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WO2018095379A1 - 金属有机配合物、高聚物、组合物及有机电子器件 - Google Patents

金属有机配合物、高聚物、组合物及有机电子器件 Download PDF

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Publication number
WO2018095379A1
WO2018095379A1 PCT/CN2017/112700 CN2017112700W WO2018095379A1 WO 2018095379 A1 WO2018095379 A1 WO 2018095379A1 CN 2017112700 W CN2017112700 W CN 2017112700W WO 2018095379 A1 WO2018095379 A1 WO 2018095379A1
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group
atoms
organic
substituted
alkane
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PCT/CN2017/112700
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English (en)
French (fr)
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潘君友
施超
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广州华睿光电材料有限公司
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Priority to CN201780059736.8A priority Critical patent/CN109790194B/zh
Priority to US16/463,500 priority patent/US11634444B2/en
Publication of WO2018095379A1 publication Critical patent/WO2018095379A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/08—Copper compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/12—Gold compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic 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
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • 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
    • 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
    • H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
    • 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
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • 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

  • OLEDs Organic light-emitting diodes
  • Organic light-emitting diodes using fluorescent materials have high reliability, but their internal electroluminescence quantum under electric field excitation The efficiency is limited to 25%, because the probability ratio of exciton generating single-excited and triple-excited states is 1:3.
  • Professor Thomson of the University of Southern California and Professor Forrest of Princeton University will be three (2- Phenylpyridine) ruthenium Ir(ppy) 3 was doped into N,N-dicarbazole biphenyl (CBP), and a green electrophosphorescent device was successfully prepared, which caused a strong interest in complex phosphorescent materials.
  • CBP N,N-dicarbazole biphenyl
  • a metal organic complex having the following general formula:
  • Ar 1 is selected from an aromatic hydrocarbon group, substituted by R 1 is an aromatic hydrocarbon group, heteroaromatic hydrocarbon group and an aromatic ring substituted by R 1 heteroaromatic ring of one hydrocarbon group;
  • Ar 2 is one selected from the group consisting of a heteroaromatic cyclic hydrocarbon group containing an N atom and a heteroaromatic cyclic hydrocarbon group containing an N atom substituted by R 1 ;
  • R 1 is selected from the group consisting of H, F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 2 ) 2 , Si(R 2 ) 3 , linear alkane, and linear substituted by R 2 alkane group, an ether group alkane, substituted alkane R 2 is an ether group, a thioether group alkane, R 2 is substituted with a thioether group alkane, a branched alkane group, substituted alkane group branched R 2, cycloalkane group and One of the cycloalkane groups substituted by R 2 ;
  • R 2 is selected from the group consisting of H, D, an aliphatic alkane group, an aromatic group, an aromatic ring group, and a heteroaryl group;
  • L is selected from the group consisting of a monodentate neutral ligand, a monodentate anionic ligand, a bidentate neutral ligand, and a bidentate anionic ligand;
  • n is any integer from 1 to 3;
  • n is any integer from 0 to 2.
  • a high polymer comprising a repeating unit comprising a metal organic complex as described above.
  • a composition comprising one of the above metal organic complexes and the above-mentioned high polymer.
  • An organic electronic device comprising the above metal organic complex, the above high polymer, and one of the above compositions.
  • the present invention provides a metal organic complex, a high polymer, a composition, and an organic electronic device.
  • the present invention will be further described in detail below in order to clarify the purpose, the technical solution, and the effect of the present invention. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
  • Ar 2 is one selected from the group consisting of a heteroaromatic cyclic hydrocarbon group containing an N atom and a heteroaromatic cyclic hydrocarbon group containing an N atom substituted by R 1 . Among them, Ar 2 has 5 to 22 C atoms. Further, Ar 2 has 5 to 20 C atoms. Further, Ar 2 has 5 to 18 C atoms. Specifically, Ar 2 has 5 to 12 C atoms.
  • R 2 and R 3 are each selected from the group consisting of H, D, an aliphatic alkane group, an aryl group, an aromatic ring group, and a heteroaryl group.
  • the heteroaryl group includes a substituted and unsubstituted heteroaryl group.
  • M is a transition metal element.
  • L is selected from one of a monodentate neutral ligand, a monodentate anionic ligand, a bidentate neutral ligand, and a bidentate anionic ligand.
  • n is any integer from 1 to 3.
  • n is any integer from 0 to 2.
  • An aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system.
  • the heteroaromatic group refers to a hydrocarbon group (containing a hetero atom) containing at least one heteroaromatic ring, and the hydrocarbon group of the heteroaromatic ring includes a monocyclic group and a polycyclic ring group.
  • These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring.
  • These ring species of polycyclic ring, at least one ring species are aromatic or heteroaromatic.
  • an aromatic group or a heteroaryl group in an aromatic ring group or a heteroaromatic ring group may be interrupted by a short non-aromatic unit.
  • the non-aromatic unit is less than 10% of a non-H atom (hydrogen atom). Further, the non-aromatic unit is less than 5% of a non-H atom.
  • the non-aromatic unit is a C atom (carbon atom), an N atom (nitrogen atom), or an O atom (oxygen atom). Therefore, a ring system such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine or diaryl ether is also considered to be an aromatic ring system.
  • the aromatic group is selected from the group consisting of benzene, a derivative of benzene, a derivative of naphthalene, naphthalene, a derivative of ruthenium, osmium, a derivative of phenanthrene, phenanthrene, a perylene, a derivative of perylene, Derivatives of tetracene and tetracene, derivatives of ruthenium and osmium, derivatives of benzopyrene, benzopyrene, derivatives of triphenylene, triphenylene, derivatives of ruthenium and osmium, derivatives of ruthenium and osmium One of them.
  • the heteroaromatic group is selected from the group consisting of furan, a derivative of furan, a derivative of benzofuran, benzofuran, a derivative of thiophene, thiophene, a derivative of benzothiophene, benzothiophene, pyrrole, pyrrole Derivatives, derivatives of pyrazoles, pyrazoles, derivatives of triazoles, triazoles, imidazoles, derivatives of imidazoles, derivatives of oxazoles, oxazoles, oxadiazoles, derivatives of oxadiazoles, thiazoles, Derivatives of thiazole, derivatives of tetrazole, tetrazole, derivatives of ruthenium and osmium, derivatives of oxazole, oxazole, pyrroloimidazole, derivatives of pyrroloimidazole, pyrrolopyrrole, pyrrolopyrrole
  • Ar 1 is selected from the group consisting of a non-aromatic ring group having 2 to 20 carbon atoms, a non-aromatic ring group having 2 to 20 carbon atoms substituted by R, and The triplet level of the metal organic complex is increased to facilitate the acquisition of green or blue light emitters.
  • the non-aromatic ring group has from 1 to 10 carbon atoms in the ring. Further, the non-aromatic cyclic group has 1 to 6 carbon atoms in the ring. Non-aromatic cyclic groups include saturated cyclic systems and unsaturated cyclic systems. Further, a cyclic system of a non-aromatic ring group is substituted with a group R.
  • R includes at least one hetero atom of Si, N, P, O, S, and Ge. Further, R includes at least one of Si, N, P, O, and S. Wherein R is selected from the group consisting of a cyclohexyl group, a piperidinyl group, and a cyclooctadiene ring group.
  • R may also be selected from one of a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 2 -C 10 aryl group, and a C 2 -C 10 heteroaryl group.
  • C 1 -C 10 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2 -methylbutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoromethyl, 2, 2,2-Trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, One of cycloocten
  • the C 2 -C 10 aryl or heteroaryl group may be selected to be monovalent or divalent depending on whether the metal organic complex is used as a red illuminant or a green illuminant.
  • the C 2 -C 10 aryl or heteroaryl group is selected from the group consisting of benzene, naphthalene, anthracene, quinone, dihydroanthracene, fluorene, fluorene, fluoranthene, butyl, pentane, benzopyrene, furan, benzene.
  • the aromatic ring group and the heteroaromatic ring group may also be selected from the group consisting of a biphenylylene group, a linoleylene, an anthracene, a stilbene, a dihydrophenanthrene, a tetrahydroanthracene, and a cis and trans fluorene.
  • Ar 1 is selected from the formula and One of them;
  • a plurality of X 1 are each independently selected from one of CR 1 and N;
  • R 1 , R 2 and R 3 are each independently selected from H, D, a linear alkyl group having 1 to 20 C atoms, an alkoxy group having 1 to 20 C atoms, and having 1 to 20 C groups. a thioalkoxy group of an atom, a branched alkyl group having 3 to 20 C atoms, a cyclic alkyl group having 3 to 20 C atoms, an alkoxy group having 3 to 20 C atoms, a thioalkoxy group having 3 to 20 C atoms, a silyl group having 3 to 20 C atoms, a substituted ketone group having 1 to 20 C atoms, and having 2 to 20 C atoms Alkoxycarbonyl, aryloxycarbonyl having 7 to 20 C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate Acid ester group, hydroxyl group
  • R 1 , R 2 and R 3 can bond to an aliphatic or aromatic ring group, and R 1 , R 2 and R 3 themselves can also be bonded to an aliphatic ring group or an aromatic ring group, respectively.
  • the crosslinkable group means a functional group containing an unsaturated bond such as an alkenyl group or an alkynyl group.
  • R 1 , R 2 and R 3 are each selected from the group consisting of H, D, a linear alkyl group having 1 to 10 C atoms, an alkoxy group having 1 to 10 C atoms, and having 1 to 10 a thioalkoxy group of a C atom, a branched alkyl group having 3 to 10 C atoms, a cyclic alkyl group having 3 to 10 C atoms, and having 3 to 10 C atoms An alkoxy group, a thioalkoxy group having 3 to 10 C atoms, a silyl group having 3 to 10 C atoms, a substituted ketone group having 1 to 10 C atoms, An alkoxycarbonyl group having 2 to 10 C atoms, an aryloxycarbonyl group having 7 to 10 C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, Isocyanato group, isocyan
  • R 1 , R 2 and R 3 can bond to an aliphatic or aromatic ring group, and R 1 , R 2 and R 3 themselves can also be bonded to an aliphatic ring group or an aromatic ring group, respectively.
  • the crosslinkable group means a functional group containing an unsaturated bond such as an alkenyl group or an alkynyl group.
  • Ar 1 is selected from one of the following groups:
  • H in the group can be further substituted.
  • Ar 2 is selected from the formula
  • a plurality of X 1 are each independently selected from one of CR 1 and N, and at least one of the plurality of X 1 is N;
  • R 1 , R 2 and R 3 are each selected from the group consisting of H, D, a linear alkyl group having 1 to 20 C atoms, an alkoxy group having 1 to 20 C atoms, and having 1 to 20 C atoms. a thioalkoxy group, a branched alkyl group having 3 to 20 C atoms, a cyclic alkyl group having 3 to 20 C atoms, an alkoxy group having 3 to 20 C atoms, having a thioalkoxy group having 3 to 20 C atoms, a silyl group having 3 to 20 C atoms, a substituted ketone group having 1 to 20 C atoms, and having 2 to 20 C atoms Alkoxycarbonyl, aryloxycarbonyl having 7 to 20 C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate Ester group, hydroxy
  • R 1 , R 2 and R 3 can bond to an aliphatic or aromatic ring group, and R 1 , R 2 and R 3 themselves can also be bonded to an aliphatic ring group or an aromatic ring group, respectively.
  • the crosslinkable group means a functional group containing an unsaturated bond such as an alkenyl group or an alkynyl group.
  • Ar 2 is selected from one of the following groups:
  • the metal organic complex of the present embodiment can function as a phosphorescent emitter whose emission wavelength depends on the triplet level T 1 .
  • the ligand of the metal organic complex has a very important influence on its triplet level T 1 .
  • the general formula of the ligand L0 of the metal organic complex is as follows, and the triplet level T 1 of the ligand L0 is ⁇ 2.0 eV.
  • the number of C atoms of the substructure La of the ligand L0 does not exceed 26. Further, the number of C atoms of the substructure La does not exceed 22. Further, the number of C atoms of the substructure La does not exceed 20. Further, the number of C atoms of the substructure La does not exceed 18.
  • the number of C atoms of the substructure Lb of the ligand L0 does not exceed 30.
  • the substructure La has no more than 26 C atoms. Further, the number of C atoms of the substructure La does not exceed 22. Further, the number of C atoms of the substructure La does not exceed 20.
  • E1(La) ⁇ E1(Lb). In another embodiment, E1(Lb) ⁇ E1(La). Wherein E1(La) represents the first singlet excited state energy level of La, and E1(Lb) represents the first singlet excited state energy level of Lb.
  • the metal organic complex is selected from one of the following formulae:
  • x is Any integer in , y is Any integer in , z is Any integer in the formula, m is any integer from 1 to 3.
  • n is equal to 1.
  • m is not limited to being equal to 1, for example, m is equal to 2.
  • m is equal to 3, as long as m is any integer from 1 to 3.
  • the broken line indicates a key directly connected to M, u is any integer from 0 to 2, v is any integer from 0 to 3, w is any integer from 0 to 4, and t is 0 to 5. Any integer.
  • L is selected from the formula
  • R 20 to R 89 are each selected from the group consisting of H, F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 2 ) 2 , Si(R 2 ) 3 , linear alkane, alkane An ether group, an alkane sulfide group having 1 to 10 carbon atoms, a branched alkane group having 1 to 10 carbon atoms, a cycloalkane group having 1 to 10 carbon atoms, and 3 to 10 One of an alkane ether group of a carbon atom, an alkane sulfide group having 3 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
  • M is a transition metal element. Specifically, M is selected from the group consisting of chromium (Cr), molybdenum (Mo), tungsten (W), ruthenium (Ru), rhodium (Rh), nickel (Ni), silver (Ag), copper (Cu), and zinc (Zn).
  • M is selected from one of Cu, Au, Ir, and Pt.
  • the metal organic complex is selected from one of the following structures:
  • the molecular weight of the metal organic complex is ⁇ 700 g/mol.
  • the metal organic complex has a molecular weight of ⁇ 800 g/mol. More preferably, the metal organic complex has a molecular weight of ⁇ 900 g/mol. More preferably, the metal organic complex has a molecular weight of ⁇ 1000 g/mol. Most preferably, the molecular weight of the metal organic complex is > 1100 g/mol.
  • the metal organic complex When the metal organic complex is a luminescent material, the metal organic complex has an emission wavelength of 300 nm to 1000 nm. Further, the metal organic complex has an emission wavelength of 350 nm to 900 nm. Further, the metal organic complex has an emission wavelength of 400 nm to 800 nm.
  • the luminescent material refers to a photo luminescent material or an electroluminescent material.
  • the photoluminescence efficiency of the metal organic complex is ⁇ 30%. Further, the photoluminescence efficiency of the metal organic complex is ⁇ 40%. Further, the photoluminescence efficiency of the metal organic complex is ⁇ 50%. Specifically, the photoluminescence efficiency of the metal organic complex is ⁇ 60%.
  • the metal organic complex is not limited to a luminescent material, and may be a non-luminescent material, and may be used as other functional materials, for example, an electron transporting material, a hole transporting material, a host material, an organic dye, or the like.
  • the high polymer of one embodiment includes a repeating unit comprising the above metal organic complex.
  • the high polymer includes a non-conjugated high polymer and a conjugated high polymer.
  • the high polymer is a conjugated high polymer.
  • a conjugated polymer is a type of high polymer.
  • the backbone of the conjugated polymer is mainly composed of sp 2 hybrid orbitals of C atoms.
  • C atom in the main chain can also be substituted by other non-C atoms, and the sp 2 hybridization of the C atom in the main chain is interrupted by some natural defects.
  • the conjugated polymer may also contain an aryl amine, an aryl phosphine, and other heteroarmotics, metal organic complexes in the main chain. (organometallic complexes) and so on.
  • a film prepared from the above metal organic complex or the above high polymer can be used for the preparation of an organic electronic device. Specifically, the film is prepared by spin coating.
  • the composition of one embodiment includes the above-described metal organic complex and organic functional material, or includes the above-described high polymer and organic functional material.
  • the organic functional material is a small molecule or a high polymer material.
  • the small molecule described herein refers to non-polymerization Molecules of non-oligomers, non-dendrimers, and non-blends. There are no repeating structures in small molecules. Among them, the molecular weight of the small molecule is ⁇ 3000 g/mol. Further, the molecular weight of the small molecule is ⁇ 2000 g/mol. Further, the molecular weight of the small molecule is ⁇ 1500 g/mol.
  • the organic functional material is selected from the group consisting of a hole injecting material (HIM), a hole transporting material (HTM), an electron transporting material (ETM), an electron injecting material (EIM), an electron blocking material (EBM), and a hole blocking material ( At least one of HBM), a luminescent material, an organic host material (Host), and an organic dye.
  • HIM hole injecting material
  • HTM hole transporting material
  • ETM electron transporting material
  • EIM electron injecting material
  • EBM electron blocking material
  • HBM hole blocking material
  • HBM hole blocking material
  • the organic functional material may be an organic functional material as disclosed in WO2010135519A1, US20090134784A1 and WO2011110277A1.
  • the metal organic complex When the composition includes a metal organic complex and an organic functional material, the metal organic complex has a mass percentage of 0.01% to 30%. Further, the metal organic complex has a mass percentage of 0.5% to 20%. Further, the metal organic complex has a mass percentage of 2% to 15%. Specifically, the metal organic complex has a mass percentage of 5% to 15%.
  • the organic functional material is a triplet matrix material.
  • the organic functional material is a thermally activated delayed fluorescent luminescent material (TADF).
  • TADF thermally activated delayed fluorescent luminescent material
  • the organic functional material is a thermally activated delayed fluorescent luminescent material (TADF).
  • TADF thermally activated delayed fluorescent luminescent material
  • triplet matrix material the triplet emitter, and the TADF.
  • Any metal complex or organic compound can be used as a matrix for the triplet matrix material as long as its triplet energy is higher than that of the illuminant, especially higher than that of the triplet emitter (phosphorescent emitter).
  • the metal complex of the triplet matrix material has the following general formula:
  • M is a metal
  • (Y 3 -Y 4 ) is a bidentate ligand
  • Y 3 and Y 4 are each independently selected from one of C, N, O, P and S
  • L is an auxiliary ligand
  • the value of m has a maximum coordination number from 1 to M
  • m+n is the maximum coordination number of M.
  • M is selected from the group consisting of Cu, Au, Ir, and Pt.
  • metal complex of the triplet matrix material has the following general formula:
  • (O-N) is a bidentate ligand, and the metal is coordinated to the O atom and the N atom.
  • the organic compound which can be used as the triplet matrix material is a compound containing a cyclic aromatic hydrocarbon group or a compound containing an aromatic heterocyclic group.
  • the compound containing a cyclic aromatic hydrocarbon group includes: benzene, biphenyl, triphenyl, benzo and anthracene; and the compound containing an aromatic heterocyclic group includes: dibenzothiophene, dibenzofuran, dibenzoselenophene , furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, carbazole, pyridinium, pyrrole dipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, dioxin Oxazole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine,
  • the organic compound which can be used as the triplet matrix material may also be a group containing a 2-ring to 10-ring structure, for example, a cyclic aromatic hydrocarbon group or an aromatic heterocyclic group. Wherein each group is directly bonded to each other or is bonded through at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group.
  • the organic compound of the triplet matrix material comprises at least one of the following groups:
  • n is any integer from 0 to 20;
  • X 1 -X 8 are each selected from one of CR 1 and N;
  • X 9 is selected from one of CR 1 R 2 and NR 1 ;
  • R 1 - R 7 Each is independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.
  • the triplet matrix material is selected from one of the following structures:
  • Triplet emitters are also known as phosphorescent emitters.
  • the triplet emitter is a metal complex containing the formula M(L)n. Wherein M is a metal element, L is an organic ligand, and L is bonded to M through one or more position linkages or coordination; n is an integer greater than 1, preferably n is selected from 1, 2, 3, 4 One of 5, 6 and 6.
  • the metal complex is coupled to the polymer through one or more locations. Specifically, the metal complex is coupled to the polymer via an organic ligand.
  • M is selected from one of a transition metal element, a lanthanoid element, and a lanthanoid element.
  • M is selected from one of Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu, and Ag. More preferably, M is selected from one of Os, Ir, Ru, Rh, Cu, Au, and Pt.
  • the organic ligand is selected from the group consisting of a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative, and a 2-phenylquinoline derivative. One of them. Further, the organic ligands may all be substituted, for example by fluorine or trifluoromethyl.
  • the ancillary ligand is selected from one of acetic acid acetone and picric acid.
  • the metal complex of the triplet emitter has the following general formula:
  • M is a metal.
  • M is selected from one of a transition metal element, a lanthanoid element, and a lanthanide element;
  • Ar 1 is a cyclic group in which Ar 1 contains at least one donor atom, that is, an atom having a lone pair of electrons such as nitrogen or phosphorus, and the cyclic group is coordinated to the metal through a donor atom;
  • Ar 2 is a cyclic group, wherein Ar 2 contains at least one C atom, and the cyclic group is bonded to the metal through a C atom;
  • L is an ancillary ligand.
  • L is a bidentate chelate ligand. More preferably, L is a monoanionic bidentate chelate ligand;
  • n is any integer from 1 to 3.
  • m is 2 or 3. More preferably, m is 3;
  • n is any integer from 0 to 2.
  • n is 0 or 1. More preferably, n is zero.
  • the material of the triplet illuminant and its use can be WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005/0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099852, WO 2010102709, US 20070087219A1, US 20090061681A1, US 20010053462A1, Baldo, Thompson et al.
  • the triplet emitter is selected from one of the following structures:
  • TDF Thermally activated delayed fluorescent luminescent material
  • the thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials.
  • Such materials generally have a small singlet-triplet energy level difference ( ⁇ Est), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. Therefore, the singlet excitons and triplet excitons formed under electrical excitation can be fully utilized, so that the quantum efficiency in the organic electronic device can reach 100%.
  • ⁇ Est singlet-triplet energy level difference
  • TADF needs to have a small singlet-triplet energy level difference ( ⁇ Est).
  • ⁇ Est of the TADF is ⁇ 0.3 eV.
  • ⁇ Est of the TADF is ⁇ 0.2 eV.
  • ⁇ Est of the TADF is ⁇ 0.1 eV.
  • ⁇ Est of the TADF is ⁇ 0.05 eV.
  • the TADF may be CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064(A1), Adachi, et. al. Adv. Mater., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett., 101 , 2012, 093306, Adachi, et.al. Chem.
  • the TADF is selected from one of the following structures:
  • the composition comprises the above metal organic complex and an organic solvent, or comprises the above high polymer and organic solvent.
  • the composition includes the above metal organic complex, the above organic functional material and an organic solvent, or includes the above high polymer, the above organic functional material, and an organic solvent.
  • the organic solvent comprises at least one of an aromatic solvent and a heteroaromatic solvent.
  • the organic solvent includes at least one of an aliphatic chain-substituted aromatic solvent, an aliphatic ring-substituted aromatic solvent, an aromatic ketone solvent, and an aromatic ether solvent.
  • the organic solvent is an aromatic based solvent or a heteroaromatic based solvent such as p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene.
  • aromatic based solvent or a heteroaromatic based solvent such as p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene.
  • the above organic solvent is an aliphatic ketone such as 2-nonanone, 3-fluorenone, 5-fluorenone, 2-nonanone, 2,5-hexanedione, 2,6,8-trimethyl- 4-anthrone, phorone, di-n-pentyl ketone, etc.; or an aliphatic ether, for example, pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene Alcohol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether and tetraethylene glycol dimethyl ether .
  • an aliphatic ketone such as 2-nonanone, 3-fluorenone, 5-fluorenone, 2-non
  • the above organic solvent further includes an additional solvent.
  • the additional solvent is selected from the group consisting of methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, P-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1, At least one of 1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, and anthracene .
  • the composition when used as a printing ink, is a solution or suspension. Viscosity and surface tension are important parameters of the composition.
  • the surface tension parameters of suitable compositions are suitable for the particular substrate and the particular printing process.
  • the surface tension of the composition is from 19 dyne/cm to 50 dyne/cm at an operating temperature or at 25 °C. Further, the composition has a surface tension of 22 dyne/cm to 35 dyne/cm. Further, the surface tension of the composition is from 25 dyne/cm to 33 dyne/cm.
  • the solubility of the metal organic complex in the toluene solution at 25 ° C is ⁇ 2 mg / ml. Further, the solubility of the metal organic complex in the toluene solution is ⁇ 3 mg/ml. Still further, the solubility of the metal organic complex in the toluene solution is ⁇ 4 mg/ml. Further, the solubility of the metal organic complex in the toluene solution is ⁇ 5 mg/ml.
  • the viscosity of the composition when the composition is used in ink jet printing, is from 1 cps to 100 cps at an operating temperature or 25 °C. Further, the viscosity of the composition is from 1 cps to 50 cps. Still further, the viscosity of the composition is from 1.5 cps to 20 cps. Further, the viscosity of the composition is from 4.0 cps to 20 cps.
  • Viscosity can be adjusted by a number of methods, for example, by selecting a solvent and adjusting the concentration of the functional material in the composition.
  • the above composition can appropriately adjust the viscosity of the composition according to the printing method.
  • the organic functional material has a mass percentage of 0.3% to 30%. Further, the organic functional material has a mass percentage of 0.5% to 20%. Further, the organic functional material has a mass percentage of 0.5% to 15%. Further, the organic functional material has a mass percentage of 0.5% to 10%. Further, the organic functional material has a mass percentage of 1% to 5%.
  • an organic electronic device can be produced by a printing or coating method.
  • printing or coating methods include, but are not limited to, inkjet printing, Nozzle Printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion roller printing, lithography.
  • the method of printing or coating is selected from one of ink jet printing, slit type extrusion coating, jet printing, and gravure printing.
  • the above composition further comprises an additive selected from at least one of a surface active compound, a lubricant, a wetting agent, a dispersing agent, a hydrophobic agent and a binder.
  • the additive is used to adjust the viscosity, film forming properties, adhesion, and the like of the composition.
  • the organic electronic device of one embodiment includes one of the above-described metal organic complex, the above-mentioned high polymer, and the above composition.
  • the organic electronic device is selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, an organic spintronic One of a device, an organic sensor, and an organic plasmon emitting diode (Organic Plasmon Emitting Diode).
  • OLED organic light emitting diode
  • OCV organic photovoltaic cell
  • OFET organic field effect transistor
  • organic light emitting field effect transistor an organic laser
  • organic spintronic One of a device an organic sensor
  • organic plasmon emitting diode Organic Plasmon Emitting Diode
  • the organic electronic device includes a substrate, an anode, a light emitting layer, and a cathode.
  • the substrate may be opaque or transparent.
  • a transparent substrate can be used to make a transparent light-emitting component.
  • the substrate may be a substrate as disclosed in Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606.
  • the substrate can be rigid or elastic.
  • the substrate is selected from the group consisting of plastics, metals, semiconductor wafers, and glass.
  • the substrate has a smooth surface. More specifically, the surface of the substrate is free from defects.
  • the substrate is flexible and the substrate is a polymeric film or plastic.
  • the glass transition temperature Tg of the substrate is 150 ° C or higher.
  • the glass transition temperature Tg of the substrate is 200 ° C or higher.
  • the glass transition temperature Tg of the substrate is 250 ° C or higher.
  • the substrate has a glass transition temperature Tg of 300 ° C or more.
  • the flexible substrate is polyethylene terephthalate (PET) or polyethylene glycol (2,6-naphthalene) (PEN).
  • the anode material includes, but not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like.
  • the anode material can be obtained by a method of technical deposition, such as physical vapor deposition, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • Patterned ITO conductive substrates are commercially available and can be used to make organic electronic devices.
  • the cathode can also easily inject electrons into the EIL or ETL or directly into the light-emitting layer.
  • the work function of the cathode and the absolute value of the LUMO energy level difference of the illuminant in the luminescent layer, or the work function of the cathode and the electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer is less than 0.5 eV.
  • the work function of the cathode and the absolute value of the LUMO energy level difference of the illuminant in the luminescent layer or the work function of the cathode and n as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL)
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the absolute value of the difference between the LUMO level or the conduction band level of the type semiconductor material is less than 0.3 eV.
  • the work function of the cathode and the absolute value of the LUMO energy level difference of the illuminant in the luminescent layer or the work function of the cathode and the electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL)
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • cathode materials for organic electronic devices.
  • the cathode material is one selected from the group consisting of Al, Au, Ag, Ca, Ba, Mg, LiF/Al, Mg/Ag alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, and ITO.
  • the cathode material can be prepared by physical vapor deposition. Among them, physical vapor deposition methods include radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) and the like.
  • the OLED may further include other functional layers including a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and an empty layer. Hole blocking layer (HBL) and so on.
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EIL electron injection layer
  • ETL electron transport layer
  • empty layer empty layer. Hole blocking layer (HBL) and so on.
  • the light-emitting layer comprises the above-mentioned metal organic complex or high polymer. Further, the luminescent layer is prepared by a solution processing method.
  • the light-emitting device has an emission wavelength of 300 nm to 1000 nm.
  • the above-described light emitting device has an emission wavelength of 350 nm to 900 nm. More preferably, the above-described light-emitting device has an emission wavelength of 400 nm to 800 nm.
  • Phenanthrene (2.08 g, 10 mmol), pyridine-2-carbaldehyde (1.07 g, 10 mmol) and ammonium acetate (7.7 g, 100 mmol) were placed in a dry flask, then 2 mL glacial acetic acid was added, refluxed for 3 h, cooled to Aqueous ammonia was added dropwise at room temperature to precipitate a precipitate, which was then recrystallized from ethanol to give a solid 3a (1.47 g).
  • HOMO(eV) ((HOMO(Gaussian) ⁇ 27.212)-0.9899)/1.1206
  • HOMO(G) and LUMO(G) are direct calculation results of Gaussian 03W, and the unit is Hartree.
  • the results are shown in Table 1:
  • the OLED device was prepared by using the metal organic complexes obtained in Examples 1 to 3, respectively.
  • the specific steps are as follows:
  • a, cleaning of the conductive glass substrate when used for the first time, can be washed with a variety of solvents, such as chloroform, ketone, isopropyl alcohol, and then UV ozone plasma treatment;
  • HTL 60 nm
  • EML 45 nm
  • ETL 35 nm
  • hot evaporation in a high vacuum (1 ⁇ 10 -6 mbar, mbar);
  • cathode LiF / Al (1nm / 150nm) in a high vacuum (1 ⁇ 10 -6 mbar) in the thermal evaporation;
  • the device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.
  • the OLED devices prepared by the metal organic complexes obtained in Examples 1 to 3 each have the following structure:
  • OLED-1 ITO/NPD (60 nm) / 15% Ir-1: mCP (45 nm) / TPBi (35 nm) / LiF (1 nm) / Al (150 nm) / cathode;
  • OLED-2 ITO/NPD (60 nm) / 15% Cu-1: mCP (45 nm) / TPBi (35 nm) / LiF (1 nm) / Al (150 nm) / cathode;
  • OLED-3 ITO/NPD (60 nm) / 15% Cu-2: mCP (45 nm) / TPBi (35 nm) / LiF (1 nm) / Al (150 nm) / cathode.
  • the current-voltage brightness (JVL) characteristics of each OLED device are characterized by an evaporation or spin coating apparatus while recording important parameters such as efficiency and external quantum efficiency.
  • OLED-1, OLED-2 and OLED-3 The maximum external quantum efficiencies of OLED-1, OLED-2 and OLED-3 were 15.1%, 10.2% and 8.4%, respectively.
  • the structure of the device can be further optimized, such as the combination of HTM, ETM and host materials, which can further improve the performance of the device, especially efficiency, driving voltage and lifetime.

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Abstract

一种金属有机配合物，具有如下通式(I)： Ar1选自芳香烃基、被R1取代的芳香烃基、杂芳香环烃基及被R1取代的杂芳香环烃基中的一种；Ar2选自包含N原子的杂芳香环烃基、被R1取代的包含N原子的杂芳香环烃基中的一种；M为过渡族金属元素；L选自单齿中性配体、单齿阴离子配体、双齿中性配体及双齿阴离子配体中的一种；m为1～3中的任一整数；n为0～2中的任一整数。

Description

金属有机配合物、高聚物、组合物及有机电子器件 技术领域：
本发明涉及有机电子器件领域，尤其涉及一种金属有机配合物、高聚物、组合物及有机电子器件。
背景技术：
由于有机半导体材料在合成上具有多样性、制造成本相对较低和优良的光学与电学性能，有机发光二极管(OLED)在光电器件(例如平板显示器和照明)的应用方面具有很大的潜力。
为了提高有机发光二极管的发光效率，各种基于荧光和磷光的发光材料体系已被开发出来，使用荧光材料的有机发光二极管具有可靠性高的特点，但其在电场激发下其内部电致发光量子效率被限制为25％，这是因为激子产生单重激发态和三重激发态的概率比为1:3。1999年，美国南加州大学的Thomson教授和普林斯顿大学的Forrest教授将三(2-苯基吡啶)合铱Ir(ppy)3掺杂到N,N-二咔唑联苯(CBP)中，成功制备了绿色电致磷光器件，这引起人们对配合物磷光材料的浓厚兴趣。由于重金属的引入，提高了分子自旋轨道耦合，缩短了磷光寿命，增强了分子的系间窜越，使磷光得以顺利发射。而且这类配合物反应温和，可以方便的改变配合物结构和取代基团，调节发射波长，得到性能优良的电致磷光材料。至今，磷光OLED的内部量子效率已接近100％。然而，大多数磷光材料主要集中在铱和铂配合物，配合物的种类比较单一。
发明内容：
基于此，提供一种新型的金属有机配合物。
此外，还提供了一种高聚物、组合物及有机电子器件。
一种金属有机配合物，具有如下通式：
Figure PCTCN2017112700-appb-000001
其中，
Ar1选自芳香烃基、被R1取代的芳香烃基、杂芳香环烃基及被R1取代的杂芳香环烃基中的一种；
Ar2选自包含N原子的杂芳香环烃基、被R1取代的包含N原子的杂芳香环烃基中的一种；
R1选自H、F、Cl、Br、I、D、CN、NO2、CF3、B(OR2)2、Si(R2)3、直链烷烃基、被R2取代的直链烷烃基、烷烃醚基、被R2取代的烷烃醚基、烷烃硫醚基、被R2取代的烷烃硫醚基、支链烷烃基、被R2取代的支链烷烃基、环烷烃基及被R2取代的环烷烃基中的一种；
R2选自H、D、脂肪族烷烃基、芳香基、芳香环基、杂芳香基中的一种；
M为过渡族金属元素；
L选自单齿中性配体、单齿阴离子配体、双齿中性配体及双齿阴离子配体中的一种；
m为1～3中的任一整数；
n为0～2中的任一整数。
一种高聚物，包括重复单元，重复单元包含上述的金属有机配合物。
一种组合物，包括上述的金属有机配合物及上述的高聚物中的一种。
一种有机电子器件，包括上述的金属有机配合物、上述的高聚物及上述的组合物中的一种。
本发明的一个或多个实施例的细节在下面的附图和描述中提出。本发明的其它特征、目的和优点将从说明书、附图以及权利要求书变得明显。
具体实施方式
本发明提供一种金属有机配合物、高聚物、组合物及有机电子器件，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
一实施方式的金属有机配合物，具有如下通式：
Figure PCTCN2017112700-appb-000002
其中，
Ar1选自芳香烃基、被R1取代的芳香烃基、杂芳香环烃基、被R1取代的杂芳香环烃基、非芳香族环基及被R1取代的非芳香族环基中的一种。其中，Ar1具有5个～22个C原子。进一步，Ar1具有5个～18个C原子。更进一步地，Ar1具有5个～12个C原子。其中，C原子是指碳原子(下同)。
Ar2选自包含N原子的杂芳香环烃基、被R1取代的包含N原子的杂芳香环烃基中的一种。其中，Ar2具有5个～22个C原子。进一步地，Ar2具有5个～20个C原子。更进一步地，Ar2具有5个～18个C原子。具体地，Ar2具有5个～12个C原子。
R1选自H、F、Cl、Br、I、D、CN、NO2、CF3、B(OR2)2、Si(R2)3、直链烷烃基、被R2取代的直链烷烃基、烷烃醚基、被R2取代的烷烃醚基、烷烃硫醚基、被R2取代的烷烃硫醚基、支链烷烃基、被R2取代的支链烷烃基、环烷烃基及被R2取代的环烷烃基中的一种。
进一步地，直链烷烃基、被R2取代的直链烷烃基、环烷烃基及被R2取代的环烷烃基中的一个或多个非相邻的亚甲基被R2C＝CR2、C＝C、Si(R2)2、Ge(R2)2、Sn(R2)2、C＝O、C＝S、C＝Se、C＝N(R2)、O、S、-COO-、CONR2中的至少一个替换。
具体地，B(OR2)2、Si(R2)3、直链烷烃基、被R2取代的直链烷烃基、烷烃醚基、被R2取代的烷烃醚基、烷烃硫醚基、被R2取代的烷烃硫醚基、支链烷烃基、被R2取代的支链烷烃基、环烷烃基及被R2取代的环烷烃基中的H原子被D、F、Cl、Br、I、CN、NO2、R2、被芳香基和杂芳香环基取代的芳香胺基、咔唑基及被R3取代的咔唑基中的一种替换。
R2和R3分别选自H、D、脂肪族烷烃基、芳香基、芳香环基、杂芳香基中的一种。其中，杂芳香基包括取代和未被取代的杂芳香基。
M为过渡族金属元素。
L选自单齿中性配体、单齿阴离子配体、双齿中性配体及双齿阴离子配体中的一种。
m为1～3中的任一整数。
n为0～2中的任一整数。
芳族基团指至少包含一个芳环的烃基，包括单环基团和多环的环系统。杂芳族基团指包含至少一个杂芳环的烃基(含有杂原子)，杂芳环的烃基包括单环基团和多环的环基。这些多环的环可以具有两个或多个环，其中两个碳原子被两个相邻的环共用，即稠环。多环的这些环种，至少一个环种是芳族或杂芳族。其中，芳香族环基或杂芳香族环基中的芳香基或杂芳香基可以被短的非芳族单元间断。其中，非芳族单元为小于10％的非H原子(氢原子)。进一步地，非芳族单元为小于5％的非H原子。例如，非芳族单元为C原子(碳原子)、N原子(氮原子)或O原子(氧原子)。因此，像9,9'-螺二芴、9,9-二芳基芴、三芳胺及二芳基醚等环系，同样认为是芳香族环系。
具体地，芳族基团选自苯、苯的衍生物、萘、萘的衍生物、蒽、蒽的衍生物、菲、菲的衍生物、二萘嵌苯、二萘嵌苯的衍生物、并四苯、并四苯的衍生物、芘、芘的衍生物、苯并芘、苯并芘的衍生物、三亚苯、三亚苯的衍生物、苊、苊的衍生物、芴及芴的衍生物中的一种。
具体地，杂芳族基团选自呋喃、呋喃的衍生物、苯并呋喃、苯并呋喃的衍生物、噻吩、噻吩的衍生物、苯并噻吩、苯并噻吩的衍生物、吡咯、吡咯的衍生物、吡唑、吡唑的衍生物、三唑、三唑的衍生物、咪唑、咪唑的衍生物、噁唑、噁唑的衍生物、噁二唑、噁二唑的衍生物、噻唑、噻唑的衍生物、四唑、四唑的衍生物、吲哚、吲哚的衍生物、咔唑、咔唑的衍生物、吡咯并咪唑、吡咯并咪唑的衍生物、吡咯并吡咯、吡咯并吡咯的衍生物、噻吩并吡咯、噻吩并吡咯的衍生物、噻吩并噻吩、噻吩并噻吩的衍生物、呋喃并吡咯、呋喃并吡咯的衍生物、呋喃并呋喃、呋喃并呋喃的衍生物、噻吩并呋喃、噻吩并呋喃的衍生物、苯并异噁唑、苯并异噁唑的衍生物、苯并异噻唑、苯并异噻唑的衍生物、苯并咪唑、苯并咪唑的衍生物、吡啶、吡啶的衍生物、吡嗪、吡嗪的衍生物、哒嗪、哒嗪的衍生物、嘧啶、嘧啶的衍生物、三嗪、三嗪的衍生物、喹啉、喹啉的衍生物、异喹啉、异喹啉的衍生物、邻二氮萘、邻二氮萘的衍生物、喹喔啉、喹喔啉的衍生物、菲啶、菲啶的衍生物、伯啶、伯啶的衍生物、喹唑啉、喹唑啉的衍生物、喹唑啉酮及喹唑啉酮的衍生物中的一种。
在其中一个实施例中，Ar1选自具有2个～20个碳原子的非芳香族环基、被R取代的具有2个～20个碳原子的非芳香族环基中的一种，而使金属有机配合物的三线态能级提高，从而便 于获得绿光或蓝光发光体。
其中，非芳香族环基的环中具有1个～10个碳原子。进一步地，非芳香族环基的环中具有1～6个碳原子。非芳香族环基包括饱和的环状体系和不饱和的环状体系。进一步地，非芳香族环基的环状体系被基团R取代。
R包括Si、N、P、O、S及Ge中的至少一种杂原子。进一步地，R包括Si、N、P、O及S中的至少一种杂原子。其中，R选自类环己基、类哌啶基及类环辛二烯环基中的一种。
在另一个实施例中，R还可以选自C1～C10烷基、C1～C10烷氧基、C2～C10芳基及C2～C10杂芳基中的一种。
其中，C1～C10烷基选自甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、环丁基、2-甲基丁基、正戊基、正己基、环己基、正庚基、环庚基、正辛基、环辛基、2-乙基己基、三氟甲基、五氟甲基、2,2,2-三氟乙基、乙烯基、丙烯基、丁烯基、戊烯基、环戊烯基、己烯基、环己烯基、庚烯基、环庚烯基、辛烯基、环辛烯基、乙炔基、丙炔基、丁炔基、戊炔基、己炔基及辛炔基中的一种。
其中，C1～C10烷氧基选自甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基及2-甲基丁氧基中的一种。
其中，C2～C10芳基或杂芳基可根据金属有机配合物用作红光发光体或绿光发光体来选择是一价还是二价的。具体地，C2～C10芳基或杂芳基选自苯、萘、蒽、嵌二萘、二氢芘、屈、茈、萤蒽、丁省、戊省、苯并芘、呋喃、苯并呋喃、异苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、异苯并噻吩、硫芴、吡咯、吲哚、异吲哚、咔唑、吡啶、喹啉、异喹啉、吖啶、菲啶、苯并-5,6-喹啉、苯并-6,7-喹啉、苯并-7,8-喹啉、吩噻嗪、吩恶嗪、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑、菲并咪唑、吡啶并咪唑、吡嗪并咪唑、喹喔啉并咪唑、恶唑、苯并恶唑、萘并恶唑、蒽并恶唑、菲并恶唑、异恶唑、1,2-噻唑、1,3-噻唑、苯并噻唑、哒嗪、苯并哒嗪、嘧啶、苯并嘧啶、喹喔啉、吡嗪、二氮蒽、1,5-二氮杂萘、氮咔唑、苯并咔啉、菲咯啉、1,2,3-三唑、1,2,4-三唑、苯并三唑、1,2,3-恶二唑、1,2,4-恶二唑、1,2,5-恶二唑、1,3,4-恶二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑、1,3,4-噻二唑、1,3,5-三嗪、1,2,4-三嗪、1,2,3-三嗪、四唑。1,2,4,5-四嗪、1,2,3,4-四嗪、1,2,3,5-四嗪、嘌呤、蝶啶、中氮茚及苯并噻二唑中的一种。
在其他实施例中，芳香族环基和杂芳族环基还可以选自亚联苯基、亚三联苯、芴、螺二芴、二氢菲、四氢芘及顺式及反式茚并芴中的一种。
其中，Ar1选自通式
Figure PCTCN2017112700-appb-000003
及
Figure PCTCN2017112700-appb-000004
中的一种；
其中，多个X1分别独立地选自CR1和N中的一种；
Y1选自CR2R3、SiR2R3、NR2、C(＝O)、S及O中的一种；
R1、R2及R3分别独立选自H、D、具有1个～20个C原子的直链烷基、具有1个～20个C原子的烷氧基、具有1个～20个C原子的硫代烷氧基、具有3个～20个C原子的支链烷基、具有3个～20个C原子的环状的烷基、具有3个～20个C原子的烷氧基、具有3个～20个C原子的硫代烷氧基、具有3个～20个C原子的甲硅烷基、具有1个～20个C原子的取代的酮基、具有2个～20个C原子的烷氧基羰基、具有7个～20个C原子的芳氧基羰基、氰基、氨基甲酰基、卤甲酰基、甲酰基、异氰基、异氰酸酯基、硫氰酸酯基、异硫氰酸酯基、羟基、硝基、CF3基、Cl、Br、F、可交联的基团、具有5个～40个C原子的芳族环基、具有5个～40个C原子的杂芳族环基、具有5个～40个C原子的芳氧基及具有5个～40个C原子的杂芳氧基中的至少一种。其中，R1、R2及R3之间能够键合成脂族环基或芳族环基，同时R1、R2及R3本身也能够分别键合成脂族环基或芳族环基。其中，可交联的基团是指含有不饱和键如烯基、炔基等官能团。
进一步地，R1、R2及R3分别选自H、D、具有1个～10个C原子的直链烷基、具有1个～10个C原子的烷氧基、具有1个～10个C原子的硫代烷氧基基团、具有3个～10个C原子的支链烷基、具有3个～10个C原子的环状烷基、具有3个～10个C原子的的烷氧基、具有3个～10个C原子的硫代烷氧基基、具有3个～10个C原子的甲硅烷基基团、具有1个～10个C原子的被取代的酮基、具有2个～10个C原子的烷氧基羰基、具有7个～10个C原子的芳氧基羰基、氰基基团、氨基甲酰基基团、卤甲酰基基团、甲酰基基团、异氰基基团、异氰酸酯基团、硫氰酸酯基团、异硫氰酸酯基团、羟基基团、硝基基团、CF3基、Cl、Br、F、可交联的基团、具有5个～20个C原子的芳基、具有5个～20个C原子的杂芳族环基、具有5个 ～20个C原子的芳氧基、具有5个～20个C原子的杂芳氧基中的至少一种。其中，R1、R2及R3之间能够键合成脂族环基或芳族环基，同时R1、R2及R3本身也能够分别键合成脂族环基或芳族环基。其中，可交联的基团是指含有不饱和键如烯基、炔基等官能团。
具体地，Ar1选自以下基团中的一种：
Figure PCTCN2017112700-appb-000005
Figure PCTCN2017112700-appb-000006
及
Figure PCTCN2017112700-appb-000007
其中，基团中的H能够进一步被取代。
其中，Ar2选自通式
Figure PCTCN2017112700-appb-000008
及
Figure PCTCN2017112700-appb-000009
中的一种；
其中，多个X1分别独立地选自CR1和N中的一个，且多个X1中的至少一个为N；
Y1选自CR2R3、SiR2R3、NR2、C(＝O)、S及O中的一种；
R1、R2及R3分别选自H、D、具有1个～20个C原子的直链烷基、具有1个～20个C原子的烷氧基、具有1个～20个C原子的硫代烷氧基、具有3个～20个C原子的支链烷基、具有3个～20个C原子的环状的烷基、具有3个～20个C原子的烷氧基、具有3个～20个C原子的硫代烷氧基、具有3个～20个C原子的甲硅烷基、具有1个～20个C原子的取代的酮基、具有2个～20个C原子的烷氧基羰基、具有7个～20个C原子的芳氧基羰基、氰基、氨基甲酰基、卤甲酰基、甲酰基、异氰基、异氰酸酯基、硫氰酸酯基、异硫氰酸酯基、羟基、硝基、CF3基、Cl、Br、F、可交联的基团、具有5个～40个C原子的芳族环基、具有5个～40个C 原子的杂芳族环基、具有5个～40个C原子的芳氧基及具有5个～40个C原子的杂芳氧基中的至少一种。其中，R1、R2及R3之间能够键合成脂族环基或芳族环基，同时R1、R2及R3本身也能够分别键合成脂族环基或芳族环基。其中，可交联的基团是指含有不饱和键如烯基、炔基等官能团。
具体地，Ar2选自以下基团中的一种：
Figure PCTCN2017112700-appb-000010
Figure PCTCN2017112700-appb-000011
及
Figure PCTCN2017112700-appb-000012
其中，基团中的H能够进一步被取代。
本实施例的金属有机配合物能够作为磷光发光体，其发光波长取决于三线态能级T1。其中，金属有机配合物的配体对其三线态能级T1有很重要的影响。
金属有机配合物的配体L0的通式如下，配体L0的三线态能级T1≥2.0eV。优选地，T1≥2.2eV。较优选地，T1≥2.4eV。更优选地，T1≥2.6eV。最优选地，T1≥2.7eV。
Figure PCTCN2017112700-appb-000013
其中，在去除取代基的情况下，配体L0的子结构La的C原子数不超过26个。进一步地，子结构La的C原子数不超过22个。再进一步地，子结构La的C原子数不超过20个。更进一步地，子结构La的C原子数不超过18个。
其中，在去除取代基的情况下，配体L0的子结构Lb的C原子数不超过30个。进一步 地，子结构La的C原子数不超过26个。再进一步地，子结构La的C原子数不超过22个。更进一步地，子结构La的C原子数不超过20个。
在其中一个实施例中，E1(La)≥E1(Lb)。在另一个实施例中，E1(Lb)≥E1(La)。其中，E1(La)表示La的第一单重激发态能级，E1(Lb)表示Lb的第一单重激发态能级。
在其中一个实施例中，金属有机配合物选自如下通式中的一种：
Figure PCTCN2017112700-appb-000014
Figure PCTCN2017112700-appb-000015
其中，x为
Figure PCTCN2017112700-appb-000016
中的任一整数，y为
Figure PCTCN2017112700-appb-000017
中的任一整数，z为
Figure PCTCN2017112700-appb-000018
中的任一整数，m为1～3中的任一整数。
具体地，m等于1。当然m不限于等于1，例如，m等于2。又例如，m等于3，只要m为1～3中的任一整数即可。
其中，L选自通式
Figure PCTCN2017112700-appb-000019
Figure PCTCN2017112700-appb-000020
及
Figure PCTCN2017112700-appb-000021
中的一种；
其中，虚线表示与M直接相连的键，u为0～2中的任一整数，v为0～3中的任一整数，w为0～4中的任一整数，t为0～5中的任一整数。
进一步地，L选自通式
Figure PCTCN2017112700-appb-000022
Figure PCTCN2017112700-appb-000023
Figure PCTCN2017112700-appb-000024
及
Figure PCTCN2017112700-appb-000025
中的一种；
其中，R20至R89分别选自H、F、Cl、Br、I、D、CN、NO2、CF3、B(OR2)2、Si(R2)3、直链烷烃基、烷烃醚基、含1个～10个碳原子的烷烃硫醚基、含1个～10个碳原子的支链烷烃基、含1个～10个碳原子的环烷烃基，含3个～10个碳原子的烷烃醚基、含3个～10个碳原子的烷烃硫醚基及含6个～10个碳原子的芳基中的一种。
M是一种过渡金属元素。具体地，M选自铬(Cr)、钼(Mo)、钨(W)、钌(Ru)、铑(Rh)、镍(Ni)、银(Ag)、铜(Cu)、锌(Zn)、钯(Pd)、金(Au)、饿(Os)、铼(Re)、铱(Ir)及铂(Pt)中的一种。优选地，M选自Cu、Au、Ir及Pt中的一种。
从重原子效应来看，M选自Ir和Pt中的一种。优选地，M为Ir。因为Ir是化学稳定的，且具有显著的重原子效应，能产生高的发光效率。而从价格优势来看，M也可以为Cu或者Au。
具体地，金属有机配合物选自并不限于以下结构中的一种：
Figure PCTCN2017112700-appb-000026
Figure PCTCN2017112700-appb-000027
Figure PCTCN2017112700-appb-000028
Figure PCTCN2017112700-appb-000029
在其中一个实施例中，当金属有机配合物作为蒸镀型OLED的材料时，金属有机配合物的分子量≤1100g/mol。优选地，金属有机配合物的分子量≤1000g/mol。较优选地，金属有机配合物的分子量≤950g/mol。更优选地，金属有机配合物的分子量≤900g/mol。最优选地，金属有机配合物的分子量≤800g/mol。
当金属有机配合物作为印刷OLED的材料时，金属有机配合物的分子量≥700g/mol。优选地，金属有机配合物的分子量≥800g/mol。较优选地，金属有机配合物的分子量≥900g/mol。更优选地，金属有机配合物的分子量≥1000g/mol。最优选地，金属有机配合物的分子量≥1100g/mol。
当金属有机配合物为发光材料时，金属有机配合物的发光波长为300nm～1000nm。进一步地，金属有机配合物的发光波长为350nm～900nm。更进一步地，金属有机配合物的发光波长为400nm～800nm。其中，发光材料是指光致发光材料或电致发光材料。
进一步地，当金属有机配合物为光致发光材料时，金属有机配合物的光致发光效率≥30％。进一步地，金属有机配合物的光致发光效率≥40％。更进一步地，金属有机配合物的光致发光效率≥50％。具体地，金属有机配合物的光致发光效率≥60％。
需要说明的是，金属有机配合物不限于为发光材料，也可以为不发光材料，而用作其他功能材料，例如，电子传输材料、空穴传输材料、主体材料、有机染料等。
一实施方式的高聚物，包括重复单元，重复单元包含上述的金属有机配合物。该高聚物包括非共轭高聚物和共轭高聚物。优选地，高聚物为共轭高聚物。
高聚物(Polymer)包含均聚物(homopolymer)，共聚物(copolymer)，镶嵌共聚物(block copolymer)。另外在本申请中，高聚物也包含树状物(dendrimer)，有关树状物的合成及应用请参见Dendrimers and Dendrons,Wiley-VCH Verlag GmbH & Co.KGaA,2002,Ed.George R.Newkome,Charles N.Moorefield,Fritz Vogtle中的介绍。
共轭高聚物(conjugated polymer)是高聚物的一种。共轭高聚物的主链(backbone)主要是由C原子的sp2杂化轨道构成。例如：聚乙炔(polyacetylene)和poly(phenylene vinylene)，其主链上的C原子的也可以被其他非C原子取代，而且当主链上的C原子的sp2杂化被一些自然的缺陷打断时，仍然被认为是共轭高聚物。另外在本申请中，共轭高聚物的主链上也可以包含有芳基胺(aryl amine)、芳基磷化氢(aryl phosphine)及其他杂环芳烃(heteroarmotics)、金属有机络合物(organometallic complexes)等。
一种由上述金属有机配合物或上述高聚物制备的薄膜，能够用于制备有机电子器件。具体地，薄膜是采用旋涂法制备得到的。
一实施方式的组合物包括上述的金属有机配合物和有机功能材料，或包括上述的高聚物和有机功能材料。其中，有机功能材料为小分子或高聚物材料。本文所述的小分子是指非聚 合物、非低聚物、非树枝状聚合物及非共混物的分子。小分子中没有重复结构。其中，小分子的分子量≤3000克/摩尔。进一步地，小分子的分子量≤2000克/摩尔。更进一步地，小分子的分子量≤1500克/摩尔。
具体地，有机功能材料选自空穴注入材料(HIM)、空穴传输材料(HTM)、电子传输材料(ETM)、电子注入材料(EIM)、电子阻挡材料(EBM)、空穴阻挡材料(HBM)、发光材料、有机基质材料(Host)及有机染料中的至少一种。
其中，发光材料为单重态发光体(荧光发光体)、热激活延迟荧光发光材料(TADF)或三重态发光体(磷光发光体)。进一步地，磷光发光体为发光金属有机配合物。
具体地，有机功能材料可以为WO2010135519A1、US20090134784A1和WO2011110277A1中公开的有机功能材料。
当组合物包括金属有机配合物和有机功能材料时，金属有机配合物的质量百分含量为0.01％～30％。进一步地，金属有机配合物的质量百分含量为0.5％～20％。更进一步地，金属有机配合物的质量百分含量为2％～15％。具体地，金属有机配合物的质量百分含量为5％～15％。
进一步地，当组合物包括金属有机配合物和有机功能材料时，有机功能材料为三重态基质材料。
进一步地，当组合物包括金属有机配合物和有机功能材料时，有机功能材料包括三重态基质材料和三重态发光体。
在另一个实施例中，当组合物包括金属有机配合物和有机功能材料时，有机功能材料为热激活延迟荧光发光材料(TADF)。
在另一个实施例中，当组合物包括高聚物和有机功能材料时，有机功能材料为热激活延迟荧光发光材料(TADF)。
下面对三重态基质材料、三重态发光体和TADF作一些较详细的说明。
1、三重态基质材料(TripletHost)：
任何金属配合物或有机化合物都可以作为三重态基质材料的基质，只要其三重态能量比发光体的能量更高，特别是比三重态发光体(磷光发光体)的能量更高。
具体地，三重态基质材料的金属配合物具有如下通式：
Figure PCTCN2017112700-appb-000030
其中，M为金属；(Y3-Y4)为二齿配体；Y3和Y4分别独立地选自C、N、O、P及S中的一种；L为辅助配体；m为整数，m的值从1到M的最大配位数；m+n是M的最大配位数。
在其中一个实施例中，M选自Cu、Au、Ir及Pt中的一种。
进一步地，三重态基质材料的金属配合物具有如下通式：
Figure PCTCN2017112700-appb-000031
其中，(O-N)为两齿配体，金属与O原子和N原子配位。
其中，可作为三重态基质材料的有机化合物为包含有环芳香烃基的化合物或包含有芳香杂环基的化合物。其中，包含有环芳香烃基的化合物包括：苯、联苯、三苯基、苯并及芴；包含有芳香杂环基的化合物包括：二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑、吡啶吲哚、吡咯二吡啶、吡唑、咪唑、三唑类、恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪类、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、恶唑、二苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、邻二氮杂萘、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、苯并呋喃吡啶、呋喃并吡啶、苯并噻吩吡啶、噻吩吡啶、苯并硒吩吡啶及硒吩苯并二吡啶。
此外，可作为三重态基质材料的有机化合物还可以为包含有2环～10环结构的基团，例如：环芳香烃基团或芳香杂环基团。其中，每个基团之间直接连接，或通过氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链结构单元及脂肪环基团中的至少一个连接。进一步地，每个芳香基团(Ar)被氢、烷基、烷氧基、氨基、烯基、炔基、芳烷基、杂烷基、芳基及杂芳基中的一种所取代。
在其中一个实施例中，三重态基质材料的有机化合物包含以下基团中的至少一个:
Figure PCTCN2017112700-appb-000032
Figure PCTCN2017112700-appb-000033
及
Figure PCTCN2017112700-appb-000034
其中，n为0～20的任一整数；X1-X8分别选自CR1和N中的一种；X9选自CR1R2和NR1中的一种；R1-R7分别独立地选自氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基及杂芳基中的一种。
具体地，三重态基质材料选自如下结构中的一种：
Figure PCTCN2017112700-appb-000035
Figure PCTCN2017112700-appb-000036
及
Figure PCTCN2017112700-appb-000037
2、三重态发光体(Triplet Emitter)
三重态发光体也称磷光发光体。三重态发光体为含有通式M(L)n的金属配合物。其中，M为金属元素，L为有机配体，L通过一个或多个位置键接或配位连接到M上；n为大于1的整数，优选地，n选自1、2、3、4、5及6中的一个。
进一步地，金属配合物通过一个或多个位置联接到聚合物上。具体地，金属配合物通过有机配体联接到聚合物上。
进一步地，M选自过渡金属元素、镧系元素及锕系元素中的一种。优选地，M选自Ir、Pt、Pd、Au、Rh、Ru、Os、Sm、Eu、Gd、Tb、Dy、Re、Cu及Ag中的一种。更优选地，M选自Os、Ir、Ru、Rh、Cu、Au及Pt中的一种。
其中，三重态发光体包含有螯合配体，即配体。配体通过至少两个结合点与金属配位。进一步地，三重态发光体包含有2个～3个的双齿配体或多齿配体。螯合配体有利于提高金属配合物的稳定性。
有机配体选自苯基吡啶衍生物、7,8-苯并喹啉衍生物、2(2-噻吩基)吡啶衍生物、2(1-萘基)吡啶衍生物及2苯基喹啉衍生物中的一种。进一步地，有机配体都可被取代，例如被含氟或三氟甲基取代。辅助配体选自乙酸丙酮和苦味酸中的一种。
具体地，三重态发光体的金属配合物具有如下通式：
Figure PCTCN2017112700-appb-000038
其中，M为金属。优选地，M选自过渡金属元素、镧系元素及锕系元素中的一种；
Ar1为环状基团，其中，Ar1至少包含有一个施主原子，即有一孤对电子的原子，如氮或 磷，通过施主原子使环状基团与金属配位连接；
Ar2为环状基团，其中，Ar2至少包含有一个C原子，通过C原子使环状基团与金属连接；
Ar1和Ar2由共价键联接在一起；Ar1和Ar2可各自携带一个或多个取代基团，Ar1和Ar2也可再通过取代基团联接在一起；
L为辅助配体。优选地，L为双齿螯合配体。更优选地，L为单阴离子双齿螯合配体；
m为1～3中的任一整数。优选地，m为2或3。更优选地，m为3；
n是0～2中的任一整数。优选地，n为0或1。更优选地，n为0。
其中，三重态发光体的材料及其应用可以为WO 200070655、WO 200141512、WO 200202714、WO 200215645、EP 1191613、EP 1191612、EP 1191614、WO 2005033244,、WO 2005019373、US 2005/0258742、WO 2009146770、WO 2010015307、WO 2010031485、WO 2010054731、WO 2010054728、WO 2010086089、WO 2010099852、WO 2010102709、US 20070087219A1、US 20090061681A1、US 20010053462A1、Baldo,Thompson et al.Nature 403,(2000),750-753、US 20090061681A1、US 20090061681A1、Adachi et al.Appl.Phys.Lett.78(2001),1622-1624、J.Kido et al.Appl.Phys.Lett.65(1994),2124、Kido et al.Chem.Lett.657,1990、US 2007/0252517A1、Johnson et al.,JACS 105,1983,1795、Wrighton,JACS 96,1974,998、Ma et al.,Synth.Metals 94,1998,245、US 6824895、US 7029766、US 6835469、US 6830828、US 20010053462A1、WO 2007095118A1、US 2012004407A1、WO 2012007088A1、WO2012007087A1、WO 2012007086A1、US 2008027220A1、WO 2011157339A1、CN 102282150A及WO 2009118087A1中公开的三重态发光体的材料及其应用。
具体地，三重态发光体选自如下结构中的一种:
Figure PCTCN2017112700-appb-000039
Figure PCTCN2017112700-appb-000040
Figure PCTCN2017112700-appb-000041
3、热激活延迟荧光发光材料(TADF)：
传统有机荧光材料只能利用电激发形成25％的单线态激子发光，有机电子器件的内量子效率较低(最高为25％)。尽管磷光材料由于重原子中心强的自旋-轨道耦合增强了系间穿越，可以有效利用电激发形成的单线态激子和三线态激子发光，使有机电子器件的内量子效率达到100％。但磷光材料昂贵，材料稳定性差，器件效率滚降严重等问题限制了其在OLED中的应用。热激活延迟荧光发光材料是继有机荧光材料和有机磷光材料之后发展的第三代有机发光材料。该类材料一般具有小的单线态-三线态能级差(ΔEst)，三线态激子可以通过反系间穿越转变成单线态激子发光。因此，可以充分利用电激发下形成的单线态激子和三线态激子，使有机电子器件内量子效率可达到100％。
TADF需要具有较小的单线态-三线态能级差(ΔEst)。其中，TADF的ΔEst<0.3eV。进一步地，TADF的ΔEst<0.2eV。再进一步地，TADF的ΔEst<0.1eV。更进一步地，TADF的ΔEst<0.05eV。
在其中一个实施例中，TADF可以为CN103483332(A)、TW201309696(A)、TW201309778(A)、TW201343874(A)、TW201350558(A)、US20120217869(A1)、WO2013133359(A1)、WO2013154064(A1)、Adachi,et.al.Adv.Mater.,21,2009,4802、Adachi,et.al.Appl.Phys.Lett.,98,2011,083302、Adachi,et.al.Appl.Phys.Lett.,101,2012,093306、Adachi,et.al.Chem.Commun.,48,2012,11392、Adachi,et.al.Nature Photonics,6,2012,253、Adachi,et.al.Nature,492,2012,234、Adachi,et.al.J.Am.Chem.Soc,134,2012,14706、Adachi,et.al.Angew.Chem.Int.Ed,51,2012,11311、Adachi,et.al.Chem.Commun.,48,2012,9580、Adachi,et.al.Chem.Commun.,48,2013,10385、Adachi,et.al.Adv.Mater.,25,2013,3319、Adachi,et.al.Adv.Mater.,25,2013,3707、Adachi,et.al.Chem.Mater.,25,2013,3038、Adachi,et.al.Chem.Mater.,25,2013,3766、Adachi,et.al.J.Mater.Chem.C.,1,2013,4599及Adachi,et.al.J.Phys.Chem.A.,117,2013,5607中公开的TADF。
具体地，TADF选自如下结构中的一种：
Figure PCTCN2017112700-appb-000042
Figure PCTCN2017112700-appb-000043
Figure PCTCN2017112700-appb-000044
在另一个实施例中，组合物包括上述金属有机配合物和有机溶剂，或包括上述高聚物和有机溶剂。进一步地，组合物包括上述金属有机配合物、上述有机功能材料和有机溶剂，或包括上述高聚物、上述有机功能材料和有机溶剂。其中，有机溶剂包括芳族溶剂和杂芳族溶剂中的至少一种。进一步地，有机溶剂包括脂肪族链取代的芳族溶剂、脂肪族环取代的芳族溶剂、芳族酮溶剂及芳族醚溶剂中的至少一种。
具体地，有机溶剂为基于芳族的溶剂或基于杂芳族的溶剂，例如：对二异丙基苯、戊苯、四氢萘、环己基苯、氯萘、1,4-二甲基萘、3-异丙基联苯、对甲基异丙苯、二戊苯、三戊苯、戊基甲苯、邻二甲苯、间二甲苯、对二甲苯、邻二乙苯、间二乙苯、对二乙苯、1,2,3,4-四甲苯、1,2,3,5-四甲苯、1,2,4,5-四甲苯、丁苯、十二烷基苯、二己基苯、二丁基苯、对二异丙基苯、1-甲氧基萘、环己基苯、二甲基萘、3-异丙基联苯、对甲基异丙苯、1-甲基萘、1,2,4-三氯苯、1,3-二丙氧基苯、4,4-二氟二苯甲烷、1,2-二甲氧基-4-(1-丙烯基)苯、二苯甲烷、2-苯基吡啶、3-苯基吡啶、N-甲基二苯胺、4-异丙基联苯、α,α-二氯二苯甲烷、4-(3-苯基丙基)吡啶、苯甲酸苄酯、1,1-双(3,4-二甲基苯基)乙烷、2-异丙基萘、二苄醚等；基于酮的溶剂:1-四氢萘酮，2-四氢萘酮，2-(苯基环氧)四氢萘酮，6-(甲氧基)四氢萘酮，苯乙酮、苯丙酮、二苯甲酮、及它们的衍生物，如4-甲基苯乙酮、3-甲基苯乙酮、2-甲基苯乙酮、4-甲基苯丙酮、3-甲基苯丙酮、2-甲基苯丙酮，异佛尔酮、2,6,8-三甲基-4-壬酮、葑酮、2-壬酮、3-壬酮、5-壬酮、2-癸酮、2,5-己二酮、佛尔酮、二正戊基酮；芳族醚溶剂：3-苯氧基甲苯、丁氧基苯、苄基丁基苯、对茴香醛二甲基乙缩醛、四氢-2-苯氧基-2H-吡喃、1,2-二甲氧基-4-(1-丙烯基)苯、1,4-苯并二噁烷、1,3-二丙基苯、2,5-二甲氧基甲苯、4-乙基本乙醚、1,2,4-三甲氧基苯、4-(1-丙烯基)-1,2-二甲氧基苯、1,3-二甲氧基苯、缩水甘油基苯基醚、二苄基醚、4-叔丁基茴香醚、反式-对丙烯基茴香醚、1,2-二甲氧基苯、1-甲氧基萘、二苯醚、2-苯氧基甲醚、2-苯氧基四氢呋喃、乙基-2-萘基醚、戊醚c己醚、二辛醚、乙二醇二丁醚、二乙二醇二乙醚、二乙二醇丁基甲醚、二乙二醇二丁醚、三乙二醇二甲醚、三乙二醇乙基甲醚、三乙二醇丁基甲醚、三丙二醇二甲醚、四乙二醇二甲醚；酯溶剂：辛酸烷酯、癸二酸烷酯、硬脂酸烷酯、苯甲酸 烷酯、苯乙酸烷酯、肉桂酸烷酯、草酸烷酯、马来酸烷酯、烷内酯及油酸烷酯等。
进一步，上述有机溶剂为脂肪族酮，例如：2-壬酮、3-壬酮、5-壬酮、2-癸酮、2,5-己二酮、2,6,8-三甲基-4-壬酮、佛尔酮、二正戊基酮等；或脂肪族醚，例如，戊醚、己醚、二辛醚、乙二醇二丁醚、二乙二醇二乙醚、二乙二醇丁基甲醚、二乙二醇二丁醚、三乙二醇二甲醚、三乙二醇乙基甲醚、三乙二醇丁基甲醚、三丙二醇二甲醚及四乙二醇二甲醚等。
其中，上述有机溶剂还包括附加溶剂。附加溶剂选自甲醇、乙醇、2-甲氧基乙醇、二氯甲烷、三氯甲烷、氯苯、邻二氯苯、四氢呋喃、苯甲醚、吗啉、甲苯、邻二甲苯、间二甲苯、对二甲苯、1,4二氧杂环己烷、丙酮、甲基乙基酮、1,2二氯乙烷、3-苯氧基甲苯、1,1,1-三氯乙烷、1,1,2,2-四氯乙烷、醋酸乙酯、醋酸丁酯、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、四氢萘、萘烷及茚中的至少一种。
在其中一个实施例中，当组合物作为印刷油墨时，组合物为溶液或悬浮液。粘度和表面张力是组合物的重要参数。合适的组合物的表面张力参数适合于特定的基板和特定的印刷方法。
其中，在工作温度或在25℃下，组合物的表面张力为19dyne/cm～50dyne/cm。进一步地，组合物的表面张力为22dyne/cm～35dyne/cm。更进一步地，组合物的表面张力为25dyne/cm～33dyne/cm。
其中，在25℃下，金属有机配合物在甲苯溶液中的溶解度≥2mg/ml。进一步地，金属有机配合物在甲苯溶液中的溶解度≥3mg/ml。再进一步地，金属有机配合物在甲苯溶液中的溶解度≥4mg/ml。更进一步地，金属有机配合物在甲苯溶液中的溶解度≥5mg/ml。
在另一个实施例中，当组合物用于喷墨印刷时，在工作温度或25℃下，组合物的粘度为1cps～100cps。进一步地，组合物的粘度为1cps～50cps。再进一步地，组合物的粘度为1.5cps～20cps。更进一步地，组合物的粘度为4.0cps～20cps。
粘度可以通过很多方法调节，例如，通过选取溶剂和调节组合物中功能材料的浓度来调节粘度。其中，上述组合物可以根据印刷方法来适当调节组合物的粘度。当上述组合物包括金属有机配合物、有机功能材料和有机溶剂，或包括高聚物、有机功能材料和有机溶剂时，有机功能材料的质量百分含量为0.3％～30％。进一步地，有机功能材料的质量百分含量为0.5％～20％。再进一步地，有机功能材料的质量百分含量为0.5％～15％。更进一步地，有机功能材料的质量百分含量为0.5％～10％。更进一步地，有机功能材料的质量百分含量为1％～5％。
当上述组合物作为涂料或印刷油墨时，能够通过打印或涂布的方法制备有机电子器件。其中，打印或涂布的方法包括但不限于喷墨打印，喷印(Nozzle Printing)，活版印刷，丝网印刷，浸涂，旋转涂布，刮刀涂布，辊筒印花，扭转辊印刷，平版印刷，柔版印刷，轮转印刷，喷涂，刷涂、移印、喷印刷(Nozzle printing)及狭缝型挤压式涂布等。优选地，打印或涂布的方法选自喷墨印刷、狭缝型挤压式涂布、喷印刷及凹版印刷中的一种。
其中，上述组合物还包括添加剂，添加剂选自表面活性化合物、润滑剂、润湿剂、分散剂、疏水剂及粘接剂中的至少一种。添加剂用于调节组合物的粘度、成膜性能及附着性等。
其中，关于打印技术及对溶液的相关要求，如溶剂及浓度，粘度等详细信息，请参见Helmut Kipphan主编的《印刷媒体手册:技术和生产方法》(Handbook of Print Media:Technologies and Production Methods),ISBN 3-540-67326-1。
一实施方式的有机电子器件，包括上述的金属有机配合物、上述的高聚物及上述的组合物中的一种。
有机电子器件选自但不限于有机发光二极管(OLED)、有机光伏电池(OPV)、有机发光电池(OLEEC)、有机场效应管(OFET)、有机发光场效应管、有机激光器、有机自旋电子器件、有机传感器及有机等离激元发射二极管(Organic Plasmon Emitting Diode)中的一种。进一步地，有机电子器件为OLED。具体地，将上述的金属有机配合物用于OLED器件的发光层中。
在其中一个实施例中，有机电子器件包括功能层。其中，功能层的材料包含上述的金属有机配合物及高聚物中的一种。
进一步地，有机电子器件包括基片、阳极、发光层及阴极。其中，基片可以是不透明的或透明的。透明的基片可以用来制造一个透明的发光元器件。基片可以为Bulovic等Nature 1996,380,p29，和Gu等，Appl.Phys.Lett.1996,68,p2606中公开的基片。基片可以是刚性的或弹性的。进一步地，基片选自塑料、金属、半导体晶片及玻璃中的一种。具体地，基片有一个平滑的表面。更具体地，基片的表面无缺陷。
在其中一个实施例中，基片是柔性的，基片为聚合物薄膜或塑料。其中，基片的玻璃化温度Tg为150℃以上。进一步地，基片的玻璃化温度Tg为200℃以上。再进一步地，基片的玻璃化温度Tg为250℃以上。更进一步地，基片的玻璃化温度Tg为300℃以上。具体地，柔性的基片为聚对苯二甲酸乙二醇酯(PET)或聚乙二醇(2,6-萘)(PEN)。
阳极包括导电金属、金属氧化物及导电聚合物中的一种。阳极能够容易地注入空穴到空 穴注入层(HIL)或空穴传输层(HTL)或发光层中。在一个的实施例中，阳极的功函数和发光层中的发光体HOMO能级之间能级差绝对值，或阳极的功函数和作为HIL或HTL或电子阻挡层(EBL)的p型半导体材料的HOMO能级或价带能级的差的绝对值小于0.5eV。进一步地，小于0.3eV。更进一步地，小于0.2eV。
其中，阳极材料包括但不限于：Al、Cu、Au、Ag、Mg、Fe、Co、Ni、Mn、Pd、Pt、ITO、铝掺杂氧化锌(AZO)等。阳极材料可以使用技术沉积的方法获取，如物理气相沉积法，包括射频磁控溅射，真空热蒸发，电子束(e-beam)等。
其中，阳极是图案结构化的。图案化的ITO导电基板可在市场上买到，并且可以用来制备有机电子器件。
其中，阴极还可以容易地注入电子到EIL或ETL或直接到发光层中。在一个的实施例中，阴极的功函数和发光层中发光体LUMO能级差的绝对值，或阴极的功函数与作为电子注入层(EIL)或电子传输层(ETL)或空穴阻挡层(HBL)的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.5eV。进一步地，阴极的功函数和发光层中发光体LUMO能级差的绝对值，或阴极的功函数与作为电子注入层(EIL)或电子传输层(ETL)或空穴阻挡层(HBL)的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.3eV。更进一步地，阴极的功函数和发光层中发光体LUMO能级差的绝对值，或阴极的功函数与作为电子注入层(EIL)或电子传输层(ETL)或空穴阻挡层(HBL)的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.2eV。
一般地，可用作OLED的阴极的材料都可作为有机电子器件的阴极材料。阴极材料选自Al、Au、Ag、Ca、Ba、Mg、LiF/Al、Mg/Ag合金、BaF2/Al、Cu、Fe、Co、Ni、Mn、Pd、Pt及ITO中的一种。阴极材料可以采用物理气相沉积法制备。其中，物理气相沉积法包括射频磁控溅射，真空热蒸发，电子束(e-beam)等。
OLED还可以包括其他功能层，其他功能层包括空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、电子注入层(EIL)、电子传输层(ETL)及空穴阻挡层(HBL)等。
其中，发光层包含上述的金属有机配合物或高聚物。进一步地，发光层通过溶液加工的方法制备而成。
其中，上述的发光器件的发光波长为300nm～1000nm。优选地，上述的发光器件的发光波长为350nm～900nm。更优选地，上述的发光器件的发光波长为400nm～800nm。
上述有机电子器件可应用于电子设备中。其中，电子设备包括显示设备、照明设备、光源及传感器等。
具体实施例
实施例1：合成化合物Ir-1
Figure PCTCN2017112700-appb-000045
(1)合成中间体1a
将2-氨基-9,9-二甲基芴(4g，19mmol)溶于100mL冰醋酸，在0℃下滴加乙酸酐(16mL，16.9mmol)，然后升至室温反应12h，加水析出固体，抽滤，滤饼用丙酮和水的混合溶液重结晶1a(3.8g)。
(2)合成中间体1b
将中间体1a(5g，19.9mmol)溶于100mL丙酮，50mL冰醋酸和20mL浓硫酸的混合溶液，在0℃下滴加3mL浓硝酸，然后升至室温，等反应液变黑后，加水淬灭，抽滤，滤饼用丙酮和水的混合溶液重结晶1b(4.7g)
(3)合成中间体1c
将中间体1b(4.5g，15mmol)溶于100mL乙醇，然后加入10mL浓硫酸，90℃下反应24h，冷却到室温，向反应溶液中加水，抽滤，滤饼用丙酮和水的混合溶液重结晶1c(3.1g)。
(4)合成中间体1d
将中间体1c(4g，15.7mmol)溶于100mL乙醇，然后加入2g
Pd/C，80℃下反应3h，冷却到室温，过滤，滤液旋干，加入少量乙酸乙酯溶解，再加入石油醚析出固体1d(2.8g)。
(5)合成中间体1e
中间体1d(0.224g，1mmol)，2-吡啶甲醛(0.107g，1mmol)溶于20mL甲醇，然后加入2mL磷酸，60℃下反应3h，浓缩，加水，用乙酸乙酯萃取，最后用乙酸乙酯：石油醚：乙醇＝10:2:1过柱得到固体1e(0.248g)。
(6)合成化合物Ir-1
在一个干燥的双口瓶里放置中间体1e(0.6g，1.9mmol)，2-苯基吡啶铱氯桥(1.14g，0.95mmol)，抽真空充氮气循环三次，然后加入5mL二氯甲烷和5mL甲醇，常温搅拌过夜，浓缩，用二氯甲烷/石油醚＝1:10过柱得到Ir-1(0.46g)。
Figure PCTCN2017112700-appb-000046
实施例2：合成化合物Cu-1
Figure PCTCN2017112700-appb-000047
(1)合成中间体2a
将2，6-二异丙基胺(19.7g，111mmol)和冰醋酸(1mL)溶于50mL甲苯，室温下搅拌，然后缓慢滴加乙二醛(5.1g，88mmol)的甲醇溶液50mL，继续反应6小时，抽滤，滤饼用甲醇冲洗，真空干燥得到固体2a(16.6g)。
(2)合成中间体2b
将中间体2a(4g，10.6mmol)，多聚甲醛(0.4g)溶于80mL乙酸乙酯，室温搅拌10分钟，然后滴加三甲基氯硅烷(2mL)的乙酸乙酯溶液4mL，滴加完毕后继续搅拌2小时，冷却到0℃，抽滤，滤饼用二氯甲烷和乙酸乙酯的混合溶液重结晶，得到固体2b(3.5g)。
(3)合成中间体2c
将中间体2b(0.42g，1mmol)，氯化亚铜(0.098g，1mmol)和碳酸钾(0.28g，2mmol)放置在一干燥的反应瓶中，然后加入15mL丙酮，在60℃下搅拌反应24小时，冷却到室温，过滤，滤液浓缩，用正戊烷重结晶，得到2c(0.43g)。
(4)合成化合物Cu-1
在氮气保护下，在一个干燥的双口瓶里放置氢化钠(16mg，0.4mmol，60％矿物油)，加入10mL干燥THF，室温下搅拌30分钟，然后加入1e的四氢呋喃溶液10mL(124.6mg，0.4mmol)，室温下搅拌1小时，然后加入2c(195mg，0.4mmol)，继续搅拌3小时，过滤，浓缩，用二氯甲烷和乙醚的混合溶剂重结晶得到固体Cu-1(0.12g)。
Figure PCTCN2017112700-appb-000048
实施例3：合成化合物Cu-2
Figure PCTCN2017112700-appb-000049
(1)合成中间体3a
将菲二酮(2.08g，10mmol)，吡啶-2-甲醛(1.07g，10mmol)和醋酸铵(7.7g，100mmol)置于一干燥的烧瓶中，然后加入2mL冰醋酸，回流3h，冷却到室温，逐滴加入氨水，析出沉淀，然后用乙醇重结晶得到固体3a(1.47g)。
(2)合成化合物Cu-2
在氮气保护下，在一个干燥的双口瓶里放置氢化钠(16mg，0.4mmol，60％矿物油)，加入10mL干燥THF，室温下搅拌30分钟，然后加入3a的四氢呋喃溶液10mL(118mg，0.4mmol)，室温下搅拌1小时，然后加入2c(195mg，0.4mmol)，继续搅拌3小时，过滤，浓缩，用二氯甲烷和乙醚的混合溶剂重结晶得到固体Cu-2(0.1g)。
Figure PCTCN2017112700-appb-000050
测试：
通过量子计算实施例1～3得到的金属有机配合物Ir-1，Cu-1和Cu-2的能级。比如利用TD-DFT(含时密度泛函理论)通过Gaussian03W(Gaussian Inc.)计算得到。具体的模拟方法可参见WO2011141110。首先用半经验方法“Ground State/Hartree-Fock/Default Spin/LanL2MB”(Charge 0/Spin Singlet)来优化分子几何结构，然后有机分子的能量结构由TD-DFT(含时密度泛函理论)方法算得“TD-SCF/DFT/Default Spin/B3PW91/gen geom＝connectivity pseudo＝lanl2”(Charge 0/Spin Singlet)。HOMO和LUMO能级按照下面的校准公式计算，S1和T1直接使用。
HOMO(eV)＝((HOMO(Gaussian)×27.212)-0.9899)/1.1206
LUMO(eV)＝((LUMO(Gaussian)×27.212)-2.0041)/1.385
其中HOMO(G)和LUMO(G)是Gaussian 03W的直接计算结果，单位为Hartree。结果如表1所示：
表1
材料 HOMO[eV] LUMO[eV] Tl[eV] Sl[eV]
Ir-I -5.11 -2.67 2.28 2.49
Cu-I -4.93 -2.16 2.61 3.06
Cu-2 -4.88 -2.15 2.50 3.07
分别采用实施例1～3得到的金属有机配合物制备OLED器件，具体步骤如下：
a、导电玻璃基片的清洗：首次使用时，可用多种溶剂进行清洗，例如氯仿、酮、异丙醇进行清洗，然后进行紫外臭氧等离子处理；
b、HTL(60nm)，EML(45nm)，ETL(35nm)：在高真空(1×10-6毫巴，mbar)中热蒸镀而 成；
c、阴极：LiF/Al(1nm/150nm)在高真空(1×10-6毫巴)中热蒸镀而成；
d、封装：器件在氮气手套箱中用紫外线硬化树脂封装。
通过实施例1～3得到的金属有机配合物制备的OLED器件分别具有如下结构：
(1)OLED-1：ITO/NPD(60nm)/15％Ir-1:mCP(45nm)/TPBi(35nm)/LiF(1nm)/Al(150nm)/阴极；
(2)OLED-2：ITO/NPD(60nm)/15％Cu-1:mCP(45nm)/TPBi(35nm)/LiF(1nm)/Al(150nm)/阴极；
(3)OLED-3：ITO/NPD(60nm)/15％Cu-2:mCP(45nm)/TPBi(35nm)/LiF(1nm)/Al(150nm)/阴极。
测试：
各OLED器件的电流电压亮度(JVL)特性通过蒸镀或旋涂设备来表征，同时记录重要的参数如效率及外部量子效率。
经检测，OLED-1、OLED-2及OLED-3的最大外部量子效率分别为15.1％，10.2％及8.4％。
其中，器件的结构可进一步的优化，例如HTM，ETM及主体材料的组合，能够进一步提高器件的性能，特别是效率，驱动电压及寿命。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (20)

  1. 一种金属有机配合物，具有如下通式：
    Figure PCTCN2017112700-appb-100001
    其中，
    Ar1选自芳香烃基、被R1取代的芳香烃基、杂芳香环烃基、被R1取代的杂芳香环烃基、非芳香族环基及被R1取代的非芳香族环基中的一种中的一种；
    Ar2选自包含N原子的杂芳香环烃基及被R1取代的包含N原子的杂芳香环烃基中的一种；
    R1选自H、F、Cl、Br、I、D、CN、NO2、CF3、B(OR2)2、Si(R2)3、直链烷烃基、被R2取代的直链烷烃基、烷烃醚基、被R2取代的烷烃醚基、烷烃硫醚基、被R2取代的烷烃硫醚基、支链烷烃基、被R2取代的支链烷烃基、环烷烃基及被R2取代的环烷烃基中的一种；
    R2选自H、D、脂肪族烷烃基、芳香基、芳香环基及杂芳香基中的一种；
    M为过渡族金属元素；
    L选自单齿中性配体、单齿阴离子配体、双齿中性配体及双齿阴离子配体中的一种；
    m为1～3中的任一整数；
    n为0～2中的任一整数。
  2. 根据权利要求1的金属有机配合物，其特征在于，所述金属有机配合物的通式选自
    Figure PCTCN2017112700-appb-100002
    Figure PCTCN2017112700-appb-100003
    Figure PCTCN2017112700-appb-100004
    中的一种；
    其中，x为0～2中的任一整数，y为0～3中的任一整数，z为0～4中的任一整数。
  3. 根据权利要求1所述的金属有机配合物，其特征在于，所述Ar1选自通式
    Figure PCTCN2017112700-appb-100005
    Figure PCTCN2017112700-appb-100006
    中的一种
    其中，多个X1分别独立地选自CR1和N中的一种；
    Y1选自CR2R3、SiR2R3、NR2、C(＝O)、S及O中的一种；
    R1、R2及R3分别独立地选自H、D、具有1个～20个C原子的直链烷基、具有1个～20个C原子的烷氧基、具有1个～20个C原子的硫代烷氧基、具有3个～20个C原子的支链烷基、具有3个～20个C原子的环状的烷基、具有3个～20个C原子的烷氧基、具有3个～20个C原子的硫代烷氧基、具有3个～20个C原子的甲硅烷基、具有1个～20个C 原子的取代的酮基、具有2个～20个C原子的烷氧基羰基、具有7个～20个C原子的芳氧基羰基、氰基、氨基甲酰基、卤甲酰基、甲酰基、异氰基、异氰酸酯基、硫氰酸酯基、异硫氰酸酯基、羟基、硝基、CF3基、Cl、Br、F、可交联的基团、具有5个～40个C原子的芳族环基、具有5个～40个C原子的杂芳族环基、具有5个～40个C原子的芳氧基及具有5个～40个C原子的杂芳氧基中的至少一种；其中，R1、R2及R3之间能够键合成脂族环基或芳族环基，同时R1、R2及R3本身也能够分别键合成脂族环基或芳族环基。
  4. 根据权利要求1或3所述的金属有机配合物，其特征在于，所述Ar1选自以下基团中的一种：
    Figure PCTCN2017112700-appb-100007
    其中，基团中的H能够进一步被取代。
  5. 根据权利要求1所述的金属有机配合物，其特征在于，所述Ar2选自通式
    Figure PCTCN2017112700-appb-100008
    Figure PCTCN2017112700-appb-100009
    中的一种；
    其中，多个X1分别独立地选自CR1和N中的一个，且多个所述X1中至少一个为N；
    Y1分别选自CR2R3、SiR2R3、NR2、C(＝O)、S及O中的一种；
    R1、R2及R3分别选自H、D、具有1个～20个C原子的直链烷基、具有1个～20个C原子的烷氧基、具有1个～20个C原子的硫代烷氧基、具有3个～20个C原子的支链烷基、具有3个～20个C原子的环状的烷基、具有3个～20个C原子的烷氧基、具有3个～20个C原子的硫代烷氧基、具有3个～20个C原子的甲硅烷基、具有1个～20个C原子的取代的酮基、具有2个～20个C原子的烷氧基羰基、具有7个～20个C原子的芳氧基羰基、氰基、氨基甲酰基、卤甲酰基、甲酰基、异氰基、异氰酸酯基、硫氰酸酯基、异硫氰酸酯基、羟基、硝基、CF3基、Cl、Br、F、可交联的基团、具有5个～40个C原子的芳族环基、具有5个～40个C原子的杂芳族环基、具有5个～40个C原子的芳氧基及具有5个～40个C原子的杂芳氧基中的至少一种；其中，R1、R2及R3之间能够键合成脂族环基或芳族环基，同时R1、R2及R3本身也能够分别键合成脂族环基或芳族环基。
  6. 根据权利要求1或5所述的金属有机配合物，其特征在于，所述Ar2选自以下基团中的一种：
    Figure PCTCN2017112700-appb-100010
    其中，基团中的H能够进一步被取代。
  7. 根据权利要求1所述金属有机配合物，其特征在于，所述金属有机配合物的配体的通式如下，所述配体的三线态能级T1≥2.0eV。
    Figure PCTCN2017112700-appb-100011
  8. 根据权利要求1～2任意一项所述的金属有机配合物，其特征在于，所述M选自铬、钼、钨、钌、铑、镍、银、铜、锌、钯、金、饿、铼、铱及铂中的一种。
  9. 根据权利要求1～2任意一项所述的金属有机配合物，其特征在于，所述L选自通式
    Figure PCTCN2017112700-appb-100012
    Figure PCTCN2017112700-appb-100013
    中的一种；
    其中，虚线表示与所述M直接相连的键，u为
    Figure PCTCN2017112700-appb-100014
    中的任一整数，v为
    Figure PCTCN2017112700-appb-100015
    中的任一整数，w为
    Figure PCTCN2017112700-appb-100016
    中的任一整数，t为
    Figure PCTCN2017112700-appb-100017
    中的任一整数。
  10. 根据权利要求1～2和9任意一项的金属有机配合物，其特征在于，所述L选自
    Figure PCTCN2017112700-appb-100018
    Figure PCTCN2017112700-appb-100019
    中的一种；
    其中，R20至R89分别独立地选自H、F、Cl、Br、I、D、CN、NO2、CF3、B(OR2)2、Si(R2)3、直链烷烃基、烷烃醚基、含1个～10个碳原子的烷烃硫醚基、含1个～10个碳原子的支链烷烃基、含1个～10个碳原子的环烷烃基，含3个～10个碳原子的烷烃醚基、含3个～10个碳原子的烷烃硫醚基及含6个～10个碳原子的芳基中的一种。
  11. 一种高聚物，其特征在于，包括重复单元，所述重复单元包含权利要求1～10任意一项所述的金属有机配合物。
  12. 根据权利要求11所述的高聚物，其特征在于，所述高聚物为共轭高聚物。
  13. 一种组合物，包括如权利要求1～10任意一项所述的金属有机配合物及如权利要求11～12任意一项所述的高聚物中的一种。
  14. 根据权利要求13所述的组合物，其特征在于，还包括有机功能材料，所述有机功能材料选自空穴注入材料、空穴传输材料、空穴阻挡材料、电子传输材料、电子注入材料、电子阻挡材料、发光材料、有机基质材料及有机染料中的至少一种。
  15. 根据权利要求14所述的组合物，其特征在于，所述发光材料选自单重态发光体、热激活延迟荧光发光材料及三重态发光体中的一种。
  16. 根据权利要求14所述的组合物，其特征在于，所述组合物包括如权利要求1～10任意一项所述的金属有机配合物和有机功能材料，所述金属有机配合物的质量百分含量为0.01％～30％。
  17. 根据权利要求13～16任意一项所述的组合物，其特征在于，还包括有机溶剂。
  18. 根据权利要求17所述的组合物，其特征在于，还包括有机功能材料，所述有机功能材料选自空穴注入材料、空穴传输材料、空穴阻挡材料、电子传输材料、电子注入材料、电子阻挡材料、发光材料、有机基质材料及有机染料中的至少一种。
  19. 一种有机电子器件，包括如权利要求1～10任意一项所述的金属有机配合物、如权利要求11～12所述的高聚物及如权利要求13～18任意一项所述的组合物中的一种。
  20. 根据权利要求19所述的有机电子器件，其特征在于，所述有机电子器件选自有机发光二极管、有机光伏电池、有机发光电池、有机场效应管、有机发光场效应管、有机激光器、有机自旋电子器件、有机传感器及有机等离激元发射二极管中的一种。
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