WO2015027060A1 - Complexes métalliques tétradentates phosphorescents présentant des spectres d'émission modifiés - Google Patents

Complexes métalliques tétradentates phosphorescents présentant des spectres d'émission modifiés Download PDF

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WO2015027060A1
WO2015027060A1 PCT/US2014/052084 US2014052084W WO2015027060A1 WO 2015027060 A1 WO2015027060 A1 WO 2015027060A1 US 2014052084 W US2014052084 W US 2014052084W WO 2015027060 A1 WO2015027060 A1 WO 2015027060A1
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group
substituted
unsubstituted
mono
mmol
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PCT/US2014/052084
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Jian Li
Guijie Li
Jason Brooks
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Arizona Board Of Regents On Behalf Of Arizona State University
Universal Display Corporation
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Priority claimed from US14/300,832 external-priority patent/US9673409B2/en
Application filed by Arizona Board Of Regents On Behalf Of Arizona State University, Universal Display Corporation filed Critical Arizona Board Of Regents On Behalf Of Arizona State University
Priority to US14/913,306 priority Critical patent/US9899614B2/en
Publication of WO2015027060A1 publication Critical patent/WO2015027060A1/fr

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    • 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 Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0086—Platinum compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present disclosure relates to multidentate metal complexes and compositions including the same that can be useful as emitters in display and lighting applications, as well as devices including these complexes and compositions.
  • photo-absorbing devices such as solar- and photo-sensitive devices, organic light emitting diodes (OLEDs), photo-emitting devices, or devices capable of both photo-absorption and emission and as markers for bio-applications.
  • OLEDs organic light emitting diodes
  • photo-emitting devices or devices capable of both photo-absorption and emission and as markers for bio-applications.
  • FIG. 1 depicts an example of an OLED.
  • OLED 100 may include a layer of indium tin oxide (ITO) as an anode 102, a layer of hole-transporting materials (HTL) 104, a layer of emissive materials (EML) 106 including emitter(s) and host(s), a layer of electron-transporting materials (ETL) 108, and a metal cathode layer 110 on substrate 1 12.
  • the emission color of OLED 100 may be determined by the emission energy (optical energy gap) of the emitter(s) in the layer of emissive materials.
  • Multidentate metal complexes and compositions including one or more of the complexes described herein can be useful as emitters in organic light emitting diodes (OLEDs), displays and lighting applications, and photovoltaic devices.
  • OLEDs organic light emitting diodes
  • displays and lighting applications and photovoltaic devices.
  • a chemical structural change will affect the electronic structure of the compounds, which thereby affects the optical properties of the compounds (e.g., emission and absorption spectra).
  • the compounds described herein can be tailored or tuned to a particular emission or absorption energy.
  • the optical properties of the compounds disclosed herein can be tuned by varying the structure of the ligand surrounding the metal center. For example, compounds having a ligand with electron donating substituents or electron withdrawing substituents generally exhibit different optical properties, including different emission and absorption spectra.
  • the emission spectra of the compounds can be modified by altering one or more of the substitution groups of the ancillary ligands.
  • one or more features of an emission spectrum becomes narrower or broader, exhibits a blue shift or a red shift, or a combination thereof.
  • a composition includes one or more compounds of the formulas:
  • (L 1A L 2 ) represents an emitting portion of the compound
  • (L A L 4 ) represents an ancillary portion of the compound
  • L , L and L each independently represents a substituted or unsubstituted aromatic ring, heterocyclic group, carbene group, or N-heterocyclic carbene,
  • L 4 represents a substituted or unsubstituted aromatic ring, heterocyclic group, carbene group, N-heterocyclic carbene, chlorine (CI), fluorine (F), nitrile, substituted alkyl, substituted alkenyl, or C3-C6 alkynyl,
  • L 2 and L 3 are linked directly or through a linking atom A 1 , wherein A 1 represents oxygen (0), sulfur (S), nitrogen ( ⁇ ), carbon (C), phosphorous (P), silicon (Si), or boron (B), L 3 and L 4 are unlinked, linked directly, or, when L 4 represents a substituted or unsubstituted aromatic ring, heterocyclic group, carbene group, or N-heterocyclic carbene, linked through a linking atom A 2 , wherein A 2 represents oxygen (0), sulfur (S), nitrogen ( ⁇ ), carbon (C), phosphorous (P), silicon (Si), or boron (B),
  • V 1 , V 2 , V 3 and V 4 represent coordinated atoms of L 1 , L 2 , L 3 or L 4 , respectively, wherein V 1 , V 2 , V 3 and V 4 each independently represents nitrogen ( ⁇ ), carbon (C), phosphorous (P), boron (B), or silicon (Si),
  • M represents platinum (Pt), gold (Au), iridium (Ir), rhodium (Rh), ruthenium (Ru), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), mercury (Hg), cadmium (Cd), or zirconium (Zr), and
  • R , R b , R c and R d each independently represents mono-, di-, tri, or tetra-substitution, and each independently represents one or more of hydrogen, deuterium, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted mono- or dialkylamino group, a substituted or unsubstituted mono- or diarylamino group, a substituted or unsubstitute
  • R a , R b , R c and R d may not be hydrogen.
  • Implementations may include one or more of the following features.
  • the polymeric group includes a polyalkylene, a polyether, or a polyester.
  • R a is fused to L 1
  • R b is fused to L 2
  • R c is fused to L 3
  • R d is fused to L 4 .
  • the composition, or a compound of the composition may have a neutral charge.
  • a light emitting device in a second general aspect, includes the composition of the first general aspect.
  • the light emitting device includes an organic light emitting diode.
  • the light emitting device is an organic light emitting diode.
  • a device in a third general aspect, includes the composition of the first general aspect or the light emitting device of the second general aspect.
  • the device may include, for example, a full color display, a photovoltaic device, or a luminescent or phosphorescent display device.
  • the device includes an organic light emitting diode. In certain cases, the device is an organic light emitting diode.
  • FIG. 1 depicts an organic light emitting device (OLED).
  • FIG. 2 shows emission spectra of PtNIN, PtNlNMe, PtNlN-tBu, PtNlNPh and PtNlNCF 3 in CH 2 C1 2 at room temperature.
  • FIG. 3 shows emission spectra of PtON6, PtON6-tBu and PtON6Ph in CH 2 C1 2 at room temperature.
  • FIG. 4 shows emission spectra of PtONl, PtONlMe 4 , PtONlMe 5 , PtONlMe 6 , PtONl-tBu, PtONlPh, PtONlNMe 2 , PtONlF and PtONlCF 3 in CH 2 C1 2 at room temperature.
  • FIG. 5 shows emission spectra of PtONlMe 4 in CH 2 C1 2 at room temperature and in 2-methyl-THF at 77 K.
  • FIG. 6 shows emission spectra of PtONlMe 5 in CH 2 C1 2 at room temperature and in 2-methyl-THF at 77 K.
  • FIG. 7 shows emission spectra of PtONlMe 6 in CH 2 C1 2 at room temperature and in 2-methyl-THF at 77 K.
  • FIG. 8 shows emission spectra of PtONl-tBu in CH 2 C1 2 at room temperature and in 2-methyl-THF at 77 K.
  • FIG. 9 shows emission spectra of PtONlNMe 2 in CH 2 C1 2 at room temperature and in 2-methyl-THF at 77 K.
  • FIG. 10 shows emission spectra of PtONlPh in CH 2 C1 2 at room temperature and in 2-methyl-THF at 77K.
  • FIG. 11 shows emission spectra of PtONlF in CH 2 C1 2 at room temperature and in 2-methyl-THF at 77 K.
  • FIG. 12 shows emission spectra of PtONlCF 3 in CH 2 C1 2 at room temperature and in 2-methyl-THF at 77 K.
  • FIG. 13 shows emission spectra of PtONIN in CH 2 C1 2 at room temperature and in 2-methyl-THF at 77 K.
  • FIG. 14 shows emission spectra of PtONICz in CH 2 C1 2 at room temperature and in 2-methyl-THF at 77 K.
  • FIG. 15 shows normalized photo luminescent intensity for Composition A (PtONl) and for Composition B (PtON6).
  • FIG. 16 shows normalized photoluminescent intensity for Composition A
  • PMMA (PtONl) and for Composition B PMMA:(PtON6).
  • FIGS. 17A-17D show emission spectra and chemical structures for Pt IN, PPtNlpyCl, PtNl(acac), and PfNlppy, respectively, at room temperature (solid lines) and 77K (dotted lines).
  • the initial brightness (Lo) of devices at 20 mA/cm are presented in the inset of FIG. 19B.
  • FIG. 20A shows emission spectra of PtON7-t-Bu, PtNIN, PtN7N and PtN8ppy at room temperature;
  • FIG. 20B shows plots of external quantum efficiency vs. brightness;
  • FIG. 20C shows electroluminescent spectra;
  • FIG. 20D shows color coordinates of devices in CIE chromaticity diagram for PtON7-t-Bu, PtNIN and PtN8ppy in a general device structure of ITO/HATCN/NPD/TAPC/emitter:26mCPy/DPPS/BmPyPB/LiF/Al.
  • the chemical structures of PtON7-t-Bu, PtN7N and PtN8ppy are shown in FIG. 20D.
  • the CIE values of PtN7N are calculated based on its room temperature emission spectrum in a solution of dichloromethane.
  • ranges expressed herein as from “about” one particular value to “about” another particular value include from the one particular value and/or to the other particular value.
  • values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another aspect.
  • the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
  • there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10" is also disclosed.
  • each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
  • compositions described herein Disclosed are the components to be used to prepare the compositions described herein as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary.
  • a linking atom can connect two groups such as, for example, a N and C group.
  • the linking atom can optionally, if valency permits, have other chemical moieties attached.
  • an oxygen would not have any other chemical groups attached as the valency is satisfied once it is bonded to two atom (e.g., N or C).
  • two additional chemical moieties can be attached to the carbon.
  • cyclic structure or the like terms used herein refer to any cyclic chemical structure which includes, but is not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclic carbene,
  • the term "substituted" is contemplated to include all permissible substituents of organic compounds.
  • the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds.
  • Illustrative substituents include, for example, those described below.
  • the permissible substituents can be one or more and the same or different for appropriate organic compounds.
  • heteroatoms, such as nitrogen can have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms.
  • substitution or “substituted with” include the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc.). It is also contemplated that, in certain aspects, unless expressly indicated to the contrary, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).
  • a 1 ,” “A 2 ,” “A 3 ,” and “A 4 " are used herein as generic symbols to represent various specific substituents. These symbols can be any substituent, not limited to those disclosed herein, and when they are defined to be certain substituents in one instance, they can, in another instance, be defined as some other substituents.
  • alkyl as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, «-propyl, isopropyl, «-butyl, isobutyl, 5-butyl, ?-butyl, w-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like.
  • the alkyl group can be cyclic or acyclic.
  • the alkyl group can be branched or unbranched.
  • the alkyl group can also be substituted or unsubstituted.
  • the alkyl group can be substituted with one or more groups including, but not limited to, optionally substituted alkyl, cycloalkyl, alkoxy, amino, ether, halide, hydroxy, nitro, silyl, sulfo-oxo, or thiol, as described herein.
  • a "lower alkyl” group is an alkyl group containing from one to six (e.g., from one to four) carbon atoms.
  • alkyl is generally used to refer to both unsubstituted alkyl groups and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the specific substituent(s) on the alkyl group.
  • halogenated alkyl or “haloalkyl” specifically refers to an alkyl group that is substituted with one or more halide, e.g., fluorine, chlorine, bromine, or iodine.
  • alkoxyalkyl specifically refers to an alkyl group that is substituted with one or more alkoxy groups, as described below.
  • alkylamino specifically refers to an alkyl group that is substituted with one or more amino groups, as described below, and the like.
  • alkyl is used in one instance and a specific term such as “alkylalcohol” is used in another, it is not meant to imply that the term “alkyl” does not also refer to specific terms such as “alkylalcohol” and the like.
  • cycloalkyl refers to both unsubstituted and substituted cycloalkyl moieties
  • the substituted moieties can, in addition, be specifically identified herein; for example, a particular substituted cycloalkyl can be referred to as, e.g., an "alkylcycloalkyl.”
  • a substituted alkoxy can be specifically referred to as, e.g., a "halogenated alkoxy”
  • a particular substituted alkenyl can be, e.g., an "alkenylalcohol,” and the like.
  • cycloalkyl as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms.
  • examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and the like.
  • heterocycloalkyl is a type of cycloalkyl group as defined above, and is included within the meaning of the term “cycloalkyl,” where at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus.
  • the cycloalkyl group and heterocycloalkyl group can be substituted or unsubstituted.
  • the cycloalkyl group and heterocycloalkyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halide, hydroxy, nitro, silyl, sulfo-oxo, or thiol as described herein.
  • amine or “amino” as used herein are represented by the formula NA A A , where A , A “ , and A are independently hydrogen, optionally substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
  • alkoxy and alkoxyl as used herein to refer to an alkyl or cycloalkyl group bonded through an ether linkage; that is, an “alkoxy” group can be defined as— OA 1 where A 1 is alkyl or cycloalkyl as defined above.
  • Alkoxy also includes polymers of alkoxy
  • an alkoxy can be a polyether such as— OA— OA or
  • OA 1 — (OA 2 ) a — OA 3 where "a" is an integer of from 1 to 200 and A 1 , A 2 , and A 3 are each independently alkyl groups, cycloalkyl groups, or a combination thereof.
  • alkenyl as used herein is a hydrocarbon group of from 2 to 24 carbon atoms with a structural formula containing at least one carbon-carbon double bond.
  • the alkenyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, as described herein.
  • groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, as described here
  • cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl,
  • heterocycloalkenyl is a type of cycloalkenyl group as defined above, and is included within the meaning of the term
  • cycloalkenyl where at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus.
  • the cycloalkenyl group and heterocycloalkenyl group can be substituted or unsubstituted.
  • the cycloalkenyl group and heterocycloalkenyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein.
  • alkynyl is a hydrocarbon group of 2 to 24 carbon atoms with a structural formula containing at least one carbon-carbon triple bond.
  • the alkynyl group can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, as described herein.
  • cycloalkynyl as used herein is a non-aromatic carbon-based ring composed of at least seven carbon atoms and containing at least one carbon-carbon triple bond.
  • cycloalkynyl groups include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like.
  • heterocycloalkynyl is a type of cycloalkenyl group as defined above, and is included within the meaning of the term “cycloalkynyl,” where at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus.
  • the cycloalkynyl group and heterocycloalkynyl group can be substituted or unsubstituted.
  • the cycloalkynyl group and heterocycloalkynyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein.
  • aryl as used herein is a group that contains any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like.
  • aryl also includes “heteroaryl,” which is defined as a group that contains an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus.
  • non-heteroaryl which is also included in the term “aryl,” defines a group that contains an aromatic group that does not contain a heteroatom.
  • the aryl group can be substituted or unsubstituted.
  • the aryl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein.
  • biasing is a specific type of aryl group and is included in the definition of "aryl.”
  • Biaryl refers to two aryl groups that are bound together via a fused ring structure, as in naphthalene, or are attached via one or more carbon-carbon bonds, as in biphenyl.
  • alkylamino as used herein is represented by the formula— H(-alkyl) where alkyl is as described herein.
  • Representative examples include, but are not limited to, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, (sec-butyl)amino group, (tert-butyl)amino group, pentylamino group, isopentylamino group, (tert-pentyl)amino group, hexylamino group, and the like.
  • dialkylamino as used herein is represented by the formula— N(-alkyl) 2 where alkyl is as described herein.
  • Representative examples include, but are not limited to, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, diisobutylamino group, di(sec-butyl)amino group, di(tert-butyl)amino group, dipentylamino group, diisopentylamino group, di(tert-pentyl)amino group, dihexylamino group, N-ethyl-N-methylamino group, N-methyl-N-propylamino group, N-ethyl-N-propylamino group and the like.
  • esters as used herein is represented by the formula— OC(0)A 1 or — C(0)OA 1 , where A 1 can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl as described herein.
  • polyester as used herein is represented by the formula— (A 1 0(0)C-A 2 -C(0)0) a — or— (A'OCOjC-A ⁇ OQO))—, where A 1 and A 2 can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and "a” is an integer from 1 to 500.
  • Polyyester is as the term used to describe a group that is produced by the reaction between a compound having at least two carboxylic acid groups with a compound having at least two hydroxyl groups.
  • ether as used herein is represented by the formula A ⁇ A 2 , where A 1 and A 2 can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein.
  • polyether as used herein is represented by the formula— (A 1 0-A 2 0) a — , where A 1 and A 2 can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and "a" is an integer of from 1 to 500.
  • Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutylene oxide.
  • polymeric includes polyalkylene, polyether, polyester, and other groups with repeating units, such as, but not limited to -(CH 2 0) n -CH 3 , -(CH 2 CH 2 0) n -CH 3 ,
  • n is an integer (e.g., n > 1 or n > 2).
  • halide refers to the halogens fluorine, chlorine, bromine, and iodine.
  • heterocyclyl refers to single and multi-cyclic non-aromatic ring systems and “heteroaryl as used herein refers to single and multi-cyclic aromatic ring systems: in which at least one of the ring members is other than carbon.
  • the term includes azetidine, dioxane, furan, imidazole, isothiazole, isoxazole, morpholine, oxazole, oxazole, including, 1,2,3-oxadiazole, 1,2,5-oxadiazole and 1,3,4-oxadiazole, piperazine, piperidine, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, tetrahydrofuran, tetrahydropyran, tetrazine, including 1, 2,4,5 -tetrazine, tetrazole, including 1,2,3,4-tetrazole and 1,2,4,5-tetrazole, thiadiazole, including, 1,2,3-thiadiazole,
  • 1,2,5-thiadiazole, and 1,3,4-thiadiazole 1,2,5-thiadiazole, and 1,3,4-thiadiazole, thiazole, thiophene, triazine, including 1,3,5-triazine and 1,2,4-triazine, triazole, including, 1,2,3-triazole, 1,3,4-triazole, and the like.
  • hydroxyl as used herein is represented by the formula— OH.
  • ketone as used herein is represented by the formula A 1 C(0)A 2 , where
  • a and A can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
  • nitrile as used herein is represented by the formula— CN.
  • sil as used herein is represented by the formula— SiA 1 A 2 A 3 , where A 1 , A 2 , and A 3 can be, independently, hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein,
  • sulfo-oxo is represented by the formulas— S(0)A 1 , — S(0) 2 A 1 ,— OS(0) 2 A 1 , or— OS(0) 2 OA 1 , where A 1 can be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
  • a 1 can be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
  • sulfonyl is used herein to refer to the sulfo-oxo group represented by the formula— S(0)2A 1 , where A 1 can be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
  • sulfone as used herein is represented by the formula A 1 S(0)2A 2 , where A 1 and A 2 can be, independently, an alkyl, cycloalkyl, alkenylcycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
  • sulfoxide as used herein is represented by the formula A S(0)A , where A and A can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
  • R 1 ,” “R 2 ,” “R 3 ,” “R n ,” where n is an integer, as used herein can, independently, possess one or more of the groups listed above.
  • R 1 is a straight chain alkyl group
  • one of the hydrogen atoms of the alkyl group can optionally be substituted with a hydroxyl group, an alkoxy group, an alkyl group, a halide, and the like.
  • a first group can be incorporated within second group or, alternatively, the first group can be pendant (i.e., attached) to the second group.
  • an alkyl group comprising an amino group the amino group can be incorporated within the backbone of the alkyl group.
  • the amino group can be attached to the backbone of the alkyl group.
  • the nature of the group(s) that is (are) selected will determine if the first group is embedded or attached to the second group.
  • a structure of a compound may be represented by a formula:
  • n typically an integer. That is, R" is understood to represent five independent substituents, R" (a) , R n(b) , R" (c) , R" (d) , R" (e) .
  • independent substituents it is meant that each R substituent can be independently defined. For example, if in one instance R" ⁇ is halogen, then R M(b) is not necessarily halogen in that instance.
  • R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , etc. are made in chemical structures and moieties disclosed and described herein. Any description of R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , etc. in the specification is applicable to any structure or moiety reciting R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , etc. respectively, unless otherwise noted.
  • Multidentate (e.g., tetradentate) cyclometalated complexes are described herein. In some cases, such complexes can be incorporated with heptacyclic or higher order materials. In another aspect, such complexes can be useful, for example, in displays and lighting applications.
  • composition includes one or more compounds.
  • the compounds disclosed herein can include one or more of platinum (Pt) complexes, palladium (Pd) complexes, gold (Au) complexes, iridium (Ir) complexes, rhodium (Rh) complexes, ruthenium (Ru) complexes, iron (Fe) complexes, cobalt (Co) complexes, nickel (Ni) complexes, copper (Cu) complexes, zinc (Zn) complexes, silver (Ag) complexes, mercury (Hg) complexes, cadmium (Cd) complexes, zirconium (Zr) complexes, or other metal complexes not specifically recited herein which are capable of emitting light and are thus useful as an emissive materials in devices.
  • the present application discloses platinum (Pt), palladium (Pd), gold (Au), iridium (Ir), rhodium (Rh), ruthenium (Ru), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), mercury (Hg), cadmium (Cd), and/or zirconium (Zr) complexes that can emit electromagnetic radiation.
  • the emission of the complexes can be tuned (e.g. from ultraviolet to near-infrared), by, for example, modifying the ligand structure.
  • the complexes are emissive over a majority of the visible spectrum.
  • the complexes can emit light over a range of from about 400 nm to about 700 nm. In another aspect, the complexes have improved stability and efficiency over traditional emission complexes. In yet another aspect, the complexes can be useful as luminescent labels in, for example, bio-applications, anti-cancer agents, or a combination thereof. In another aspect, the complexes can be useful in light emitting devices, such as, for example, emitters in organic light emitting diodes (OLEDs), compact fluorescent lamps (CFLs), light emitting diodes (LEDs), incandescent lamps, and combinations thereof.
  • OLEDs organic light emitting diodes
  • CFLs compact fluorescent lamps
  • LEDs light emitting diodes
  • incandescent lamps and combinations thereof.
  • R, R a , R b , R c , R d , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , Rl 2 , R 13 and R 14 can, in various aspects, each independently represent a hydrogen, a deuterium, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substututed or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substututed or unsubstituted aralkyl group, a substututed or unsubstituted alkenyl group, a substututed or unsubstituted alkynyl group, a sub
  • any two or more substitutions can represent the same or a different group.
  • the letters "m”, “n”, “o”, “p”, “q” and “r” can, in various aspects, represent an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12 ... etc., and any two or more letters can represent the same or a different number.
  • one or more of R, R a , R b , R c , R d , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , Rl 2 , R 13 and R 14 may not be hydrogen.
  • composition may include one or more compounds of the formulas:
  • (L 1 L 2 ) represents an emitting portion of the compound
  • (L 3A L 4 ) represents an ancillary portion of the compound
  • L , L and L each independently represents a substituted or unsubstituted aromatic ring, heterocyclic group, carbene group, or N-heterocyclic carbene,
  • L 4 represents a substituted or unsubstituted aromatic ring, heterocyclic group, carbene group, N-heterocyclic carbene, chlorine (CI), fluorine (F), nitrile, substituted alkyl, substituted alkenyl, or C3-C6 alkynyl,
  • L 2 and L 3 are linked directly or through a linking atom A 1 , wherein A 1 represents oxygen (0), sulfur (S), nitrogen ( ⁇ ), carbon (C), phosphorous (P), silicon (Si), or boron (B),
  • L 3 and L 4 are unlinked, linked directly, or, when L 4 represents a substituted or unsubstituted aromatic ring, heterocyclic group, carbene group, or N-heterocyclic carbene, linked through a linking atom A 2 , wherein A 2 represents oxygen (0), sulfur (S), nitrogen ( ⁇ ), carbon (C), phosphorous (P), silicon (Si), or boron (B),
  • V 1 , V 2 , V 3 and V 4 represent coordinated atoms of L 1 , L 2 , L 3 or L 4 , respectively, wherein V 1 , V 2 , V 3 and V 4 each independently represents nitrogen ( ⁇ ), carbon (C), phosphorous (P), boron (B), or silicon (Si),
  • M represents platinum (Pt), gold (Au), iridium (Ir), rhodium (Rh), ruthenium (Ru), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), mercury (Hg), cadmium (Cd), or zirconium (Zr), and
  • R , R b , R° and R d each independently represents mono-, di-, tri, or tetra-substitution, and each independently represents one or more of hydrogen, deuterium, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted mono- or dialkylamino group, a substituted or unsubstituted mono- or diarylamino group, a substituted or unsubstituted
  • R a , R b , R c and R d may not be hydrogen.
  • R is fused to ligand L 1
  • R b is fused to ligand L 2
  • R c is fused to ligand L 3
  • R d is fused to ligand L 4 .
  • the composition, each compound therein, or both are neutral in charge.
  • polymeric includes a polyalkylene, a polyether, a polyester, or a combination thereof.
  • a chemical structural change will affect the electronic structure of the compounds, which thereby affects the optical properties of the compounds (e.g., emission and absorption spectra).
  • the compounds described herein can be tailored or tuned to a particular emission or absorption energy.
  • the optical properties of the compounds disclosed herein can be tuned by varying the structure of the ligand surrounding the metal center. For example, compounds having a ligand with electron donating substituents or electron withdrawing substituents generally exhibit different optical properties, including different emission and absorption spectra,
  • the emission spectra of the compounds can be modified by altering one or more of the substitution groups of the ancillary ligands.
  • one or more features of an emission spectrum become narrower or broader, exhibits a blue shift or a red shift, or a combination thereof.
  • L' 5 L" "L' and " L' are intended to illustrate that L and L' are either linked directly or that L and L' are linked by a linkage group
  • each of the linkage groups may independently represent oxygen (O), sulfur (S), nitrogen (N), phosphorous (P), carbon (C), silicon (Si), or boron (B).
  • O oxygen
  • S sulfur
  • N nitrogen
  • P phosphorous
  • C carbon
  • Si silicon
  • B boron
  • ⁇ , / ⁇ and ⁇ may each independently represent the following:
  • R, R 1 , and R 2 each independently represents hydrogen, deuterium, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, an amino group, a mono- or dialkylamino group, a mono-
  • alkoxycarbonyl group an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfmyl group, a ureido group, a phosphoramide group, a mercapto group, a sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof.
  • V 1 , V 2 , V 3 and V 4 represent atoms coordinated to L 1 , L 2 , L 3 or L 4 , where V 1 , V 2 , V 3 , and V 4 may each independently represent nitrogen (N), carbon (C), phosphorous (P), boron (B), or silicon (Si).
  • N nitrogen
  • C carbon
  • P phosphorous
  • B boron
  • Si silicon
  • ⁇ and / ⁇ may each independently represent the followin :
  • R, , R and R each independently represents hydrogen, deuterium, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, an alkoxycarbonyl group, an acyloxy group, an acylamino
  • / ⁇ may represent the following:
  • n is an integer
  • R 1 , R 2 , R 3 , and R 4 each independently represents hydrogen, deuterium, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, an alkoxycarbonyl group, an acyloxy
  • R, R and R " each independently represents hydrogen, deuterium, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, an
  • alkoxycarbonyl group an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfmyl group, a ureido group, a phosphoramide group, a mercapto group, a sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof.
  • R, R 1 , and R 2 each independently represents mono-, di-, tri, or tetra-substitution, and independently represents hydrogen, deuterium, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group,
  • n, and o each independently represents an integer from 1 to 4 indicating mono-, di-, tri, or tetra-substitution
  • R 1 and R 2 each independently represents hydrogen, deuterium, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group,
  • R 1 and R 2 each independently represents hydrogen, deuterium, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group,
  • a composition may include one or more of the following:
  • compositions disclosed herein include one or more of the following:
  • compositions disclosed herein include one or more of the following:
  • compositions disclosed herein include one or more of the
  • compositions disclosed herein include one or more of the following:
  • compositions disclosed herein include one or more of the following:
  • compositions disclosed herein include one or more of the following:
  • compositions or compounds disclosed herein include one or more derivatives and/or analogues of the compounds described herein, provided that such compounds exhibit desirable properties and have emission or absorption spectra or both that can be tuned via the selection of appropriate ligands.
  • compositions disclosed herein are generally suited for use in a wide variety of optical and electro-optical devices, including, for example, photo-absorbing devices such as solar- and photo-sensitive devices, photovoltaic devices, organic light emitting diodes (OLEDs), photo-emitting devices, or devices capable of both photo-absorption and emission and as markers for bio-applications.
  • Compositions described herein include one or more multidentate metal complexes, or compounds.
  • a composition includes one multidentate metal complex
  • a composition includes two or more multidentate metal complexes.
  • multidentate metal complexes described herein are combined to cover a range of wavelengths.
  • FIG. 2 shows emission spectra of PtNIN, PtNlNMe, PtNlN-tBu, PtNlNPh and PtNlNCF 3 in CH 2 C1 2 at room temperature.
  • FIG. 3 shows emission spectra of PtON6, PtON6-tBu and PtON6Ph in CH2CI2 at room temperature.
  • FIG. 2 shows emission spectra of PtNIN, PtNlNMe, PtNlN-tBu, PtNlNPh and PtNlNCF 3 in CH 2 C1 2 at room temperature.
  • FIG. 3 shows emission spectra of PtON6, PtON6-tBu and PtON6Ph in CH2CI2 at room temperature.
  • compositions disclosed herein are used as host materials for OLED applications, such as full color displays.
  • compositions disclosed herein can be useful in a wide variety of applications, such as, for example, lighting devices.
  • one or more of the complexes can be useful as host materials for an organic light emitting display device.
  • compositions disclosed herein are useful in a variety of applications, for example, as light emitting materials.
  • the compounds can be useful in organic light emitting diodes (OLEDs), luminescent devices and displays, and other light emitting devices.
  • compositions disclosed herein can provide improved efficiency and/or operational lifetimes in lighting devices.
  • compositions disclosed herein can provide improved efficiency and/or operational lifetimes for organic light emitting devices as compared to conventional materials.
  • compositions disclosed herein can be useful as, for example, host materials for OLEDs, lighting applications, and combinations thereof.
  • compositions disclosed herein can be prepared using a variety of methods, including, but not limited to those recited in the examples provided herein,
  • Temperatures, catalysts, concentrations, reactant compositions, and other process conditions can vary, and one of skill in the art, in possession of this disclosure, could readily select appropriate reactants and conditions for a desired complex.
  • Platinum complex PtNIN can be prepared according to the following scheme: Just recrystalized in
  • 2-bromo-9H-carbazole 1 (8.33 g, 34 mmol, 1.0 eq)
  • 2-bromopyridine (10.61 g, 68 mmol, 2.0 eq)
  • L-proline (0.78 g, 6.8 mmol, 0.2 eq)
  • K 2 C0 3 11.75 g, 85 mmol, 2.5 eq
  • Cul (0.44 g, 3.4 mmol, 0.1 eq) and DMSO (68 mL) were added. The mixture was bubbled with nitrogen for 10 minutes and then the tube was sealed.
  • the tube was taken out of the glove box and heated to 90 °C in an oil bath. After stirring at 90 °C for 3 days, the mixture was cooled to ambient temperature and quenched with water (250 mL). The mixture was then extracted with ethyl acetate three times and the combined organic layer was washed with water three times, dried over magnesium sulfate, then filtered and washed with ethyl acetate. The filtrate was concentrated and the residue was purified through column chromatography on silica gel using hexane and ethyl acetate (20 : 1 - 10 : 1 ) as eluent to obtain the desired product,
  • the tube was taken out of the glove box and heated to 105-1 15 °C in an oil bath. The reaction was monitored by TLC and about 68 hours later the starting material 5 was consumed completely. Then the mixture was cooled to ambient temperature, diluted with ethyl acetate, then filtered and washed with ethyl acetate. The filtrate was concentrated and the residue was purified through column chromatography on silica gel using hexane and ethyl acetate (10: 1-3: 1) as eluent to obtain the desired product, l-(2'-nitrobiphenyl-4-yl)-lH-pyrazole 4, as a off-white solid (7.5 g in 94% yield).
  • l-(2'-nitrobiphenyl-4-yl)-lH-pyrazole 4 (7.23 g, 27.26 mmol) was added to a three-necked flask equipped with a magnetic stir bar and a condenser. The flask was evacuated and backfilled with nitrogen. The evacuation and backfill procedure was repeated twice, and then P(OEt) 3 (150 mL) was added under nitrogen. The mixture was stirred in an oil bath at a temperature of 150-165 °C for 24 hours. The mixture was then cooled and the excess P(OEt) 3 was removed by distillation under high vacuum. The residue was recrystallized in ethyl acetate to yield the desired product as a white solid (3.60 g).
  • the mixture was bubbled with nitrogen for 10 minutes and then the tube was sealed.
  • the tube was taken out of the glove box and heated to 95-105 °C in an oil bath.
  • the reaction was monitored by TLC and about 6 hours later the starting material 5 was consumed completely.
  • the mixture was cooled to ambient temperature and diluted with ethyl acetate.
  • the mixture was concentrated and the residue was purified through column chromatography on silica gel using hexane and ethyl acetate (10: 1-5: 1-3: 1) as eluent to obtain the desired product,
  • the tube was taken out of the glov e box and the mixture was stirred at room temperature for 20 hours. Then the mixture was heated to 105-1 15 °C in an oil bath and stirred at that temperature for three days, cooled to ambient temperature and water (180 mL) was added slowly. After stirring at room temperature for 10 minutes, the precipitate was filtered off and washed with water three times. Then the solid was dried in air under reduced pressure. The collected solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain the desired product,
  • FIG. 1 shows an emission spectrum of PtNIN in CH 2 C1 2 at room temperature.
  • Platinum complex PtNlNMe can be prepared according to the followin scheme:
  • FIG. 1 shows an emission spectrum of PtNlNMe in CH 2 C1 2 at room temperature.
  • FIG. 1 shows an emisison spectrum of PtNlN-tBu in CH 2 C1 2 at room temperature.
  • FIG. 1 shows an emission spectrum of PtNlNPh in CH 2 C1 2 at room temperature.
  • Platinum complex PtNlNCF 3 can be prepared according to the following scheme:
  • the tube was sealed and the mixture was stirred in an oil bath at a temperature of 95-105 °C for 2 days. Then the mixture was cooled to ambient temperature. The solvent was removed under reduced pressure and the residue was purified through column chromatography on silica gel using hexane and ethyl acetate (10: 1-5: 1) as eluent to obtain the desired product,
  • FIG. 1 shows an emisison spectrum of PtNlNCF 3 in CH 2 C1 2 at room temperature.
  • Platinum complex PtON6-tBu can be prepared according to the following scheme:
  • trans- 1,2-cyclohexanediamine (123 mg, 1.08 mmol, 0.20 eq) and dioxane (12 mL) were added.
  • the mixture was bubbled with nitrogen for 30 minutes and then the tube was sealed.
  • the mixture was stirred in an oil bath at a temperature of 110 °C for three days and then cooled to ambient temperature.
  • the solvent was removed under reduced pressure and the residue was purified through column chromatography on silica gel using hexane and ethyl acetate (10: 1 -5 : 1 -3 : 1) as eluent to obtain the desired product,
  • FIG. 2 shows an emisison spectrum of PtON6-tBu in CH 2 C1 2 at room temperature. ! H NMR (DMSO-c , 400 MHz): ⁇
  • Platinum complex PtON6Ph can be prepared according to the following scheme:
  • FIG. 2 shows an emisison spectrum of PtON6Ph in CH 2 C1 2 at room temperature.
  • Platinum complex PtONl can be prepared according to the following scheme:
  • FIG. 3 shows an emisison spectrum of PtONl in CH 2 C1 2 at room temperature.
  • Platinum complex PtONlMe 4 can be prepared according to the following scheme:
  • PtONlMe 4 was synthesized according to the procedure of synthesis of PtONl.
  • FIG. 3 shows an emisison spectrum of PtOMe 4 in CH2CI2 at room temperature.
  • Platinum complex PtONlMe 5 can be prepared according to the following scheme:
  • PtONlMe 5 was synthesized according to the procedure of synthesis of PtONl .
  • PtONlMe 6 was synthesized according to the procedure of synthesis of PtONl .
  • Platinum complex PtONl-tBu can be prepared according to the following scheme:
  • PtONl-tBu was synthesized according to the procedure of synthesis of PtONl.
  • FIG. 3 shows an emission spectrum of PtONl-tBu at room temperature. Emission spectra of PtONl-tBu at room temperature in CH 2 C1 2 and at 77 K in 2-methyl-THF are shown in FIG. 9. !
  • Platinum complex PtONlNMe 2 can be prepared according to the following scheme:
  • PtONlNMe 2 was synthesized according to the procedure of synthesis of PtONl.
  • FIG. 3 shows an emission spectrum of PtONlNMe 2 at room temperature. Emission spectra of PtONlNMe 2 at room temperature in CH 2 C1 2 and at 77 K in 2-methyl-THF are shown in FIG. 9.
  • Platinum complex PtONlPh can be prepared according to the following scheme: PtONI Ph
  • PtONlPh was synthesized according to the procedure of synthesis of PtONl.
  • Platinum complex PtONlF can be prepared according to the following scheme:
  • PtONlF was synthesized according to the procedure of synthesis of PtONl.
  • Platinum complex PtONlCF 3 can be prepared according to the following scheme:
  • PtONlCF 3 was synthesized according to the procedure of synthesis of PtONl.
  • FIG. 3 shows an emission spectrum of PtONlCF 3 at room temperature. Emission spectra of PtONlCF 3 at room temperature in CH 2 C1 2 and at 77 K in 2-methyl-THF are shown in FIG. 12. !
  • Platinum complex PtONIN can be prepared according to the following scheme:
  • PtONIN was synthesized according to the procedure of synthesis of PtONl.
  • Platinum complex PtONICz can be prepared according to the following scheme:
  • PtONICz was synthesized according to the procedure of synthesis of PtONl.
  • composition A PtONl
  • Photoluminescent quantum yield measurements suggested quenching interactions between the dopant and host material of the composition.
  • thin films prepared from Composition B PtON6
  • Photoluminescent (PL) spectra for Composition A and Composition B in room temperature 2-methyltetrahydrofuran solution are shown in FIG. 15, where Composition B exhibits more vibronic character and bluer and narrower emission compared to Composition A.
  • FIG. 16 shows a comparison of the emission spectra for the two compounds as doped into a polymethylmethacrylate (PMMA) optically inert matrix.
  • PMMA polymethylmethacrylate
  • Composition B exhibits a narrower emission spectrum having a more desirable blue emission. Both compounds exhibit a photoluminescent quantum yield (PLQY) in PMMA of about 80%.
  • PLQY photoluminescent quantum yield
  • the excited state lifetime in a 77 K 2-methyltetrahydrofuran solution for Composition B is 9.3 microseconds compared to 9.7 microseconds for Composition A.
  • phenyl substitution does not negatively affect the PLQY or dramatically increase the excited state lifetime by enabling a more ligand based emission.
  • molecular phosphorescent emitters with FWHM values of less than 30 nm can be prepared and color-tuned in a full visible spectrum through a judicious molecular design and can demonstrate a peak electron-to-photon conversion efficiency close to unity in a device setting.
  • QDs colloidal quantum dots
  • CdSe(ZnS) nanocrystal QDs can be continuously tunable crossing the visible spectrum, with a high PL quantum efficiency and a FWHM value less than 30nm, yet, the synthetic condition of QDs needs to be strictly controlled in order to prevent a larger particle size distribution and maintain a narrow emission spectral bandwidth.
  • QD-based LEDs have progressed rapidly in the past decade with reported device efficiency over 18% for red LEDs and reasonable device operational stability.
  • blue QD LEDs remain a big challenge due to the stringent constraints on the small particle size and uniformity.
  • blue QD LEDs exhibit very low external quantum efficiencies of much less than 1%, although a few recent reports have demonstrated greater external quantum efficiencies, with the highest reported to date of 7.1% which is much lower than state-of-the-art deep blue OLEDs ( ⁇ 20%). Additionally, there is no clear solution to solve the problem of poor interfacial energy barriers between QD emissive layers and organic transporting layers, and furthermore, the energy transfer processes at these interfaces remains poorly understood.
  • OLEDs using an organic emitter with a narrow emission spectral bandwidth (or a narrow-band emission).
  • a narrow-band emission spectrum can be easily achieved if the radiative decay process originates from atomic excited states as in lanthanide complexes, in which the emission bands as well as absorption bands (f-f transitions) are extremely sharp, in the range of 10-15 nm.
  • these emitters have not demonstrated high electron-to-photon conversion efficiency in devices due to inefficient energy transfer from organic ligand to lanthanide metal ions as well as poor energy transfer process between host materials and lanthanide based emitters.
  • rigid macrocyclic complexes like like
  • PtNlN is prepared as a green-emitting phosphorescent emitter with a FWHM of 18 nm and a S M value of 0.3 at room temperature.
  • the chemical structure of PtNlN is illustrated in the inset of FIG. 17A, where the tetradentate cyclometalatmg ligand is designed to include a rigid ligand of pyrazolyl-carbazole (functioning as a lumophore) bonded to pyridyl-carbazole (functioning as an ancillary ligand).
  • the PL quantum efficiency of PfNIN in a doped PMMA film is experimentally determined to be 0.90 ⁇ 0.05, close to unity.
  • the PtNIN retained the impressive narrow band emission in the device setting resulting in a FWHM value of only 18 nm for the 2% PtNIN device. Additionally, excimer emission was not observed at increased dopant concentrations and the EL spectra of PtNIN devices are not significantly broadening with FWHM values only increasing to 22 nm.
  • the components of ancillary ligands were also modified accordingly to t-butyl-pyridyl carbazole for blue-emitting PtON7-t-Bu and phenyl-pyridine for orange-emitting PfN8ppy.
  • the room temperature emission spectra and the chemical structures of PtON7-t-Bu, PtN7N and PfN8ppy are shown in FIGS. 20A and 20D.
  • the highly saturated colors from our developed narrowband phosphorescent emitters enable us to achieve the color coordinates within proximity to the blue and green points in the CIE chromaticity diagram.
  • Phosphorescence lifetime measurements were performed on the same spectrometer with a time correlated single photon counting method using a LED excitation source.
  • the absolute PL quantum efficiency measurements of doped PMMA film were carried out on a Hamamatsu C9920 system equipped with a xenon lamp, integrating sphere and a model CI 0027 photonic multi-channel analyzer.
  • HATCN 1,4,5,8,9, 11-hexaazatriphenylene-hexacarbonitrile.
  • NPD N,N'-diphenyl-N,N'
  • TAPC di-(4-N,N-ditolyl-amino-phenyl) cyclohexane.
  • 26mCPy 2,6-bis(N-carbazolyl) pyridine.
  • DPPS 2,6-bis(N-carbazolyl)
  • the layer sequence for OLEDs containing PtNlN of various concentrations are as below: ITO/ PEDOT:PSS/NPD (30 nm)/ TAPC (lOmn)/ x% PtNlN:26mCPy (25nm)/ P015 (lOnm)/ BmPyPB (30nm)/ LiF (lnm)/ Al (90nm) where x is either 2%, 7%, or 14% dopant concentration by mass.
  • ITO/ HATCN (10 nm)/NPD (40 nm)/ TAPC (lOnm)/ x% dopant:26mCPy (25nm)/ DPPS (lOnm)/ BmPyPB (40nm)/' LiF (lnm)/ Al (90nm) where the dopant is either PtNlN, PtON7-t-Bu, or PtN8ppy.
  • Table 2 provides a summary of device characteristics at peak value and 100 cd/m 2 for the devices with two different structures.
  • Device type I PEDOT:PSS/NPD/TAPC/x%
  • PtNlN 26mCPy/P015/BmPyPB/LiF/Al.
  • Device type II ITO/HATCN/NPD/TAPC/x%
  • the mixture was bubbled with nitrogen for 30 minutes, sealed before being taken out of the glove box, and stirred at room temperature for 20 hours followed by three days at 105-1 15 °C .
  • the mixture was cooled down to ambient temperature and water (180 mL) was added slowly. After stirring at room temperature for 10 minutes, the precipitate was filtered off and washed with water three times. Then the solid was dried in air under reduced pressure.
  • the collected solid was purified through column chromatography on silica gel using dichloromethane as eluent to obtain the desired product PtNIN as a yellow solid 872 mg in 44% yield.
  • hexafluorophosphate(V) (95 mg, 0.15 mmol, 1.0 eq), PtCL (40 mg, 0.15 mmol, 1.0 eq) and DMF (10 mL) solvent were added a pressure tube equipped with a magnetic stir bar in a nitrogen filled glove box. The pressure tube was sealed and the mixture was stirred in an oil bath at a temperature of 120 °C for three days and then cooled down to ambient temperature. The mixture was poured into water (20 mL), then extracted with dichloromethane (20 mL*3). The combined organic layer was washed with water (10 mL> ⁇ 3), dried over sodium sulphate, filtered and the filtrate was concentrated under reduced pressure.
  • the mixture was bubbled with nitrogen for 30 minutes, sealed before being taken out of the glove box, and stirred in an oil bath at a temperature of 108-1 15 °C for three days.
  • the mixture was cooled down to ambient temperature and water (90 mL) was added slowly.
  • the precipitate was filtered off and washed with water three times. Then the solid was dried in air under reduced pressure.
  • the collected solid was purified through column chromatography on silica gel using dichloromethane as eluent.
  • the filtrate was concentrated and the black precipitate was filtered off, then dried under reduced pressure to obtain the desired product PtN8ppy 23.4 mg in 5% yield. !

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Abstract

La présente invention concerne des complexes métalliques multidentates utiles comme émetteurs phosphorescents dans des applications d'affichage et d'éclairage dont les structures sont décrites dans la description. Les complexes métalliques multidentates et les compositions comprenant un ou plusieurs des complexes décrits dans la description peuvent être utiles comme émetteurs dans des diodes électroluminescentes organiques (OLED), des applications d'affichage et d'éclairage, et des dispositifs photovoltaïques. De manière générale, un changement de structure chimique affectera la structure électronique des composés, qui affectera alors les propriétés optiques des composés (par exemple, les spectres d'émission et d'absorption). Ainsi, les composés décrits dans la description peuvent être adaptés ou modifiés pour obtenir une énergie d'émission ou d'absorption particulière. Selon certains aspects, les propriétés optiques des composés décrits dans la description peuvent être modifiées en modifiant la structure du ligand entourant le centre métallique.
PCT/US2014/052084 2013-06-10 2014-08-21 Complexes métalliques tétradentates phosphorescents présentant des spectres d'émission modifiés WO2015027060A1 (fr)

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