EP1817805A1 - Utilisation de phenothiazin-s-oxydes et de phenothiazine-s,s-dioxydes en tant que matieres matricielles pour diodes luminescentes organiques - Google Patents

Utilisation de phenothiazin-s-oxydes et de phenothiazine-s,s-dioxydes en tant que matieres matricielles pour diodes luminescentes organiques

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Publication number
EP1817805A1
EP1817805A1 EP05808298A EP05808298A EP1817805A1 EP 1817805 A1 EP1817805 A1 EP 1817805A1 EP 05808298 A EP05808298 A EP 05808298A EP 05808298 A EP05808298 A EP 05808298A EP 1817805 A1 EP1817805 A1 EP 1817805A1
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Prior art keywords
phenothiazine
formula
mmol
compounds
light
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German (de)
English (en)
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Thomas Gessner
Wolfgang Kowalsky
Christian Schildknecht
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BASF SE
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BASF SE
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
    • 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
    • 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

Definitions

  • the present invention relates to the use of phenothiazine S-oxides and -S, S-dioxides as matrix materials for organic light-emitting diodes, in particular as matrix materials in the light-emitting layer of organic light-emitting diodes, organic light emitting diodes comprising a light-emitting layer, which at least at least one phenothiazine S-oxide or -S, S-dioxide as a matrix material and at least one further substance distributed therein as an emitter, light-emitting Schich ⁇ th which at least one phenothiazine S-oxide or -S, S-dioxide as Matrix material and at least one further substance distributed therein as an emitter, Licht ⁇ emitting layers, which consist of one or more phenothiazine S-oxides or - S, S-dioxides as matrix material and at least one further distributed therein substance as emitter emitter, organic Light-emitting diodes
  • OLEDs organic light emitting diodes
  • the property of materials is used to emit light when excited by electric current.
  • OLEDs are of particular interest as an alternative to cathode ray tubes and liquid crystal displays for the production of flat screens. Due to the very compact design and the intrinsically low power consumption, devices containing OLEDs are particularly suitable for mobile applications, for example for applications in mobile phones, laptops, etc.
  • Phenoxazine and phenothiazine derivatives are generally used in the art as charge transport materials.
  • EP-A 0 517 542 relates to aromatic amino compounds which are distinguished by good heat stability and may, inter alia, comprise a phenothiazine unit. These aromatic amino compounds are used as hole transport materials in OLEDs.
  • EP-A 0 562 883 also relates to hole transport materials which are used in OLEDs and which have high heat stability. As hole transport materials were ⁇ the tris-phenothiazinyl-triphenylamine derivatives or tris-phenoxazinyl-triphenylamine derivatives used.
  • DE-A 101 43 249 relates to a process for the preparation of conjugated oligo- and polyphenothiazines and their use as hole conductors in organic light emitting diodes and field effect transistors.
  • the oligo- and Polyphenothiazine be prepared by Kreuz ⁇ coupling of functionalized phenothiazine derivatives.
  • EP-A 0 535 672 discloses an electrophotographic photoreceptor which contains an organic conductive material in its photosensitive layer.
  • Suitable organic conductive materials include compounds having phenothiazine structural units.
  • US 5,942,615 and JP-A 11-158165 relate to phenothiazine and phenoxazine derivatives, a charge transport material containing these derivatives, and an electrophotographic photoreceptor containing the disclosed charge transport material.
  • the phenothiazine or phenoxazine derivatives are derivatives of the following formula:
  • Ar 1 and Ar 2 are aryl groups, R 1 and R 2 are H, lower alkyl or aryl, R 3 is lower alkyl, an alicyclic hydrocarbon radical having 5 to 7 carbon atoms, aryl or aralkyl, XS or O and m and n is 0 or 1.
  • a luminescence in particular an electroluminescence, of the abovementioned compounds, both US Pat. No. 5,942,615 and JP-A 11-158165 contain no information.
  • phenothiazine and phenoxazine derivatives are known from the prior art which are used as luminescent materials in the light-emitting layer of an OLED.
  • JP-A 2003-007466 relates to an OLED which has a long lifetime and high luminance which contains as the luminescent material a polymer which has repeating units based on phenothiazine or phenoxazine derivatives.
  • JP-07-109449 inter alia, the phentazine S, S-dioxide derivative
  • JP-A 2000-328052 relates to luminescent material which emits light in the yellow to red region of the electromagnetic spectrum and is composed of a monocyclic or condensed polycyclic compound having two specific substituents. These particular substituents are substituents of the following formula:
  • R 1 is H, alkyl or aryl
  • R 2 , R 3 are independently selected from H, CN, halogen, alkylcarbonyl and alkoxycarbonyl, preferably R 2 and R 3 are CN.
  • KR 2003-0029394 relates to red phosphors which are suitable for organic electroluminescence. These phosphors have a phenocyanidine group, has good hole transport properties and an anthracenyl, the * nentransportcons a good electrical features. Depending on the substitution pattern of the phosphors can These not only show luminescence in the yellow and red, but also in the green region of the electromagnetic spectrum. These particular phosphors have one of the following formulas
  • the radicals R 1 and R 2 may be H, aryl, heteroaryl, halogen or saturated or unge ⁇ saturated hydrocarbons.
  • a special feature of these compounds is that they not only have light emission properties but also hole transport properties and electron transport properties due to their particular substitution pattern.
  • JP-A 2004-075750 relates to phenoxazine derivatives of the formula
  • R 1 is an aromatic or aliphatic linking group and R 2 is an alkyl, alkenyl, alkyl ether, alkoxy, amino, aryl or aryloxy group.
  • the phenoxazine derivatives are used in the light-emitting layer of an OLED as fluorescent substances.
  • the object of the present application is to provide matrix materials for use in O-LEDs, in particular in the light-emitting layers of the OLEDs, which are easily accessible and in combination with the actual emitter (s) good luminance and quantum yields OLEDs effect.
  • X is a group SO or SO 2 ,
  • R 1 is hydrogen, alkyl, cyclic alkyl, heterocyclic alkyl, aryl, heteroaryl, a grouping of formula II
  • X 1 , X 2 , X 3 are independently of one another and independently of X a group SO or SO 2 ,
  • R, FT, R 1, R 7 , R 8 , R 11 , R 12, independently of one another, are alkyl, aryl or heteroaryl,
  • n, q, r, t, u, x, y are independently 0, 1, 2 or 3, R 6 , R 9 , R 10 independently of one another alkyl, aryl, alkoxy or aryloxy,
  • s. v. w independently 0, 1 or 2
  • B is an alkylene bridge -CH 2 -C k H 2K -. wherein one or more non-adjacent CH 2 groups of the unit -C ⁇ ⁇ H 2k - may be replaced by oxygen or NR,
  • R is hydrogen or alkyl
  • the matrix materials of the formula I used according to the invention are readily accessible and, in combination with the actual emitter (s), have good luminous densities and quantum yields when used in OLEDs.
  • alkyl radicals and the alkyl radicals of the alkoxy groups according to the present application can be straight-chain as well as branched and / or optionally substituted with substituents selected from the group consisting of aryl, alkoxy and halo.
  • the alkyl radicals are preferably unsubstituted. Suitable aryl substituents are mentioned below.
  • the cyclic alkyl radicals and the cyclic alkyl radicals of the alkoxy groups according to the present application may optionally be substituted by substituents selected from the group consisting of aryl, alkoxy and halogen.
  • the cyclic alkyl radicals are preferably unsubstituted. Suitable aryl substituents are mentioned below.
  • Suitable halogen substituents are fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine, more preferably fluorine and chlorine.
  • alkyl groups examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl. Both the n-isomers of these radicals and also branched isomers such as isopropyl, isobutyl, isopentyl, sec-butyl, tert-butyl, neopentyl, 3,3-dimethylbutyl, 2-ethylhexyl, etc. included.
  • Preferred alkyl groups are methyl and ethyl.
  • Suitable cyclic alkyl radicals are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. If appropriate, these may also be polycyclic ring systems, such as decalinyl, norbomanyl, boranonyl or adamantyl.
  • the cyclic alkyl radicals may be unsubstituted or, if appropriate, substituted by one or more further radicals, as has been mentioned by way of example above for the alkyl radicals.
  • Suitable alkoxy groups are derived according to the alkyl radicals as defined above.
  • OCH 3 , OC 2 H 5 , OC 3 H 7 , OC 4 H 9 and OC 8 Hi 7 may be mentioned here .
  • C 3 H 7 , C 4 H 9 and OC 8 Hi 7 include both the n-isomers and branched isomers such as isopropyl, isobutyl, sec-butyl, tert-butyl and 2-ethylhexyl. Particularly preferred are methoxy, ethoxy, n-octoxy and 2-ethyl-hexoxy.
  • Aryl in the present invention refers to radicals which are derived from monocyclic or bicyclic aromatics which contain no ring heteroatoms. Unless they are monocyclic systems, the term aryl for the second ring also denotes the saturated form (Perhydroform) or the partially unsaturated form (for example, the dihydroform or tetrahydroform), if the respective forms are known and stable, possible. That is, in the present invention, the term aryl includes, for example, bicyclic groups in which both both of the groups are aromatic and bicyclic groups in which only one of the rings is aromatic.
  • aryl examples include: phenyl, naphthyl, indanyl, 1, 2-dihydronaphthenyl, 1, 4-dihydronaphthenyl, indenyl or 1, 2,3,4-tetrahydronaphthyl.
  • Aryl is particularly preferably phenyl or naphthyl, very particularly preferably phenyl.
  • the aryl radicals may be unsubstituted or substituted by one or more further radicals. Suitable further radicals are selected from the group consisting of alkyl, aryl, alkoxy, aryloxy, arylcarbonyloxy, heteroaryl, hydroxy and halogen. Preferred alkyl, aryl, alkoxy and halogen radicals have already been mentioned above.
  • the aryl radicals are preferably unsubstituted or substituted by one or more alkoxy groups. More preferably, aryl is unsubstituted phenyl, 4-alkylphenyl, 4-alkoxyphenyl, 2,4,6-trialkylphenyl or
  • 2,4,6-trialkoxyphenyl where as 4-alkylphenyl, 4-alkoxyphenyl, 2,4,6-trialkylphenyl and 2,4,6-trialkoxyphenyl, in particular 4-methylphenyl, 4-methoxyphenyl, 2,4,6-tri- methyl-phenyl and 2,4,6-trimethoxyphenyl come into consideration.
  • Suitable aryloxy and arylcarbonyloxy groups are derived respectively from the aryl radicals as defined above. Particularly preferred is phenoxy and phenylcarbonyloxy.
  • Heteroaryl is to be understood as meaning monocyclic or bicyclic heteroaromatics which can be derived in part from the abovementioned aryl by replacing at least one carbon atom in the aryl skeleton by a heteroatom.
  • Preferred heteroatoms are N, O and S.
  • Particularly preferred is the optionally fused backbone selected from systems such as pyridine and five-membered heteroaromatics such as thiophene, pyrrole, imidazole or furan.
  • the backbone may be substituted at one, several or all substitutable positions, suitable substituents being the same as those already mentioned under the definition of aryl.
  • the heteroaryl radicals are unsubstituted.
  • pyridin-2-yl pyridin-3-yl, pyridin-4-yl, thiophen-2-yl, thiophen-3-yl, pyrrol-2-yl, pyrrol-3-yl, furan-2 -yl, furan-3-yl and imidazol-2-yl and the corresponding benza- nell investigating radicals.
  • Heterocyclic alkyl is to be understood as meaning radicals which differ from the above-mentioned cyclic alkyl in that at least one carbon atom in the cyclic alkyl backbone is replaced by a heteroatom. Preferred heteroatoms are N, O and S.
  • the backbone may be substituted at one, several or all substitutable positions, suitable substituents being those already mentioned under the definition of aryl. Particular mention should be made here of the nitrogen-containing radicals pyrrolidin-2-yl, pyrrolidin-3-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl.
  • the moiety -C k H 2k - of the alkylene bridge B is especially the linear alkylene chains -CH 2 -, - (CH 2 Jr, - (CH Z ) 3 -, - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 6 -, - (CH 2 ) 7 - and - (CH 2 ) 8 - but these may also be branched such that, for example, chains -CH (CH 3 ) -, -C (CH 3 ) 2 -, -CH 2 -CH (CH 3 ) -, -CH (CH 3 ) -CH (CH 3 ) -, ⁇ (CH 1 -C 4 H 1 -), -CH (CHG ) -CH 2 -CH (CH 3 ) -, -CH (CH 3 HCH 2 ) 2 -CH (CH 3 ) -, -CH (CH 3 ) - (CH 2 )
  • a of the alkylene bridge B or more non-adjacent CH 2 groups may be replaced by oxygen or NR
  • Examples are in particular -0-C 2 H 4 -O-, -O- (C 2 H 4 -O-);., -NR-C 2 H 4 -NR- or -NR- (C 2 H 4 -NR-J 2 , where R is in particular for Wasser ⁇ fabric, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl or tert-butyl.
  • R 1 assumes the meaning of a grouping of the formula II with z equal to 2, the two (R 4 ) q and (R 5 ) r may each be different from one another according to type and number. Furthermore, the two X 1 can be different from each other.
  • R 1 assumes the meaning of a group of the formula III
  • the optionally substituted phenothiazine skeletons of the formulas I and III are preferably identical, ie (R 2 ) m and (R 8 ) u , (R 3 ) n and (R 7 ) t and X and X 2 each have the same meaning.
  • R 1 assumes the meaning of a group of the formula IV
  • the optionally substituted phenothiazine skeletons of the formulas I and IV are preferably identical, ie (R 2 ) m and (R 11 ) x , (R 3 ) n and (R 12 ) y and X and X 3 each have the same meaning.
  • the present invention relates to the use of compounds of the formula I in which the variables have the following meanings:
  • X is a group SO or SO 2 ,
  • R 1 is hydrogen, methyl, ethyl, cyclohexyl, pyrrolidin-2-yl, pyrrolidin-3-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, phenyl, 4-alkylphenyl, 4-alkoxy phenyl, 2,4,6-trialkylphenyl, 2,4,6-trialkoxyphenyl, furan-2-yl, furan-3-yl, pyrrol-2-yl, pyrrol-3-yl, thiophen-2-yl, thiophene 3-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidine
  • X 1 , X 2 , X 3 are independent of one another and independently of X.
  • R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 11 , R 12 are independently aryl
  • n, q, r, t, u, x, y are independently 0 or 1
  • R 6 , R 9 , R 10 independently of one another are alkyl or alkoxy
  • s, v, w are independently 0 or 1
  • B is an alkylene bridge -CH 2 -C k H 2K -
  • k 0, 1, 2, 3, 4, 5, 6, 7 or 8
  • Aryl is preferably in the radicals R 2, R 3, R ⁇ R 5, R 7, R 8, R 11 and R 12 independently of one another, phenyl, naphth-1-yl or naphth-2-yl.
  • R 1 assumes the meaning of a grouping of the formula II with z equal to 2, the two (R 4 ) q and (R 5 ) r may each be different from one another according to type and number. Furthermore, the two X 1 can be different from each other.
  • R 1 assumes the meaning of a moiety of formula III, which if appropriate substituted phenothiazine skeletons of the formulas I and III are preferably the same, ie (R 2) m and (R 8) U1 (R 3) n and (R 7 ) t and X and X 2 each have the same meaning.
  • R 1 assumes the meaning of a group of the formula IV
  • the optionally substituted phenothiazine skeletons of the formulas I and IV are preferably identical, ie (R 2 ) m and (R 11 ) x , (R 3 ) n and (R 12 ) y and X and X 3 each have the same meaning.
  • R 1 is one of the following groups
  • k in the formulas I / IV a and I / IV c can each assume the values O or 1 to 8 and for the formulas I / IV b and I / IV d the value of j in the bridge unit - (B) j - CH 2 - is equal to O, respectively.
  • phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives of the formula I used according to the invention can be prepared by processes known to the person skilled in the art.
  • the preparation of the compounds of the formula I is preferably carried out by appropriate substitution of the commercially available phenothiazine skeleton (ie m and n are both equal to O).
  • the radicals R 2 and / or R 3 are thereby introduced by electrophilic aromatic substitution. Suitable reaction conditions are known to the person skilled in the art.
  • the radical R 1 is - if it is not hydrogen - introduced by electrophilic substitution on the nitrogen, for example by reaction with a suitable alkyl or aryl halide.
  • the oxidation of the sulfur in the phenothiazine skeleton to the SO or SO 2 group usually takes place in the last synthesis step.
  • the preparation of the compounds of the formula I can also be carried out starting from already functionalized building blocks which are suitable for the preparation of the phenothiazine S-oxide or phenothiazine SS-dioxide derivatives.
  • the phenothiazine derivatives used according to the invention can be prepared starting from sulfurized with the radicals R 2 and / or R 3 functionalized diphenylamine derivatives by heating.
  • the preparation of the functionalized diphenylamine derivatives is known to the person skilled in the art.
  • the oxidation of the sulfur in the phenothiazine skeleton to the SO or SO 2 group usually takes place in the last synthesis step.
  • Suitable processes for the oxidation of the phenothiazines to the phenothiazine S-oxides and phenothiazine S, S-dioxides used according to the invention are known to the person skilled in the art and are described, for example, in M. Tosa et al. Heterocyclic Communications, Vol. 7, no. 3, 2001, pp. 277-282.
  • oxidation to phenothiazine S-oxide derivatives is carried out for example by means of H 2 O 2 in ethanol, ethanol-acetone mixtures or oxalic acid, by means of ammonium persulfate, nitric acid, nitrous acid, inorganic nitrogen oxides, optionally together with (air) oxygen, NO + BF 4 VO 2 , CrO 3 in pyridine, ozone, tetramethyloxirane, perfluoroalkyloxaziridines or by electrochemical methods.
  • oxidation to phenothiazine S, S-dioxide derivatives is carried out, for example, by means of peracids, such as peracetic acid, which is accessible for example from H 2 O 2 and AcOH, or m-chloroperbenzoic acid, sodium perborate, NaOCl or heavy metal systems such as KMnO 4 ZH 2 O, Et 3 PhN + MnO 4 ' in organic media, OsO 4 / N-methylmorpholine N-oxide.
  • peracids such as peracetic acid, which is accessible for example from H 2 O 2 and AcOH, or m-chloroperbenzoic acid, sodium perborate, NaOCl or heavy metal systems such as KMnO 4 ZH 2 O, Et 3 PhN + MnO 4 ' in organic media, OsO 4 / N-methylmorpholine N-oxide.
  • the phenothiazine derivative and the oxidizing agent preferably m-chloroperbenzoic acid, in a molar Ver ⁇ ratio of generally 1: 1, 8 to 1: 4, preferably 1: 1, 9 to 1: 3.5, more preferably 1: 1, 9 to 1: 3 used.
  • the phenothiazine derivative and the oxidizing agent are used in a molar ratio of generally 1: 0.8 to 1: 1, 5, preferably 1: 1 to 1: 1, 3.
  • Oxidizing agents with which no further oxidation to the corresponding S, S-dioxide derivatives takes place for example H 2 O 2 , can be used in a greater excess than the above-mentioned with respect to the Phe ⁇ nothiazin derivative.
  • the oxidation is generally carried out in a solvent, preferably in a solvent selected from the group consisting of halogenated hydrocarbons and dipolar aprotic solvents.
  • a solvent selected from the group consisting of halogenated hydrocarbons and dipolar aprotic solvents.
  • the former or the latter are methylene chloride or acetonitrile and sulfolane.
  • the oxidation to the phenothiazine-S-oxide derivatives usually takes place at atmospheric pressure in a temperature range from -10 0 C to + 50 0 C and the oxidation to the phenothiazine-SS-dioxide derivatives usually at atmospheric pressure in a temperature range of 0 to + 100 ° C.
  • the reaction time of the oxidation is generally 0.25 to 24 hours.
  • the suitable conditions for the oxidation of the respective phenothiazine derivatives to give the corresponding phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives can be determined in any case by a person skilled in the art without any problems in preliminary experiments.
  • the progress of the oxidation can be monitored by analytical methods, such as IR spectroscopy.
  • the phenothiazine S-oxide derivatives are prepared by oxidation of the corresponding I phenothiazine derivatives of the formula I with m-chloro-perbenzoic acid as the oxidizing agent in CH 2 Cl 2 at 0 to 20 0 C of the formula.
  • the phenothiazine S, S-dioxide derivatives of the formula I are preferably prepared by oxidation of the corresponding phenothiazine derivatives of the formula I with m-chloroperbenzoic acid as the oxidant in CH 2 Cl 2 at 0 to 40 ° C.
  • step aa) is carried out only when R 1 is different from hydrogen (in the following statements for the preparation of the compounds of formula I under N-alkylation or N-arylation and N-alkylated or N-arylated with respect to Definition of the radical R 1 not only the N-substitution with alkyl radicals but also the N-substitution with cyclic alkyl radicals and heterocyclic alkyl radicals or not only the N-substitution with aryl radicals but also the N-substitution with heteroaryl radicals are understood;
  • the meaning of the corresponding alkyl or aryl reagents for N-alkylation or N-arylation is also cycloalkyl and heterocycloalkyl or heteroaryl reagents).
  • Suitable reaction conditions for carrying out steps aa), ab), ac) and ad) are known to the person skilled in the art. In the following, preferred variants of steps aa), ab), ac) and ad) are mentioned.
  • N-alkylation or N-arylation is preferably carried out by reacting the basic skeleton of the formula 1 with an alkyl halide or aryl halide of the formula R 1 -Hal, where R 1 has already been defined above and Hal is Cl, Br or I, preferably I , meaning. In this case, work is carried out in the presence of bases, these being known to the person skilled in the art.
  • alkali metal or alkaline earth metal hydroxides such as NaOH, KOH, Ca (OH) 2
  • alkali metal hydrides such as NaH 1 KH
  • alkali metal amides such as NaNH 2
  • alkali or alkaline earth metal carbonates such as K 2 CO 3
  • alkali metal alkoxides such as NaOMe, NaO.
  • mixtures of the abovementioned bases are suitable. Particular preference is given to NaOH, KOH or NaH.
  • N-alkylation (described, for example, in M. Tosa et al., Heterocycl Communications, Vol. 7, No. 3, 2001, pp. 277-282) or N-arylation (for example in H. Gilman and DA Shira).
  • ley, J. Am. Chem. Soc., 66 (1944) 888; D. Li et al., Dyes and Pigments 49 (2001) 181-186) is preferably carried out in a solvent.
  • Suitable solvents are e.g. polar aprotic solvents, such as dimethyl sulfoxide, dimethylformamide or alcohols.
  • reaction may further be carried out in a nonpolar aprotic solvent, e.g. Toluene, when a phase transfer catalyst, e.g. tetra-n-butylammonium hydrogensulfate, an ⁇ is essential (as disclosed, for example, in I. Gozlan et al., J. Heterocycl Chem 21 (1984) 613-614).
  • a phase transfer catalyst e.g. tetra-n-butylammonium hydrogensulfate
  • N-arylation can also be carried out by copper-catalyzed coupling of the compound of formula 1 with an aryl halide, preferably an aryl iodide (Ullmann reaction).
  • an aryl halide preferably an aryl iodide
  • Ullmann reaction A suitable method for N-arylation of phenothiazine in the presence of copper bronze is described, for example, in H. Gilman et al., J. Am. Chem. Soc. 66 (1944) 888-893.
  • the molar ratio of the compound of the formula 1 to the alkyl halide or aryl halide of the formula R 1 -Hal is generally 1: 1 to 1: 2, preferably 1: 1 to 1: 1.5.
  • the N-alkylation or N-arylation is typically conducted at atmospheric pressure and in a temperature range from 0 to 220 0 C or to the boiling point of the solu- used sungsffens.
  • the reaction time is usually 0.5 to 48 hours.
  • the suitable conditions for the N-alkylation or N-arylation of the compound of the formula 1 can be determined in any case by a person skilled in the art without any problems in preliminary experiments.
  • the progress of N-alkylation or N-arylation can be monitored by analytical methods, such as IR spectroscopy.
  • halogenation can be carried out according to methods known to the person skilled in the art.
  • bromination or iodination takes place in the 3- and 7-position of the optionally N-alkylated or N-arylated skeleton of the formula 1.
  • a bromination of the optionally in step aa) N-alkylated or N-arylated backbone of formula 1 in the 3- and 7-position of the backbone can, for. B. according to M. Jovanovich et al. J. Org. Chem. 1984, 49, 1905 - 1908 by reaction with bromine in acetic acid. Furthermore, bromination can be carried out according to the method described in C. Bodea et al. Acad. Rep. Rome. 13 (1962) 81-87.
  • N-alkylated or N-arylated Grund ⁇ backbone of the formula 1 in the 3- and 7-position of the backbone can, for example, according to the in M. Sailer et al. J. Org. Chem. 2003, 68, 7509-7512. Initially, a lithiation of the corresponding, optionally N-alkylated or N-arylated, 3,7-dibromo-substituted backbone of the formula 1 is carried out, followed by iodination of the lithiated product.
  • the lithiation with a lithium base such as n-butyllithium or lithium diisopropylamide, is generally conducted at temperatures from -78 to +25 ° C, preferably -78 to 0 0 C, particularly preferably -78 ° C according to known in the art Method für ⁇ led. Subsequently, the reaction mixture is warmed to room temperature and worked up in accordance with methods known in the art.
  • a lithium base such as n-butyllithium or lithium diisopropylamide
  • the (non-oxidized) phenothiazine derivatives on which the phenothiazine S-oxide and -SS-dioxide derivatives of the formula I are used are preferably prepared by coupling reaction with precursor compounds which correspond to the desired radicals R 2 and R 3 , produced.
  • Suitable coupling reactions are, for example, the Suzuki coupling or the Yamamoto coupling, the Suzuki coupling being preferred.
  • Suzuki coupling can be used to prepare compounds which are substituted by the desired radicals R 2 and R 3 at positions 3 and 7 of the (optionally N-alkylated or N-arylated) phenothiazine skeleton of the formula 1, by the corresponding 3,7-halogenated, in particular 3,7-brominated, phenothiazines under Pd (0) catalysis and in the presence of a base with boronic acids or boronic acid esters which correspond to the desired radicals R 2 and R 3 reacted ⁇ the.
  • boronic acids or boronic esters corresponding to the desired radicals R 2 and R 3 it is also possible to use other boron-containing compounds which carry the desired radicals R 2 and R 3 in the reaction with the halogenated phenothiazine derivatives.
  • Such boron-containing compounds correspond for example to the general formulas R 2 -B (O- [C (R ' ) 2 ] n -O) and R 3 -B (O- [C (R ' ) 2 ] n -O), wherein R 2 and R 3 have the meanings given above and R 'are identical or different radicals hydrogen or C 1 -C 20 -AikyI, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec Butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n Heptyl, isoheptyl, n-octyl, n-
  • the boronic acids, boronic esters and boron-containing compounds corresponding to the desired radicals R 2 and R 3 can be prepared by processes known in the art or are commercially available. For example, it is possible to prepare the boronic acids and boronic esters by reacting Grignard or lithium reagents with boranes, diboranes or borates.
  • Pd (0) catalysts all conventional Pd (0) catalysts are suitable.
  • tris (dibenzylideneacetone) dipalladium (0) or tetrakis (triphenylphosphine) palladium (0) can be used.
  • a Pd (II) salt can be used in admixture with a ligand, for example Pd (ac) 2 or PdCl 2 and PPh 3 , where Pd (O) is formed in situ.
  • Pd (O) is formed in situ.
  • an excess of PPh 3 can be added.
  • the catalysts are generally used in an amount of 0.001 to 15 mol%, preferably 0.01 to 10 mol%, particularly preferably 0.1 to 5 mol%, based on the halogenated phenothiazine derivative used.
  • the base is generally used in 2 to 200 times, preferably 2 to 100 times, more preferably 2 to 80 times the molar excess, based on the halogenated phenothiazine derivative used.
  • the component corresponding to the desired radicals R 2 and R 3 (boronic acid, the corresponding boronic acid ester or the other suitable boron-containing compounds) is present in a ratio of 100 to 400 mol%, preferably 100 to 300 mol%, particularly preferably 100 to 150 mol% to the halogenated phenothiazine derivative ein ⁇ set.
  • the reaction is usually carried out under atmospheric pressure at a temperature of 40 to 140 0 C, preferably 60 to 120 ° C, particularly preferably 70 to 100 0 C.
  • the reaction generally takes place in the absence of oxygen.
  • the reaction is usually carried out in a solvent such as benzene, toluene, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, dimethylformamide, ethanol or petroleum ether. It is also possible to use a mixture of tetrahydrofuran, dimethoxyethane or ethanol and water as solvent.
  • a halogenated phenothiazine derivative is introduced in solution under protective gas and is present with the base, which is preferably dissolved (for example in a dimethoxyethane / water mixture) and which desired Residues R 2 and R 3 are added to corresponding boronic acids.
  • the Pd (0) catalyst is added under protective gas. It is stirred for a period of generally from 2 to 120 hours, preferably from 4 to 72 hours, more preferably from 6 to 48 hours, at the abovementioned temperatures and pressures. Following this, the reaction mixture is worked up by the methods known to the person skilled in the art.
  • a solution, preferably a DMF solution, of the catalyst prepared from a Ni (0) compound, preferably Ni (COD) 2 , and bipyridyl in equimolar amounts are used.
  • the halogenated, preferably brominated, phenothiazine derivative and the halogen compounds corresponding to the desired radicals R 2 and R 3 , in particular bromine compounds, in a solvent, preferably toluene, are added to this solution, with exclusion of oxygen. added.
  • reaction conditions in the preparation of the phenothiazine derivatives by Ya ⁇ mamoto coupling such as temperature, pressure, solvent and ratio of haloge- nated, preferably brominated, phenothiazine derivative to the R 2 and R 3 corresponding components corresponding to those of Suzuki coupling.
  • Ni (0) compounds for the preparation of the catalyst all customary Ni (O) compounds are suitable.
  • Ni (C 2 H 4 J 3 , Ni (1,5-cyclooctadiene) 2 Are (,, Ni (COD) 2 ").
  • Ni (1,6-cyclodecadiene) 2 or Ni (1, 5,9-all-trans-Cyclododeratrien) 2 sets Sheet ⁇
  • the catalysts are. Generally in an amount of 1 to 100 mol%, preferably 5 to 80 mol%, particularly preferably 10 to 70 mol%, based on the halogenated phenothiazine derivative used.
  • Suzuki-Miyaura cross-coupling A. Suzuki, J. Organomet. Chem. 576 (1999) 147-168; B-alkyl Suzuki-Miyaura cross-coupling: S.R. Chemler et al., Angew. Chem. 2001, 113, 4676-4701 and the literature cited therein.
  • Preferred oxidizing agents and process conditions for the oxidation of the phenothiazines to the corresponding phenothiazine S, S-dioxide derivatives have been mentioned above and are described, for example, in M. Tosa et al., Heterocyclic Commun. 7 (2001) 277-282.
  • Step bc) is advantageously carried out in analogy to step aa).
  • the unbalanced unit biphenal additionally contains the PT 3 -biphen-PT 1 isomeric compound PT 1 -biphen-PT 3 .
  • PT 1 and PT 3 each represents a different phenothiazine unit derived from the corresponding compounds of formulas 1a and 1c, or biphene for an optionally substituted biphenylyl moiety derived from the corresponding compound of formula 3 ,
  • the aryl halide or biphenyl dihalogenide can be initially charged together with the copper powder and the first phenothiazine (PT 1 -H), if appropriate also dissolved in the same inert solvent, can be added.
  • the formation of isomers Products PT 2 -phen-PT 1 or PT 3- biphen-PT 1 can be in the normal case! but not influenced by such a procedure.
  • step bc a base-catalyzed reaction of the compounds of formulas 1a and 1b
  • Suitable bases in this case are the compounds mentioned under step aa).
  • NaH is suitable as the base.
  • Step cc) is carried out analogously to the N-alkylation as described under step aa).
  • the compounds of the formula I are outstandingly suitable for use as matrix materials in organic light-emitting diodes (OLEDs).
  • OLEDs organic light-emitting diodes
  • they are ideally suited as matrix materials in the light-emitting layer of the OLEDs.
  • Another object of the present invention is therefore the use of the compounds of formula I as matrix materials in the light-emitting layer of the organic light emitting diode.
  • the use of the compounds of the formula I as matrix materials is not intended to preclude these compounds themselves also emitting light.
  • the matrix materials used according to the invention have the effect that, in the case of compounds which are used as emitters in OLEDs, an increase in the luminous density and quantum yield compared to otherwise conventional matrix materials is normally achieved if they are embedded in the former.
  • emitter compounds are based on metal complexes, in which case the complexes of the metals Ru 1 Rh, Ir, Pd and Pt, in particular the complexes of Ir have attained significance.
  • the compounds of the formula I used according to the invention are particularly suitable as matrix materials for emitters based on such metal complexes. In particular, they are suitable for use as matrix materials together with complexes of Ru, Rh, Ir, Pd and Pt, particularly preferably for use together with complexes of Ir.
  • Suitable metal complexes for use together with the compounds of the formula I as matrix materials in OLEDs are described, for example, in the publications WO 02/60910 A1, WO 02/68453 A1, US 2001/0015432 A1, US 2001/0019782 A1 US 2002/0055014 A1, US 2002/0024293 A1, US 2002/0048689 A1, EP 1 191 612 A2, EP 1 191 613 A2, EP 1 211 257 A2, US 2002/0094453 A1, WO 02/02714 A2, WO 00/70655 A2, WO 01/41512 A1 and WO 02/15645 A1.
  • Suitable metal complexes for use with the compounds of formula I as matrix materials in OLEDs are e.g. also carbene complexes, as described in the earlier international application PCT / EP / 04/09269.
  • the disclosure of this application is hereby explicitly referred to and this disclosure is to be considered incorporated into the content of the present application.
  • suitable metal complexes for use together with the compounds of formula I as matrix materials in OLEDs carbene ligands of nach ⁇ following, in the earlier international application PCT / EP / 04/09269 disclosed structures (the designation of the variables was from the application PCT / EP / 04/09269, with a view to a more precise definition of the variables, reference is expressly made to this application):
  • z, z are the same or different, CH or N;
  • R 12 , R 12 are identical or different, an alkyl, aryl, heteroaryl or alkenyl radical, be ⁇ preferably an alkyl or aryl radical or in each case 2 radicals R 12 or R 12 together form a fused ring, optionally at least one He
  • R 12 or R 12 is a radical having donor or acceptor activity, preferably selected from the group consisting of halo genresten, preferably F, Cl, Br, particularly preferably F; Alkoxy, aryloxy, carbonyl, ester, amino, amide, CHF 2 , CH 2 F, CF 3 , CN, thio groups and SCN;
  • t and t ' are identical or different, preferably equal to 0 to 3, where, when t or t'> 1, the radicals R 12 and R 12 may be identical or different, preferably t or t 'is 0 or 1, the radical R 12 or R 12 is, when t or t 'is 1, in the ortho, meta or para position to the point of attachment to the nitrogen atom adjacent to the carbene carbon atom;
  • R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 11 are hydrogen, alkyl, aryl, heteroaryl, alkenyl or a substituent with donor or acceptor action, preferably selected from halogen radicals, preferably F, Cl, Br, particularly preferably F, 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 and SCN groups, preferably hydrogen, alkyl, heteroaryl or aryl,
  • R 10 is alkyl, aryl, heteroaryl or alkenyl, preferably alkyl, heteroaryl or aryl, or in each case 2 radicals R 10 together form a fused ring which may optionally contain at least one heteroatom, preferably nitrogen, preferably 2 radicals R 10 in each case together form a fused aromatic C 6 ring, wherein one or more further aromatic rings may optionally be fused to this, preferably six-membered, aromatic ring, any conceivable annulation being possible, and the fused radicals in turn being able to be substituted; or R 10 means one NEN remainder with donor or acceptor, preferably selected from the group consisting of halogen radicals, preferably F, Cl, Br, most preferably F; Alkoxy, aryloxy, carbonyl, ester, amino, amide, CHF 2 , CH 2 F, CF 3 , CN, thio groups and SCN
  • v is 0 to 4, preferably 0, 1 or 2, most preferably 0, wherein when v
  • suitable metal complexes for use together with the compounds of the formula I as matrix materials in OLEDs contain Ir carbene complexes of the following structures disclosed in the earlier international application PCT / EP / 04/09269:
  • M is Ru (III), Rh (III), Ir (III), Pd (II) or Pt (II)
  • n Ru (III), Rh (III) and Ir (III) is 3, for Pd (II) and Pt (II) assumes the value 2 and Y 2 and Y 3 signify hydrogen, methyl, ethyl, n-propyl, isopropyl or tert-butyl.
  • M is Ir (III) with n equal to 3.
  • Y 3 is preferably methyl, ethyl, n-propyl, iso-propyl or tert-butyl.
  • M is Ru (III), Rh (III), Ir (III) 1 Pd (II) or Pt (II), n is Ru (III), Rh (III) and Ir (IIl) is 3, for Pd (II) and Pt (II) is 2 and Y 3 is hydrogen, methyl, ethyl, n-propyl, iso-propyl or tert-butyl.
  • M is Ir (III) with n equal to 3.
  • Y 3 is preferably methyl, ethyl, n-propyl, iso-propyl or tert-butyl.
  • M is Ru (III), Rh (III) and especially Ir (III), Pd (II) or Pt (II), n is Ru (III), Rh (III) and Ir (III) is 3 and for Pd (II) and Pt (II) assumes the value 2.
  • M is Ru (III), Rh (III) and especially Ir (III), Pd (II) or Pt (II), n is Ru (III), Rh (III) and Ir (III) is 3 and for Pd (II) and Pt (II) assumes the value 2.
  • Y 2 is hydrogen, methyl, ethyl, n-propyl, isopropyl or tert-butyl and Y 3 methyl, ethyl, n-propyl, iso-propyl or tert-butyl. designated.
  • Suitable ligands L are, in particular, the acetylacetonate and its derivatives, the picolinate, Schiff's bases, amino acids and the bidentate monoanionic ligands mentioned in WO 02/15645; In particular, the acetylacetonate and pico linat of interest. In the case of complexes L 2 ML ' , the ligands L may be the same or different.
  • Y 3 denotes hydrogen, methyl, ethyl, n-propyl, isopropyl or tert-butyl, in particular methyl, ethyl, n-propyl or iso-propyl.
  • the present invention therefore relates to organic light-emitting diodes comprising a light-emitting layer which contains at least one compound of the formula I as matrix material and at least one further substance distributed therein as emitter.
  • Another object of the present invention is also a light-emitting layer containing at least one compound of formula I as a matrix material and at least one further substance distributed therein as an emitter.
  • a further subject of the present invention is a light-emitting layer consisting of one or more compounds of the formula I as matrix material and at least one further substance distributed therein as an emitter.
  • OLEDs Organic light-emitting diodes
  • the OLED does not have all of the layers mentioned, for example an OLED with the layers (1) (anode), (3) (light-emitting layer) and (5) (cathode) is also suitable , wherein the functions of the layers (2) (hole-transprotating layer) and (4) (electron-transprotective layer) are taken over by the adjacent layers.
  • OLEDs comprising layers (1), (2), (3) and (5) or layers (1), (3), (4) and (5) are also suitable.
  • phenothiazine S-oxide and phenothiazine S, S-dioxide derivatives of the formula I can be used as charge-transporting, in particular hole-transporting materials, but they are preferably used as matrix materials in the light-emitting layer.
  • the phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives of the formula I used according to the invention can be present as the sole matrix material-without further additives-in the light-emitting layer.
  • further compounds are present in the light-emitting layer.
  • a fluorescent dye may be present to alter the emission color of the emitter molecule present.
  • a diluent material can be used.
  • CBP 4,4'-N 1 N'-dicarbazolebiphenyl
  • Phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives of the formula I in the light-emitting layer generally still at least 40 wt .-%, preferably 50 to 100 wt .-% based on the total weight of phenothiazine -S-oxide or phenothiazine S, S-dioxide derivative and diluent.
  • the individual of the abovementioned layers of the OLED can in turn be composed of 2 or more layers.
  • the hole-transporting layer may be composed of a layer into which holes are injected from the electrode and a layer that transports the holes away from the hole-injecting layer into the light-emitting layer.
  • the electron-transporting layer may also consist of several layers, for example a layer in which electrons are injected through the electrode and a layer which receives electrons from the electron-injecting layer and transports them into the light-emitting layer. These layers are selected in each case according to factors such as energy level, temperature resistance and charge carrier mobility, as well as the energy difference of said layers with the organic layers or the metal electrodes.
  • the expert is able to structure the
  • OLEDs to be chosen so that it is optimally adapted to the inventively used as emitter substances organic compounds.
  • the HOMO (highest occupied molecular orbital) of the hole-transporting layer should be aligned with the work function of the anode
  • the LUMO (lowest unoccupied molecular orbital) of the electron-transporting layer should be aligned with the work function of the cathode
  • Another object of the present application is an OLED containing a light-emitting layer which contains at least one compound of formula I as Mat ⁇ rixmaterial and at least one further substance distributed therein as an emitter, or which consists of one or more compounds of formula I as a matrix material and at least one further substance distributed therein as an emitter.
  • the anode (1) is an electrode that provides positive charge carriers. It can be constructed, for example, of materials which contain 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 include the metals of groups Ib, IVa, Va and VIa of the Periodic Table of the Elements as well as the transition metals of the group Villa. When the anode is to be transparent, mixed metal oxides of groups IIb, IMb and IVb of the Periodic Table of the Elements (old IUPAC version), for example indium tin oxide (ITO), are generally used.
  • ITO indium tin oxide
  • the anode (1) contains an organic material, for example polyaniline, as described for example in Nature, Vol. 357, Pages 477 to 479 (June 11, 1992). At least either the anode or the cathode should be at least partially transparent in order to be able to decouple the light formed.
  • organic material for example polyaniline
  • Suitable hole transport materials for the layer (2) of the OLED according to the invention are disclosed, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pages 837 to 860, 1996. Both hole transporting molecules and polymers can be used as hole transport material.
  • Commonly used hole transporting molecules are selected from the group consisting of 4,4'-bis [N- (1-naphthyl) -N-phenyl-amino] biphenyl ( ⁇ -NPD), N, N'-diphenyl-N , N'-bis (3-methylphenylH1, 1'-biphenyl] -4,4'-diamine (TPD) 1 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 ⁇ -methylphenyO-NNN'.N' ⁇ .
  • ⁇ -phenylenediamine PDA
  • ⁇ -phenyl-4-N N-diphenylaminostyrene
  • DEH p- (diethylamino) -benzaldehyde diphenylhydrazone
  • triphenylamine TPA
  • bis [ 4- (N, N -diethylamino) -2-methylphenyl) (4-methylphenyl) ethane MPMP
  • 1,2-trans-bis (9H-carbazol-9-yl) cyclobutane DCZB
  • N, N, N ', N'-tetrakis (4-methylphenyl) - (1, 1 -biphenyl) -4,4'-diamine TAB
  • 4,4 1, 4 "-tris
  • the employed hole-transporting polymers are selected from the group consisting of polyvinylcarbazoles, (phenylmethyl) polysilanes and polyanilines. It is also possible to obtain holes-transporting polymers by doping holes-transporting molecules into polymers such as polystyrene and polycarbonate. Suitable hole transporting molecules are the molecules already mentioned above.
  • oxinoid compounds such as tris (8-quinolinolato) aluminum (Alq 3 )
  • phenanthroline-based compounds such as 2,9-dimethyl-4,7-diphen
  • the layer (4) can serve both to facilitate the electron transport and as a buffer layer or as a barrier layer, in order to avoid quenching of the exciton at the boundary surfaces of the layers of the OLED.
  • the layer (4) improves the mobility of the electrons and reduces quenching of the exciton.
  • hole transport materials and electron transport materials some may serve several functions.
  • some of the electron-conducting materials are simultaneously hole-blocking materials if they have a deep HOMO.
  • the charge transport layers can also be electronically doped in order to improve the transport properties of the materials used, on the one hand to make the layer thicknesses more generous (avoidance of pinholes / short circuits) and, on the other hand, to minimize the operating voltage of the device.
  • the hole transport materials can be doped with electron acceptors, for example phthalocyanines or arylamines such as TPD or TDTA can be doped with tetrafluorotetracyanchinodimethane (F4-TCNQ).
  • the electron transport materials may be doped with alkali metals, for example Alq 3 with lithium.
  • the electronic doping is known to the person skilled in the art and described, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, no. 1, 1 July 2003 (p-doped organic layers); AG 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.
  • the cathode (5) is an electrode which serves to introduce electrons or negative charge carriers.
  • Suitable materials for the cathode are selected from the group consisting of alkali metals of group Ia, for example Li, Cs, alkaline earth metals of group IIa, for example calcium, barium or magnesium, metals of group IIb of the Periodic Table of the Elements (old IUPAC). Version) comprising the lanthanides and actinides, for example samarium.
  • metals such as aluminum or indium, as well as combinations of all the metals mentioned.
  • lithium-containing organometallic compounds or LiF can be applied between the organic layer and the cathode to reduce the operating voltage.
  • the OLED according to the present invention may additionally contain further layers which are known to the person skilled in the art.
  • a layer can be applied between the layer (2) and the light-emitting layer (3), which facilitates the transport of the positive charge and / or adapts the band gap of the layers to one another.
  • this further layer can serve as a protective layer.
  • additional layers may be present between the light-emitting layer (3) and the layer (4) in order to facilitate the transport of the negative charge and / or to adapt the band gap between the layers to one another.
  • this layer can serve as a protective layer.
  • the OLED according to the invention contains at least one of the further layers mentioned below: a hole injection layer between the anode (1) and the hole-transporting layer (2); a block 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
  • the OLED does not have all of the layers (1) to (5) mentioned, for example an OLED having the layers (1) (anode), (3) (light-emitting layer) and (5 ) (Cathode), wherein the functions of the layers (2) (hole-transporting layer) and (4) (electron-transporting layer) are taken over by the adjacent layers.
  • OLEDs comprising layers (1), (2), (3) and (5) or layers (1), (3), (4) and (5) are also suitable.
  • Suitable materials for the individual layers are known to those skilled in the art and e.g. in WO 00/70655.
  • each of the mentioned layers of the OLED according to the invention can be developed from two or more layers. Furthermore, it is possible that some or all of the layers (1), (2), (3), (4), and (5) are surface treated to increase the efficiency of charge carrier transport. The selection of materials for each of said layers is preferably determined by obtaining an OLED having a high efficiency and lifetime.
  • the preparation of the OLEDs according to the invention can be carried out by methods known to the person skilled in the art.
  • the OLED according to the invention is produced by successive vapor deposition (vapor deposition) of the individual layers on a suitable substrate.
  • Suitable substrates are, for example, glass or polymer films.
  • vapor deposition conventional techniques can be used such as thermal evaporation, chemical vapor deposition and others.
  • the organic layers can be coated from solutions or dispersions in suitable solvents, using coating techniques known to those skilled in the art.
  • the various layers have the following thicknesses: anode (1) 500 to 5000 A, preferably 1000 to 2000 A; Hole-transporting layer (2) 50 to 1000 A, preferably 200 to 800 A, light-emitting layer (3) 10 to 1000 A, preferably 100 to 800 A 1 electron-transporting layer (4) 50 to 1000 A, preferably 200 to 800 A, cathode (5) 200 to 10,000 A 1, preferably 300 to 5000 A.
  • the location of the recombination zone of holes and electrons in the inventive OLED and thus the emission spectrum of the OLED can be affected by the relative thickness of each layer. That is, the thickness of the electron transport layer should preferably be selected so that the electron / holes recombination zone is in the light-emitting layer.
  • the ratio of the layer thicknesses of the individual layers in the OLED depends on the materials used.
  • the layer thicknesses of optionally used additional layers are known to the person skilled in the art.
  • OLEDs can be obtained with high efficiency.
  • the efficiency of the OLEDs according to the invention can be further improved by optimizing the other layers.
  • highly effi ⁇ cient cathodes such as Ca or Ba, optionally in combination with an intermediate layer of LiF, can be used.
  • Shaped substrates and new hole-transporting materials which bring about a reduction in the operating voltage or an increase in the quantum efficiency can likewise be used in the OLEDs according to the invention.
  • additional layers may be present in the OLEDs to adjust the energy levels of the various layers and to facilitate electroluminescence.
  • the OLEDs according to the invention can be used in all devices where electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile screens. Stationary screens are e.g. Screens of computers, televisions, screens in printers, kitchen appliances, billboards, lighting and signboards. Mobile screens are e.g. Screens in mobile phones, laptops, digital cameras, vehicles and destination displays on buses and trains.
  • Stationary screens are e.g. Screens of computers, televisions, screens in printers, kitchen appliances, billboards, lighting and signboards.
  • Mobile screens are e.g. Screens in mobile phones, laptops, digital cameras, vehicles and destination displays on buses and trains.
  • the phenothiazine-S-oxide or phenothiazine-S.S-dioxide derivatives of the formula I used according to the invention can be used in OLEDs with inverse structure.
  • the compounds of the formula I used according to the invention in these inverse OLEDs are preferably used in turn as matrix materials in the light-emitting layer.
  • the structure of inverse OLEDs and the usual materials used therein are known in the art.
  • the precipitate was filtered off, washed successively with 125 ml of ethanol and hot water and dried at 70 0 C in vacuo.
  • Example 5 a) 1, 3-phenylene-10,10 '-bis (phenothiazine)
  • the preparation was carried out according to D. Li et al., Dyes and Pigments 49 (2001) 181-186.
  • the crude product (16.6 g) was refluxed in 500 ml of ethanol for 2 hours and then diluted with 200 ml of water. The precipitate was filtered off, dried in vacuo at 80 0 C (10.5 g) and dissolved in 150 ml of toluene. The solution was filtered through silica gel. After concentrating the filtrate, 7.22 g light brown Mikrokris- were metals having a melting point of 192 -. 200 0 C obtained.
  • Example 12 Benzoic acid 4- (5,5-dioxo-phenothiazin-10-yl) -phenyl ester
  • a reaction mixture of 21, 40 g (95.3 mmol) of 98% 4-iodophenol, 12.19 g (95.3 mmol) of 99% benzyl chloride, 20.73 g (150 mmol) of potassium carbonate and 250 ml of acetone were added Heated to reflux and heated to boiling for 30 hours. After cooling to room temperature, the reaction mixture was filtered. The filtrate was concentrated and then cooled in an ice bath, whereupon a precipitate precipitated out. This was separated via a blue band filter and then dried.
  • the crude product (23.22 g) was recrystallized from 70 ml of ethanol. 17.20 g (58% of theory) of colorless microcrystals having a melting point of 61.degree.-62.degree. C. (Lit 62 0 C) were obtained.
  • the beige crude product (6.52 g) was recrystallized from 125 ml of ethanol. 4.79 g (45% of theory) of beige-colored microcrystals having a melting point of 144 ° -146 ° C. were obtained.
  • Example 15 10- (3,5-Difluorophenyl) phenothiazine-5,5-dioxide
  • the filtrate was chromatographed on silica gel with an eluent of 40 parts hexane and 1 part ethyl acetate. After removal of the solvent-means of the residue at 8O 0 C and 1.8 X NG "was 5 mbar, with a portion of the substance sublimed. The residual in the original solid was recrystallized from 40 ml of ethanol. There was added 1.18 g (7.6% of theory) of analytically pure colorless microcrystals having a melting point of 111-115 ° C.
  • the colorless solid (1.87 g) was dissolved in 20 ml of a mixture of 99 parts of methylene chloride and one part of methanol and purified on silica gel. The purified solution was concentrated to dryness. After this Drying of the residue at 70 ° C in vacuo, this was recrystallized from 10 ml of acetic acid. There were 1.09 g
  • the ITO substrate used as the anode is first with commercial judgesmit ⁇ stuffs for the LCD production (Deconex 20NS ® and neutralizing agent 25ORGAN- ACID ®) and subsequently cleaned in an acetone / isopropanol mixture in an ultrasonic bath. To remove possible organic residues, the substrate is exposed to a continuous flow of ozone for another 25 minutes in an ozone furnace. This treatment also improves hole injection of the ITO.
  • Example 5b in a thickness of 20 nm, with the former compound acting as emitter, the latter as matrix material. Thereafter, a BCP Lochblocker- and electron conductor layer in a thickness of 47.5 nm, a 0.75 nm thick lithium fluoride layer and finally a 110 nm thick Al electrode is evaporated.
  • electroluminescence spectra are recorded at different currents or voltages. Furthermore, the current voltage voltage characteristic in combination with the radiated light output. The light output can be converted into photometric variables by calibration with a luminance meter.

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  • Materials Engineering (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne l'utilisation de phénothiazin-S-oxydes et de phénothiazine-S,S-dioxydes en tant que matières matricielles pour diodes luminescentes organiques, en particulier en tant que matières matricielles dans la couche luminescente des diodes luminescentes organiques. L'invention a également pour objet des diodes luminescentes organiques comprenant une couche luminescente qui contient au moins un phénothiazin-S-oxyde ou un phénothiazine-S,S-dioxyde en tant que matière matricielle, ainsi qu'au moins une autre substance répartie dans celle-ci, en tant qu'émetteur. L'invention se rapporte aussi à des couches luminescentes qui contiennent au moins un phénothiazin-S-oxyde ou un phénothiazine-S,S-dioxyde en tant que matière matricielle, ainsi qu'au moins une autre substance répartie dans celle-ci, en tant qu'émetteur, ainsi que des couches luminescentes qui consistent en un ou plusieurs phénothiazin-S-oxydes ou phénothiazine-S,S-dioxydes en tant que matière matricielle, ainsi qu'au moins une autre substance répartie dans celle-ci, en tant qu'émetteur. L'invention concerne aussi des diodes luminescentes organiques qui comprennent des couches luminescentes correspondantes, ainsi que des dispositifs qui contiennent des diodes luminescentes organiques correspondantes.
EP05808298A 2004-11-25 2005-11-23 Utilisation de phenothiazin-s-oxydes et de phenothiazine-s,s-dioxydes en tant que matieres matricielles pour diodes luminescentes organiques Withdrawn EP1817805A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004057073A DE102004057073A1 (de) 2004-11-25 2004-11-25 Verwendung von Phenothiazin-S-oxiden und -S,S-dioxiden als Matrixmaterialien für organische Leuchtdioden
PCT/EP2005/012527 WO2006056416A1 (fr) 2004-11-25 2005-11-23 Utilisation de phenothiazin-s-oxydes et de phenothiazine-s,s-dioxydes en tant que matieres matricielles pour diodes luminescentes organiques

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EP1817805A1 true EP1817805A1 (fr) 2007-08-15

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US (1) US20080018238A1 (fr)
EP (1) EP1817805A1 (fr)
JP (1) JP2008522389A (fr)
KR (1) KR20070090214A (fr)
CN (1) CN101065857A (fr)
DE (1) DE102004057073A1 (fr)
WO (1) WO2006056416A1 (fr)

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KR101223720B1 (ko) * 2006-06-05 2013-01-17 삼성디스플레이 주식회사 고분자 화합물 및 이를 이용한 유기 발광 소자
JP4878932B2 (ja) * 2006-06-23 2012-02-15 株式会社リコー アクリル酸エステル及びヒドロキシ化合物、該アクリル酸エステルの（共）重合体、それを用いた電子写真感光体、画像形成方法、画像形成装置及び画像形成装置用プロセスカートリッジ
WO2008132085A1 (fr) * 2007-04-26 2008-11-06 Basf Se Silanes contenant des groupes phénothiazine-s-oxyde ou phénothiazine-s,s-dioxyde et utilisation de ceux-ci dans des diodes électroluminescentes organiques
GB2473815A (en) * 2009-09-18 2011-03-30 Zumtobel Gmbh Electroluminescent material and devices
KR101174880B1 (ko) 2010-04-02 2012-08-17 삼성디스플레이 주식회사 고분자 화합물 및 이를 포함하는 유기 발광 소자
US10177312B2 (en) 2011-05-05 2019-01-08 Merck Patent Gmbh Compounds for electronic devices
US20150239880A1 (en) * 2012-08-30 2015-08-27 Kyushu University National University Corp. Light emitting material, compound, and organic light emitting device using the same
KR101466777B1 (ko) * 2013-03-20 2014-12-01 건국대학교 산학협력단 막대형 반응성 액정화합물
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WO2006056416A1 (fr) 2006-06-01
DE102004057073A1 (de) 2006-06-08
KR20070090214A (ko) 2007-09-05
CN101065857A (zh) 2007-10-31
US20080018238A1 (en) 2008-01-24
JP2008522389A (ja) 2008-06-26

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