CN108484681A - One kind is used as transient metal complex, preparation method and the application of phosphor material - Google Patents
One kind is used as transient metal complex, preparation method and the application of phosphor material Download PDFInfo
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- CN108484681A CN108484681A CN201810229201.7A CN201810229201A CN108484681A CN 108484681 A CN108484681 A CN 108484681A CN 201810229201 A CN201810229201 A CN 201810229201A CN 108484681 A CN108484681 A CN 108484681A
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- 239000000463 material Substances 0.000 title claims abstract description 33
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 18
- 230000001052 transient effect Effects 0.000 title claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003446 ligand Substances 0.000 claims abstract description 45
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 8
- 238000006467 substitution reaction Methods 0.000 claims description 57
- -1 phosphinothioyl Chemical group 0.000 claims description 28
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 125000001072 heteroaryl group Chemical group 0.000 claims description 19
- 125000004414 alkyl thio group Chemical group 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 229910000077 silane Inorganic materials 0.000 claims description 16
- 238000006884 silylation reaction Methods 0.000 claims description 16
- 150000001491 aromatic compounds Chemical class 0.000 claims description 14
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 11
- 229910052741 iridium Inorganic materials 0.000 claims description 11
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical class C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical group 0.000 claims description 9
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical class CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 8
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 8
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000004450 alkenylene group Chemical group 0.000 claims description 8
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 8
- 125000004457 alkyl amino carbonyl group Chemical group 0.000 claims description 8
- 125000003282 alkyl amino group Chemical group 0.000 claims description 8
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000004419 alkynylene group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 125000005110 aryl thio group Chemical group 0.000 claims description 8
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 8
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052805 deuterium Inorganic materials 0.000 claims description 8
- 125000004185 ester group Chemical group 0.000 claims description 8
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 8
- 239000003205 fragrance Chemical class 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000004415 heterocyclylalkyl group Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 claims description 8
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 125000004568 thiomorpholinyl group Chemical group 0.000 claims description 8
- 229930192474 thiophene Natural products 0.000 claims description 8
- 125000001425 triazolyl group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 150000003577 thiophenes Chemical class 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000005013 aryl ether group Chemical group 0.000 claims description 5
- 125000002757 morpholinyl group Chemical group 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 150000005360 2-phenylpyridines Chemical class 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N Heptanedioic acid Natural products OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 3
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 claims 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims 1
- 125000002877 alkyl aryl group Chemical group 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims 1
- 239000003086 colorant Substances 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000005281 excited state Effects 0.000 description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PMNPSCJVKKSJSG-UHFFFAOYSA-N 1,1-diphenyl-2,3-di(propan-2-yl)guanidine Chemical class C=1C=CC=CC=1N(C(=NC(C)C)NC(C)C)C1=CC=CC=C1 PMNPSCJVKKSJSG-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- OKQKDCXVLPGWPO-UHFFFAOYSA-N sulfanylidenephosphane Chemical class S=P OKQKDCXVLPGWPO-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- MQRCTQVBZYBPQE-UHFFFAOYSA-N 189363-47-1 Chemical compound C1=CC=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC=CC=1)C=1C=CC=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MQRCTQVBZYBPQE-UHFFFAOYSA-N 0.000 description 1
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical class NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 241000736199 Paeonia Species 0.000 description 1
- 235000006484 Paeonia officinalis Nutrition 0.000 description 1
- YOOWJTSNIZYWCT-UHFFFAOYSA-N [Ir]#P Chemical compound [Ir]#P YOOWJTSNIZYWCT-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000001296 phosphorescence spectrum Methods 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000004426 substituted alkynyl group Chemical group 0.000 description 1
Classifications
-
- 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
- C07F15/006—Palladium 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
- 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
-
- 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
- H10K85/341—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to organic photoelectrical material technical fields, more particularly to a kind of transient metal complex, preparation method and application for being used as phosphor material.The present invention passes through Z1、Z2、Z3Collocation the wavelength of transmitted light of material can be adjusted in larger wave-length coverage, while main ligand further fine-tunes the wavelength of transmitting light by hetero atom, this has important value for the luminescent material for obtaining various wavelength.Not only luminous efficiency is high for complex produced by the present invention, but also the wavelength for emitting light can be in a wide range of interior adjusting.The main ligand skeleton structure having the same of such complex, by changing the position and hetero atom type of the position, hetero atom of functional group on main ligand, to realize adjusting of the wavelength of transmitted light in dark red optical range.In addition, the preparation method of different colours luminescent material is essentially identical, it is easy to operate.
Description
Technical field
The invention belongs to organic photoelectrical material technical fields, more particularly to a kind of Transition metal complexes for being used as phosphor material
Object, preparation method and application.
Background technology
Display technology of the organic electroluminescence device (OLED) as a new generation, overcomes first generation CRT monitor volume
Greatly, disadvantage heavy, power consumption is big, also overcome LCD display visual angle is small, response speed is slow, it is unusable under low temperature and itself
The deficiency that cannot be shone, it is maximum to break through the mechanical tenacity, low temperature process and sandwich-type device architecture for being material, not only may be used
It to obtain visual effect more better than conductivity structure LCD, can also be applied on any frivolous substrate, have and lure very much
The application prospect of people, development potentiality are huge.
In the research of OLED, the selection of organic material plays conclusive effect.Sandwich type OLED device is according to work(
Can classify can be divided into hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer etc., and luminescent layer
Material is called material of main part.
Due to the SO coupling effect of noble metal so that the excitation state triplet state of script spin forbidden to ground state list
The radiation transistion of line state becomes local permission, and the PhOLED (phosphorescent OLED) based on metal complex can be effective
Ground utilizes singlet exciton and triplet excitons, and theoretically internal quantum efficiency can reach 100%.And singlet excited state arrives
Triplet excited states be between alter jump probability significantly improve, promote PhOLED generate high efficiency phosphorescent shine.Compared to fluorescence OLED,
The many advantages of PhOLED make it be concerned, and become the hot spot of research.Phosphor material is repaiied as luminescent layer by materials chemistry
Decorations and device architecture optimization, the anti-concentration quenching ability enhancing of device, luminous efficiency can be promoted steadily.
It is more to use iridium, platinum, palladium element in numerous precious metals complex includes lanthanide complexes.It removes
Metallic element is outer to being affected for metal combination physical performance, Forrest and Thompson etc. be based on cyclisation metal ligand and
Assistant ligand has synthesized a series of metal complex.The minimum triplet excited state of these metal complexs by metal d tracks to
The triplet excited state of ligand π * tracks and the triplet excited state of ligand trajectory to π * tracks form, using different cyclometallated ligands
The red shift of phosphorescence spectrum can be achieved.In order to send out the phosphorescence of recombination, it is desirable that the triplet excited state energy level of assistant ligand is higher than ring
Metallize ligand and metal to ligand triplet excited state energy level.
Realize the full-color displays of OLED, suitable blue, green and red phosphorescence material are crucial.Wherein red phosphorescent material
Material there are types it is deficient, luminous efficiency is low, excitation purity is poor the problems such as.Efficient peony phosphor material is developed, is conducive to
Expand the colour gamut of full-color display, moreover it is possible to arrange in pairs or groups more blue lights and green light material.
Precious metals complex phosphor material luminescent color and device light emitting efficiency are all closely bound up with ligand.It obtains dark red
Color phosphor material needs to introduce the lumo energy of suitable ligand reduction metal complex or improves HOMO energy levels, to reduce
The energy band band gap of material, makes spectral red shift.But the selection of ligand is still design and synthesizes the hot and difficult issue of phosphor material.
Invention content
The present invention in view of the deficiency of the prior art, provides a kind of Transition metal complexes for being used as phosphor material
Object, preparation method and application.
The technical solution that the present invention solves above-mentioned technical problem is as follows：One kind is used as the Transition metal complexes of phosphor material
Object, structural formula are as follows：
Wherein, X1、X2、X3、X4Separate is N, C or B；
Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8Separate is N or CR1, wherein R1It does not take for hydrogen, deuterium, halogen, substitution or
The aryl in generation, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted heteroaryl, takes substituted or unsubstituted arlydene
Generation or unsubstituted benzheterocycle aryl, substituted or unsubstituted polyheteroaromatic, substituted or unsubstituted benzheterocycle aliphatic radical,
Substituted or unsubstituted fragrant amino, substituted or unsubstituted arylthio, substituted or unsubstituted sub- arylthio, substitution or unsubstituted
Aryl ether group, substituted or unsubstituted aryl alkyl, substituted or unsubstituted dialkyiarylsilyl, substitution or unsubstituted
Adamantane, substituted or unsubstituted diarye silyl, substituted or unsubstituted aromatic compound and its fragrance derivatives,
Substituted or unsubstituted alkyl, substituted or unsubstituted silylation, substituted or unsubstituted naphthenic base, substituted or unsubstituted Asia
Naphthenic base, substituted or unsubstituted Heterocyclylalkyl, substituted or unsubstituted sub- Heterocyclylalkyl, substituted or unsubstituted two cycloalkanes
Base, substituted or unsubstituted trialkylsilkl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkenylene, substitution
Or unsubstituted alkynyl, substituted or unsubstituted alkynylene, substituted or unsubstituted heterocycle aliphatic radical, substituted or unsubstituted phosphine sulfide
Base, substituted or unsubstituted phosphinyl, substituted or unsubstituted triazine radical, substituted or unsubstituted triazolyl, substitution do not take
The morpholinyl in generation, substituted or unsubstituted thio-morpholinyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylene oxide
Base, substituted or unsubstituted alkylthio group, substituted or unsubstituted alkylenethio, substituted or unsubstituted alkylamino, substitution or not
It is substituted benzenesulfonyl, substituted or unsubstituted quinoline sulfonyl, substituted or unsubstituted benzoyl, substituted or unsubstituted
Diazanyl, substituted or unsubstituted ester group, substituted or unsubstituted alkyl-carbonyl, substituted or unsubstituted alkoxy carbonyl, substitution
Or unsubstituted alkyl amino-carbonyl, substituted or unsubstituted silylation carbonyl, substituted or unsubstituted alkoxy silane, substitution or
Unsubstituted alkylthio group silane, substituted or unsubstituted acetylpyridine, substituted or unsubstituted fluorenes, it is substituted or unsubstituted,
Substituted or unsubstituted polycyclc aromatic compound, substituted or unsubstituted carbazole, substituted or unsubstituted thiophene, hydroxyl, carboxylic
Base, nitro or CF3Any one；
Z1、Z2And Z3Separate is N, O, S, Se, CR2、NR3Or CR4R5；Wherein, R2、R3、R4And R5It is separate
For hydrogen, deuterium, halogen, substituted or unsubstituted aryl, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl,
Substituted or unsubstituted heteroaryl, substituted or unsubstituted benzheterocycle aryl, substituted or unsubstituted polyheteroaromatic, substitution
Or unsubstituted benzheterocycle aliphatic radical, substituted or unsubstituted fragrant amino, substituted or unsubstituted arylthio, substitution or unsubstituted
Sub- arylthio, substituted or unsubstituted aryl ether group, substituted or unsubstituted aryl alkyl, substituted or unsubstituted dialkyl group virtue
Base silicyl, substituted or unsubstituted adamantane, substituted or unsubstituted diarye silyl, substituted or unsubstituted virtue
It is aroma compounds and its fragrance derivatives, substituted or unsubstituted alkyl, substituted or unsubstituted silylation, substituted or unsubstituted
Naphthenic base, substituted or unsubstituted cycloalkylidene, substituted or unsubstituted Heterocyclylalkyl, substituted or unsubstituted sub- heterocycle alkane
Base, substituted or unsubstituted trialkylsilkl, substituted or unsubstituted alkenyl, takes substituted or unsubstituted bicyclic alkyl
Generation or unsubstituted alkenylene, substituted or unsubstituted alkynyl, substituted or unsubstituted alkynylene, substituted or unsubstituted heterocycle
Aliphatic radical, substituted or unsubstituted phosphinothioyl, substituted or unsubstituted phosphinyl, substituted or unsubstituted triazine radical, substitution or not
Substituted triazolyl, substituted or unsubstituted morpholinyl, substituted or unsubstituted thio-morpholinyl, substituted or unsubstituted alcoxyl
Base, substituted or unsubstituted alkylene oxide group, substituted or unsubstituted alkylthio group, substituted or unsubstituted alkylenethio, substitution or
It is unsubstituted alkylamino, substituted or unsubstituted benzenesulfonyl, substituted or unsubstituted quinoline sulfonyl, substituted or unsubstituted
Benzoyl, substituted or unsubstituted diazanyl, substituted or unsubstituted ester group, substituted or unsubstituted alkyl-carbonyl, substitution or
Unsubstituted alkoxy carbonyl, substituted or unsubstituted alkyl amino-carbonyl, substituted or unsubstituted silylation carbonyl, substitution or not
Substituted alkoxy silane, substituted or unsubstituted alkylthio group silane, substituted or unsubstituted acetylpyridine, substitution or unsubstituted
Fluorenes, substituted or unsubstituted, substituted or unsubstituted polycyclc aromatic compound, substituted or unsubstituted carbazole, substitution
Or unsubstituted thiophene, hydroxyl, carboxyl, nitro or CF3Any one；
M is transition metal Ir, Pd or Pt；
(L^Z) it is assistant ligand, is that the main ligand in left side in bidentate ligand, with structure above is identical or different；
m>0, and m is integer；N >=0, and n is integer.
Further, aryl indicate by aromatic hydrocarbons by remove a hydrogen atom derived from organic group, be 4-7 members monocycle or
Condensed ring；
Heteroaryl is the heteroatomic aryl containing 1-4 N, O, S or Si, is 5 yuan or 6 yuan single heterocyclic aryls or polycyclic miscellaneous
Aryl.
Further, Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Z1、Z2And Z3Two groups of arbitrary neighborhood connect to form cyclic group
Group.
Further, it includes one or more hetero atom that two groups of arbitrary neighborhood, which connect the cyclic group to be formed,.
Further, Y4And Y5Pass through-(Y)xAbutment connection, the Y be O, S, Se, CR6R7、CR8、NR9, carbonyl
Or AR10R11；X >=1, and be integer；X Y is mutual indepedent；
Wherein, A C, Si or Ge；R6、R7、R8、R9、R10、R11Separate is hydrogen, deuterium, halogen, substitution or unsubstituted
Aryl, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted heteroaryl, substitution
Or it unsubstituted benzheterocycle aryl, substituted or unsubstituted polyheteroaromatic, substituted or unsubstituted benzheterocycle aliphatic radical, takes
It is generation or unsubstituted fragrant amino, substituted or unsubstituted arylthio, substituted or unsubstituted sub- arylthio, substituted or unsubstituted
It is aryl ether group, substituted or unsubstituted aryl alkyl, substituted or unsubstituted dialkyiarylsilyl, substituted or unsubstituted
Adamantane, substituted or unsubstituted diarye silyl, substituted or unsubstituted aromatic compound and its fragrance derivatives take
Generation or unsubstituted alkyl, substituted or unsubstituted silylation, substituted or unsubstituted naphthenic base, substituted or unsubstituted sub- ring
Alkyl, substituted or unsubstituted Heterocyclylalkyl, substituted or unsubstituted sub- Heterocyclylalkyl, substituted or unsubstituted bicyclic alkyl,
Substituted or unsubstituted trialkylsilkl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkenylene, substitution or not
Substituted alkynyl, substituted or unsubstituted alkynylene, substituted or unsubstituted heterocycle aliphatic radical, substituted or unsubstituted phosphinothioyl,
It is substituted or unsubstituted phosphinyl, substituted or unsubstituted triazine radical, substituted or unsubstituted triazolyl, substituted or unsubstituted
Morpholinyl, substituted or unsubstituted thio-morpholinyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylene oxide group,
Substituted or unsubstituted alkylthio group, substituted or unsubstituted alkylenethio, substituted or unsubstituted alkylamino, substitution or unsubstituted
Benzenesulfonyl, substituted or unsubstituted quinoline sulfonyl, substituted or unsubstituted benzoyl, substituted or unsubstituted hydrazine
Base, substituted or unsubstituted ester group, substituted or unsubstituted alkyl-carbonyl, substituted or unsubstituted alkoxy carbonyl, substitution or
Unsubstituted alkyl amino-carbonyl, substituted or unsubstituted silylation carbonyl, substituted or unsubstituted alkoxy silane, substitution or not
Substituted alkylthio group silane, substituted or unsubstituted acetylpyridine, substituted or unsubstituted fluorenes, it is substituted or unsubstituted, take
Generation or unsubstituted polycyclc aromatic compound, substituted or unsubstituted carbazole, substituted or unsubstituted thiophene, hydroxyl, carboxyl,
Nitro or CF3Any one.
Further, between main ligand or between main ligand and assistant ligand directly by be covalently keyed or by-
(W)zAbutment connect into tetradentate ligands or sexadentate ligand；The W is C, N, O, S, Se, CR12R13、CR14、NR15、
DR16R17, carbonyl, substituted or non-substituted aromatic radical, substituted or non-substituted heteroaryl or naphthenic base, z >=1, and be integer；Z W
Independently of each other；
Wherein, D C, Si or Ge；R12、R13、R14、R15、R16、R17It is separate for hydrogen, deuterium, halogen, substitution or do not take
The aryl in generation, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted heteroaryl, takes substituted or unsubstituted arlydene
Generation or unsubstituted benzheterocycle aryl, substituted or unsubstituted polyheteroaromatic, substituted or unsubstituted benzheterocycle aliphatic radical,
Substituted or unsubstituted fragrant amino, substituted or unsubstituted arylthio, substituted or unsubstituted sub- arylthio, substitution or unsubstituted
Aryl ether group, substituted or unsubstituted aryl alkyl, substituted or unsubstituted dialkyiarylsilyl, substitution or unsubstituted
Adamantane, substituted or unsubstituted diarye silyl, substituted or unsubstituted aromatic compound and its fragrance derivatives,
Substituted or unsubstituted alkyl, substituted or unsubstituted silylation, substituted or unsubstituted naphthenic base, substituted or unsubstituted Asia
Naphthenic base, substituted or unsubstituted Heterocyclylalkyl, substituted or unsubstituted sub- Heterocyclylalkyl, substituted or unsubstituted two cycloalkanes
Base, substituted or unsubstituted trialkylsilkl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkenylene, substitution
Or unsubstituted alkynyl, substituted or unsubstituted alkynylene, substituted or unsubstituted heterocycle aliphatic radical, substituted or unsubstituted phosphine sulfide
Base, substituted or unsubstituted phosphinyl, substituted or unsubstituted triazine radical, substituted or unsubstituted triazolyl, substitution do not take
The morpholinyl in generation, substituted or unsubstituted thio-morpholinyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylene oxide
Base, substituted or unsubstituted alkylthio group, substituted or unsubstituted alkylenethio, substituted or unsubstituted alkylamino, substitution or not
It is substituted benzenesulfonyl, substituted or unsubstituted quinoline sulfonyl, substituted or unsubstituted benzoyl, substituted or unsubstituted
Diazanyl, substituted or unsubstituted ester group, substituted or unsubstituted alkyl-carbonyl, substituted or unsubstituted alkoxy carbonyl, substitution
Or unsubstituted alkyl amino-carbonyl, substituted or unsubstituted silylation carbonyl, substituted or unsubstituted alkoxy silane, substitution or
Unsubstituted alkylthio group silane, substituted or unsubstituted acetylpyridine, substituted or unsubstituted fluorenes, it is substituted or unsubstituted,
Substituted or unsubstituted polycyclc aromatic compound, substituted or unsubstituted carbazole, substituted or unsubstituted thiophene, hydroxyl, carboxylic
Base, nitro or CF3Any one.
Further, the assistant ligand (L^Z) is acetylacetone,2,4-pentanedione, 2- pyridine carboxylic acids, 2- phenylpyridines, 2,2,6,6- tetra-
Methyl -3,5- pimelic acid, (E)-N, N'- diisopropyl benzenecarboximidamide, (Z) -2,3- diisopropyl -1,1- diphenylguanidines or 2,8- bis-
Any one in methyl -4,6- nonyl diketone.
Preferably, above-mentioned transient metal complex, structural formula are respectively：
Second object of the present invention is to provide the preparation method of above-mentioned transient metal complex, and steps are as follows：
(1) under nitrogen protection, main ligand is dissolved in ethylene glycol monoethyl ether, hydration MCl is added3And deionized water, add
Thermal response obtains chlorine bridge complex；M is transition metal Ir, Pd or Pt；
(2) under alkaline condition, by chlorine bridge complex and assistant ligand (L^Z) heating reflux reaction, transition metal is obtained
Complex；
The assistant ligand (L^Z) is bidentate ligand, identical as the main ligand in left side in structure above, Huo Zhewei
Acetylacetone,2,4-pentanedione, 2- pyridine carboxylic acids, 2- phenylpyridines, 2,2,6,6- tetramethyl -3,5- pimelic acid, (E)-N, N'- diisopropyl benzenes
Any one in carbonamidine, (Z) -2,3- diisopropyl -1,1- diphenylguanidines, 2,8- dimethyl -4,6- nonyl diketone.
Third object of the present invention is to provide above-mentioned transient metal complex as electroluminescent material, in Organic Electricity
Application in electroluminescence device.
The beneficial effects of the invention are as follows：
1, the present invention passes through Z1、Z2、Z3Collocation can larger wave-length coverage adjust material wavelength of transmitted light, simultaneously
Main ligand further fine-tunes the wavelength of transmitting light by hetero atom, this has weight for the luminescent material for obtaining various wavelength
It is worth.
2, not only luminous efficiency is high for complex produced by the present invention, but also the wavelength for emitting light can be in a wide range of interior adjusting.
The main ligand skeleton structure having the same of such complex, by the position of change functional group, hetero atom on main ligand
Position and hetero atom type, to realize adjusting of the wavelength of transmitted light in dark red optical range.In addition, different colours luminescent material
Preparation method is essentially identical, easy to operate.
Description of the drawings
Fig. 1 is the OLED structure schematic diagram of electroluminescent organic material；
Fig. 2 is the emission spectroanalysis figure of application examples 1-3；
In figure, 1, glass substrate；2, anode layer；3, hole injection layer；4, hole transmission layer；5, luminescent layer；6, electronics passes
Defeated layer；7, electron injecting layer；8, cathode layer.
Specific implementation mode
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
The synthesis of complex of iridium Ir10, reaction equation are as follows：
(1) chlorine bridge dimer is synthesized
(2) object synthesizes
Embodiment 2
The synthesis of complex of iridium Ir11, reaction equation are as follows：
(1) chlorine bridge dimer is synthesized
(2) object synthesizes
Embodiment 3
The synthesis of complex of iridium Ir9, reaction equation are as follows：
(1) chlorine bridge dimer is synthesized
(2) object synthesizes
As shown in Figure 1, the structure of organic electroluminescence device (OLED) includes the glass substrate 1 for stacking gradually combination, sun
Pole layer 2, hole injection layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6, electron injecting layer 7 and cathode layer 8.This is sent out
Bright iridium phosphor material obtained is applied in the luminescent layer of OLED, each composition of layer compositions of the OLED that table 1 is application examples 1-3.
Table 1
Application examples 1
The tin indium oxide (ITO) that a layer thickness is 100nm is deposited on glass bottom liner 1 is used as transparent anode layer 2；Transparent
Vacuum evaporation thickness is NPB (N, N '-two (1- naphthalenes)-N, the N '-diphenyl -1,1 '-biphenyl -4-4 '-of 10nm on anode layer 2
Diamines) hole mobile material as hole injection layer 3, wherein doping mass ratio 3% F4-TCNQ (2,3,5,6- tetra- fluoro- 7,
Tetra- cyanogen dimethyl-parabenzoquinone of 7', 8,8'-)；Be on hole injection layer 3 a layer thickness be 100nm spiro-TAD (2,2', 7,
(the diphenyl amino) -9,9'- of 7'- tetra- spiro-bisfluorenes) it is used as hole transmission layer 4；Vacuum evaporation a layer thickness on hole transmission layer 4
It is used as luminescent layer 5 for the TRZ (2,4,6- tri- (9- carbazyls) -1,3,5-triazines) of 40nm, wherein doped with 6wt% complex of iridium
Ir10；The TPQ (2,3,5,8- tetraphenyls quinoxaline) that vacuum evaporation a layer thickness is 30nm successively on luminescent layer 5 again is as electricity
Sub- transport layer 6, the Liq that thickness is 1nm are finally deposited on electron injecting layer 7 using vacuum evaporation coating as electron injecting layer 7
Technology deposition thickness is cathode layer 8 of the metallic aluminium (Al) of 100nm as device.
Know through performance test, the maximum luminous wavelength of the electroluminescent spectrum of the device is located at 655nm, maximum current effect
Rate is 24d/A, and maximum external quantum efficiency is 11%.
Application examples 2
It is identical as application examples 1, with application examples 1 the difference is that：Luminescent layer 5 is the TRZ (2,4,6- tri- of thickness 40nm
(9- carbazyls) -1,3,5-triazines), wherein doped with 6wt% complex of iridium Ir11.
Know through performance test, the maximum luminous wavelength of the electroluminescent spectrum of the device is located at 665nm, maximum current effect
Rate is 27cd/A, and maximum external quantum efficiency is 12%.
Application examples 3
It is identical as application examples 1, with application examples 1 the difference is that：Luminescent layer 5 is the TRZ (2,4,6- tri- of thickness 40nm
(9- carbazyls) -1,3,5-triazines), wherein doped with 6wt% complex of iridium Ir9.
Know through performance test, the maximum luminous wavelength of the electroluminescent spectrum of the device is located at 675nm, maximum current effect
Rate is 25cd/A, and maximum external quantum efficiency is 11%.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (10)
1. one kind is used as the transient metal complex of phosphor material, which is characterized in that its structural formula is as follows：
Wherein, X1、X2、X3、X4Separate is N, C or B；
Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8Separate is N or CR1, wherein R1For hydrogen, deuterium, halogen, substituted or unsubstituted virtue
Base, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted heteroaryl, substitution or not
Substituted benzheterocycle aryl, substituted or unsubstituted polyheteroaromatic, substituted or unsubstituted benzheterocycle aliphatic radical, substitution or
Unsubstituted fragrant amino, substituted or unsubstituted arylthio, substituted or unsubstituted sub- arylthio, substituted or unsubstituted aryl oxide
Base, substituted or unsubstituted aryl alkyl, substituted or unsubstituted dialkyiarylsilyl, substituted or unsubstituted Buddha's warrior attendant
Alkane, substituted or unsubstituted diarye silyl, substituted or unsubstituted aromatic compound and its fragrance derivatives, substitution or
Unsubstituted alkyl, substituted or unsubstituted silylation, substituted or unsubstituted naphthenic base, substituted or unsubstituted sub- cycloalkanes
Base, substituted or unsubstituted sub- Heterocyclylalkyl, substituted or unsubstituted bicyclic alkyl, takes substituted or unsubstituted Heterocyclylalkyl
Generation or unsubstituted trialkylsilkl, substituted or unsubstituted alkenylene, substitution or do not take substituted or unsubstituted alkenyl
The alkynyl in generation, substituted or unsubstituted heterocycle aliphatic radical, substituted or unsubstituted phosphinothioyl, takes substituted or unsubstituted alkynylene
It is generation or unsubstituted phosphinyl, substituted or unsubstituted triazine radical, substituted or unsubstituted triazolyl, substituted or unsubstituted
Quinoline base, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylene oxide group, takes substituted or unsubstituted thio-morpholinyl
It is generation or unsubstituted alkylthio group, substituted or unsubstituted alkylenethio, substituted or unsubstituted alkylamino, substituted or unsubstituted
Benzenesulfonyl, substituted or unsubstituted quinoline sulfonyl, substituted or unsubstituted benzoyl, substituted or unsubstituted diazanyl,
Substituted or unsubstituted ester group, substituted or unsubstituted alkyl-carbonyl, substituted or unsubstituted alkoxy carbonyl, substitution do not take
The alkyl amino-carbonyl in generation, substituted or unsubstituted silylation carbonyl, substituted or unsubstituted alkoxy silane, substitution or unsubstituted
Alkylthio group silane, substituted or unsubstituted acetylpyridine, substituted or unsubstituted fluorenes, it is substituted or unsubstituted, substitution or
Unsubstituted polycyclc aromatic compound, substituted or unsubstituted carbazole, substituted or unsubstituted thiophene, hydroxyl, carboxyl, nitro
Or CF3Any one；
Z1、Z2And Z3Separate is N, O, S, Se, CR2、NR3Or CR4R5；Wherein, R2、R3、R4And R5It is separate for hydrogen,
Deuterium, halogen, substituted or unsubstituted aryl, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substitution or
Unsubstituted heteroaryl, substituted or unsubstituted benzheterocycle aryl, substituted or unsubstituted polyheteroaromatic, substitution do not take
The benzheterocycle aliphatic radical in generation, substituted or unsubstituted fragrant amino, substituted or unsubstituted arylthio, substituted or unsubstituted sub- virtue
Sulfenyl, substituted or unsubstituted aryl ether group, substituted or unsubstituted aryl alkyl, substituted or unsubstituted di alkylaryl first silicon
Alkyl, substituted or unsubstituted adamantane, substituted or unsubstituted diarye silyl, substituted or unsubstituted aromatics
Object and its fragrance derivatives, substituted or unsubstituted alkyl, substituted or unsubstituted silylation, substituted or unsubstituted cycloalkanes
Base, substituted or unsubstituted Heterocyclylalkyl, substituted or unsubstituted sub- Heterocyclylalkyl, takes substituted or unsubstituted cycloalkylidene
Generation or unsubstituted bicyclic alkyl, substituted or unsubstituted trialkylsilkl, substituted or unsubstituted alkenyl, substitution or not
Substituted alkenylene, substituted or unsubstituted alkynyl, substituted or unsubstituted alkynylene, substituted or unsubstituted heterocycle aliphatic radical,
It is substituted or unsubstituted phosphinothioyl, substituted or unsubstituted phosphinyl, substituted or unsubstituted triazine radical, substituted or unsubstituted
Triazolyl, substituted or unsubstituted thio-morpholinyl, substituted or unsubstituted alkoxy, takes substituted or unsubstituted morpholinyl
Generation or unsubstituted alkylene oxide group, substituted or unsubstituted alkylthio group, substituted or unsubstituted alkylenethio, substitution or unsubstituted
Alkylamino, substituted or unsubstituted benzenesulfonyl, substituted or unsubstituted quinoline sulfonyl, substituted or unsubstituted benzoyl
Base, substituted or unsubstituted diazanyl, substituted or unsubstituted ester group, substituted or unsubstituted alkyl-carbonyl, substitution or unsubstituted
Alkoxy carbonyl, substituted or unsubstituted alkyl amino-carbonyl, substituted or unsubstituted silylation carbonyl, substituted or unsubstituted
Alkoxy silane, substituted or unsubstituted alkylthio group silane, substituted or unsubstituted acetylpyridine, substituted or unsubstituted fluorenes,
Substituted or unsubstituted, substituted or unsubstituted polycyclc aromatic compound, substituted or unsubstituted carbazole, substitution do not take
Thiophene, hydroxyl, carboxyl, nitro or the CF in generation3Any one；
M is transition metal Ir, Pd or Pt；
(L^Z) it is assistant ligand, is that the main ligand in left side in bidentate ligand, with structure above is identical or different；
m>0, and m is integer；N >=0, and n is integer.
2. transient metal complex according to claim 1, which is characterized in that aryl is indicated by aromatic hydrocarbons by removing one
Organic group derived from hydrogen atom is the monocycle or condensed ring of 4-7 members；
Heteroaryl is the heteroatomic aryl containing 1-4 N, O, S or Si, is 5 yuan or 6 yuan single heterocyclic aryls or polycyclic heteroaryl
Base.
3. according to transient metal complex described in claim 1, which is characterized in that Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Z1、Z2With
Z3Two groups of arbitrary neighborhood connect to form cyclic group.
4. transient metal complex according to claim 3, which is characterized in that two groups of arbitrary neighborhood connect to be formed
Cyclic group include one or more hetero atom.
5. transient metal complex according to claim 3, which is characterized in that Y4And Y5Pass through-(Y)xAbutment connection,
The Y is O, S, Se, CR6R7、CR8、NR9, carbonyl or AR10R11；X >=1, and be integer；X Y is mutual indepedent；
Wherein, A C, Si or Ge；R6、R7、R8、R9、R10、R11Separate is hydrogen, deuterium, halogen, substituted or unsubstituted virtue
Base, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted heteroaryl, substitution or not
Substituted benzheterocycle aryl, substituted or unsubstituted polyheteroaromatic, substituted or unsubstituted benzheterocycle aliphatic radical, substitution or
Unsubstituted fragrant amino, substituted or unsubstituted arylthio, substituted or unsubstituted sub- arylthio, substituted or unsubstituted aryl oxide
Base, substituted or unsubstituted aryl alkyl, substituted or unsubstituted dialkyiarylsilyl, substituted or unsubstituted Buddha's warrior attendant
Alkane, substituted or unsubstituted diarye silyl, substituted or unsubstituted aromatic compound and its fragrance derivatives, substitution or
Unsubstituted alkyl, substituted or unsubstituted silylation, substituted or unsubstituted naphthenic base, substituted or unsubstituted sub- cycloalkanes
Base, substituted or unsubstituted sub- Heterocyclylalkyl, substituted or unsubstituted bicyclic alkyl, takes substituted or unsubstituted Heterocyclylalkyl
Generation or unsubstituted trialkylsilkl, substituted or unsubstituted alkenylene, substitution or do not take substituted or unsubstituted alkenyl
The alkynyl in generation, substituted or unsubstituted heterocycle aliphatic radical, substituted or unsubstituted phosphinothioyl, takes substituted or unsubstituted alkynylene
It is generation or unsubstituted phosphinyl, substituted or unsubstituted triazine radical, substituted or unsubstituted triazolyl, substituted or unsubstituted
Quinoline base, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylene oxide group, takes substituted or unsubstituted thio-morpholinyl
It is generation or unsubstituted alkylthio group, substituted or unsubstituted alkylenethio, substituted or unsubstituted alkylamino, substituted or unsubstituted
Benzenesulfonyl, substituted or unsubstituted quinoline sulfonyl, substituted or unsubstituted benzoyl, substituted or unsubstituted diazanyl,
Substituted or unsubstituted ester group, substituted or unsubstituted alkyl-carbonyl, substituted or unsubstituted alkoxy carbonyl, substitution do not take
The alkyl amino-carbonyl in generation, substituted or unsubstituted silylation carbonyl, substituted or unsubstituted alkoxy silane, substitution or unsubstituted
Alkylthio group silane, substituted or unsubstituted acetylpyridine, substituted or unsubstituted fluorenes, it is substituted or unsubstituted, substitution or
Unsubstituted polycyclc aromatic compound, substituted or unsubstituted carbazole, substituted or unsubstituted thiophene, hydroxyl, carboxyl, nitro
Or CF3Any one.
6. transient metal complex according to claim 1, which is characterized in that between main ligand or main ligand with it is auxiliary
It helps between ligand directly by being covalently keyed or by-(W)zAbutment connect into tetradentate ligands or sexadentate ligand；It is described
W be C, N, O, S, Se, CR12R13、CR14、NR15、DR16R17, it is carbonyl, substituted or non-substituted aromatic radical, substituted or non-substituted miscellaneous
Aryl or naphthenic base, z >=1, and be integer；Z W is mutual indepedent；
Wherein, D C, Si or Ge；R12、R13、R14、R15、R16、R17It is separate for hydrogen, it is deuterium, halogen, substituted or unsubstituted
Aryl, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted heteroaryl, substitution or
Unsubstituted benzheterocycle aryl, substituted or unsubstituted polyheteroaromatic, substituted or unsubstituted benzheterocycle aliphatic radical, substitution
Or unsubstituted fragrant amino, substituted or unsubstituted arylthio, substituted or unsubstituted sub- arylthio, substituted or unsubstituted virtue
Ether, substituted or unsubstituted aryl alkyl, substituted or unsubstituted dialkyiarylsilyl, substituted or unsubstituted gold
Rigid alkane, substituted or unsubstituted diarye silyl, substituted or unsubstituted aromatic compound and its fragrance derivatives, substitution
Or unsubstituted alkyl, substituted or unsubstituted silylation, substituted or unsubstituted naphthenic base, substituted or unsubstituted sub- cycloalkanes
Base, substituted or unsubstituted sub- Heterocyclylalkyl, substituted or unsubstituted bicyclic alkyl, takes substituted or unsubstituted Heterocyclylalkyl
Generation or unsubstituted trialkylsilkl, substituted or unsubstituted alkenylene, substitution or do not take substituted or unsubstituted alkenyl
The alkynyl in generation, substituted or unsubstituted heterocycle aliphatic radical, substituted or unsubstituted phosphinothioyl, takes substituted or unsubstituted alkynylene
It is generation or unsubstituted phosphinyl, substituted or unsubstituted triazine radical, substituted or unsubstituted triazolyl, substituted or unsubstituted
Quinoline base, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylene oxide group, takes substituted or unsubstituted thio-morpholinyl
It is generation or unsubstituted alkylthio group, substituted or unsubstituted alkylenethio, substituted or unsubstituted alkylamino, substituted or unsubstituted
Benzenesulfonyl, substituted or unsubstituted quinoline sulfonyl, substituted or unsubstituted benzoyl, substituted or unsubstituted diazanyl,
Substituted or unsubstituted ester group, substituted or unsubstituted alkyl-carbonyl, substituted or unsubstituted alkoxy carbonyl, substitution do not take
The alkyl amino-carbonyl in generation, substituted or unsubstituted silylation carbonyl, substituted or unsubstituted alkoxy silane, substitution or unsubstituted
Alkylthio group silane, substituted or unsubstituted acetylpyridine, substituted or unsubstituted fluorenes, it is substituted or unsubstituted, substitution or
Unsubstituted polycyclc aromatic compound, substituted or unsubstituted carbazole, substituted or unsubstituted thiophene, hydroxyl, carboxyl, nitro
Or CF3Any one.
7. transient metal complex according to claim 1, which is characterized in that the assistant ligand (L^Z) is acetyl
Acetone, 2- pyridine carboxylic acids, 2- phenylpyridines, 2,2,6,6- tetramethyl -3,5- pimelic acid, (E)-N, N'- diisopropyl benzenecarboximidamide,
(Z) any one in -2,3- diisopropyls -1,1- diphenylguanidines or 2,8- dimethyl -4,6- nonyl diketone.
8. transient metal complex according to claim 1, which is characterized in that its structural formula is：
9. the preparation method of transient metal complex described in a kind of claim 1, which is characterized in that steps are as follows：
(1) under nitrogen protection, main ligand is dissolved in ethylene glycol monoethyl ether, hydration MCl is added3And deionized water, heating reaction
Obtain chlorine bridge complex；M is transition metal Ir, Pd or Pt；
(2) under alkaline condition, by chlorine bridge complex and assistant ligand (L^Z) heating reflux reaction, Transition metal complexes are obtained
Object；
The assistant ligand (L^Z) is bidentate ligand, identical as the main ligand in left side in structure above, or is acetyl
Acetone, 2- pyridine carboxylic acids, 2- phenylpyridines, 2,2,6,6- tetramethyl -3,5- pimelic acid, (E)-N, N'- diisopropyl benzenecarboximidamide,
(Z) any one in -2,3- diisopropyls -1,1- diphenylguanidines, 2,8- dimethyl -4,6- nonyl diketone.
10. a kind of any one of claim 1-8 transient metal complexes are as electroluminescent material, in organic electroluminescent
Application in device.
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| CN111655706A (en) * | 2018-05-14 | 2020-09-11 | 株式会社Lg化学 | Compound and organic light emitting device including the same |
| CN114163480A (en) * | 2021-10-26 | 2022-03-11 | 奥来德(上海)光电材料科技有限公司 | Organic iridium metal complex with long service life and high efficiency and application thereof |
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| CN104520308A (en) * | 2012-08-07 | 2015-04-15 | 默克专利有限公司 | Metal complexes |
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| CN1589307A (en) * | 2001-10-17 | 2005-03-02 | 通用显示公司 | Phosphorescent compounds and devices comprising the same |
| CN104520308A (en) * | 2012-08-07 | 2015-04-15 | 默克专利有限公司 | Metal complexes |
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| CN111655706A (en) * | 2018-05-14 | 2020-09-11 | 株式会社Lg化学 | Compound and organic light emitting device including the same |
| CN111655706B (en) * | 2018-05-14 | 2023-08-08 | 株式会社Lg化学 | Compound and organic light emitting device comprising the same |
| CN114163480A (en) * | 2021-10-26 | 2022-03-11 | 奥来德(上海)光电材料科技有限公司 | Organic iridium metal complex with long service life and high efficiency and application thereof |
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