl i-octyl R86
    186 i-octyl R86 R86
    187 n-nonyl n-nonyl n-nonyl
    188 n-nonyl n-nonyl R86
    189 n-nonyl R86 R86
    190 cyclohexyl cyclohexyl cyclohexyl
    191 cyclohexyl cyclohexyl R86
    192 cyclohexyl R86 R86
    193 cyclooctyl cyclooctyl cyclooctyl
    194 cyclooctyl cyclooctyl R86
    195 cyclooctyl R86 R86
    196 n-C10H21 n-C10H21 n-C10H21
    197 n-C10H21 n-C10H21 R86
    198 n-C10H21 R86 R86
    199 n-C11H23 n-C11H23 n-C10H23
    200 n-C11H23 n-C11H23 R86
    201 n-C11H23 R86 R86
    202 n-C12H25 n-C12H25 n-C12H25
    203 n-C12H25 n-C12H25 R86
    204 n-C12H25 R86 R86
    205 n-C14H29 n-C14H29 n-C14H29
    206 n-C14H29 n-C14H29 R86
    207 n-C14H29 R86 R86
    208 n-C16H33 n-C16H33 n-C16H33
    209 n-C16H33 n-C16H33 R86
    210 n-C16H33 R86 R86
    211 n-C18H37 n-C18H37 R86
    212 n-C18H37 R86 R86
    213 n-C18H37 OEt OEt
    214 n-C18H37 R86 OMe
    215 n-C20H41 n-C20H41 n-C20H41
    216 n-C20H41 n-C20H41 R86
    217 n-C20H41 R86 R86
    218 n-C22 H45 n-C22H45 n-C22H45
    219 n-C22H45 n-C22H45 R86
    220 n-C22H45 R86 R86
    221 n-C26H53 n-C26H53 n-C26H53
    222 n-C26H53 n-C26H53 R86
    223 n-C26H53 R86 R86
    224 n-C30H61 n-C30H61 n-C30H61
    225 n-C30H61 n-C30H61 R86
    226 n-C30H61 R86 R86
    227 —CH2-cyclohexyl —CH2-cyclohexyl R86
    228 —CH2CH2CF3 —CH2CH2CF3 —CH2CH2CF3
    229 —CH2CH2CF3 —CH2CH2CF3 R86
    230 —CH2CH2CF3 R86 R86
    231 —CH2CH2(CF2)3CF3 —CH2CH2(CF2)3CF3 —CH2CH2(CF2)3CF3
    232 —CH2CH2(CF2)3CF3 —CH2CH2(CF2)3CF3 R86
    233 —CH2CH2(CF2)3CF3 R86 R86
    234 —CH2CH2(CF2)5CF3 —CH2CH2(CF2)5CF3 —CH2CH2(CF2)5CF3
    235 —CH2CH2(CF2)5CF3 —CH2CH2(CF2)5CF3 R86
    236 —CH2CH2(CF2)5CF3 R86 R86
    237 —CH2CH2(CF2)7CF3 —CH2CH2(CF2)7CF3 —CH2CH2(CF2)7CF3
    238 —CH2CH2(CF2)7CF3 —CH2CH2(CF2)7CF3 R86
    239 —CH2CH2(CF2)7CF3 R86 R86
    240 —CH2CH2(CF2)9CF3 —CH2CH2(CF2)9CF3 —CH2CH2(CF2)9CF3
    241 —CH2CH2(CF2)9CF3 —CH2CH2(CF2)9CF3 R86
    242 —CH2CH2(CF2)9CF3 R86 R86
    243 —CH2CH2(CF2)11CF3 —CH2CH2(CF2)11CF3 —CH2CH2(CF2)11CF3
    244 —CH2CH2(CF2)11CF3 —CH2CH2(CF2)11CF3 R86
    245 —CH2CH2(CF2)11CF3 R86 R86
    246 —CF2CHF2 —CF2CHF2 —CF2CHF2
    247 —CF2CHF2 —CF2CHF2 R86
    248 —CF2CHF2 R86 R86
    249 —(CF2)3CHF2 —(CF2)3CHF2 —(CF2)3CHF2
    250 —(CF2)3CHF2 —(CF2)3CHF2 R86
    251 —(CF2)3CHF2 R86 R86
    14 phenyl phenyl phenyl
    252 phenyl phenyl p-tolyl
    253 phenyl phenyl m-tolyl
    254 phenyl phenyl o-tolyl
    255 phenyl phenyl 2-xylyl
    256 phenyl phenyl 5-xylyl
    257 phenyl phenyl mesityl
    258 phenyl phenyl 9-fluorenyl
    18 phenyl phenyl R86
    259 phenyl phenyl —O—tBu (tert-butoxy)
    260 phenyl p-tolyl p-tolyl
    261 phenyl m-tolyl m-tolyl
    262 phenyl o-tolyl o-tolyl
    263 phenyl 2-xylyl 2-xylyl
    264 phenyl 5-xylyl 5-xylyl
    265 phenyl mesityl mesityl
    266 phenyl R86 R86
    267 phenyl ethoxy ethoxy
    268 p-tolyl p-tolyl p-tolyl
    269 p-tolyl p-tolyl R86
    270 p-tolyl R86 R86
    271 m-tolyl m-tolyl m-tolyl
    272 m-tolyl m-tolyl R86
    273 o-tolyl o-tolyl o-tolyl
    274 o-tolyl o-tolyl R86
    275 2-xylyl 2-xylyl 2-xylyl
    276 2-xylyl 2-xylyl R86
    277 5-xylyl 5-xylyl 5-xylyl
    278 5-xylyl 5-xylyl R86
    279 mesityl mesityl mesityl
    280 mesityl mesityl R86
    281 C6F5 C6F5 C6F5
    282 C6F5 C6F5 R86
    283 C6F5 R86 R86
    284 R86 R86 R86
    285 R86 ethoxy ethoxy
    286 R86 n-butoxy n-butoxy
    287 R86 R86 methoxy
    288 R86 R86 ethoxy
    289 R86 R86 osime3
    290 R86 R86 —(CH2)11O—(CH2)2OCH3
    291 methoxy methoxy methoxy
    292 ethoxy ethoxy ethoxy
    293 i-propoxy i-propoxy i-propoxy
    294 t-butoxy t-butoxy t-butoxy
    295 OSiMe3 OSiMe3 osime3
    296 cyclobutyl methyl
    297 cyclobutyl R86
    298 cyclobutyl p-methoxyphenyl
    299 cyclopentyl methyl
    300 cyclopentyl R86
    301 cyclohexyl methyl
    302 cyclohexyl R86
  • In this table,
  • Figure US20120205645A1-20120816-C00239
  • Particularly preferred compounds in which two units of the general formulae (XI) and/or (XI*) are bridged to one another via a linear or branched, saturated or unsaturated bridge optionally interrupted by at least one heteroatom or via O, where this bridge in the general formulae (XI) and/or (XI*) is in each case attached to the silicon atoms in place of R71, correspond to the general formula (XIII)
  • Figure US20120205645A1-20120816-C00240
  • In formula (XIII), U, R70, R71, R72, R87, R88 and R89 are each defined as follows:
  • Nr. R70 R71 R72 R87 R88 R89 U
    303 methyl R86 R86 methyl R5 R86 —CH2—
    304 methyl methyl R86 methyl methyl R86 —CH2—
    305 R86 R86 R86 R86 R86 R86 —CH2—
    306 methyl R86 R86 methyl R5 R86 —C2H4—
    307 methyl methyl R86 methyl methyl R86 —C2H4—
    308 R86 R86 R86 R86 R86 R86 —C2H4—
    309 methyl R86 R86 methyl R86 R86 —C3H6—
    310 methyl methyl R86 methyl methyl R86 —C3H6—
    311 R86 R86 R86 R86 R86 R86 —C3H6—
    312 methyl R86 R86 methyl R86 R86 —C4H8—
    313 methyl methyl R86 methyl methyl R86 —C4H8—
    314 R86 R86 R86 R86 R86 R86 —C4H8—
    315 methyl R86 R86 methyl R86 R86 —C6H12—
    316 methyl methyl R86 methyl methyl R86 —C6H1 2—
    317 R86 R86 R86 R86 R86 R86 —C6H1 2—
    318 methyl R86 R86 methyl R86 R86 —C8H16—
    319 methyl methyl R86 methyl methyl R86 —C8H16—
    320 R86 R86 R86 R86 R86 R86 —C8H16—
    321 methyl R86 R86 methyl R86 R86 —C9H18—
    322 methyl methyl R86 methyl methyl R86 —C9H18—
    323 R86 R86 R86 R86 R86 R86 —C9H18—
    324 R86 R86 R86 R86 R86 R86 —CH(C8H17)CH2—
    325 methyl R86 R86 methyl R86 R86 —C2H4(CF2)8
    C2H4—
    326 methyl methyl R86 methyl methyl R86 —C2H4(CF2)8
    C2H4—
    327 R86 R86 R86 R86 R86 R86 —C2H4(CF2)8
    C2H4—
    328 methyl R86 R86 methyl R86 R86 —C≡C—
    329 methyl methyl R86 methyl methyl R86 —C≡C—
    330 R86 R86 R86 R86 R86 R86 —C≡C—
    331 methyl R86 R86 methyl R86 R86 -1,4-(CH2)2-
    phenyl-
    (CH2)2—
    332 methyl methyl R86 methyl methyl R86 -1,4-(CH2)2-
    phenyl-
    (CH2)2—
    333 R86 R86 R86 R86 R86 R86 -1,4-(CH2)2-
    phenyl-
    (CH2)2—
    334 methyl R86 R86 methyl R86 R86 -1,3-(CH2)2-
    phenyl-
    (CH2)2—
    335 methyl methyl R86 methyl methyl R86 -1,3-(CH2)2-
    phenyl-
    (CH2)2—
    336 R86 R86 R86 R86 R86 R86 -1,3-(CH2)2-
    phenyl-
    (CH2)2—
    337 methyl R86 R86 methyl R86 R86 -1,4-(CH2)3-
    phenyl-
    (CH2)3—
    338 methyl methyl R86 methyl methyl R86 -1,4-(CH2)3-
    phenyl-
    (CH2)3—
    339 R86 R86 R86 R86 R86 R86 -1,4-(CH2)3-
    phenyl-
    (CH2)3—
    340 methyl R86 R86 methyl R86 R86 -1,3-(CH2)3-
    phenyl-
    (CH2)3—
    341 methyl methyl R86 methyl methyl R86 -1,3-(CH2)3-
    phenyl-
    (CH2)3—
    342 R86 R86 R86 R86 R86 R86 -1,3-(CH2)3-
    phenyl-
    (CH2)3—
    343 methyl R86 R86 methyl R86 R86 -1,4-phenyl-
    344 methyl methyl R86 methyl methyl R86 -1,4-phenyl-
    345 R86 R86 R86 R86 R86 R86 -1,4-phenyl-
    346 methyl R86 R86 methyl R86 R86 -1,3-phenyl-
    347 methyl methyl R86 methyl methyl R86 -1,3-phenyl-
    348 R86 R86 R86 R86 R86 R86 -1,3-phenyl-
    28 methyl methyl R86 methyl methyl R86 —O—
    349 methyl R86 R86 methyl R86 R86 —O—
    350 methyl methyl R86 methyl methyl R86 —O—Si(CH3)2—
    O—
    351 methyl methyl R86 methyl methyl R86 —O—
    Si(CH3)(Ph)—
    O—
    352 methyl methyl R86 methyl methyl R86 —O—Si(CH3)2—
    O—Si(CH3)2—
    O—
    353 methyl methyl R86 methyl methyl R86 —O—Si(CH3)2—
    O—Si(CH3)2—
    O—Si(CH3)2—
    O—
    354 methyl —OSiMe3 R86 methyl —OSiMe3 R86 —O—
    355 methyl phenyl R86 methyl phenyl R86 —O—
    356 i-propyl i-propyl R86 i-propyl i-propyl R86 —O—
    357 cyclopentyl cyclopentyl R86 cyclopentyl cyclopentyl R86 —O—
    358 phenyl phenyl R86 phenyl phenyl R86 —O—
    359 phenyl R86 R86 phenyl R86 R86 —O—
    360 R86 R86 R86 R86 R86 R86 —O—
  • In this table,
  • Figure US20120205645A1-20120816-C00241
  • Further suitable compounds of the formula (XI) and/or (XI*) are specified hereinafter. R therein is independently Me, phenyl or R86, where at least one R radical is R86:
  • Figure US20120205645A1-20120816-C00242
  • In a very particularly preferred embodiment, the present invention relates to an OLED which, as well as at least one metal-carbene complex of the general formula (I), comprises at least one compound of the general formula (X), in which case the compound of the formula (X) is most preferably at least one of the compounds specified below:
  • Figure US20120205645A1-20120816-C00243
    Figure US20120205645A1-20120816-C00244
    Figure US20120205645A1-20120816-C00245
    Figure US20120205645A1-20120816-C00246
    Figure US20120205645A1-20120816-C00247
    Figure US20120205645A1-20120816-C00248
  • In the aforementioned compounds, T is O or S, preferably O. When more than one T occurs in the molecule, all T groups have the same definition.
  • In addition to the compounds of the formula (X), according to the present invention, it is also possible to use crosslinked or polymeric materials comprising repeat units based on the general formula (X) in crosslinked or polymerized form together with at least one heteroeleptic complex of the general formula (I). Like the compounds of the general formula (X), the latter are preferably used as matrix materials.
  • The crosslinked or polymeric materials have outstanding solubility in organic solvents, excellent film-forming properties and relatively high glass transition temperatures. In addition, high charge carrier mobilities, high stabilities of color emission and long operating times of the corresponding components can be observed when crosslinked or polymeric materials according to the present invention are used in organic light-emitting diodes (OLEDs).
  • The crosslinked or polymerized materials are particularly suitable as coatings or in thin films since they are thermally and mechanically stable and relatively defect-free.
  • The crosslinked or polymerized materials comprising repeat units based on the general formula (X) can be prepared by a process comprising steps (a) and (a):
    • (a) preparation of a crosslinkable or polymerizable compound of the general formula (X) where at least one of the a″ R55 radicals or at least one of the b′ R56 radicals is a crosslinkable or polymerizable group attached via a spacer, and
    • (b) crosslinking or polymerization of the compound of the general formula (X) obtained from step (a).
  • The crosslinked or polymerized materials may be homopolymers, which means that exclusively units of the general formula (X) are present in crosslinked or polymerized form. They may also be copolymers, which means that further monomers are present in addition to the units of the general formula (X), for example monomers with hole-conducting and/or electron-conducting properties, in crosslinked or polymerized form.
  • In a further preferred embodiment of the inventive OLED, it comprises an emission layer comprising at least one inventive heteroeleptic complex of the general formula (I), at least one matrix material of the formula (X), and optionally at least one further hole-transporting matrix material.
  • The inventive OLEDs can be used in all devices in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile visual display units and illumination means. The present invention therefore also relates to a device selected from the group consisting of stationary visual display units and mobile visual display units and illumination means, comprising an inventive OLED.
  • Stationary visual display units are, for example, visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations and information panels. Mobile visual display units are, for example, visual display units in cellphones, laptops, digital cameras, mp-3 players, smartphones, vehicles, and destination displays on buses and trains.
  • In addition, the inventive heteroleptic complexes of the general formula (I) can be used in OLEDs with inverse structure. The inventive complexes are preferably used in turn in these inverse OLEDs in the light-emitting layer. The structure of inverse OLEDs and the materials typically used therein are known to those skilled in the art.
  • A further embodiment of the present invention is a white OLED comprising at least one heteroleptic complex of the general formula (I). In a preferred embodiment, the heteroleptic complex of the general formula (I) is employed in the white OLED as emitter material. Preferred embodiments of the heteroleptic complex of the general formula (I) are mentioned before. Beside the at least one heteroleptic complex of the general formula (I) the white OLED may comprise at least one compound of the formula (X). The compound of formula (X) is preferably employed as matrix material. Preferred compounds of the formula (X) are mentioned before.
  • In order to obtain white light, the OLED must generate light which colors the entire visible range of the spectrum. However, organic emitters normally emit only in a limited portion of the visible spectrum—i.e. are colored. White light can be generated by the combination of different emitters. Typically, red, green and blue emitters are combined. However, the prior art also discloses other methods for formation of white OLEDs, for example the triplet harvesting approach. Suitable structures for white OLEDs or methods for formation of white OLEDs are known to those skilled in the art.
  • The present invention also relates to an organic electronic component, preferably an organic light-emitting diode (OLED), organic photovoltaic cell (OPV), organic filed-effect transistor (OFET) or light-emitting electrochemical cell (LEEC), comprising a least one inventive heteroleptic complex of the general formula (I).
    • EXAMPLES
  • The examples which follow, especially the methods, materials, conditions, process parameters, apparatus and the like, detailed in the examples, are intended to support the present invention, but not to restrict the scope of the present invention.
  • N-(2,6-Diisopropylphenyl)-2-phenylimidazole L1 is synthesized analogously to example 14 in WO2006/121811. The synthesis of 5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole C1 is effected according to D. Enders, K. Breuer, G. Raabe, J. Runsink, J. H. Teles, J.-P. Melder, K. Ebel, S. Brode, Angew. Che—m. 1995, 107, 9, 1119-1122 or D. Enders, K. Breuer, U. Kallfass, T. Balensiefer, Synthesis 2003, 8, 1292-1295. 3-(2,6-Dimethylphenyl)-7-methylimidazo[1,2-f]phenanthridine L3 is synthesized analogously to example 10 in WO 2007/095118. The synthesis of the ligand precursor 1-isopropyl-1,2,4-triazolo[4,3-f]phenanthridinium iodide C3 is effected as described in WO 2009/050281. The synthesis of the exciton and hole blocker 2,8-bis(triphenylsilyl)-dibenzofuran LB1 is disclosed in synthesis example 4g in WO 2009/003898.
  • All experiments are performed in protective gas atmosphere.
    • Example 1 μ-Dichloro dimer D1
  • Figure US20120205645A1-20120816-C00249
  • 3.50 g (11.5 mmol) of 1-(2,6-diisopropylphenyl)-2-phenyl-1H-imidazole L1 are initially charged in 200 ml of 2-ethoxyethanol/water (ratio 3/1) and admixed with 1.84 g (5.2 mmol) of iridium(III) chloride trihydrate. The reaction mixture is heated at reflux for 18 h. After cooling, 50 ml of distilled water are added. The precipitate is filtered off, washed with distilled water and dried. This gives 3.50 g (80%) of μ-dichloro dimer D1 as a yellow powder.
  • 1H NMR (CD2Cl2, 400 MHz):
  • δ=0.95 (d, 3JH,H=6.9 Hz, 12H), 1.18 (d, 3JH,H=6.9 Hz, 12H), 1.27 (d, 3JH,H=6.9 Hz, 12H), 1.34 (d, 3JH,H=6.9 Hz, 12H), 2.80-2.91 (m, 8H), 6.08 (d, 3JH,H=7.7 Hz, 4H), 6.24 (d, 3JH,H=7.7 Hz, 4H), 6.39 (pt, 3JH,H=7.5 Hz, 4H), 6.53 (pt, 3JH,H=7.5 Hz, 4H), 6.97 (d, JH,H=1.5 Hz, 4H), 7.39-7.45 (m, 8H), 7.59 (t, 3JH,H=7.8 Hz, 4H), 7.67 (d, JH,H=1.5 Hz, 4H).
    • Complex Em1-s:
  • Figure US20120205645A1-20120816-C00250
  • 2.37 g (7.2 mmol) of 5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole Cl are heated to 90° C. under reduced pressure for 18 h. After cooling to room temperature, first 100 ml of anhydrous toluene and then a suspension of 3.00 g (1.8 mmol) of chloro dimer D1 and 150 ml of anhydrous toluene are added. The mixture is heated to 90° C. for 2 h. The white precipitate formed (1.15 g, imidazolium chloride C1*) is filtered off. The filtrate is washed with 3×40 ml of saturated NaHCO3 solution and 1×40 ml of distilled water, dried over MgSO4 and freed of the solvent under reduced pressure. The residue is washed with 2×50 ml of methanol, recrystallized from methylene chloride/methanol and then recrystallized from nitromethane. This gives 3.2 g of the complex Em1-s as a yellow powder (82%).
  • Figure US20120205645A1-20120816-C00251
  • Em1-s: The configuration of Em1-s corresponds to the configuration of the pseudo-meridional isomer S1a or S1b. Em1-s is present as the racemate; for crystal structure see FIG. 1, only one enantiomer is depicted, large sphere=C, small sphere=H. Sample for the x-ray structure analysis is crystallized from nitromethane (nitromethane still present in the crystals).
  • 1H NMR (CD2Cl2, 400 MHz):
  • δ=0.88 (d, 3JH,H=6.8 Hz, 3H), 0.91 (d, 3JH,H=6.9 Hz, 9H), 1.14 (d, 3JH,H=6.9 Hz, 3H), 1.16 (d, 3JH,H=6.8 Hz, 3H), 1.20 (d, 3JH,H=6.9 Hz, 3H), 1.28 (d, 3JH,H=6.9 Hz, 3H), 2.08 (sept, 3JH,H=6.7 Hz, 1H), 2.65-2.77 (m, 3H), 6.08-6.15 (m, 3H), 6.19-6.25 (m, 2H), 6.42-6.45 (m, 1H), 6.50-6.52 (m, 2H), 6.67 (s, b, 2H), 6.71 (dt, 3JH,H=7.4 Hz, J=1.2 Hz, 1H), 6.75 (d, J=1.5 Hz, 1H), 6.79-6.87 (m, 6H), 7.00-7.07 (m, 2H), 7.28-7.43 (m, 9H), 7.50 (t, 3JH,H=7.8 Hz, 1H), 7.56 (t, 3JH,H=7.8 Hz, 1H), 7.71 (d, 3JH,H=7.5 Hz, 1H).
  • Photoluminescence (in a film, 2% in PMMA):
  • λmax=460, 490 nm, CIE: (0.19; 0.34)
    • Example 2 Complex Em1-i
  • Figure US20120205645A1-20120816-C00252
      • racemic in each case, only one enantiomer of each depicted
  • A solution of 1.6 g of complex Em1-s in 200 ml of 3-methoxypropionitrile is irradiated at room temperature with a blacklight blue lamp for 5 h (Osram, L18W/73, λmax=370-380 nm). The solvent is removed under reduced pressure. The residue is washed with methanol and recrystallized from methylene chloride/methanol. This gives 1.2 g of Em1-i as a lemon yellow powder (75%).
  • The configuration of Em1-i corresponds to the configuration IVa or IVb of the pseudo-facial isomer S4a or S4b. Em1-i is present as the racemate; for crystal structure see FIG. 2, the sample for the x-ray structure analysis is crystallized from cyclohexane/ethyl acetate (cyclohexane still present in the crystals).
  • 1H NMR (CD2Cl2, 500 MHz):
  • δ=0.46 (d, 3JH,H=6.8 Hz, 3H), 0.75 (d, 3JH,H=6.8 Hz, 3H), 0.81 (d, 3JH,H=6.8 Hz, 3H), 1.01 (d, 3JH,H=6.8 Hz, 3H), 1.09 (d, 3JH,H=6.9 Hz, 3H), 1.14 (d, 3JH,H=6.9 Hz, 3H), 1.17 (d, 3JH,H=6.9 Hz, 3H), 1.26 (d, 3JH,H=6.8 Hz, 3H), 1.50 (sept, 3JH,H=6.8 Hz, 1H), 2.49-2.60 (m, 3H), 6.01 (d, J=1.3 Hz, 1H), 6.10 (t, 3JH,H=8.2 Hz, 2H), 6.34 (d, J=1.4 Hz, 1H), 6.38 (d, 3JH,H=7.2 Hz, 1H), 6.41-6.45 (m, 2H), 6.57-6.73 (m, 5H), 6.85 (d, J=1.4 Hz, 1H), 6.96-7.00 (m, 1H), 7.11 (d, J=1.4 Hz, 1H), 7.17-7.42 (m, 14H), 7.46 (t, 3JH,H=7.8 Hz, 1H), 7.54 (t, 3JH,H=7.8 Hz, 1H), 7.68 (d, 3JH,H=8.2 Hz, 1H).
  • Photoluminescence (in a film, 2% in PMMA):
  • λmax=456, 488 nm, CIE: (0.21; 0.37)
  • The photoluminescence quantum yield of the facial isomer Em1-i is 1.36 times the quantum yield of the meridional isomer Em1-s.
    • Example 3 4-Bromodibenzofuran
  • Figure US20120205645A1-20120816-C00253
  • 100.00 g (99%, 588.6 mmol) of dibenzofuran are dissolved in 800 ml of anhydrous THF and admixed at −40° C. with 400 ml (640.0 mmol) of n-BuLi (1.6M in hexane). The cooling bath is removed. The reaction solution is allowed to come to room temperature in a water bath within approx. 30 min and stirred for a further two hours. Thereafter, it is cooled to −78° C. and a solution of 160.34 g (99%, 844.9 mmol, 73.55 ml) of 1,2-dibromoethane in 80 ml of anhydrous THF is added dropwise. The cooling bath is removed, and the mixture is allowed to come to room temperature in a water bath within approx. 30 min and stirred for a further two hours. Subsequently, 60 ml of saturated sodium chloride solution are added cautiously (slightly exothermic reaction, temperature rise 1-2° C.). The organic phase is removed and freed of the solvent under reduced pressure. The oily red-brown residue is taken up in 900 ml of dichloromethane and washed successively with 500 ml of HCl solution (1 N) and 400 ml of water. The organic phase is dried over magnesium sulfate and freed of the solvent under reduced pressure. In the course of cooling, a yellowish solid precipitates out, which is comminuted in a mortar and washed on a frit with 2×150 ml of isopropanol. After drying, 120.36 g of beige powder are obtained (according to GC and NMR: DBF/Br-DBF ratio=10/90, corresponds to 111.93 g of Br-DBF/76% yield). After removing the solvent, a further 15.84 g of a mixture of dibenzofuran and 4-bromodibenzofuran (comprises a further approx. 7.8 g/5% Br-DBF) are obtained from the isopropanol solution. This mixture can likewise be used in the further stages.
  • 1H NMR (CDCl3, 500 MHz):
  • δ=7.92 (d, 3JH,H=7.8 Hz, 1H), 7.86 (dd, 3JH,H=7.7 Hz, 4JH,H=1.0 Hz, 1H), 7.65 (d, 3JH,H=8.2 Hz, 1H), 7.61 (dd, 3JH,H =7.8 Hz, 4JH,H=1.1 Hz, 1H), 7.50 (dt, 3JH,H=8.2 Hz, JH,H =1.3 Hz, 1H), 7.37 (dt, 3JH,H=7.8 Hz, JH,H=0.8 Hz, 1H), 7.21 (t, 3JH,H=7.8 Hz, 1H).
    • 1-Dibenzofuran-4-yl-1H-imidazole
  • Figure US20120205645A1-20120816-C00254
  • 119.00 g of the first stage (comprise 110.66 g, 447.9 mmol of 4-bromodibenzofuran) are dissolved in 700 ml of dimethylformamide and admixed successively with 37.15 g (545.7 mmol) of imidazole, 15.80 g (83.0 mmol) of copper(I) iodide and 83.20 g (602.0 mmol) of potassium carbonate. The mixture is stirred at 150° C. for 48 h, in the course of which a further 3.75 g (55.1 mmol) of imidazole are added after 24 h and a further 1.93 g (28.3 mmol) after 44 h. Thereafter, the mixture is cooled to room temperature and the insoluble constituents are filtered off. The filtrate is concentrated to dryness. The residue is taken up in 500 ml of methylene chloride, washed successively with 150 ml of ammonia solution (25%) and 150 ml of water, dried over magnesium sulfate and concentrated. This gives 82.23 g of crude product, which is used in the next stage without further purification (78% crude yield).
    • 3-Dibenzofuran-4-yl-1-methyl-3H-imidazol-1-ium iodide C2
  • Figure US20120205645A1-20120816-C00255
  • 82.03 g (350.1 mmol) of 1-dibenzofuran-4-yl-1H-imidazole (crude product) are dissolved in 1 l of tetrahydrofuran and admixed slowly with 246.06 g (1.733 mol) of methyl iodide. The mixture is stirred at room temperature for 65 h. The precipitate formed is filtered off, washed with 1 l of tetrahydrofuran and dried. This gives 98.41 g (261.6 mmol, 75%) of beige powder.
  • 1H NMR (DMSO, 500 MHz):
  • δ=10.00 (s, 1H, NCHN), 8.49 (t, J=1.9 Hz, 1H, CHAryl), 8.41 (dd, 3JH,H=7.8 Hz, J=1.0 Hz, 1H, CHAryl), 8.32-8.30 (m, 1H, CHAryl), 8.15 (t, J=1.8 Hz, 1H, CHAryl), 7.96 (dd, 3JH,H=7.9 Hz, J=1.0 Hz, 1H, CHAryl), 7.84 (d, 3JH,H=8.4 Hz, 1H, CHAryl), 7.69-7.65 (m, 2H, CHAryl), 7.53 (dt, 3JH,H=7.5 Hz, J=0.9 Hz, 1H, CHAryl), 4.12 (s, 3H, CH3).
    • Complex Em2-s:
  • Figure US20120205645A1-20120816-C00256
  • 1.01 g (2.7 mmol) of imidazolium iodide C2 and 0.31 g (1.3 mmol) of Ag2O are stirred in 200 ml of anhydrous acetonitrile at room temperature for 18 h. Then the solvent is removed under reduced pressure. The residue is taken up in 300 ml of anhydrous THF and 1.50 g (0.9 mmol) of chloro dimer D1 are added. Thereafter, the mixture is heated at reflux for 24 h. After cooling, the reaction solution is filtered. The filtrate is freed of the solvent under reduced pressure. The residue is washed with methanol and, after drying, 1.2 g of the complex Em2-s are obtained as a yellow powder (64%).
  • 1H NMR (CD2Cl2, 500 MHz):
  • δ=0.86 (d, 3JH,H=6.9 Hz, 3H), 0.96 (d, 3JH,H=6.8 Hz, 3H), 1.00 (d, 3JH,H=6.7 Hz, 3H), 1.02 (d, 3JH,H=7.1 Hz, 3H), 1.03 (d, 3JH,H=7.1 Hz, 3H), 1.06 (d, 3JH,H=6.9 Hz, 3H), 1.21 (d, 3JH,H=7.0 Hz, 3H), 1.23 (d, 3JH,H=7.0 Hz, 3H), 2.15 (sept, 3JH,H=6.9 Hz, 1H), 2.39 (sept, 3JH,H=6.9 Hz, 1H), 2.77-2.85 (m, 2H), 3.34 (s, 3H), 6.17 (bd, 3JH,H=7.8 Hz, 1H), 6.20 (bd, 3JH,H=7.8 Hz, 1H), 6.41 (d, J=1.5 Hz, 1H), 6.44-6.52 (m, 2H), 6.54 (d, J=1.5 Hz, 1H), 6.67-6.79 (m, 5H), 6.89 (d, 3JH,H=7.4 Hz, 1H), 6.95 (d, J=1.9 Hz, 1H), 7.16 (bd, 3JH,H=7.3 Hz, 1H), 7.29-7.41 (m, 7H), 7.51-7.55 (m, 2H), 7.61 (bd, 3JH,H=8.1 Hz, 1H), 7.89 (bd, 3JH,H=8.3 Hz, 1H), 8.46 (d, J=1.9 Hz, 1H).
  • Photoluminescence (in a film, 2% in PMMA):
  • λmax=460, 491 nm, CIE: (0.18; 0.33)
    • Example 4 Complex Em2-i
  • Figure US20120205645A1-20120816-C00257
  • A solution of 0.90 g of complex Em2-s in 200 ml of 3-methoxypropionitrile is irradiated at room temperature with a blacklight blue lamp for 3 h (Osram, L18W/73, λmax=370-380 nm). The solvent is removed under reduced pressure. The residue is carefully washed with methanol. This gives 0.63 g Em2-i as a yellow powder (70%).
  • The configuration of Em2-i corresponds to the configuration IVa or IVb of the pseudo-facial isomer S4a or S4b. Em2-1 is present as the racemate; for crystal structure see FIG. 3, the sample for the x-ray structure analysis was crystallized from tetra hydrofuran/n-hepta ne.
  • 1H NMR (CD2Cl2, 400 MHz):
  • δ=0.72 (d, 3JH,H=6.8 Hz, 3H), 0.85 (d, 3JH,H=6.8 Hz, 3H), 0.90 (d, 3JH,H=6.8 Hz, 3H), 0.99 (d, 3JH,H=6.9 Hz, 3H), 1.02 (d, 3JH,H=6.8 Hz, 3H), 1.11 (d, 3JH,H=6.9 Hz, 3H), 1.19 (d, 3JH,H=7.1 Hz, 3H), 1.21 (d, 3JH,H=7.1 Hz, 3H), 1.90 (sept, 3JH,H=6.8 Hz, 1H), 2.46 (sept, 3JH,H=6.8 Hz, 1H), 2.60 (sept, 3JH,H=6.9 Hz, 1H), 2.77 (sept, 3JH,H=6.9 Hz, 1H), 3.53 (s, 3H), 6.16 (bd, 3JH,H=7.7 Hz, 2H), 6.38-6.56 (m, 5H), 6.65-6.69 (m, 2H), 6.76-6.84 (m, 4H), 6.99 (d, J=1.9 Hz, 1H), 7.22 (d, 3JH,H=7.7 Hz, 1H), 7.27-7.37 (m, 6H), 7.49-7.60 (m, 3H), 7.86 (bd, 3JH,H=7.2 Hz, 1H), 8.38 (d, J=1.9 Hz, 1H).
  • Photoluminescence (in a film, 2% in PMMA):
  • λmax=462, 490 nm, CIE: (0.17; 0.29)
  • The photoluminescence quantum yield of the facial isomer Em2-i is 1.44 times the quantum yield of the isomer Em2-s.
    • Example 5 Complex Em3-s
  • Figure US20120205645A1-20120816-C00258
  • 6.0 g (15.5 mmol) of 1-isopropyl-1,2,4-triazolo[4,3-f]phenanthridinium iodide C3 and 2.9 g (12.3 mmol) of Ag2O are stirred in 400 ml of dioxane at room temperature for 40 h. Subsequently, 2.6 g (1.6 mmol) of chloro dimer D1 are added and the mixture is heated to reflux for 24 h. After cooling to room temperature, the precipitate is filtered off and washed with dichloromethane. The combined filtrates are concentrated to dryness and purified by column chromatography (silica gel, dichloromethane). After drying, 2.1 g of Em3-s are obtained as yellow powder (64%).
  • 1H NMR (CD2Cl2, 500 MHz):
  • δ=0.79 (d, 3H), 0.89 (d, 3H), 0.90 (d, 3H), 0.97 (d, 6H), 1.02 (d, 3H), 1.10 (d, 3H), 1.15 (d, 3H), 1.16 (d, 3H), 1.47 (d, 3H), 2.03 (sept, 1H), 2.47 (sept, 1H), 2.65 (sept, 1H), 2.76 (sept, 1H), 4.47 (sept, 1H), 6.13 (d, 1H), 6.21 (d, 1H), 6.35 (d, 1H), 6.46 (mc, 3H), 6.58 (dd, 2H), 6.65-6.76 (m, 3H), 6.93 (dd, 1H), 7.09 (dd, 1H), 7.15 (d, 1H), 7.25 (dd, 1H), 7.28-7.33 (m, 3H), 7.44-7.52 (m, 2H), 7.58 (dd, 1H), 7.67-7.76 (m, 2H), 8.39 (dd, 1H), 8.43 (d, 1H).
  • Photoluminescence (in a film, 2% in PMMA):
  • λmax=457, 489 nm, CIE: (0.18; 0.32)
    • Example 6 Complex Em3-i
  • Figure US20120205645A1-20120816-C00259
  • A suspension of 2.1 g of Em3-s in 2000 ml of acetonitrile is irradiated with a moderate-pressure mercury immersion lamp at room temperature for 8 h (TQ150 with Duran sheath). Subsequently, the solvent is removed under reduced pressure. The residue was stirred twice with acetone and filtered. 1.6 g of Em3-i were obtained as a yellow powder (76%).
  • 1H NMR (CD2Cl2, 500 MHz):
  • δ=0.68 (d, 3H), 0.75 (d, 3H), 0.82 (d, 3H), 0.96 (d, 3H), 0.99 (d, 3H), 1.05 (d, 3H), 1.13 (d, 3H), 1.20 (d, 3H), 1.24 (d, 3H), 1.60 (d, 3H), 1.79 (sept, 1H), 2.42 (sept, 1H), 2.51 (sept, 1H), 2.76 (sept, 1H), 4.56 (sept, 1H), 6.10 (dd, 2H), 6.30-6.35 (m, 1H), 6.38-6.45 (m, 2H), 6.53 (d, 1H), 6.61 (dd, 1H), 6.68 (d, 1H), 6.73 (d, 1H), 6.74-6.78 (m, 2H), 6.79 (d, 1H), 6.96 (dd, 1H), 7.07-7.15 (m, 1H), 7.19 (d, 1H), 7.22 (d, 1H), 7.27-7.34 (m, 3H), 7.47 (dd, 1H), 7.49 (dd, 1H), 7.66-7.72 (m, 2H), 8.34 (d, 1H), 8.40 (d, 1H).
  • Photoluminescence (in a film, 2% in PMMA):
  • λmax=456, 487 nm, CIE: (0.19; 0.32)
  • The photoluminescence quantum yield of the isomer Em3-i is 1.21 times the quantum yield of the isomer Em3-s.
    • Example 7 4-Methyl-1,3-diphenyl-1H-[1,2,4]-triazolium iodide C4
  • Figure US20120205645A1-20120816-C00260
  • Stage 1: Benzonitrile (51.5 g, 0.50 mol) is admixed with ethanol (anhydrous, 25 ml). Then a constant stream of HCl gas is introduced over 2 h and the mixture is subsequently stirred at room temp. for 48 h, in the course of which a solid forms. The solvent is drawn off from the reaction mixture under reduced pressure (95 g).
  • Stages 2+3: 12 g of stage 1 (64.6 mmol) are again dissolved in EtOH (120 ml), and phenylhydrazine (9.4 g, 84 mmol, 1.3 equiv.) is added, in the course of which a solid forms. Triethylamine (22 ml, 162 mmol, 2.5 equiv.) is added and then the mixture is stirred at room temp. for 16 h. The solvent is again removed from the reaction mixture under reduced pressure at room temp., such that the amidrazone formed remains, still moist. After the addition of formic acid (200 ml), the mixture is heated to reflux for 3.5 h. After a further 48 h at room temp., the mixture is cautiously added to an aq. potassium carbonate solution (44%, 900 ml), cooled to 0° C. After the addition of CH2Cl2 (500 ml), the phases are separated, and the organic phase is dried over Na2SO4 and concentrated under reduced pressure. The sample is recrystallized from dichloromethane/petroleum ether, from which slightly contaminated product is obtained (5.5 g, 40%). The mother liquor is column-filtered (CH2Cl2/n-hexane), from which a further batch of clean product is obtained (1.7 g, 12%).
  • Stage 4: The triazole of the preceding stage (1.5 g, 66 mmol) is dissolved in THF (anhydrous, 40 ml), admixed with MeI (14 ml) and heated to reflux for 5 days. The solid obtained is filtered off, recrystallized repeatedly (CH2Cl2/n-hexane) and dried (780 mg, 32%).
  • 1H NMR (400 MHz, CD2Cl2):
  • δ=4.26 (s, 3H), 7.53-7.71 (m, 6H), 7.74-7.76 (m, 2H), 8.09-8.11 (m, 2H), 12.27 (s, 1H).
    • Complex Em-4-s:
  • Figure US20120205645A1-20120816-C00261
  • 0.40 g (1.1 mmol) of imidazolium iodide C4 and 0.13 g (0.56 mmol) of Ag2O are stirred in 50 ml of anhydrous acetonitrile at room temperature for 18 h. Then a solution of 0.61 g (0.37 mmol) of chloro dimer D1 in 25 ml of anhydrous acetonitrile is added. Thereafter, the mixture is heated to reflux for 6 h and then stirred at room temperature for another 16 h. After cooling, the reaction solution is filtered. The filtrate is freed of the solvent under reduced pressure. After washing the residue with methanol, 0.2 g of the complex Em-4-s is obtained as a yellow powder (26%).
  • 1H NMR (500 MHz, CD2Cl2):
  • δ=0.91 (d, 3JH,H=6.9 Hz, 3H), 0.95 (d, 3JH,H=7.1 Hz, 3H), 0.97 (d, 3JH,H=7.1 Hz, 3H), 0.98 (d, 3JH,H=6.8 Hz, 3H), 1.00 (d, 3JH,H=6.9 Hz, 3H), 1.05 (d, 3JH,H=6.9 Hz, 3H), 1.20 (d, 3JH,H=6.9 Hz, 3H), 1.21 (d, 3JH,H=6.9 Hz, 3H), 2.17 (sept, 3JH,H=6.8 Hz, 1H), 2.40 (sept, 3JH,H=6.9 Hz, 1H), 2.75-2.82 (m, 2H), 3.36 (s, 3H), 6.17 (bt, 3JH,H=7.0 Hz, 2H), 6.43-6.50 (m, 3H), 6.62 (d, J=1.5 Hz, 1H), 6.66-6.82 (m, 6H), 6.88 (dd, 3JH,H=7.1 Hz, J=1.3 Hz, 1H), 6.96 (dt, 3JH,H=7.4 Hz, J=1.5 Hz, 1H), 7.08 (bd, 3JH,H=6.7 Hz, 1H), 7.31-7.37 (m, 4H), 7.51-7.59 (m, 6H), 7.69-7.72 (m, 2H).
  • Photoluminescence (in a film, 2% in PMMA):
    • Xmax=458, 488 nm, CIE: (0.19; 0.33) Example 8 Complex Em-4-i
  • Figure US20120205645A1-20120816-C00262
  • A solution of 0.15 g of complex Em-4-s in 200 ml of 3-methoxypropionitrile is irradiated with a blacklight blue lamp at room temperature for 2 h (Osram, L18W/73, λmax=370-380 nm). The solvent is removed under reduced pressure. The residue is carefully washed with methanol. This gives 0.05 g Em-4-i as a yellow powder (33%).
  • 1H NMR (500 MHz, CD2Cl2):
  • δ=0.71 (d, 3JH,H=6.9 Hz, 3H), 0.84 (d, 3JH,H=6.8 Hz, 3H), 0.88 (d, 3JH,H=6.9 Hz, 3H), 1.03 (d, 3JH,H=6.8 Hz, 3H), 1.06 (d, 3JH,H=6.7 Hz, 3H), 1.07 (d, 3JH,H=6.8 Hz, 3H), 1.18 (d, 3JH,H=6.9 Hz, 3H), 1.19 (d, 3JH,H=6.9 Hz, 3H), 1.89 (sept, 3JH,H=6.8 Hz, 1H), 2.50 (sept, 3JH,H=6.9 Hz, 1H), 2.58 (sept, 3JH,H=6.9 Hz, 1H), 2.73 (sept, 3JH,H=6.9 Hz, 1H), 6.17 (bd, 3JH,H=7.8 Hz, 2H), 6.42-6.52 (m, 3H), 6.60 (dt, 3JH,H=7.6 Hz, J=1.3 Hz, 1H), 6.64-6.70 (m, 4H), 6.76-6.78 (m, 2H), 6.81 (d, J=61.4 Hz, 1H), 6.91-6.94 (m, 2H), 7.27-7.38 (m, 4H), 7.50-7.56 (m, 6H), 7.75-7.77 (m, 2H).
  • Photoluminescence (in a film, 2% in PMMA):
  • λmax=456, 488 nm, CIE: (0.19; 0.33)
  • The photoluminescence quantum yield of the isomer Em-4-i has 1.40 times the quantum yield of the isomer Em-4-s.
    • Example 9 3,4-Diphenyl-1-o-tolyl-4H-[1,2,4]-triazolium iodide C5
  • Figure US20120205645A1-20120816-C00263
  • Stage 1: Aq. NaHCO3 solution (5%, 330 g, 190 mmol, 2.0 equiv.) is added at room temp. to a suspension of o-tolylhydrazine hydrochloride (15 g, 97 mmol) in methyl chloride (450 ml). After stirring for 30 minutes, the biphasic solution is phase-separated. The organic phase is dried over Na2SO4, freed of the solvent and dried under reduced pressure at 60° C. to isolate tolylhydrazine as a pale yellow solid (7.3 g, 62%).
  • Stage 2: Benzoyl chloride (8.4 g, 60 mmol, 1.0 equiv.) is initially charged in toluene (anhydrous, 60 ml) and cooled to 5° C. Then aniline (5.6 g, 60 mmol, 1.0 equiv.) is added, and the reaction mixture is heated to reflux for 16 h and then stirred at room temp. for a further 48 h. Then the mixture is heated to 80° C., thionyl chloride (21.4 g, 180 mmol, 3.0 equiv.) is added at this temperature and the mixture is stirred for a further 2 h. Then the mixture is cooled to room temp. and the excess thionyl chloride is drawn off under reduced pressure. The reaction mixture is admixed with THF (anhydrous, 180 ml) and triethylamine (9.1 g, 90 mmol, 1.5 equiv.) and cooled to 5° C., and then the tolylhydrazine of stage 1 (7.3 g, 60 mmol), dissolved in THF (20 ml), is added. The mixture is stirred at room temperature for 16 h. After the removal of the solvent, the residue is recrystallized from acetic acid (2%, 150 ml), washed with iPrOH (80 ml, 20 ml) and dried (10.3 g, 57%).
  • Stage 3: Triethyl orthoformate (9.0 ml, 8.1 g, 56 mmol, 5.6 equiv.) and 3 g of the hydrazone of stage 2 (10 mmol) are initially charged, ammonium iodide (1.4 g, 10 mmol, 1.0 equiv.) is added and the suspension is heated to reflux for 7 h. After cooling, the solid is filtered off with suction and washed repeatedly with n-hexane and ethyl acetate, from which the iodide salt is obtained as a gray powder (3.2 g, 73%).
  • 1H NMR (400 MHz, DMSO):
  • δ=2.55 (s, 3H), 7.47-7.90 (m, 14H), 11.07 (s, 1H).
    • Complex Mixture Em5-s:
  • Figure US20120205645A1-20120816-C00264
  • 1.12 g (2.5 mmol) of imidazolium iodide C5 are suspended in 100 ml of anhydrous toluene. At 0° C., 8.2 ml (4.1 mmol) of potassium bis(trimethylsilyl)amide (0.5M in toluene) are added dropwise within 5 min. The solution formed is allowed to warm up to 10° C. and admixed with a suspension of 1.42 g (0.85 mmol) of chloro dimer D1 and 75 ml of anhydrous toluene. The reaction mixture is heated to 90° C. and stirred at this temperature for 2 h. After cooling, the precipitate is removed. The filtrate is washed successively with 3×30 ml of aqueous NaHCO3 solution and 1×30 ml of water, dried over MgSO4 and freed of the solvent under reduced pressure. The residue is purified by column chromatography (solvent: cyclohexane/acetone=4/1). This gives 1.2 g (63%) Em5-s as a mixture of two cyclometalation isomers.
  • Photoluminescence (in a film, 2% in PMMA):
  • λmax=461, 489 nm, CIE: (0.19; 0.33)
    • Example 10 Complex Mixture Em5-i
  • Figure US20120205645A1-20120816-C00265
  • A solution of 0.60 g of Em5-s complex mixture in 200 ml of 3-methoxypropionitril is irradiated with a blacklight blue lamp at room temperature for 7 h (Osram, L18W/73, λmax=370-380 nm). The solvent is removed under reduced pressure. The residue is carefully washed with methanol. This gives 0.10 g of Em5-i as a pale yellow powder (17%, again mixture of two cyclometalation isomers).
  • MS (Maldi):
  • m/e=1110 (M+H)+
  • Photoluminescence (in a film, 2% in PMMA):
  • λmax=456, 487 nm, CIE: (0.20; 0.34)
  • The photoluminescence quantum yield of the isomerized Em5-i complex mixture has 1.50 times the quantum yield of the Em5-s complex mixture.
    • Example 11 1-Methyl-2-phenyl-1H-imidazole L2
  • Figure US20120205645A1-20120816-C00266
  • 13.0 g (90 mmol) of 2-phenylimidazole are dissolved in 600 ml of DMF, admixed slowly with 4.0 g (100 mmol) of sodium hydride (60% in mineral oil) and stirred at room temperature for 30 min. Then 14.0 g (99 mmol) of methyl iodide are added. The reaction mixture is stirred at room temperature for 1.5 h and then admixed cautiously with 350 ml of water. The mixture is extracted with 2×200 ml of ethyl acetate. The extract is dried over sodium sulfate and concentrated. This gives 12.0 g (84%) L2.
  • 1H NMR (400 MHz, CD2Cl2):
  • δ=3.74 (s, 3H), 7.00 (s, 1H), 7.05 (s, 1H), 7.40-7.43 (m, 1H), 7.45-7.48 (m, 2H), 7.62-7.63 (m, 2H).
    • μ-Dichloro Dimer D2:
  • Figure US20120205645A1-20120816-C00267
  • The synthesis is performed analogously to D1. The precipitate obtained is extracted with dichloromethane. After removing the solvent, D2 is obtained from the extract in a yield of 36%.
  • 1H NMR (CD2Cl2, 400 MHz):
  • δ=4.13 (s, 12H), 6.05 (d, 3JH,H=7.7 Hz, 4H), 6.55 (t, 3JH,H=7.5 Hz, 4H), 6.74 (t, 3JH,H=7.5 Hz, 4H), 6.94 (s, 4H), 7.27 (s, 4H), 7.37 (d, 3JH,H=7.7 Hz, 4H).
    • Complex Em6-s:
  • Figure US20120205645A1-20120816-C00268
  • 1.20 g (3.6 mmol) of 5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole Cl are heated to 90° C. under reduced pressure for 20 h. After cooling to room temperature, first 1.21 of anhydrous toluene and then 0.99 g (0.9 mmol) of chloro dimer D2 are added. The mixture is heated to reflux for 8 h. The precipitate formed is filtered off. The filtrate is concentrated to approx. 800 ml and washed successively with 3×500 ml of saturated NaHCO3 solution and 1×500 ml of distilled water, dried over Na2SO4 and freed of the solvent under reduced pressure. The residue is purified by column chromatography (cyclohexane/acetone=5/1). This gives 118 mg of the complex Em6-s (8%).
  • 1H NMR (CD2Cl2, 400 MHz):
  • δ=3.95 (s, 3H), 4.03 (s, 3H), 6.00 (bd, 3JH,H=7.3 Hz, 1H), 6.23 (bt, 3JH,H=7.3 Hz, 1H), 6.27 (d, J=1.5 Hz, 1H), 6.47 (bd, 3JH,H=7.1 Hz, 1H), 6.51 (d, J=1.5 Hz, 1H), 6.60 (bt, 3JH,H=7.5 Hz, 1H), 6.67-6.72 (m, 4H), 6.79-6.88 (m, 6H), 6.95 (dt, 3JH,H=7.5 Hz, J=1.5 Hz, 1H), 7.05 (bt, 3JH,H=7.5 Hz, 1H), 7.24-7.27 (m, 2H), 7.33-7.36 (m, 4H), 7.47 (bd, 3JH,H=6.8 Hz, 1H), 7.61 (bd, 3JH,H=6.9 Hz, 1H).
  • Photoluminescence (in a film, 2% in PMMA):
  • λmax=456, 486 nm, CIE: (0.21; 0.33)
    • Example 12 Complex Em7-s
  • Figure US20120205645A1-20120816-C00269
  • 0.67 g (2.0 mmol) of 5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole Cl are heated to 90° C. under reduced pressure for 20 h. After cooling to room temperature, the residue is dissolved in 50 ml of anhydrous toluene and added to a suspension of 1.00 g (0.9 mmol) of chloro dimer D2 and 0.36 g (1.9 mmol) of AgBF4 in 1.2 I of anhydrous toluene. The mixture is stirred under reflux for 8 h. The precipitate formed is filtered off. The filtrate is concentrated to approx. 800 ml and washed successively with 3×500 ml of saturated NaHCO3 solution and 1×500 ml of distilled water, dried over Na2SO4 and freed of the solvent under reduced pressure. The residue is purified by column chromatography (cyclohexane/acetone=5/1). This gives 70 mg of the complex Em7-s (5%).
  • MS (Maldi):
  • m/e=943 (M+H)+
  • 1H NMR (CD2Cl2, 400 MHz):
  • δ=3.70 (s, 3H), 5.86 (d, J=1.3 Hz, 1H), 5.96 (bd, 3JH,H=8.1 Hz, 2H), 6.10 (d, J=1.3 Hz, 1H), 6.56 (bd, 3JH,H=7.2 Hz, 1H), 6.72-6.75 (m, 4H), 6.80 (bt, 3JH,H=7.3 Hz, 1H), 6.86-6.92 (m, 3H), 6.94 (bt, 3JH,H=7.5 Hz, 1H), 7.02-7.12 (m, 5H), 7.19-7.40 (m, 13H), 7.56 (bd, 3JH,H=7.7 Hz, 1H), 7.70 (bd, 3JH,H=7.0 Hz, 1H).
  • Photoluminescence (in a film, 2% in PMMA):
  • λmax=476, 502 nm, CIE: (0.22; 0.37)
    • Example 13 Complex Em7-s*
  • Figure US20120205645A1-20120816-C00270
  • 0.90 g (2.7 mmol) of 5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole Cl are heated to 90° C. under reduced pressure for 20 h. After cooling to room temperature, first 800 ml of anhydrous toluene and then 0.99 g (0.9 mmol) of chloro dimer D2 are added. The mixture is stirred under reflux for 3 h. The precipitate formed is filtered off. The filtrate is washed successively with 3×50 ml of saturated NaHCO3 solution and 1×50 ml of distilled water, dried over MgSO4 and freed of the solvent under reduced pressure. The residue is purified by column chromatography (cyclohexane/acetone=2/1). As well as 50 mg of the complex Em6-s, 150 mg of the complex Em7-s* are obtained.
  • 1H NMR (CD2Cl2, 500 MHz):
  • δ=3.86 (s, 3H), 5.95 (bd, 3JH,H=7.3 Hz, 2H), 6.23 (bd, J=1.4 Hz, 1H), 6.38 (bt, 3JH,H=7.3 Hz, 1H), 6.44 (bd, 3JH,H=7.3 Hz, 1H), 6.54 (bt, 3JH,H=7.5 Hz, 1H), 6.61-6.67 (m, 4H), 6.78-6.91 (m, 5H), 6.96 (bt, 3JH,H=7.5 Hz, 1H), 7.07-7.13 (m, 4H), 7.19-7.36 (m, 12H), 7.53 (bd, 3JH,H=7.0 Hz, 1H), 7.76 (bd, 3JH,H=7.3 Hz, 1H).
  • Photoluminescence (in a film, 2% in PMMA):
  • λmax=482, 508 nm, CIE: (0.24; 0.40)
    • Example 14 μ-Dichloro Dimer D3
  • Figure US20120205645A1-20120816-C00271
  • The synthesis is performed analogously to D1. Yield: 87%.
  • 1H NMR (CD2Cl2, 400 MHz):
  • δ=2.21 (s, 12H), 2.28 (s, 12H), 2.44 (s, 12H), 6.38 (d, 3JH,H=7.4 Hz, 4H), 7.09 (d, 3JH,H=8.7 Hz, 4H), 7.19 (m, 4H), 7.30 (bd, 3JH,H=8.7 Hz, 4H), 7.42 (m, 8H), 7.55 (m, 4H), 7.86 (s, 4H), 8.00 (d, 3JH,H=8.4 Hz, 4H), 8.48 (bs, 4H).
    • Complex Em8-s:
  • Figure US20120205645A1-20120816-C00272
  • 0.37 g (1.1 mmol) of 5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole Cl are heated to 90° C. under reduced pressure for 18 h. After cooling to room temperature, first 120 ml of anhydrous toluene and then 0.50 g (0.28 mmol) of chloro dimer D3 are added. The mixture is heated to 75° C. for 3 h. The white precipitate formed is filtered off. The filtrate is washed with 3×30 ml of saturated NaHCO3 solution and 1×30 ml of distilled water, dried over MgSO4 and freed of the solvent under reduced pressure. The residue is purified by column chromatography (silica gel, ethyl acetate:cyclohexane=1:5). This gives 0.19 g of the complex Em8-s (28%).
  • 1H NMR (CD2Cl2, 500 MHz):
  • δ=2.03 (s, 3H), 2.10 (s, 3H), 2.20 (s, 3H), 2.28 (s, 3H), 2.44 (s, 3H), 2.48 (s, 3H), 6.21 (d, 3JH,H=7.6 Hz, 1H), 6.63-7.39 (m, 28H), 7.45 (d, 3JH,H=7.9 Hz, 1H), 7.67 (d, 3JH,H=7.9 Hz, 1H), 7.70 (d, 3JH,H=7.6 Hz, 1H), 8.21 (bs, 2H).
  • Photoluminescence (in a film, 2% in PMMA):
  • λmax=456 nm, CIE: (0.24; 0.29)
    • Example 15 Comparative Example, Noninventive Complex CEm1
  • Figure US20120205645A1-20120816-C00273
  • CEm1 corresponds to compound (N-3) from WO 2006067074
  • The synthesis is analogous to WO 2006067074.
  • λPL (PMMA): 472 nm, 491 nm, quantum yieldPL: 2%
  • Owing to its very low phosphorescence quantum yield, complex CEm1 is not suitable as an emitter in OLEDs.
    • Example 16 Comparative Example, Noninventive Complex CEm2
  • Figure US20120205645A1-20120816-C00274
  • CEm2 corresponds to the compound “Compound 3” from WO 2006121811. The synthesis was analogous WO 2006121811.
    • Example 17 Production of an OLED Comparison of Different Emitters
  • The ITO substrate used as the anode is cleaned first with commercial detergents for LCD production (Deconex® 20NS, and 25ORGAN-ACID® neutralizing agent) and then in an acetone/isopropanol mixture in an ultrasound bath. To eliminate possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for a further 25 minutes. This treatment also improves the hole injection properties of the ITO. Next, the hole injection layer AJ20-1000 from Plexcore respectively PEDT: PSS (CLEVIOS P AR 4083) from H. C. Starck is spun on from solution.
  • Thereafter, the organic materials specified below are applied by vapor deposition to the cleaned substrate at about 10−7-10−9 mbar at a rate of approx. 0.5-5 nm/min. The hole conductor and exciton blocker applied to the substrate is Ir(DPBIC)3 with a thickness of 45 nm, of which the first 35 nm are doped with MoOx to improve the conductivity,
  • Figure US20120205645A1-20120816-C00275
  • (for preparation see Ir complex (7) in the application PCT/EP/04/09269).
  • Subsequently, a mixture of emitter and of the compound Ma1 is applied by vapor deposition with a thickness of 40 nm, the latter compound functioning as a matrix material. Subsequently, the material Ma1 is applied by vapor deposition with a thickness of 10 nm as an exciton and hole blocker.
  • Figure US20120205645A1-20120816-C00276
  • Next, an electron transporter BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) is applied by vapor deposition in a thickness of 20 nm, as are a 0.75 nm-thick lithium fluoride layer and finally a 100 nm-thick Al electrode. All components are adhesive-bonded to a glass lid in an inert nitrogen atmosphere.
  • To characterize the OLED, electroluminescence spectra are recorded at different currents and voltages. In addition, the current-voltage characteristic is measured in combination with the light output emitted. The light output can be converted to photometric parameters by calibration with a photometer. The lifetime t1/2 of the diode is defined by the time taken for the luminance to fall to 50% of its initial value. The lifetime measurement is carried out at a constant current.
  • For the different emitters in the above-described OLED structure, the following electrooptical data are obtained:
  • Cd/A @ t1/2 @ 1000nits (normalized to the
    Emitter CIE 300nits value of CEm2)
    Em1-i 0.22/0.37 23.2 cd/A 594%
    Em3-i 0.18/0.28 19.5 cd/A 135%
    Em2-i 0.17/0.25 24.5 cd/A 245%
    CEm2 0.20/0.35 10.3 cd/A 100%
    • Example 18 Comparison of Different Isomers of One Emitter
  • By way of example, the influence of the different isomers on the OLED performance is shown in two cases. For the different emitters and isomers in the above-described OLED structure, the following electrooptical data are obtained:
  •
    Cd/A @ t1/2 @ 1000nits (normalized to the
    Emitter CIE 300nits value of Em1-s)
    Em1-s 0.19/0.31 18.2 cd/A 100%
    Em1-i 0.22/0.37 23.2 cd/A 406%
    Cd/A @ t1/2 @ 1000nits (normalized to the
    Emitter CIE 300nits value of Em2-s)
    Em2-s 0.21/0.35 15.4 cd/A 100%
    Em2-i 0.17/0.25 24.5 cd/A 178%
    • Example 19 Influence of a Mixed Electron Conductor Layer
  • The example which follows shows the influence of the doping of the BCP electron conductor layer with Liq.
  • Figure US20120205645A1-20120816-C00277
  • The following OLED structure is used:
  • ITO-40 nm AJ20-1000-35 nm Ir(DPBIC)3 mixed with MoOx-10 nm Ir(DPBIC)3-40 nm Ma1 mixed with 20 wt % Em1-i-5 nm Ma1-40 nm electron conductor-1 nm Liq-100 nm Al. The preparation of the OLED is carried out in analogy to Example 17.
  • Electron Cd/A @ t1/2 @ 1000nits (normalized to the
    conductor CIE 300nits value of BCP)
    BCP 0.22/0.36 16.8 cd/A 100%
    BCP:Liq 50% 0.21/0.36 21.7 cd/A 170%
    • Example 20 Complex Em9-s
  • Figure US20120205645A1-20120816-C00278
  • Imidazoliumiodide C6 corresponds to a pre-intermediate of the compound “example 1” in WO 2006056418. The synthesis is carried out in analogy to the synthesis of the compound “example 1” in WO 2006056418.
  • 2.0 g (6.4 mmol) of imidazoliumiodide C6 and 0.75 g (3.2 mmol) Ag2O are stirred in 170 ml anhydrous acetonitrile for 4 h at 50° C. The solvent is then removed in vacuo. To the residue 170 ml anhydrous toluene is added and 3.6 g (2.1 mmol) chlorodimer D1 are added. Subsequently it is heated under reflux for 24 h. After cooling the reaction mixture is filtered. The filtrate is freed from solvent in vacuo. To the residue methylene chloride is added, washed with water, reduced after drying and purified by chromatography (cyclohexane/acetic ester), where by 0.26 g Em9-s are isolated (6%) and 0.63 g of a mixed fraction of complex Em9-s with not complexed phenylimidazol-ligand as well as 0.10 mg of a further complex with inverse ligand stoichiometry. Further 1.3 g of chlorodimer D1 (36%) are reisolated.
  • 1H-NMR (CD2Cl2, 400 MHz):
  • δ=0.83 (d, 3H), 0.89-0.96 (m, probably interpreted as 4×d, 12H), 1.00 (d, 3H), 1.13 (d, 3H), 1.15 (d, 3H), 1.98 (sept, 1H), 2.31 (sept, 1H), 2.70 (sept, 1H), 2.74 (sept, 1H), 3.21 (s, 3H), 6.10 (dd, 2H), 6.37-6.45 (m, 4H), 6.56-6.65 (m, 4H), 6.70 (dd, 1H), 6.83 (mc, 1H), 6.95 (d, 1H), 7.06 (mc, 1H), 7.19 (mc, 2H), 7.25-7.31 (m, 4H), 7.44-7.50 (m, 3H).
  • MS (Maldi):
  • m/e=979 (M+H)+
  • photoluminescence (in film, 2% in PMMA):
  • λmax=456, 487 nm, CIE: (0.20; 0.30)
    • Example 21 Complex Em9-i
  • Figure US20120205645A1-20120816-C00279
  • A solution of 0.17 g of complex Em9-s in 2000 ml acetonitril are irradiated at 15° C. for 9.5 h with a blacklight-blue-lamp (Osram, L18W/73, λmax=370-380 nm). The solvent is removed in vacuo. The residue is purified by chromatography (cyclohexane/acetic ester). 0.055 g of Em9-i (32%, contaminated with traces of a further complex) are obtained as well as 0.075 g of reisolated Em9-s (44%) are reisolated.
  • 1H-NMR [CD2Cl2, 400 MHz, sample comprises traces of a further complex observable for example at 0.77 (m), 0.83 (d), 1.04 (d), 1.21 (m), 1.92 (sept), 2.34 (sept), 7.20-7.23 (m), 7.31-7.34 (m)]:
  • δ=0.65 (d, 3H), 0.77 (d, 3H), 0.85 (d, 3H), 0.97 (d, 3H), 0.98 (d, 3H), 1.02 (d, 3H), 1.13 (d, 6H), 1.82 (sept, 1H), 2.33 (sept, 1H), 2.54 (sept, 1H), 2.67 (sept, 1H), 3.04 (s, 3H), 6.09 (dd, 2H), 6.37 (td, 1H), 6.40-6.44 (m, 3H), 6.50 (m, 1H), 6.59 (d, 1H), 6.61 (td, 1H), 6.68 (d, 1H), 6.70 (d, 1H), 6.72 (d, 1H), 6.86 (d, 1H), 6.96 (br.s, 1H), 7.14 (mc, 2H), 7.20-7.23 (m, 1H), 7.23-7.31 (m, 3H), 7.44-7.50 (m, 3H).
  • MS (Maldi):
  • m/e=979 (M+H)+
  • photoluminescence (in film, 2% in PMMA):
  • λmax=457, 485 nm, CIE: (0.17; 0.26)
  • The photoluminescence quantum efficiency of the isomer Em9-i has the 1.14-fold value of the quantum efficiency of the isomer Em9-s.
    • Example 22 Complex Em10-s 1,3-Diphenyl-4,5-di-o-tolyl-imidazolium-tetrafluoroborate C7
  • Figure US20120205645A1-20120816-C00280
    • Step 1: Preparation of 2-anilino-1,2-di-o-toluene-ethanone
  • A solution of 18.00 g (74.91 mmol) o-toluoine are dissolved in 100 ml anhydrous toluene and 21.00 g (224.9 mmol) of anilin and 0.2 g conc. HCl are added at room temperature. The reaction mixture is heated for 10 hours to boiling under reflux, where by the water formed is revolved out. After cooling to room temperature the reaction mixture is diluted with 100 ml acetic ester and then shaked two times with 70 ml 1 n HCl each. Subsequently the organic phase is washed with 100 ml of water and 70 ml of brine, dryed over magnesium sulfate and reduced to a yellow resin. The crude product is purified chromatographically on silica gel with methylene chloride as eluent. After removal of the solvent 19.6 g (83%) of a yellow oil are obtained.
    • Step 2: Preparation of N-(2-oxo-1,2-di-o-tolyl-ethyl)-N-phenyl-formamide
  • A solution of 19.50 g (58.7 mmol) 2-anilino-1,2-di-o-tolyl-ethanone in 80 ml of tetrahydrofuran is meaned with 7.80 g (88.1 mmol) acetformylanhydride and stirred for 17 hours at room temperature. The reaction mixture is reduced at a rotarap to a syrup and purified at silica gel with a petrol ether-acetic ester solution as eluent at first in a ratio of 10:1 then 1:1. After removal of the solvent 18.4 g (91%) of a nearly colorless syrup are obtained.
    • Step 3: Preparation of 3-phenyl-4,5-di-o-tolyl-oxazolium-tetrafluoroborate
  • To 9.80 g (55.9 mmol) of 50% tetrafluoroboric acid 63 g trifluoroacetic anhydride are added by a syringe at 5-10° C. in 15 min (exothermic!). The cooled solution is subsequently added dropwise to a suspension of 20.00 g (55.3 mmol) N-(2-oxo-1,2-di-o-tolyl-ethyl)-N-phenyl-formamide in 60 g of trifluoroacetic anhydride at room temperature in 10 min, whereby the temperature rises to 28° C. The reaction mixture is stirred for 3 hours at 20-25° C. and then reduced at a rotarap to an oil. After addition of 100 ml diethylether 9.7 g (55.3 mmol) 50% tetrafluoroboric acid are added dropwise by stirring, whereby a precipitate is formed. After stirring for one hour the precipitate is drawn off, washed three times with 10 ml diethyl ether each and dried. 22.55 g (99%) of a colorless powder are obtained.
    • Step 4: Preparation of 1,3-diphenyl-4,5-di-o-tolylimidazolium-tetrafluoroborate C7
  • To a suspension of 3.50 g (8.47 mmol) 3-phenyl-4,5-di-o-tolyl-oxazolium-tetrafluoroborate in 35 ml of ethanol 1.58 g (16.9 mmol) of aniline are added. After stirring for 45 min at room temperature, the solution is reduced to an orange colored resin and subsequently 15 mol sulfuric acid are added. The solution is stirred for 2 hours at room temperature. The reaction solution is stirred in 300 ml ice water where by a precipitate is formed. The suspension is stirred for a further hour and then filtered over a suction filter. The residue is washed with water and sucked to dryness to a large extend. The residue is stirred in an Erlenmeyer flask with 40 ml of diethyl ether, sucked and washed with 10 ml of diethyl ether. The stirring in diethyl ether with subsequent suction is repeated two times. After drying 3.10 g (71% d.th.) of a colorless powder are obtained.
    • Complex Em10-s:
  • Figure US20120205645A1-20120816-C00281
  • A suspension of 1.61 g (3.30 mmol) 1,3-diphenyl-4,5-di-o-tolyl-imidazolium-tetrafluoroborate in 25 ml of toluene are stirred for 15 min under argon at room temperature and then cooled to 0° C. 12.6 ml (6.29 mmol) 0.5 M potassium-bis(trimethylsilyl)-amide in toluene are added with 1 min. The reaction solution is then stirred for 15 min at 0-12° C., and subsequently, 2.50 g (1.50 mmol) bis(iridium-p-chloro-complex) D1 are added. It is purged with 5 ml of toluene. The orange-yellow suspension is heated under reflux to boiling. After 75 min the reaction solution is cooled to room temperature diluted with 20 ml acetic ester and then extracted two times with 20 ml of phosphate buffer solution (ph 7). The organic phase is separated, dryed over sodium sulfate and then reduced to dryness. The solid is shortly heated in 150 ml of methanol under reflux to boiling. After cooling of the suspension to 50° C. the solid is sucked, washed two times with 10 ml of methanol each and dryed. 2.52 g of a yellow solid are obtained. The filtrate is reduced to 40 ml and stirred overnight at room temperature. The precipitate is sucked, washed with a small amount of methanol and dried. 0.28 g of a yellow solid are obtained, which is combined with the residue.
  • Therefore, alltogether 2.80 g (78% of th.) of a yellow solid melting at 282-283° C. are obtained.
  • MS (Maldi):
  • m/e=1197.4 (M+H)+
  • Photoluminescence (in film, 2% in PMMA):
  • λmax=464, 493 nm, CIE: (0.19; 0.35)
    • Example 23 Complexes Em10-i and Em10-i*
  • Figure US20120205645A1-20120816-C00282
  • 0.50 g (0.42 mmol) of Em10-s are dissolved in 300 ml of acetonitril and irradiated with a mercury pressure dipping lamp TQ 150 (365 nm, 150 W) for 5.5 hours. The solution is freed from the solvent. The residue is dissolved in 30 ml of methanol by heating. After cooling the precipitate is sucked, washed with methanol and dried. The complex isomer Em10-i [0.19 g (38%)] is obtained as yellow powder melting at 316-317° C.
  • MS (Maldi):
  • m/e=1196.7 (M)+
  • Photoluminescence (in film, 2% in PMMA):
  • λmax=460, 491 nm, CIE: (0.18; 0.32)
  • The filtrate is reduced to dryness, stirred with 10 ml of n-pentane, sucked, washed with pentane and dried. The complex isomer Em10-i* [0.16 g (32%)] is obtained as ocher yellow solid melting at 207-209° C.
  • MS (Maldi):
  • m/e=1197.8 (M+H)+
  • Photoluminescence (in film, 2% in PMMA):
  • λmax=458, 490 nm, CIE: (0.19; 0.33)
    • I) Diode Examples concerning Em1-s Example 24 Influence of the Matrix Materials on Em1-s Diode Structure:
  • ITO-PEDT:PSS-35 nm Ir(DPBIC)3 mixed with 10 wt.-% MoOx-10 nm Ir(DPBIC)3-40 nm Matrix MaX mixed with 15 wt.-% Em1-s-10 nm LB1-20 nm electron conductor BCP-0.70 nm LiF-100 nm Al.
  • The preparation of the diode is carried out in analogy to Example 17.
  • Exciton and hole blocker LB1:
  • Figure US20120205645A1-20120816-C00283
  • EQE @ 300 nits and
    Matrix Voltage in Cd/A @ normalized to the value
    “MaX” CIE V@300 nits 300 nits of Ma2
    Ma21 0.20/0.36 8.8 10.1 100%
    Ma3 0.20/0.32 5.5 20.5 166%
    Ma42 0.19/0.32 6.5 16.3 134%
    Ma5 0.20/0.31 6.2 13.9 115%
    Ma63 0.19/0.30 6.2 22.8 195%
    1In this case 40 nm BCP were used as electron conductor.
    2In this case 30 nm BCP were used as electron conductor.
    3In this case AJ20 - 1000 of Plexcore instead of PEDT: PSS were used as hole injection layer.

    Structures of the Matrices “MaX” (=Ma2-Ma6) and Description of their Synthesis in WO2010/079051:
  • Synthesis of MaX
    described in
    Matrix “MaX” WO2010/079051 as Structure
    Ma2 BS 10
    Figure US20120205645A1-20120816-C00284
    Ma3 BS15
    Figure US20120205645A1-20120816-C00285
    Ma4 BS18
    Figure US20120205645A1-20120816-C00286
    Ma5 BS20
    Figure US20120205645A1-20120816-C00287
    Ma6 BS 31
    Figure US20120205645A1-20120816-C00288
    • II) Diode Examples concerning Em1-i Example 25 Influence of the Matrix Materials on Em1-i
  • Structure A: ITO-AJ20-1000-35 nm Ir(DPBIC)3 mixed with 50 wt.-% MoO3-10 nm Ir(DPBIC)3-40 nm “MaX” mixed with 20 wt.-% Em1-i-5 nm “MaX”-40 nm electron conductor BCP:Liq 50 wt.-%-1 nm Liq-100 nm Al. The preparation of the diode is carried out in analogy to Example 17.
  • Structure B: ITO-AJ20-1000-35 nm Ir(DPBIC)3 mixed with 10 wt.-% MoO3-10 nm Ir(DPBIC)3-40 nm “MaX” mixed with 15 wt.-% Em1-i-10 nm LB1-20 nm electron conductor BCP-0.70 nm LiF-100 nm Al. The preparation of the diode is carried out in analogy to Example 17.
  • Voltage EQE@300
    in nits nor-
    Matrix Diode V Cd/ malized to
    MaX structure CIE @300nits A@300nits the value of
    Ma7 Structure A 0.22/0.36 5.8 18.8 100%
    Ma8 Structure B 0.23/0.38 7.0 17.3  91%
    Ma9 Structure A1 0.23/0.38 4.3 17.9  95%
    1In this case 5 nm Ma1 are used as excition and hole blocker.

    Structures of the Matrices MaX and Description of their Synthesis in WO2010/079051:
  • Matrix Compound in
    MaX WO2010/079051 Structure
    Ma7 BS26
    Figure US20120205645A1-20120816-C00289
    Ma8 BS29
    Figure US20120205645A1-20120816-C00290
    Ma9 BS28
    Figure US20120205645A1-20120816-C00291
    • Example 26 Influence of the Matrix Materials on Em1-i
  • ITO-AJ20-1000-10 nm Ma1 mixed with 10 wt.-% MoOx-10 nm Ma10 mixed with 15 wt.-% Em1-i and 15 wt.-% Ma1-5 nm Ma1-20 nm electron conductor BCP mixed with 20 wt.-% Ma1-1 nm Cs2CO3-100 nm Al. The preparation of the diode is carried out in analogy to Example 17.
  • The synthesis of matrix material Ma10 is described in JP2009046408, compound B, [0039], p. 13.
    • Ma10
  • Figure US20120205645A1-20120816-C00292
  • Matrix Voltage
    MaX CIE in V @ 300 units
    Ma10 0.19/0.35 3.8

Claims (21)

1. A heteroleptic complex of the general formula (I)
Figure US20120205645A1-20120816-C00293
in which M, A1, A2, n, m, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are each defined as follows:
M is a metal atom selected from the group consisting of Ir and Pt,
A1, A2 are each independently N or C,
n, m are each independently 1 or 2, where, if M is Pt, the sum of n and m is 2, or, if M is Ir, the sum of n and m is 3,
R1 is a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 5 to 18 carbon atoms and/or heteroatoms,
R2, R3 are each independently hydrogen, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 5 to 18 carbon atoms and/or heteroatoms,
R4, R5,
R6, R7 are each independently hydrogen, substituent with donor or acceptor action, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 5 to 18 carbon atoms and/or heteroatoms,
or
R4 and R5 or R5 and R6 and/or R6 and R7 together form a saturated, unsaturated or aromatic carbon ring optionally interrupted by at least one heteroatom and having a total of 5 to 30 carbon atoms or heteroatoms,
R8, R9 are each independently a free electron pair if A1 or A2 is N, or, if A1 or A2 is C, hydrogen, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 5 to 18 carbon atoms and/or heteroatoms,
R10 linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 5 to 18 carbon atoms and/or heteroatoms
R11, R12,
R13, R14 are each independently hydrogen, substituent with donor or acceptor action, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 5 to 18 carbon atoms and/or heteroatoms,
or
R11 and R12 or R12 and R13 and/or R13 and R14 together form a saturated, unsaturated or aromatic carbon ring optionally interrupted by at least one heteroatom and having a total of 5 to 30 carbon atoms and/or heteroatoms
and/or
R1 and R14 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused,
and/or
if A1 is C, R7 and R8 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused.
2. A heteroleptic complex according to claim 1, wherein M, A1, A2, n, m, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are each defined as follows:
M is Ir,
A1, A2 is C,
n, m are each independently 1 or 2, where the sum of n and m is 3,
R1 is a linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms,
R2, R3 are each independently hydrogen, linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms,
R4, R5,
R6, R7 are each hydrogen
or
R4 and R5 or R5 and R6 or R6 and R7 together form a saturated, unsaturated or aromatic ring optionally interrupted by at least one heteroatom and having a total of 5 to 30 carbon atoms and/or heteroatoms,
R8, R9 are each hydrogen,
R10 is a linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, and
R11, R12,
R13, R14 are each independently hydrogen or linear or branched alkyl radical having 1 to 20 carbon atoms,
and/or
R1 and R14 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused,
and/or
R7 and R8 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused.
3. A heteroleptic complex according to claim 1, wherein M, A1, A2, n, m, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are each defined as follows:
M is Ir,
A1, A2 are each N or C, where A1=N when A2=C and A1=C when A2=N
n, m are each independently 1 or 2, where the sum of n and m is 3,
R1 is a linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms,
R2, R3 are each independently hydrogen, linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms,
R4, R5,
R6, R7 are each hydrogen
or
R4 and R5 or R5 and R6 or R6 and R7 together form a saturated, unsaturated or aromatic ring optionally interrupted by at least one heteroatom and having a total of 5 to 30 carbon atoms and/or heteroatoms,
R8, R9 are each independently a free electron pair if A1 or A2 is N, or, if A1 or A2 is C, hydrogen, linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms,
R10 linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, and
R11, R12,
R13, R14 hydrogen or linear or branched alkyl radical having 1-20 carbon atoms
and/or
R1 and R14 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused,
and/or
if A1 is C, R7 and R8 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused.
4. A heteroleptic complex according to claim 1, wherein M, A1, A2, n, m, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are each defined as follows:
M is Ir,
A1 is C,
A2 is N or C,
n, m are each independently 1 or 2, where the sum of n and m is 3,
R1 is a linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms,
R2, R3 are each independently hydrogen, linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms,
R4, R5,
R6 are each independently hydrogen, linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms,
R7, R8 together form an unsaturated C2 bridge, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, may be fused,
R9 is a free electron pair if A2 is N or, if A2 is C, hydrogen, linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms,
R10 is a linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, and
R11, R12,
R13, R14 are each independently hydrogen or linear or branched alkyl radical having 1 to 20 carbon atoms,
and/or
R1 and R14 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused.
5. A heteroleptic complex according to any of claims 1 to 4, wherein R1 is an aryl radical which has 6 to 30 carbon atoms and is substituted in the ortho,ortho′ positions in each case by a linear or branched alkyl radical having 1 to 10 carbon atoms.
6. A heteroleptic complex according to any of claims 1 to 5, wherein R1 and R14 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, preferably a six-membered aromatic ring, is optionally fused.
7. A heteroleptic complex according to any of claims 1 to 5, wherein R4 and R5, R5 and R6 or R6 and R7 together form a cycle of the general formula (IIa) or (IIb)
Figure US20120205645A1-20120816-C00294
8. A heteroleptic complex according to any of claims 1 to 7 with the specified definitions of M, A1, A2, n, m, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14, which has one of the following configurations IIIa, IIIb, IVa or IVb:
Figure US20120205645A1-20120816-C00295
9. A process for preparing a heteroleptic complex according to any of claims 1 to 8 by
contacting at least one precursor compound comprising the metal M and the at least one ligand which, in the complexes of the general formula (I), is attached to M via noncarbene bonds with at least one ligand which, in the complexes of the general formula (I), is attached to M via at least one carbene bond, or the ligand precursor thereof, for example a corresponding imidazolium salt,
or
by contacting at least one precursor compound comprising the metal M and a ligand which, in the complexes of the general formula (I), is bonded to M via at least one carbene bond with at least one ligand which, in the complexes of the general formula (I), is attached to M via noncarbene bonds.
10. An OLED comprising at least one heteroleptic complex according to any of claims 1 to 8.
11. An OLED comprising a heteroleptic complex according to any of claims 1 to 8, and at least one compound of the formula (X)
Figure US20120205645A1-20120816-C00296
In which
T is NR57, S, O or PR57, preferably S or O, more preferably O;
R57 is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl;
Q′ is —NR58R59, —P(O)R60R61, —PR62R63, —S(O)2R64, —S(O)R65, —SR66 or —OR67, preferably —NR58R59; more preferably
Figure US20120205645A1-20120816-C00297
wherein
R68, R69 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl; preferably methyl, carbazolyl, dibenzofuryl or dibenzothienyl;
y, z are each independently 0, 1, 2, 3 or 4, preferably 0 or 1;
R55, R56 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, SiR70R71R72, a group Q′ or a group with donor or acceptor action;
a″ 0, 1, 2, 3 or 4;
b′ 0, 1, 2 or 3;
R58, R59 together with the nitrogen atom form a cyclic radical which has 3 to 10 ring atoms and may be unsubstituted or substituted by one or more substitutents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action and/or may be fused to one or more further cyclic radicals having 3 to 10 ring atoms, where the fused radicals may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action;
R70, R71, R72, R60, R61, R62, R63, R64, R65, R66, R67 are each independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl,
or
two units of the general formula (X) are bridged by a linear or branched, saturated or unsaturated bridge, optionally interrupted by at least one heteroatom, by a bonding or by O.
12. OLED according to claim 11 comprising at least one compound of formula (XI) or (XI*)
Figure US20120205645A1-20120816-C00298
wherein
T is NR57, S, O or PR57;
R57 is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl;
Q′ is —NR58R59, —P(O)R60R61, —PR62R63, —S(O)2R64, —S(O)R65, —SR66 or —OR67;
R70, R71, R72 are each independently aryl, heteroaryl, alkyl, cycloalkyl, heterocycloalkyl, wherein of at least one of the radicals R70, R71, R72 comprises at least two carbon atoms or OR73,
R55, R56 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, a group Q or a group with donor or acceptor action;
a′, b′ are for the compound of formula (XI): each independently 0, 1, 2, 3; for the compound of formula (XI*) a′ is 0, 1, 2 and bis′ 0, 1, 2, 3, 4;
R58, R59 together with the nitrogen atom form a cyclic radical which has 2 to 10 ring atoms and may be unsubstituted or substituted by one or more substitutents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action and/or may be fused to one or more further cyclic radicals having 3 to 10 ring atoms, where the fused radicals may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action;
R73 is independently SiR74R75R76, aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, optionally substituted with a group OR77
R77 is independently SiR74R75R76, aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl,
R60, R61, R62, R63, R64, R65, R66, R67, R74, R75, R76
are each independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl,
or
two units of the general formulae (XI) and/or (XI*) are bridged by a linear or branched, saturated or unsaturated bridge, optionally interrupted by at least one heteroatom or by O, wherein said bridge is bonded in the general formulae (XI) and/or (XI*) each time instead of R71 to the Si-atoms.
13. OLED according to claim 12, wherein in the compounds of the general formulae (XI) or (XI*) R70 and/or R71 and/or R72 are aromatic units of the general formulae (XIi) and/or (XIi*)
Figure US20120205645A1-20120816-C00299
wherein R55, R56, Q′, T, a′ and b′ have the same meanings as in claim 12.
14. A light-emitting layer comprising at least one heteroleptic complex according to any of claims 1 to 8.
15. An OLED comprising a light-emitting layer according to claim 14.
16. The OLED according to any of claim 10 to 13 or 15, which comprises an electron-transporting layer comprising at least two different materials, of which at least one material should be electron-conductive.
17. The OLED according to claim 16, wherein the electron-transporting layer comprises at least one phenanthroline derivative.
18. The OLED according to claim 16, wherein the electron-transporting layer comprises at least one phenanthroline derivative and at least one alkali metal hydroxyquinolate complex.
19. A device selected from the group consisting of illuminating elements, stationary visual display units and mobile visual display units, comprising at least one OLED according to any of claims 10 to 13 or 15 to 18.
20. The use of a heteroleptic complex according to any of claims 1 to 8 in OLEDs.
21. The use according to claim 20, wherein the heteroleptic complexes are used as emitter, matrix material, charge transport material and/or charge blocker.
US13/504,725 2009-10-28 2010-10-28 Heteroleptic carbene complexes and the use thereof in organic electronics Abandoned US20120205645A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/504,725 US20120205645A1 (en) 2009-10-28 2010-10-28 Heteroleptic carbene complexes and the use thereof in organic electronics

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US25549909P 2009-10-28 2009-10-28
US13/504,725 US20120205645A1 (en) 2009-10-28 2010-10-28 Heteroleptic carbene complexes and the use thereof in organic electronics
PCT/EP2010/066400 WO2011051404A1 (en) 2009-10-28 2010-10-28 Heteroleptic carbene complexes and use thereof in organic electronics

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/066400 A-371-Of-International WO2011051404A1 (en) 2009-10-28 2010-10-28 Heteroleptic carbene complexes and use thereof in organic electronics

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US16/294,403 Continuation US11189806B2 (en) 2009-10-28 2019-03-06 Heteroleptic carbene complexes and the use thereof in organic electronics

Publications (1)

Publication Number Publication Date
US20120205645A1 true US20120205645A1 (en) 2012-08-16

Family

ID=43478148

Family Applications (4)

Application Number Title Priority Date Filing Date
US13/504,725 Abandoned US20120205645A1 (en) 2009-10-28 2010-10-28 Heteroleptic carbene complexes and the use thereof in organic electronics
US16/294,403 Active US11189806B2 (en) 2009-10-28 2019-03-06 Heteroleptic carbene complexes and the use thereof in organic electronics
US17/526,503 Active 2031-02-20 US11871654B2 (en) 2009-10-28 2021-11-15 Heteroleptic carbene complexes and the use thereof in organic electronics
US18/517,812 Pending US20240130221A1 (en) 2009-10-28 2023-11-22 Heteroleptic carbene complexes and the use thereof in organic electronics

Family Applications After (3)

Application Number Title Priority Date Filing Date
US16/294,403 Active US11189806B2 (en) 2009-10-28 2019-03-06 Heteroleptic carbene complexes and the use thereof in organic electronics
US17/526,503 Active 2031-02-20 US11871654B2 (en) 2009-10-28 2021-11-15 Heteroleptic carbene complexes and the use thereof in organic electronics
US18/517,812 Pending US20240130221A1 (en) 2009-10-28 2023-11-22 Heteroleptic carbene complexes and the use thereof in organic electronics

Country Status (6)

Country Link
US (4) US20120205645A1 (en)
EP (1) EP2493906B1 (en)
JP (1) JP5939984B2 (en)
KR (2) KR101986469B1 (en)
CN (1) CN102741265B (en)
WO (1) WO2011051404A1 (en)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140131687A1 (en) * 2011-06-08 2014-05-15 Universal Display Corporation Heteroleptic iridium carbene complexes and light emitting device using them
JP2014101307A (en) * 2012-11-20 2014-06-05 Konica Minolta Inc Method of manufacturing facial body of iridium complex
US9236535B2 (en) 2011-02-24 2016-01-12 Basf Se Illumination devices
US9406894B2 (en) 2011-06-03 2016-08-02 Semiconductor Energy Laboratory Co., Ltd. Organometallic complex, organic light-emitting element, light-emitting device, electronic device, and lighting device
US9406848B2 (en) 2011-06-10 2016-08-02 Basf Se Color converter
US9487548B2 (en) 2009-12-14 2016-11-08 Udc Ireland Limited Metal complexes comprising diazabenzimidazolocarbene ligands and the use thereof in OLEDs
US9583719B2 (en) 2011-08-12 2017-02-28 Basf Se Carbazolocarbazol-bis(dicarboximides) and their use as semiconductors
US9701773B2 (en) 2013-08-12 2017-07-11 Sabic Global Technologies, B.V. Catalyst system for polymerisation of an OLEFIN
US9711665B2 (en) 2011-05-10 2017-07-18 Basf Se Color converters
JP2017200929A (en) * 2017-06-05 2017-11-09 コニカミノルタ株式会社 Method of manufacturing facial body of iridium complex
US20170373259A1 (en) * 2016-06-20 2017-12-28 Universal Display Corporation Organic Electroluminescent Materials and Devices
US9873753B2 (en) 2013-12-20 2018-01-23 Saudi Basic Industries Corporation Catalyst system for polymerization of an olefin
US9905784B2 (en) 2013-11-15 2018-02-27 Universal Display Corporation Organic electroluminescent materials and devices
US20180097185A1 (en) * 2016-06-20 2018-04-05 Universal Display Corporation Organic electroluminescent materials and devices
US20190140191A1 (en) * 2016-06-20 2019-05-09 Universal Display Corporation Organic electroluminescent materials and devices
US10290817B2 (en) 2013-07-31 2019-05-14 Udc Ireland Limited Luminescent diaza-monoaza-and benzimidazole metal carbene complexes for use in electronic devices such as OLEDs
GB2569635A (en) * 2017-12-21 2019-06-26 Sumitomo Chemical Co Compound
US20190334100A1 (en) * 2018-04-27 2019-10-31 Samsung Display Co., Ltd. Organometallic compound and organic light-emitting device including the same
CN111587494A (en) * 2017-12-20 2020-08-25 诺瓦尔德股份有限公司 Organic electronic devices comprising inverse coordination complexes and methods of making the same
US11038138B2 (en) 2017-08-11 2021-06-15 Lg Chem, Ltd. Organic electroluminescent device and method for manufacturing the same
US11165028B2 (en) * 2018-03-12 2021-11-02 Universal Display Corporation Organic electroluminescent materials and devices

Families Citing this family (146)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102103062B1 (en) 2006-02-10 2020-04-22 유니버셜 디스플레이 코포레이션 METAL COMPLEXES OF CYCLOMETALLATED IMIDAZO[1,2-f]PHENANTHRIDINE AND DIIMIDAZO[1,2-A:1',2'-C]QUINAZOLINE LIGANDS AND ISOELECTRONIC AND BENZANNULATED ANALOGS THEREOF
EP2493906B1 (en) * 2009-10-28 2015-10-21 Basf Se Heteroleptic carben complexes and their use in organig electronics
US8288187B2 (en) 2010-01-20 2012-10-16 Universal Display Corporation Electroluminescent devices for lighting applications
US8691401B2 (en) 2010-04-16 2014-04-08 Basf Se Bridged benzimidazole-carbene complexes and use thereof in OLEDS
US9806270B2 (en) 2011-03-25 2017-10-31 Udc Ireland Limited 4H-imidazo[1,2-a]imidazoles for electronic applications
KR101951852B1 (en) 2011-03-25 2019-02-26 유디씨 아일랜드 리미티드 4h-imidazo[1,2-a]imidazoles for electronic applications
JP6015124B2 (en) * 2011-05-18 2016-10-26 東ソー株式会社 Organic thin-film electronic devices containing carbene compound derivatives
US8748012B2 (en) 2011-05-25 2014-06-10 Universal Display Corporation Host materials for OLED
US9315724B2 (en) 2011-06-14 2016-04-19 Basf Se Metal complexes comprising azabenzimidazole carbene ligands and the use thereof in OLEDs
JP6300722B2 (en) 2011-06-14 2018-03-28 ユー・ディー・シー アイルランド リミテッド Metal complexes with azabenzimidazole carbene ligands and their use in organic light-emitting diodes
US8409729B2 (en) * 2011-07-28 2013-04-02 Universal Display Corporation Host materials for phosphorescent OLEDs
JP5742586B2 (en) * 2011-08-25 2015-07-01 コニカミノルタ株式会社 Organic electroluminescence element, lighting device and display device
CN108440531B (en) 2011-11-10 2021-11-02 Udc 爱尔兰有限责任公司 4H-imidazo [1,2-a ] imidazoles for electronic applications
CN104136449A (en) * 2011-12-28 2014-11-05 索尔维公司 Preparation of heteroleptic metal complexes
KR102012047B1 (en) 2012-01-06 2019-08-19 유니버셜 디스플레이 코포레이션 Highly efficient phosphorescent materials
JP5978843B2 (en) 2012-02-02 2016-08-24 コニカミノルタ株式会社 Iridium complex compound, organic electroluminescence device material, organic electroluminescence device, lighting device and display device
US9386657B2 (en) 2012-03-15 2016-07-05 Universal Display Corporation Organic Electroluminescent materials and devices
WO2013150909A1 (en) * 2012-04-03 2013-10-10 コニカミノルタ株式会社 Organic electroluminescent element
CN108191870A (en) 2012-07-10 2018-06-22 Udc 爱尔兰有限责任公司 For benzimidazole simultaneously [1,2-A] benzimidizole derivatives of electronic application
US9540329B2 (en) 2012-07-19 2017-01-10 Universal Display Corporation Organic electroluminescent materials and devices
US20150207080A1 (en) 2012-08-24 2015-07-23 Konica Minolta Inc. Transparent electrode, electronic device, and method for manufacturing transparent electrode
TWI623539B (en) 2012-09-20 2018-05-11 Ｕｄｃ愛爾蘭責任有限公司 Azadibenzofurans for electronic applications
US9252363B2 (en) 2012-10-04 2016-02-02 Universal Display Corporation Aryloxyalkylcarboxylate solvent compositions for inkjet printing of organic layers
US9196860B2 (en) 2012-12-04 2015-11-24 Universal Display Corporation Compounds for triplet-triplet annihilation upconversion
US8716484B1 (en) 2012-12-05 2014-05-06 Universal Display Corporation Hole transporting materials with twisted aryl groups
US9653691B2 (en) 2012-12-12 2017-05-16 Universal Display Corporation Phosphorescence-sensitizing fluorescence material system
KR102046153B1 (en) * 2013-03-12 2019-12-02 삼성전자주식회사 Organometallic complexes, organic electroluminescence device using the same and display
US10374172B2 (en) 2013-03-20 2019-08-06 Udc Ireland Limited Azabenzimidazole carbene complexes as efficiency booster in OLEDs
JP6048281B2 (en) * 2013-03-29 2016-12-21 コニカミノルタ株式会社 Organic electroluminescence element, lighting device and display device
JP6350518B2 (en) 2013-03-29 2018-07-04 コニカミノルタ株式会社 ORGANIC ELECTROLUMINESCENCE ELEMENT, LIGHTING DEVICE AND DISPLAY DEVICE HAVING THE SAME
US20160043334A1 (en) 2013-03-29 2016-02-11 Konica Minolta, Inc. Material for organic electroluminescent elements, organic electroluminescent element, display device and lighting device
EP2991997B1 (en) 2013-04-29 2018-02-21 UDC Ireland Limited Transition metal complexes with carbene ligands and the use thereof in oleds
CN104183754A (en) * 2013-05-22 2014-12-03 海洋王照明科技股份有限公司 Organic light-emitting device and preparation method thereof
CN104183723A (en) * 2013-05-22 2014-12-03 海洋王照明科技股份有限公司 Organic light emitting diode and preparation method thereof
CN109438518B (en) 2013-07-02 2021-06-15 Udc 爱尔兰有限责任公司 Monosubstituted diazabenzimidazole carbene metal complexes for use in organic light emitting diodes
EP2837634A1 (en) 2013-08-12 2015-02-18 Saudi Basic Industries Corporation Catalyst system for polymerisation of an olefin
EP3063153B1 (en) 2013-10-31 2018-03-07 Idemitsu Kosan Co., Ltd. Azadibenzothiophenes for electronic applications
US9876173B2 (en) 2013-12-09 2018-01-23 Universal Display Corporation Organic electroluminescent materials and devices
DE102013225682A1 (en) 2013-12-12 2015-06-18 Friedrich-Alexander-Universität Erlangen-Nürnberg Metal ion adducts of neutral phosphorescent emitters for use in light emitting organic optoelectronic devices
EP3916822A1 (en) 2013-12-20 2021-12-01 UDC Ireland Limited Highly efficient oled devices with very short decay times
WO2015150203A1 (en) 2014-03-31 2015-10-08 Basf Se Metal complexes, comprising carbene ligands having an o-substituted non-cyclometalated aryl group and their use in organic light emitting diodes
US9450198B2 (en) 2014-04-15 2016-09-20 Universal Display Corporation Organic electroluminescent materials and devices
WO2016016791A1 (en) 2014-07-28 2016-02-04 Idemitsu Kosan Co., Ltd (Ikc) 2,9-functionalized benzimidazolo[1,2-a]benzimidazoles as hosts for organic light emitting diodes (oleds)
EP2982676B1 (en) 2014-08-07 2018-04-11 Idemitsu Kosan Co., Ltd. Benzimidazo[2,1-B]benzoxazoles for electronic applications
DE102014112618B4 (en) * 2014-09-02 2023-09-07 Pictiva Displays International Limited Organic light emitting device
EP2993215B1 (en) 2014-09-04 2019-06-19 Idemitsu Kosan Co., Ltd. Azabenzimidazo[2,1-a]benzimidazoles for electronic applications
KR102308117B1 (en) 2014-10-17 2021-10-01 삼성전자주식회사 Carbazole-based compound and organic light emitting device including the same
EP3015469B1 (en) 2014-10-30 2018-12-19 Idemitsu Kosan Co., Ltd. 5-(benzimidazol-2-yl)benzimidazo[1,2-a]benzimidazoles for electronic applications
WO2016079667A1 (en) 2014-11-17 2016-05-26 Idemitsu Kosan Co., Ltd. Indole derivatives for electronic applications
EP3034506A1 (en) 2014-12-15 2016-06-22 Idemitsu Kosan Co., Ltd 4-functionalized carbazole derivatives for electronic applications
EP3034507A1 (en) 2014-12-15 2016-06-22 Idemitsu Kosan Co., Ltd 1-functionalized dibenzofurans and dibenzothiophenes for organic light emitting diodes (OLEDs)
EP3053918B1 (en) 2015-02-06 2018-04-11 Idemitsu Kosan Co., Ltd. 2-carbazole substituted benzimidazoles for electronic applications
EP3054498B1 (en) 2015-02-06 2017-09-20 Idemitsu Kosan Co., Ltd. Bisimidazodiazocines
JP5831654B1 (en) 2015-02-13 2015-12-09 コニカミノルタ株式会社 Aromatic heterocycle derivative, organic electroluminescence device using the same, illumination device and display device
US9929361B2 (en) 2015-02-16 2018-03-27 Universal Display Corporation Organic electroluminescent materials and devices
GB2535476A (en) * 2015-02-16 2016-08-24 Cambridge Display Tech Ltd Compound, composition and organic light-emitting device
EP3061759B1 (en) 2015-02-24 2019-12-25 Idemitsu Kosan Co., Ltd Nitrile substituted dibenzofurans
US11056657B2 (en) 2015-02-27 2021-07-06 University Display Corporation Organic electroluminescent materials and devices
EP3070144B1 (en) 2015-03-17 2018-02-28 Idemitsu Kosan Co., Ltd. Seven-membered ring compounds
EP3072943B1 (en) 2015-03-26 2018-05-02 Idemitsu Kosan Co., Ltd. Dibenzofuran/carbazole-substituted benzonitriles
EP3075737B1 (en) 2015-03-31 2019-12-04 Idemitsu Kosan Co., Ltd Benzimidazolo[1,2-a]benzimidazole carrying aryl- or heteroarylnitril groups for organic light emitting diodes
US9859510B2 (en) 2015-05-15 2018-01-02 Universal Display Corporation Organic electroluminescent materials and devices
US10418568B2 (en) 2015-06-01 2019-09-17 Universal Display Corporation Organic electroluminescent materials and devices
JP6662913B2 (en) 2015-06-03 2020-03-11 ユー・ディー・シー アイルランド リミテッド Highly efficient OLED device with extremely short decay time
US11127905B2 (en) 2015-07-29 2021-09-21 Universal Display Corporation Organic electroluminescent materials and devices
US10361381B2 (en) 2015-09-03 2019-07-23 Universal Display Corporation Organic electroluminescent materials and devices
EP3356369B1 (en) 2015-10-01 2022-05-04 Idemitsu Kosan Co., Ltd Benzimidazolo[1,2-a]benzimidazole carrying triazine groups for organic light emitting diodes
EP3150606B1 (en) 2015-10-01 2019-08-14 Idemitsu Kosan Co., Ltd. Benzimidazolo[1,2-a]benzimidazoles carrying benzofurane or benzothiophene groups for organic light emitting diodes
US20180291028A1 (en) 2015-10-01 2018-10-11 Idemitsu Kosan Co., Ltd. Benzimidazolo[1,2-a]benzimidazole carrying benzimidazolo[1,2-a]benzimidazolyl groups, carbazolyl groups, benzofurane groups or benzothiophene groups for organic light emitting diodes
EP3150604B1 (en) 2015-10-01 2021-07-14 Idemitsu Kosan Co., Ltd. Benzimidazolo[1,2-a]benzimidazole carrying benzimidazolo[1,2-a]benzimidazolylyl groups, carbazolyl groups, benzofurane groups or benzothiophene groups for organic light emitting diodes
US20180319813A1 (en) 2015-11-04 2018-11-08 Idemitsu Kosan Co., Ltd Benzimidazole fused heteroaryls
WO2017093958A1 (en) 2015-12-04 2017-06-08 Idemitsu Kosan Co., Ltd. Benzimidazolo[1,2-a]benzimidazole derivatives for organic light emitting diodes
JP6160685B2 (en) * 2015-12-24 2017-07-12 コニカミノルタ株式会社 Organic electroluminescence element, lighting device and display device
JP6788314B2 (en) 2016-01-06 2020-11-25 コニカミノルタ株式会社 Organic electroluminescence element, manufacturing method of organic electroluminescence element, display device and lighting device
US20170229663A1 (en) 2016-02-09 2017-08-10 Universal Display Corporation Organic electroluminescent materials and devices
US10236456B2 (en) 2016-04-11 2019-03-19 Universal Display Corporation Organic electroluminescent materials and devices
US10968229B2 (en) 2016-04-12 2021-04-06 Idemitsu Kosan Co., Ltd. Seven-membered ring compounds
US11482683B2 (en) 2016-06-20 2022-10-25 Universal Display Corporation Organic electroluminescent materials and devices
US10862054B2 (en) 2016-06-20 2020-12-08 Universal Display Corporation Organic electroluminescent materials and devices
US10672997B2 (en) 2016-06-20 2020-06-02 Universal Display Corporation Organic electroluminescent materials and devices
US10608186B2 (en) 2016-09-14 2020-03-31 Universal Display Corporation Organic electroluminescent materials and devices
US10680187B2 (en) 2016-09-23 2020-06-09 Universal Display Corporation Organic electroluminescent materials and devices
US11196010B2 (en) 2016-10-03 2021-12-07 Universal Display Corporation Organic electroluminescent materials and devices
US11011709B2 (en) 2016-10-07 2021-05-18 Universal Display Corporation Organic electroluminescent materials and devices
US20180130956A1 (en) 2016-11-09 2018-05-10 Universal Display Corporation Organic electroluminescent materials and devices
US10680188B2 (en) 2016-11-11 2020-06-09 Universal Display Corporation Organic electroluminescent materials and devices
US11780865B2 (en) 2017-01-09 2023-10-10 Universal Display Corporation Organic electroluminescent materials and devices
US10844085B2 (en) 2017-03-29 2020-11-24 Universal Display Corporation Organic electroluminescent materials and devices
US10944060B2 (en) 2017-05-11 2021-03-09 Universal Display Corporation Organic electroluminescent materials and devices
US20180370999A1 (en) 2017-06-23 2018-12-27 Universal Display Corporation Organic electroluminescent materials and devices
US11228010B2 (en) 2017-07-26 2022-01-18 Universal Display Corporation Organic electroluminescent materials and devices
US11744142B2 (en) 2017-08-10 2023-08-29 Universal Display Corporation Organic electroluminescent materials and devices
US20190161504A1 (en) 2017-11-28 2019-05-30 University Of Southern California Carbene compounds and organic electroluminescent devices
EP3492480B1 (en) 2017-11-29 2021-10-20 Universal Display Corporation Organic electroluminescent materials and devices
US11937503B2 (en) 2017-11-30 2024-03-19 Universal Display Corporation Organic electroluminescent materials and devices
US11542289B2 (en) 2018-01-26 2023-01-03 Universal Display Corporation Organic electroluminescent materials and devices
CN108191827A (en) * 2018-02-09 2018-06-22 广东省石油与精细化工研究院 A kind of quinoline triazole type rare earth compounding and its preparation method and application
CN108586539B (en) * 2018-04-13 2020-06-05 苏州科技大学 Dibenzothiophene ring-containing metal iridium complex and application thereof as luminescent layer doping material of organic electroluminescent device
US20200075870A1 (en) 2018-08-22 2020-03-05 Universal Display Corporation Organic electroluminescent materials and devices
TWI826522B (en) 2018-09-12 2023-12-21 德商麥克專利有限公司 Electroluminescent devices
TW202030902A (en) 2018-09-12 2020-08-16 德商麥克專利有限公司 Electroluminescent devices
CN112639052A (en) 2018-09-12 2021-04-09 默克专利有限公司 Material for organic electroluminescent device
US11737349B2 (en) 2018-12-12 2023-08-22 Universal Display Corporation Organic electroluminescent materials and devices
US11780829B2 (en) 2019-01-30 2023-10-10 The University Of Southern California Organic electroluminescent materials and devices
US20200251664A1 (en) 2019-02-01 2020-08-06 Universal Display Corporation Organic electroluminescent materials and devices
US20220127286A1 (en) 2019-03-04 2022-04-28 Merck Patent Gmbh Ligands for nano-sized materials
JP2020158491A (en) 2019-03-26 2020-10-01 ユニバーサル ディスプレイ コーポレイション Organic electroluminescent materials and devices
US20220181552A1 (en) 2019-04-11 2022-06-09 Merck Patent Gmbh Materials for organic electroluminescent devices
US20210032278A1 (en) 2019-07-30 2021-02-04 Universal Display Corporation Organic electroluminescent materials and devices
US20210047354A1 (en) 2019-08-16 2021-02-18 Universal Display Corporation Organic electroluminescent materials and devices
EP4055642A1 (en) 2019-11-04 2022-09-14 Merck Patent GmbH Materials for organic electroluminescent devices
US20210135130A1 (en) 2019-11-04 2021-05-06 Universal Display Corporation Organic electroluminescent materials and devices
TW202134252A (en) 2019-11-12 2021-09-16 德商麥克專利有限公司 Materials for organic electroluminescent devices
TW202136181A (en) 2019-12-04 2021-10-01 德商麥克專利有限公司 Materials for organic electroluminescent devices
US20210217969A1 (en) 2020-01-06 2021-07-15 Universal Display Corporation Organic electroluminescent materials and devices
US20220336759A1 (en) 2020-01-28 2022-10-20 Universal Display Corporation Organic electroluminescent materials and devices
CN115052865A (en) 2020-01-29 2022-09-13 默克专利有限公司 Benzimidazole derivatives
KR20220157456A (en) 2020-03-23 2022-11-29 메르크 파텐트 게엠베하 Materials for organic electroluminescent devices
EP3937268A1 (en) 2020-07-10 2022-01-12 Universal Display Corporation Plasmonic oleds and vertical dipole emitters
US20220158096A1 (en) 2020-11-16 2022-05-19 Universal Display Corporation Organic electroluminescent materials and devices
US20220165967A1 (en) 2020-11-24 2022-05-26 Universal Display Corporation Organic electroluminescent materials and devices
US20220162243A1 (en) 2020-11-24 2022-05-26 Universal Display Corporation Organic electroluminescent materials and devices
US20220271241A1 (en) 2021-02-03 2022-08-25 Universal Display Corporation Organic electroluminescent materials and devices
EP4059915A3 (en) 2021-02-26 2022-12-28 Universal Display Corporation Organic electroluminescent materials and devices
EP4060758A3 (en) 2021-02-26 2023-03-29 Universal Display Corporation Organic electroluminescent materials and devices
US20220298192A1 (en) 2021-03-05 2022-09-22 Universal Display Corporation Organic electroluminescent materials and devices
US20220298190A1 (en) 2021-03-12 2022-09-22 Universal Display Corporation Organic electroluminescent materials and devices
US20220298193A1 (en) 2021-03-15 2022-09-22 Universal Display Corporation Organic electroluminescent materials and devices
US20220340607A1 (en) 2021-04-05 2022-10-27 Universal Display Corporation Organic electroluminescent materials and devices
US20220352478A1 (en) 2021-04-14 2022-11-03 Universal Display Corporation Organic eletroluminescent materials and devices
US20230006149A1 (en) 2021-04-23 2023-01-05 Universal Display Corporation Organic electroluminescent materials and devices
US20220407020A1 (en) 2021-04-23 2022-12-22 Universal Display Corporation Organic electroluminescent materials and devices
US20230133787A1 (en) 2021-06-08 2023-05-04 University Of Southern California Molecular Alignment of Homoleptic Iridium Phosphors
EP4151699A1 (en) 2021-09-17 2023-03-22 Universal Display Corporation Organic electroluminescent materials and devices
EP4212539A1 (en) 2021-12-16 2023-07-19 Universal Display Corporation Organic electroluminescent materials and devices
EP4231804A3 (en) 2022-02-16 2023-09-20 Universal Display Corporation Organic electroluminescent materials and devices
US20230292592A1 (en) 2022-03-09 2023-09-14 Universal Display Corporation Organic electroluminescent materials and devices
JP2023148087A (en) 2022-03-30 2023-10-13 学校法人関西学院 metal complex
US20230337516A1 (en) 2022-04-18 2023-10-19 Universal Display Corporation Organic electroluminescent materials and devices
US20230389421A1 (en) 2022-05-24 2023-11-30 Universal Display Corporation Organic electroluminescent materials and devices
EP4293001A1 (en) 2022-06-08 2023-12-20 Universal Display Corporation Organic electroluminescent materials and devices
US20240016051A1 (en) 2022-06-28 2024-01-11 Universal Display Corporation Organic electroluminescent materials and devices
US20240107880A1 (en) 2022-08-17 2024-03-28 Universal Display Corporation Organic electroluminescent materials and devices
EP4362631A3 (en) 2022-10-27 2024-05-08 Universal Display Corporation Organic electroluminescent materials and devices
EP4362630A2 (en) 2022-10-27 2024-05-01 Universal Display Corporation Organic electroluminescent materials and devices
EP4362645A3 (en) 2022-10-27 2024-05-15 Universal Display Corporation Organic electroluminescent materials and devices

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020086180A1 (en) * 2000-12-28 2002-07-04 Satoshi Seo Luminescent device
US20050260448A1 (en) * 2004-05-18 2005-11-24 Chun Lin Novel organometallic compounds for use in electroluminescent devices
US20050258433A1 (en) * 2004-05-18 2005-11-24 Entire Interest Carbene metal complexes as OLED materials
US20060246315A1 (en) * 2005-04-27 2006-11-02 Begley William J Phosphorescent oled with mixed electron transport materials
US20070190359A1 (en) * 2006-02-10 2007-08-16 Knowles David B Metal complexes of cyclometallated imidazo[1,2-ƒ]phenanthridine and diimidazo[1,2-a:1',2'-c]quinazoline ligands and isoelectronic and benzannulated analogs thereof
US20080106188A1 (en) * 2006-11-08 2008-05-08 Seok-Hwan Hwang Silanylamine-based compound, method of preparing the same and organic light emitting device including organic layer comprising the silanylamine-based compound
US20090017330A1 (en) * 2007-07-10 2009-01-15 Idemitsu Kosan Co., Ltd. Material for organic electroluminescence device and organic electroluminescence device utilizing the same
US20120012821A1 (en) * 2009-01-07 2012-01-19 Basf Se Silyl- and heteroatom-substituted compounds selected from carbazoles, dibenzofurans, dibenzothiophenes and dibenzophospholes, and use thereof in organic electronics
US8383828B2 (en) * 2006-04-04 2013-02-26 Basf Aktiengesellschaft Transition metal complexes comprising one noncarbene ligand and one or two carbene ligands and their use in OLEDs
US8692241B1 (en) * 2012-11-08 2014-04-08 Universal Display Corporation Transition metal complexes containing triazole and tetrazole carbene ligands
US9812656B2 (en) * 2011-06-08 2017-11-07 Universal Display Corporation Organic electroluminescent materials and devices

Family Cites Families (83)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5984539A (en) 1997-11-06 1999-11-16 Eastman Kodak Company Method and apparatus of applying a solution of a predetermined viscosity to photosensitive material to form a protective coating thereon
EP3321954A1 (en) 1999-05-13 2018-05-16 The Trustees of Princeton University Very high efficiency organic light emitting devices based on electrophosphorescence
JP3924648B2 (en) 1999-11-02 2007-06-06 ソニー株式会社 Organic electroluminescence device
DE10104426A1 (en) 2001-02-01 2002-08-08 Covion Organic Semiconductors Process for the production of high-purity, tris-ortho-metallated organo-iridium compounds
DE10338550A1 (en) 2003-08-19 2005-03-31 Basf Ag Transition metal complexes with carbene ligands as emitters for organic light-emitting diodes (OLEDs)
WO2005113704A2 (en) 2004-05-18 2005-12-01 The University Of Southern California Luminescent compounds with carbene ligands
DE102004037451A1 (en) 2004-08-02 2006-03-16 Niels Raeder Packaging, in particular bag, with an information carrier
DE102004057072A1 (en) 2004-11-25 2006-06-01 Basf Ag Use of Transition Metal Carbene Complexes in Organic Light Emitting Diodes (OLEDs)
KR101269497B1 (en) 2004-12-23 2013-05-31 시바 홀딩 인크 Electroluminescent metal complexes with nucleophilic carbene ligands
US9051344B2 (en) * 2005-05-06 2015-06-09 Universal Display Corporation Stability OLED materials and devices
US7902374B2 (en) 2005-05-06 2011-03-08 Universal Display Corporation Stability OLED materials and devices
US7989644B2 (en) 2005-05-30 2011-08-02 Basf Se Electroluminescent device
JP4935024B2 (en) * 2005-08-25 2012-05-23 コニカミノルタホールディングス株式会社 ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE AND LIGHTING DEVICE USING THE SAME
US8148891B2 (en) * 2005-10-04 2012-04-03 Universal Display Corporation Electron impeding layer for high efficiency phosphorescent OLEDs
DE502005009802D1 (en) 2005-11-10 2010-08-05 Novaled Ag Doped organic semiconductor material
DE102005058543A1 (en) 2005-12-08 2007-06-14 Merck Patent Gmbh Organic electroluminescent devices
EP1970976B1 (en) 2006-01-05 2017-07-19 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
US20090091253A1 (en) 2006-03-17 2009-04-09 Konica Minolta Holdings, Inc. Organic electroluminescent element, display device and lighting device
ES2310380T3 (en) 2006-03-21 2009-01-01 Novaled Ag RADICAL OR DIRRADICAL HETEROCICLIC, ITS DIMEROS, OLIGOMEROS, POLYMERS, DIESPIRO COMPOUNDS AND POLICICLOS, ITS USE, ORGANIC SEMICONDUCTOR MATERIAL AS WELL AS ELECTRONIC COMPONENT.
EP2557138B1 (en) * 2006-03-23 2016-08-10 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
US20070224446A1 (en) 2006-03-24 2007-09-27 Idemitsu Kosan Co., Ltd. Material for organic electroluminescence device and organic electroluminescence device using the same
WO2007114244A1 (en) 2006-03-30 2007-10-11 Konica Minolta Holdings, Inc. Organic electroluminescent device, illuminating device and display device
KR101431844B1 (en) 2006-04-05 2014-08-25 바스프 에스이 Heteroleptic transition metal-carbene complexes and their use in organic light-emitting diodes (oleds)
JP5055818B2 (en) 2006-04-19 2012-10-24 コニカミノルタホールディングス株式会社 ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL, ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE AND LIGHTING DEVICE
JP5298460B2 (en) * 2006-06-08 2013-09-25 コニカミノルタ株式会社 Organic electroluminescence element, display device and lighting device
WO2008000727A1 (en) 2006-06-26 2008-01-03 Basf Se Use in oleds of transition metal carbene complexes that contain no cyclometallation via non-carbenes
JP2008021687A (en) 2006-07-10 2008-01-31 Mitsubishi Chemicals Corp Material for organic electric field light emitting element, composition for organic electric field light emitting element and organic electric field light emitting element
JP2008066569A (en) 2006-09-08 2008-03-21 Konica Minolta Holdings Inc Organic electroluminescence element, lighting system and display device
WO2008029729A1 (en) 2006-09-08 2008-03-13 Konica Minolta Holdings, Inc. Organic electroluminescent device, illuminating device and display
US8852757B2 (en) 2006-09-08 2014-10-07 Konica Minolta Holdings, Inc. Organic electroluminescence element, lighting device and display device
JP5556014B2 (en) 2006-09-20 2014-07-23 コニカミノルタ株式会社 Organic electroluminescence device
JP5589251B2 (en) 2006-09-21 2014-09-17 コニカミノルタ株式会社 Organic electroluminescence element material
EP3457452B1 (en) 2006-09-21 2022-11-02 UDC Ireland Limited Oled display with extended lifetime
JP5011908B2 (en) 2006-09-26 2012-08-29 コニカミノルタホールディングス株式会社 Organic electroluminescence element, display device and lighting device
WO2008072596A1 (en) 2006-12-13 2008-06-19 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
GB0625540D0 (en) 2006-12-22 2007-01-31 Oled T Ltd Electroluminescent devices
WO2008090912A1 (en) 2007-01-23 2008-07-31 Konica Minolta Holdings, Inc. Method for manufacturing organic electroluminescent device, organic electroluminescent device manufactured by the method, display device and illuminating device
JP2008207520A (en) 2007-02-28 2008-09-11 Konica Minolta Holdings Inc Organic thin film, method for producing the same, electronic device, organic luminescence element, display device and lightening equipment
EP1988587B1 (en) 2007-04-30 2016-12-07 Novaled GmbH Oxocarbon, pseudo oxocarbon and radialene compounds and their use
JP5564942B2 (en) 2007-05-16 2014-08-06 コニカミノルタ株式会社 Organic electroluminescence element, display device and lighting device
JP5359869B2 (en) 2007-05-30 2013-12-04 コニカミノルタ株式会社 ORGANIC ELECTROLUMINESCENT ELEMENT, METHOD FOR PRODUCING ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE AND LIGHTING DEVICE
WO2008156105A1 (en) 2007-06-21 2008-12-24 Konica Minolta Holdings, Inc. Organic electroluminescence element material, organic electroluminescence element, display device and illuminating device
CN101688114B (en) 2007-07-05 2014-07-16 巴斯夫欧洲公司 Organic light-emitting diodes comprising at least one disilyl compound selected from disilylcarbazoles, disilyldibenzofurans, disilyldibenzothiophenes, disilyldibenzophospholes, disilyldibenzothiophen
JP5675349B2 (en) * 2007-07-05 2015-02-25 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Carbene transition metal complex luminophore and at least one selected from disilylcarbazole, disilyldibenzofuran, disilyldibenzothiophene, disilyldibenzophosphole, disilyldibenzothiophene S-oxide and disilyldibenzothiophene S, S-dioxide Light-emitting diodes containing two compounds
JP5194596B2 (en) 2007-07-11 2013-05-08 コニカミノルタホールディングス株式会社 Organic electroluminescence element, display device and lighting device
FR2918892B1 (en) 2007-07-16 2010-02-12 Fabre Pierre Dermo Cosmetique ANTI-INFLAMMATORY DERMATOLOGICAL COMPOSITION COMPRISING CORTICIDES AND HYALURONATE FRAGMENTS, AND USES THEREOF
JP2009046408A (en) 2007-08-17 2009-03-05 Konica Minolta Holdings Inc Dihalo polycyclic aromatic compound, pyrrolyl polycyclic aromatic compound and method for producing the same
JP5186843B2 (en) 2007-08-30 2013-04-24 コニカミノルタホールディングス株式会社 Organic electroluminescence element, lighting device and display device
JP5194652B2 (en) * 2007-09-03 2013-05-08 コニカミノルタホールディングス株式会社 ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL, ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE AND LIGHTING DEVICE
WO2009050281A1 (en) 2007-10-17 2009-04-23 Basf Se Transition metal complexes with bridged carbene ligands and use thereof in oleds
WO2009060779A1 (en) 2007-11-08 2009-05-14 Konica Minolta Holdings, Inc. Organic electroluminescent device material, organic electroluminescent device, display device and illuminating device
JP5691170B2 (en) 2007-11-08 2015-04-01 コニカミノルタ株式会社 Method for manufacturing organic electroluminescence element
WO2009060757A1 (en) 2007-11-08 2009-05-14 Konica Minolta Holdings, Inc. Organic electroluminescent device, display device and illuminating device
JP2009114370A (en) 2007-11-08 2009-05-28 Konica Minolta Holdings Inc Organic electroluminescence element material, organic electroluminescence element, display device, and lighting system
JP2009114369A (en) 2007-11-08 2009-05-28 Konica Minolta Holdings Inc Organic electroluminescent material, organic electroluminescent element, display and illuminator
JP5458890B2 (en) 2007-11-08 2014-04-02 コニカミノルタ株式会社 Organic electroluminescence element, display device and lighting device
US20100276637A1 (en) 2007-11-14 2010-11-04 Konica Minolta Holdings, Inc. Organic electroluminescent element material, organic electroluminescent element, method of manufacturing organic electroluminescent element, display device, and illuminating device
JP2009135183A (en) 2007-11-29 2009-06-18 Konica Minolta Holdings Inc Organic electroluminescence element, display, and lighting device
US20090153034A1 (en) 2007-12-13 2009-06-18 Universal Display Corporation Carbazole-containing materials in phosphorescent light emittinig diodes
JPWO2009084413A1 (en) 2007-12-28 2011-05-19 コニカミノルタホールディングス株式会社 ORGANIC ELECTROLUMINESCENT ELEMENT AND METHOD FOR PRODUCING ORGANIC ELECTROLUMINESCENT ELEMENT
US8221905B2 (en) 2007-12-28 2012-07-17 Universal Display Corporation Carbazole-containing materials in phosphorescent light emitting diodes
JP5549053B2 (en) 2008-01-18 2014-07-16 コニカミノルタ株式会社 ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL, ORGANIC ELECTROLUMINESCENT ELEMENT, METHOD FOR PRODUCING ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE AND LIGHTING DEVICE
JP2009182298A (en) 2008-02-01 2009-08-13 Konica Minolta Holdings Inc Organic electroluminescence element, lighting device, and display device
JP5381719B2 (en) 2008-02-20 2014-01-08 コニカミノルタ株式会社 White light emitting organic electroluminescence device
JP2009267255A (en) 2008-04-28 2009-11-12 Idemitsu Kosan Co Ltd Material for organic electroluminescent element and organic electroluminescent element using the material
EP2123733B1 (en) 2008-05-13 2013-07-24 Konica Minolta Holdings, Inc. Organic electroluminescent element, display device and lighting device
WO2010001830A1 (en) 2008-07-01 2010-01-07 コニカミノルタホールディングス株式会社 White light-emitting organic electroluminescent element, illuminating device and display device
JP2010021336A (en) 2008-07-10 2010-01-28 Konica Minolta Holdings Inc Organic electroluminescence device, illuminator, and display device
WO2010004877A1 (en) 2008-07-10 2010-01-14 コニカミノルタホールディングス株式会社 Organic electroluminescent element, display device and illuminating device
JP5338184B2 (en) 2008-08-06 2013-11-13 コニカミノルタ株式会社 Organic electroluminescence element, display device, lighting device
CN102246328B (en) 2008-10-07 2016-05-04 欧司朗光电半导体有限公司 The thiophene that condensed ring system replaces is coughed up and purposes in organic electronic device
WO2010044342A1 (en) 2008-10-15 2010-04-22 コニカミノルタホールディングス株式会社 Organic el element, organic el element manufacturing method, white organic el element, display device, and illumination device
EP2180029B1 (en) 2008-10-23 2011-07-27 Novaled AG Radialene compounds and their use
JP5493333B2 (en) 2008-11-05 2014-05-14 コニカミノルタ株式会社 ORGANIC ELECTROLUMINESCENT ELEMENT, WHITE ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE AND LIGHTING DEVICE
JP5707665B2 (en) 2008-12-03 2015-04-30 コニカミノルタ株式会社 ORGANIC ELECTROLUMINESCENCE ELEMENT, LIGHTING DEVICE AND DISPLAY DEVICE HAVING THE ELEMENT
JP5402942B2 (en) 2008-12-08 2014-01-29 コニカミノルタ株式会社 Organic electroluminescence element, display device, and lighting device
WO2010079678A1 (en) 2009-01-09 2010-07-15 コニカミノルタホールディングス株式会社 Organic electroluminescent element, display device, and lighting device
US20110260152A1 (en) 2009-01-28 2011-10-27 Konica Minolta Holdings, Inc. Organic electroluminescent element, display device, and illumination device
WO2010090077A1 (en) 2009-02-06 2010-08-12 コニカミノルタホールディングス株式会社 Organic electroluminescent element, and illumination device and display device each comprising the element
WO2010095564A1 (en) 2009-02-18 2010-08-26 コニカミノルタホールディングス株式会社 Organic electroluminescent element, and illuminating device and display device each comprising the element
EP2493906B1 (en) * 2009-10-28 2015-10-21 Basf Se Heteroleptic carben complexes and their use in organig electronics
US20110203649A1 (en) 2010-02-19 2011-08-25 Basf Se Use of indanthrene compounds in organic photovoltaics
US8691401B2 (en) 2010-04-16 2014-04-08 Basf Se Bridged benzimidazole-carbene complexes and use thereof in OLEDS

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020086180A1 (en) * 2000-12-28 2002-07-04 Satoshi Seo Luminescent device
US20050260448A1 (en) * 2004-05-18 2005-11-24 Chun Lin Novel organometallic compounds for use in electroluminescent devices
US20050258433A1 (en) * 2004-05-18 2005-11-24 Entire Interest Carbene metal complexes as OLED materials
US20060246315A1 (en) * 2005-04-27 2006-11-02 Begley William J Phosphorescent oled with mixed electron transport materials
US20070190359A1 (en) * 2006-02-10 2007-08-16 Knowles David B Metal complexes of cyclometallated imidazo[1,2-ƒ]phenanthridine and diimidazo[1,2-a:1',2'-c]quinazoline ligands and isoelectronic and benzannulated analogs thereof
US8383828B2 (en) * 2006-04-04 2013-02-26 Basf Aktiengesellschaft Transition metal complexes comprising one noncarbene ligand and one or two carbene ligands and their use in OLEDs
US20080106188A1 (en) * 2006-11-08 2008-05-08 Seok-Hwan Hwang Silanylamine-based compound, method of preparing the same and organic light emitting device including organic layer comprising the silanylamine-based compound
US20090017330A1 (en) * 2007-07-10 2009-01-15 Idemitsu Kosan Co., Ltd. Material for organic electroluminescence device and organic electroluminescence device utilizing the same
US20120012821A1 (en) * 2009-01-07 2012-01-19 Basf Se Silyl- and heteroatom-substituted compounds selected from carbazoles, dibenzofurans, dibenzothiophenes and dibenzophospholes, and use thereof in organic electronics
US9812656B2 (en) * 2011-06-08 2017-11-07 Universal Display Corporation Organic electroluminescent materials and devices
US9847495B2 (en) * 2011-06-08 2017-12-19 Universal Display Corporation Organic electroluminescent materials and devices
US8692241B1 (en) * 2012-11-08 2014-04-08 Universal Display Corporation Transition metal complexes containing triazole and tetrazole carbene ligands

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Ma et al., "Organic light-emitting diodes based on new n-doped electron transport layer", Synthetic Metals 158, pp. 810-814 (2008). *

Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11839140B2 (en) 2009-12-14 2023-12-05 Udc Ireland Limited Metal complexes comprising diazabenzmidazolocarbene ligands and the use thereof in OLEDS
US11444254B2 (en) 2009-12-14 2022-09-13 Udc Ireland Limited Metal complexes comprising diazabenzmidazolocarbene ligands and the use thereof in OLEDs
US10916716B2 (en) 2009-12-14 2021-02-09 Udc Ireland Limited Metal complexes comprising diazabenzmidazolocarbene ligands and the use thereof in OLEDS
US9487548B2 (en) 2009-12-14 2016-11-08 Udc Ireland Limited Metal complexes comprising diazabenzimidazolocarbene ligands and the use thereof in OLEDs
US10090476B2 (en) 2009-12-14 2018-10-02 Udc Ireland Limited Metal complexes comprising diazabenzmidazolocarbene ligands and the use thereof in OLEDs
US9236535B2 (en) 2011-02-24 2016-01-12 Basf Se Illumination devices
US9711665B2 (en) 2011-05-10 2017-07-18 Basf Se Color converters
US9406894B2 (en) 2011-06-03 2016-08-02 Semiconductor Energy Laboratory Co., Ltd. Organometallic complex, organic light-emitting element, light-emitting device, electronic device, and lighting device
US9755164B2 (en) * 2011-06-08 2017-09-05 Universal Display Corporation Organic electroluminescent materials and devices
US11063229B2 (en) 2011-06-08 2021-07-13 Universal Display Corporation Organic electroluminescent materials and devices
US20140131687A1 (en) * 2011-06-08 2014-05-15 Universal Display Corporation Heteroleptic iridium carbene complexes and light emitting device using them
US9812656B2 (en) * 2011-06-08 2017-11-07 Universal Display Corporation Organic electroluminescent materials and devices
US10978648B2 (en) * 2011-06-08 2021-04-13 Universal Display Corporation Organic electroluminescent materials and devices
US20140175408A1 (en) * 2011-06-08 2014-06-26 Universal Display Corporation Heteroleptic iridium carbene complexes and light emitting device using them
US20180019414A1 (en) * 2011-06-08 2018-01-18 Universal Display Corporation Organic electroluminescent materials and devices
US10297769B2 (en) 2011-06-08 2019-05-21 Universal Display Corporation Organic electroluminescent materials and devices
US10230023B2 (en) 2011-06-10 2019-03-12 Basf Se Color converter
US9406848B2 (en) 2011-06-10 2016-08-02 Basf Se Color converter
US9583719B2 (en) 2011-08-12 2017-02-28 Basf Se Carbazolocarbazol-bis(dicarboximides) and their use as semiconductors
JP2014101307A (en) * 2012-11-20 2014-06-05 Konica Minolta Inc Method of manufacturing facial body of iridium complex
US10290817B2 (en) 2013-07-31 2019-05-14 Udc Ireland Limited Luminescent diaza-monoaza-and benzimidazole metal carbene complexes for use in electronic devices such as OLEDs
US9701773B2 (en) 2013-08-12 2017-07-11 Sabic Global Technologies, B.V. Catalyst system for polymerisation of an OLEFIN
US9905784B2 (en) 2013-11-15 2018-02-27 Universal Display Corporation Organic electroluminescent materials and devices
US10033000B2 (en) 2013-11-15 2018-07-24 Universal Display Corporation Organic electroluminescent materials and devices
US9873753B2 (en) 2013-12-20 2018-01-23 Saudi Basic Industries Corporation Catalyst system for polymerization of an olefin
US20180097185A1 (en) * 2016-06-20 2018-04-05 Universal Display Corporation Organic electroluminescent materials and devices
US20170373259A1 (en) * 2016-06-20 2017-12-28 Universal Display Corporation Organic Electroluminescent Materials and Devices
US10686140B2 (en) * 2016-06-20 2020-06-16 Universal Display Corporation Organic electroluminescent materials and devices
US10727423B2 (en) * 2016-06-20 2020-07-28 Universal Display Corporation Organic electroluminescent materials and devices
US10651403B2 (en) * 2016-06-20 2020-05-12 Universal Display Corporation Organic electroluminescent materials and devices
US11690284B2 (en) 2016-06-20 2023-06-27 Universal Display Corporation Organic electroluminescent materials and devices
US20190140191A1 (en) * 2016-06-20 2019-05-09 Universal Display Corporation Organic electroluminescent materials and devices
US11114624B2 (en) 2016-06-20 2021-09-07 Universal Display Corporation Organic electroluminescent materials and devices
US11683981B2 (en) 2016-06-20 2023-06-20 Universal Display Corporation Organic electroluminescent materials and devices
JP2017200929A (en) * 2017-06-05 2017-11-09 コニカミノルタ株式会社 Method of manufacturing facial body of iridium complex
US11038138B2 (en) 2017-08-11 2021-06-15 Lg Chem, Ltd. Organic electroluminescent device and method for manufacturing the same
CN111587494A (en) * 2017-12-20 2020-08-25 诺瓦尔德股份有限公司 Organic electronic devices comprising inverse coordination complexes and methods of making the same
GB2569635A (en) * 2017-12-21 2019-06-26 Sumitomo Chemical Co Compound
US11856845B2 (en) 2017-12-21 2023-12-26 Sumitomo Chemical Company Limited Compound
US11165028B2 (en) * 2018-03-12 2021-11-02 Universal Display Corporation Organic electroluminescent materials and devices
US20190334100A1 (en) * 2018-04-27 2019-10-31 Samsung Display Co., Ltd. Organometallic compound and organic light-emitting device including the same

Also Published As

Publication number Publication date
KR20120096493A (en) 2012-08-30
US20220144869A1 (en) 2022-05-12
US20240130221A1 (en) 2024-04-18
KR101986469B1 (en) 2019-06-05
US11871654B2 (en) 2024-01-09
EP2493906B1 (en) 2015-10-21
EP2493906A1 (en) 2012-09-05
US11189806B2 (en) 2021-11-30
CN102741265A (en) 2012-10-17
KR101837095B1 (en) 2018-03-09
KR20180026583A (en) 2018-03-12
CN102741265B (en) 2015-12-09
JP2013509380A (en) 2013-03-14
US20200373503A1 (en) 2020-11-26
JP5939984B2 (en) 2016-06-29
WO2011051404A1 (en) 2011-05-05

Similar Documents

Publication Publication Date Title
US11871654B2 (en) Heteroleptic carbene complexes and the use thereof in organic electronics
US11839140B2 (en) Metal complexes comprising diazabenzmidazolocarbene ligands and the use thereof in OLEDS
US11605790B2 (en) Monosubstituted diazabenzimidazole carbene metal complexes for use in organic light emitting diodes
JP6626591B2 (en) Metal complexes containing carbene ligands having o-substituted non-cyclometallated aryl groups and their use in organic light emitting diodes
US9315724B2 (en) Metal complexes comprising azabenzimidazole carbene ligands and the use thereof in OLEDs
US8691401B2 (en) Bridged benzimidazole-carbene complexes and use thereof in OLEDS
EP2721043B1 (en) Metal complexes comprising azabenzimidazole carbene ligands and the use thereof in oleds
US9108998B2 (en) Dinuclear platinum-carbene complexes and the use thereof in OLEDs
EP2558476B1 (en) Bridged benzimidazole-carbene complexes and use thereof in oleds
EP2871222B1 (en) Compound for organic optoelectric device, organic optoelectric device comprising same, and display apparatus comprising organic optoelectric device
US8241764B2 (en) OLED display with extended lifetime
CN112794870A (en) Platinum complexes and devices
US20150318501A1 (en) Phenoxasiline based compounds for electronic application

Legal Events

Date Code Title Description
AS Assignment

Owner name: BASF SE, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:FUCHS, EVELYN;MOLT, OLIVER;DORMANN, KORINNA;AND OTHERS;SIGNING DATES FROM 20100121 TO 20110121;REEL/FRAME:028142/0131

Owner name: OSRAM OPTO SEMICONDUCTORS GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:FUCHS, EVELYN;MOLT, OLIVER;DORMANN, KORINNA;AND OTHERS;SIGNING DATES FROM 20100121 TO 20110121;REEL/FRAME:028142/0131

Owner name: KONINKLIJKE PHILIPS ELECTRONICS N.V., NETHERLANDS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:FUCHS, EVELYN;MOLT, OLIVER;DORMANN, KORINNA;AND OTHERS;SIGNING DATES FROM 20100121 TO 20110121;REEL/FRAME:028142/0131

AS Assignment

Owner name: OLEDWORKS GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:KONINKLIJKE PHILIPS ELECTRONICS N. V.;REEL/FRAME:037561/0857

Effective date: 20160115

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

AS Assignment

Owner name: OSRAM OLED GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:OSRAM OPTO SEMICONDUCTORS GMBH;REEL/FRAME:048273/0862

Effective date: 20181211

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION