CN106928281A - 铱错合物、使用其的有机发光二极管及具碳烯结构的含氮三牙配基 - Google Patents
铱错合物、使用其的有机发光二极管及具碳烯结构的含氮三牙配基 Download PDFInfo
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- CN106928281A CN106928281A CN201610347573.0A CN201610347573A CN106928281A CN 106928281 A CN106928281 A CN 106928281A CN 201610347573 A CN201610347573 A CN 201610347573A CN 106928281 A CN106928281 A CN 106928281A
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- misfit thing
- iridium
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 61
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 57
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical group [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims abstract description 22
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910020587 CmF2m+1 Inorganic materials 0.000 claims abstract description 14
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- 150000002431 hydrogen Chemical group 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000002019 doping agent Substances 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims 2
- 125000000623 heterocyclic group Chemical group 0.000 claims 2
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 150000002503 iridium Chemical class 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 22
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 20
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000004293 19F NMR spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 230000003595 spectral effect Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- 150000002460 imidazoles Chemical group 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000001632 sodium acetate Substances 0.000 description 5
- 235000017281 sodium acetate Nutrition 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910006400 μ-Cl Inorganic materials 0.000 description 3
- QQLRSCZSKQTFGY-UHFFFAOYSA-N (2,4-difluorophenyl)boronic acid Chemical group OB(O)C1=CC=C(F)C=C1F QQLRSCZSKQTFGY-UHFFFAOYSA-N 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910017673 NH4PF6 Inorganic materials 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical group C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical group C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical group C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- -1 iridium metals Chemical class 0.000 description 2
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical group CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SFCWCYZAJBCVHR-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene naphthalene Chemical compound C1CCCC2CCCCC21.C1=CC=CC2=CC=CC=C21 SFCWCYZAJBCVHR-UHFFFAOYSA-N 0.000 description 1
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical group C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- PYWQACMPJZLKOQ-UHFFFAOYSA-N 1,3-tellurazole Chemical group [Te]1C=CN=C1 PYWQACMPJZLKOQ-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- JBOIAZWJIACNJF-UHFFFAOYSA-N 1h-imidazole;hydroiodide Chemical compound [I-].[NH2+]1C=CN=C1 JBOIAZWJIACNJF-UHFFFAOYSA-N 0.000 description 1
- 125000004215 2,4-difluorophenyl group Chemical group [H]C1=C([H])C(*)=C(F)C([H])=C1F 0.000 description 1
- IVDHYYCFEMRCDZ-UHFFFAOYSA-N 2-(trifluoromethyl)-1h-pyrrole Chemical class FC(F)(F)C1=CC=CN1 IVDHYYCFEMRCDZ-UHFFFAOYSA-N 0.000 description 1
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 1
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical group C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 238000001296 phosphorescence spectrum Methods 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical group C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- TULWUZJYDBGXMY-UHFFFAOYSA-N tellurophene Chemical group [Te]1C=CC=C1 TULWUZJYDBGXMY-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- 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
一种铱错合物、使用其的有机发光二极管及具碳烯结构的含氮三牙配基。此铱错合物由通式(I)所表示:其中n为1、2、3或4;R1为经取代或未经取代的C1-C12烷基或经取代或未经取代的C6-C12芳基;R2为氢、氟或-CmF2m+1、经取代或未经取代的C1-C12烷基或经取代或未经取代的C6-C12芳基,m为1、2或3;R3为氢、氟、-CmF2m+1、经取代或未经取代的C1-C6烷基或经取代或未经取代的C1-C6烷氧基,m为1、2或3;各R4独立为氢或经取代或未经取代的C1-C12烷基,或多个R4可键结形成C3-C8芳香环。本发明的铱错合物的刚性更强、稳定性更高,故利于提高发光效率。
Description
技术领域
本发明是有关于一种适用于有机发光二极管(organic light-emitting diode,简称OLED)的铱错合物,特别是有关于具碳烯结构的铱错合物、使用此种铱错合物的有机发光二极管,以及适合用来形成此种铱错合物的具碳烯结构的含氮三牙配基。
背景技术
有机发光二极管元件在显示器工业上已经得到许多人的注意,特别是在平面显示器工业上,因为有机发光二极管元件能在低驱动电压下操作,又能产生高发光效率。
为了发展全彩化平面显示器,开发稳定及高发光效率的具不同色光的发光材料为现今研究OLED的主要目标。目前已知三双牙配位的铱错合物有适合的放光特性,但其刚性、稳定性仍时有不足。
发明内容
本发明提供一种具碳烯结构的铱错合物,其用于OLED的发光层时可有效提升OLED的发光效率。
本发明并提供一种使用此铱错合物的有机发光二极管。
本发明并提供适合用来形成此种铱错合物的具碳烯结构的含氮三牙配基。
本发明的铱错合物由通式(I)所表示:
其中n为1、2、3或4;R1为经取代或未经取代的C1-C12烷基或经取代或未经取代的C6-C12芳基;R2为氢、氟或-CmF2m+1、经取代或未经取代的C1-C12烷基或经取代或未经取代的C6-C12芳基,m为1、2或3;R3为氢、氟、-CmF2m+1、经取代或未经取代的C1-C6烷基或经取代或未经取代的C1-C6烷氧基,m为1、2或3;各R4独立为氢或经取代或未经取代的C1-C12烷基,或多个R4可键结而形成C3-C8含氮芳香杂环(N-heteroaromatic ring)或芳香环(aromatic ring),且多个R4可相同或不同;X1、X2、X3、X4各自独立为碳或氮;Y1、Y2、Y3各自为碳或氮,但Y1、Y2及Y3中至少一者为氮,且所述Y1^Y2^Y3三牙配基为负二价。
在一实施例中,Y1与Y2为氮且Y3为碳,所述铱错合物的结构由通式(I-1)表示:
其中R1、R2、R3、R4、n、X1、X2、X3及X4的定义与通式(I)的相同。
在一实施例中,X1、X2、X3及X4皆为碳。
在一实施例中,X1、X2、X3、X4中至少有一者为氮。
本发明的有机发光二极管包括二电极及配置于所述二电极之间的一发光层,所述发光层含有上述本发明的铱错合物。所述铱错合物可作为掺杂剂,掺入所述发光层的一主体材料(host material)中。
本发明的具碳烯结构的含氮三牙配基由通式(1)表示:
其中R1、R2、R3、R4、n、X1、X2、X3及X4的定义与通式(I)的相同。
与先前技术的三双牙配位的铱错合物相较,本发明的双三牙配位的铱错合物的刚性更强、稳定性更高,故利于提高发光效率。本发明的铱错合物亦具有金属中心与配体之间的强配位键,其能推高金属中心dd激发态(metal-centered dd excited states)的跃迁能阶,降低磷光的无辐射淬熄(non-radiative quenching of phosphorescence),进而使发光效率和色纯度提高。此外,本发明的铱错合物具有强场配体碳烯(carbene),其与铱金属生成的键结更强,因此,生成的错合物稳定性更高。
为让本发明的上述特征和优点能更明显易懂,下文特举实施例,并配合附图作详细说明如下。
附图说明
图1示出本发明实施例1~5所合成的具有碳烯结构的铱错合物的吸收光谱及荧光光谱;
图2示出本发明实施例7的用以量测铱错合物的发光特性的OLED的结构。
附图标记说明:
200:玻璃基板;202:阳极;
204:电洞传输层;206:发光层;
208:电子传输层;210:阴极。
具体实施方式
以下将通过实施方式对本发明作进一步说明,但所述实施方式仅为例示说明之用,而非用以限制本发明的范围。
[具碳烯结构的铱错合物的结构]
本发明的具碳烯结构的铱错合物的结构由通式(I)表示:
其中n为1、2、3或4;R1为经取代或未经取代的C1-C12烷基或经取代或未经取代的C6-C12芳基;R2为氢、氟或-CmF2m+1、经取代或未经取代的C1-C12烷基或经取代或未经取代的C6-C12芳基,m为1、2或3;R3为氢、氟、-CmF2m+1、经取代或未经取代的C1-C6烷基或经取代或未经取代的C1-C6烷氧基,m为1、2或3;各R4独立为氢或经取代或未经取代的C1-C12烷基,或多个R4可键结而形成C3-C8含氮芳香杂环或芳香环,且多个R4可相同或不同;X1、X2、X3、X4各自独立为碳或氮;Y1、Y2、Y3各自为碳或氮,但Y1、Y2及Y3中至少一者为氮,且所述Y1^Y2^Y3三牙配基为负二价。
上述芳香环可包括芳香烃环(aromatic hydrocarbon ring)或芳香杂环(aromatic heterocyclic ring)。芳香环或芳香杂环的特定实例包括苯环(benzenering)、吡啶环(pyridine ring)、吡嗪环(pyrazine ring)、嘧啶环(pyrimidine ring)、哒嗪环(pyridazine ring)、三嗪环(triazine ring)、吡咯环(pyrrole ring)、呋喃环(furanring)、噻吩环(thiophene ring)、硒吩环(selenophene ring)、碲吩环(tellurophenering)、咪唑环(imidazole ring)、噻唑环(thiazole ring)、硒唑环(selenazole ring)、碲唑环(tellurazole ring)、噻二唑环(thiadiazole ring)、恶二唑环(oxadiazole ring)以及吡唑环(pyrazole ring)。
在一实施例中,多个R4可键结以形成经取代或未经取代的苯环或经取代或未经取代的吡啶环。
通式(I)中右半部的配基即是本发明的具碳烯结构的含氮三牙配基,由以下通式(1)表示:
其中R1、R2、R3、R4、n、X1、X2、X3及X4的定义与通式(I)的相同。
另外,Y1^Y2^Y3三牙配基上例如也有至少一个拉电子基。Y1^Y2^Y3三牙配基可选用先前技术已知者。本发明的铱错合物的最高已占轨域(HOMO)主要是以Y1^Y2^Y3三牙配基来调整,最低未占轨域(LUMO)主要是以本发明的通式(1)所示的具碳烯结构的含氮三牙配基来调整。
当Y1与Y2为氮且Y3为碳时,上述铱错合物的结构由通式(I-1)表示:
其中R1、R2、R3、R4、n、X1、X2、X3及X4的定义与通式(I)的相同。
R2为氢、氟或-CmF2m+1、经取代或未经取代的C1-C12烷基或经取代或未经取代的C6-C12芳基,m为1、2或3;R3为氢、氟、-CmF2m+1、经取代或未经取代的C1-C6烷基或经取代或未经取代的C1-C6烷氧基,m为1、2或3;且n为1、2、3或4。当R3为C1-C6烷基、氟或-CmF2m+1(m为1~3的整数)且X1、X2、X3、X4皆为碳时,符合通式(I-1)的铱错合物的一些实际例子为:由式(I-1-1)、(I-1-2)、(I-1-3)、(I-1-4)、(I-1-5)、(I-1-6)…(I-1-24)所表示的铱错合物,后文将其简称为化合物(I-1-1)、(I-1-2)…(I-1-24)。此种简称方式亦套用于下文中以其他化学结构式表达的铱错合物。
当R3为C1-C6烷基、C1-C6烷氧基、氟或-CmF2m+1(m为1~3的整数)且X1、X2、X3、X4中至少有一者为氮时,符合通式(I-1)的具碳烯结构铱错合物的一些实际例子为:由式(I-1-25)、(I-1-26)…(I-1-31)所表示的铱错合物。式(I-1-25)、(I-1-26)…(I-1-31)所表示的铱错合物都是X1、X2、X3、X4中至少一者为氮的铱错合物,其X2和/或X4为氮的设计可以增加通式(I)的含氮三牙配基的拉电子效应。
此外,通式(I)的Y1^Y2^Y3三牙配基中的Y1、Y2、Y3皆为氮的情况(N^N’^N”),以及Y1与Y3为碳且Y2为氮的情况(C^N^C’),也是可行的。实际例子如下所示:
本发明的有机发光二极管包括二电极及配置于所述二电极之间的一发光层,所述发光层含有上述具碳烯结构的铱错合物。二电极各自的材料可选用本领域中通常使用者,各电极与发光层之间亦可依本领域所熟知的技术来加设其他功能层,例如电子传输层、电洞传输层等等。此有机发光二极管可制作于基板上,例如玻璃基板。
[具碳烯结构的铱错合物的形成方法]
本发明的具碳烯结构的含氮三牙配基例如是将其前驱物的两个质子拔除而得者,其实际例子如下所示(phimpy、phimpy-H2为本说明书使用的代号,But表叔丁基,Pri为异丙基)。
上述实际例子的前驱物phimpy-H2例如以下述方法制备。
其中步骤(i)所用试剂为咪唑、溴化四丁基铵(tetrabutylammonium bromide;NBu4Br)及氢氧化钾,步骤(ii)所用试剂为2,4-二氟苯基硼酸、Pd(dppf)Cl2及碳酸氢钾,步骤(iii)所用试剂为2-碘丙烷,步骤(iv)所用试剂为NH4PF6。
通式(I)的铱错合物中的Y1^Y2^Y3三牙配基例如是将具有对应的环结构其前驱物与必要试剂混合反应而得。
本发明的具碳烯结构铱错合物可依据各个配基的变化选用适当的反应物及反应条件进行制备,且反应制备方式可依据本领域所熟知的技术进行变化。所述铱错合物制备方法的一具体例包含以下步骤:将本发明的通式(1)的含氮三牙配基的前驱物、铱源及其他必要试剂混合反应,再将所得产物、Y1^Y2^Y3三牙配基的前驱物及其他必要试剂混合,并加热进行反应。将通式(1)的含氮三牙配基、Y1^Y2^Y3三牙配基与铱原子连接的顺序亦可倒过来,即,铱原子先与Y1^Y2^Y3三牙配基的前驱物反应再与通式(1)的含氮三牙配基的前驱物反应。
[实施例]
以下将通过数个实施例对本发明作进一步说明,但所述实施例仅为例示说明之用,而非用以限制本发明的范围。
合成例1
通式(1)的含氮三牙配基的前驱物phimpy-H2的制备:
取4-叔丁基-2,6-二氟吡啶(1.3g,6.37mmol)、咪唑(0.48g,7.01mmol)、溴化四丁基铵(1.03g,3.18mmol)和氢氧化钾(0.43g,7.64mmol)置于单颈瓶中,在80℃下反应时间12小时,再使所得咪唑鎓(imidazolium)中间产物与2,4-二氟苯基硼酸(0.88g,5.60mmol)、Pd(dppf)Cl2(0.11g,0.15mmol)和碳酸氢钾(2.07g,15.00mmol)溶于甲苯(15mL)、乙醇(3mL)与水(3mL),加热至110℃并反应12小时,而生成4-叔丁基-2-(2,4-二氟苯基)-6-(1H-咪唑-1-基)吡啶。
使所得的4-叔丁基-2-(2,4-二氟苯基)-6-(1H-咪唑-1-基)吡啶(1.15g,3.68mmol)与2-碘丙烷(0.8mL,8.07mmol)溶于甲苯(40mL),加热至110℃并反应12小时,而得咪唑碘鎓前配基(imidazolium iodide pre-ligand)。接着使所得的咪唑碘鎓前配基(1.5g,3.1mmol)与NH4PF6(4.04g,25mmol)溶于乙醇,在室温下搅拌两小时进行离子交换,之后加入水而得沉淀产物(phimph-H2)(PF6)。
(phimph-H2)(PF6)的光谱资料:1H NMR(400MHz,CDCl3):δ9.53(s,1H),8.24(s,1H),8.01~7.95(m,1H),7.88(s,1H),7.81(s,1H),7.48(s,1H),7.06~7.02(m,1H),6.97~6.92(m,1H),4.99~4.96(m,1H,CH),1.59(d,J=6.6Hz,3H,Me),1.58(d,J=6.6Hz,3H,Me),1.42(s,9H,t-Bu);19F NMR(376MHz,CDCl3):δ-70.90(d,J=712Hz,PF6),-107.10(s,1F),-111.65(s,1F)。
实施例1
化合物(I-1-7)的制备:
取[Ir(COD)(μ-Cl)]2(300mg,0.45mmol)、(phimph-H2)(PF6)(470mg,0.94mmol)和醋酸钠(183mg,2.23mmol)置于双颈瓶,以20毫升的无水乙腈(anhydrous acetonitrile)为溶剂,在80℃下反应12小时后,将温度降回室温,抽掉溶剂后再加入2-(5-三氟甲基-1H-吡唑-3-基)-6-(4-氟苯基)吡啶(316mg,1.03mmol)和醋酸钠(366mg,4.47mmol),溶于十氢化萘(decahydronaphthalene)(20mL),在200℃下反应24小时,反应结束后,经管柱层析纯化后可得产物,产率为23%。
化合物(I-1-7)的光谱资料:1H NMR(400MHz,CDCl3):δ8.14(s,1H),7.76(t,J=8.0Hz,1H),7.60~7.55(m,4H),7.37(s,1H),6.91(s,1H),6.79(d,J=2.4Hz,1H),6.56~6.51(m,1H),6.32~6.26(m,1H),5.53(d,J=8.0Hz,2H),3.53~3.29(m,1H,CH),1.54(s,9H,t-Bu),0.80(d,J=6.8Hz,3H,Me),0.74(d,J=6.8Hz,3H,Me);19F NMR(376MHz,CDCl3):δ-59.81(s,3F),-107.49(d,J=9.8Hz,1F),-110.48(d,J=9.8Hz,1F),110.52(s,1F);MS[FAB]:m/z 852.6,M+.Anal.Calcd.for C36H29F6IrN6:C,50.76;H,3.43;N,9.87.Found:C,50.64;H,3.77;N,9.48。
实施例2
化合物(I-1-8)的制备:
除了将2-(5-三氟甲基-1H-吡唑-3-基)-6-(4-氟苯基)吡啶换成2-(5-三氟甲基-1H-吡唑-3-基)-6-(4-三氟甲基苯基)吡啶之外,化合物(I-1-8)的合成步骤与化合物(I-1-7)相似,产率为26%。
化合物(I-1-8)的光谱资料:1HNMR(400MHz,CDCl3):δ8.15(s,1H),7.81(t,J=8.0Hz,1H),7.72(d,J=8.0Hz,1H),7.67(d,J=8.0Hz,1H),7.64(d,J=8.0Hz,1H),7.58(s,1H),7.39(s,1H),7.05(d,J=8.0Hz,1H),6.93(s,1H),6.81(s,1H),6.33~6.27(m,1H),6.05(s,1H),5.49(s,1H),3.33~3.27(m,1H,CH),1.53(s,9H,t-Bu),0.80(d,J=6.8Hz,3H,Me),0.74(d,J=6.8Hz,3H,Me);19F NMR(376MHz,CDCl3):δ-59.89(s,3F),-62.81(s,3F),-107.42(d,J=9.8Hz,1F),-110.35(d,J=9.8Hz,1F);MS[FAB]:m/z 902.7,M+.Anal.Calcd.for C37H29F8IrN6:C,49.28;H,3.24;N,9.32.Found:C,49.29;H,3.33;N,8.91。
实施例3
化合物(I-1-9)的制备:
取IrCl3 3H2O(200mg,0.57mmol)及(phimph-H2)(PF6)(313mg,0.62mmol)置于单颈瓶,以2-甲氧基乙醇(15mL)为溶剂,在120℃下反应12小时后,将温度降回室温。抽掉溶剂后,加入2-(5-三氟甲基-1H-吡唑-3-基)-6-(4-叔丁基苯基)吡啶(215mg,0.62mmol)和醋酸钠(209mg,2.55mmol),溶于十氢化萘(20mL),在200℃下反应24小时。反应结束后,经管住层析纯化后可得产物,产率为23%。
化合物(I-1-9)的光谱资料:1H NMR(400MHz,CDCl3):δ8.13(s,1H),7.72(t,J=8.0Hz,1H),7.59~7.56(m,3H),7.46~7.44(m,2H),6.92(s,1H),6.82(dd,J=8.0Hz,2.0Hz,1H),6.73(d,J=2.0Hz,1H),6.30~6.24(m,1H),5.64(d,J=2.0Hz,1H),5.60(dd,J=8.0Hz,2.0Hz,1H),3.39~3.32(m,1H),1.50(s,9H,t-Bu),0.92(s,9H,t-Bu),0.81(d,J=6.8Hz,3H,Me),0.69(d,J=6.8Hz,3H,Me);19F NMR(376MHz,CDCl3):δ-59.77(s,3F),-107.80(d,J=9.8Hz,1F),-111.36(d,J=9.8Hz,1F);MS[FAB]:m/z,890.7M+。
实施例4
化合物(I-1-10)的制备:
除了将2-(5-三氟甲基-1H-吡唑-3-基)-6-(4-氟苯基)吡啶换成2-(5-三氟甲基-1H-吡唑-3-基)-6-(1-萘基)吡啶之外,合成步骤与化合物(I-1-7)相似,产率为35%。
化合物(I-1-10)的光谱资料:1HNMR(400MHz,CDCl3):δ8.61(d,J=8.0Hz,1H),8.38(d,J=8.0Hz,1H),8.17(s,1H),7.82(t,J=8.0Hz,1H),7.65~7.60(m,2H),7.56(d,J=2.0Hz,1H),7.48(t,J=8Hz,1H),7.41(s,1H),7.28(t,J=8.0Hz,1H),7.10(d,J=8.0Hz,1H),6.94(s,1H),6.73(d,J=2.0Hz,1H),6.28~6.22(m,1H),6.11(d,J=8.0Hz,1H)5.45(d,J=8.0Hz,1H),3.45~3.39(m,1H,CH),1.55(s,1H,t-Bu),0.76(d,J=6.8Hz,3H,Me),0.73(d,J=6.8Hz,3H,Me);19F NMR(376MHz,CDCl3):δ-59.75(s,3F),-107.24(d,J=9.8Hz,1F),-110.65(d,J=9.8Hz,1F);MS[FAB]:m/z,884.5M+.Anal.Calcd.forC40H32F5IrN6:C,54.35;H,3.65;N,9.51.Found:C,54.26;H,4.06;N,8.90。
实施例5
化合物(I-1-11)的制备:
取[Ir(COD)(μ-Cl)]2(118mg,0.18mmol)、(phimph-H2)(PF6)(186mg,0.37mmol)和醋酸钠(72mg,0.88mmol)置于双颈瓶中,以10mL的无水乙腈为溶剂,在80℃下反应12小时后,将温度降回室温。抽掉溶剂后加入2-(5-三氟甲基-1H-吡唑-3-基)-6-苯基异喹啉(120mg,0.36mmol)和醋酸钠(144mg,1.76mmol),溶于二甲苯(25mL),在160℃下反应24小时。反应结束后,经管住层析纯化后可得产物,产率为27%。
化合物(I-1-11)的光谱资料:1HNMR(400MHz,CDCl3):δ8.95(d,J=8.0Hz,1H),8.32(d,J=8.0Hz,1H),8.14(s,1H),8.05(d,J=7.6Hz,1H),7.98(s,1H),7.73~7.67(m,2H),7.56(d,J=2.0Hz,1H),7.39(s,1H),6.94(s,1H),6.93(t,J=6.8Hz,1H),6.75(d,J=2.0Hz,1H),6.71(t,J=7.6Hz,1H),6.28~6.22(m,1H),6.06(d,J=6.8Hz,1H),5.45(m,1H),3.34~3.27(m,1H,CH),1.54(s,9H,t-Bu),0.72(d,J=6.8Hz,3H,Me),0.66(d,J=6.8Hz,3H,Me);19F NMR(376MHz,CDCl3):δ-59.65(s,3F),-107.69(d,J=9.8Hz,1F),-110.85(d,J=9.8Hz,1F);MS[FAB]:m/z,884.3M+。
实施例6
化合物(I-1-13)的制备:
取[Ir(COD)(μ-Cl)]2(50mg,0.07mmol)、(phimph-H2)(PF6)(75mg,0.15mmol)和醋酸钠(62mg,0.76mmol)置于双颈瓶中,以10mL的无水乙腈为溶剂,在80℃下反应12小时后,将温度降回室温。抽掉溶剂后加入4-叔丁基-2-苯基-6-(3-(三氟甲基)-1H-5-吡唑基)嘧啶(52mg,0.15mmol)和醋酸钠(144mg,1.76mmol),溶于二甲苯(25mL),在160℃下反应24小时。反应结束后,经管住层析纯化后可得产物,产率为31%。
化合物(I-1-13)的光谱资料:1HNMR(400MHz,CDCl3):δ8.14(s,1H),8.04(d,J=7.4Hz,1H),7.54(s,1H),7.51(s,1H),7.36(s,1H),7.07(s,1H),6.87(t,J=7.4Hz,1H),6.77~6.72(m,2H),6.28(t,J=9.6Hz,1H),5.86(d,J=7.4Hz,1H),5.54(dd,J=3.8,2.2Hz,1H),3.29~3.22(m,1H,CH),1.53(s,9H,t-Bu),0.72(d,J=6.8Hz,3H,Me),0.66(d,J=6.8Hz,3H,Me);19F NMR(376MHz,CDCl3):δ-59.92(s,3F),-107.51(d,J=9.8Hz,1F),-110.57(d,J=9.8Hz,1F);MS[FAB]:m/z,891.3M+。
实施例1~5所合成的铱错合物(I-1-7)~(I-1-11)各自的吸收光谱及磷光光谱示出于图1,且吸收峰位置(λabs)、发射峰位置(λem)、量子产率(φ)及磷光生命期(τobs)列示于下表1。
表1
化合物 | λabs/nm(ε×104M-1cm-1)a | λem/nmb | φ(%)b,c | τobs/μsb |
(I-1-7) | 304(2.25),340(1.77),398(0.38) | 473,508 | 99 | 3.10 |
(I-1-8) | 311(2.1),350(1.40),410(0.34) | 495,534,574(sh) | 91 | 3.91 |
(I-1-9) | 310(2.53),343(1.81),408(0.44) | 481,515 | ~100 | 3.01 |
(I-1-10) | 330(2.38),430(0.4),458(0.31) | 583,618 | 25 | 9.23 |
(I-1-11) | 345(2.64),448(0.60),481(0.29) | 608,663,725(sh) | 57 | 5.40 |
a于CH2Cl2中量测,浓度为10-5M;
b于除气之CH2Cl2溶液中量测;
c以溶于乙醇之香豆素(C153)(φ=58%,λmax=530nm)及溶于DMSO之4-(二氰基亚甲基)-2-甲基-6-(4-二甲胺基苯乙烯基)-4H-吡喃(φ=80%,λmax=637nm)为标准。
由图1及表1可知,化合物(I-1-7)、(I-1-8)及(I-1-9)的量子产率高;C^N^N’三牙配基上多了苯并环的化合物(I-1-10)及(I-1-11)则可增加放光团的共轭,而可缩小能隙,从而因此使放光红位移。上述化合物的其他效果说明如下。
其一,相对于吡啶配体与铱配位时形成的N-Ir键,强场配体卡宾与铱配位时生成的C-Ir键更强,因此生成的错合物稳定性更高。
其二,在发光性能方面,强的配位键能推高金属中心dd激发态的跃迁能阶,从而降低磷光的无辐射淬灭,使发光效率和色纯度提高。
其三,双三牙配位(bis-tridentate)的铱错合物比三二牙配位(tris-bidentate)或三二一牙配位的铱错合物的刚性强,利于提高发光效率,制元件稳定性高,升华性佳。
实施例7
接着使用本发明的任一种化合物来制作OLED,其结构请参照图2,包括由下而上堆叠的玻璃基板200、阳极202、电洞传输层204、发光层206、电子传输层208及阴极210。阳极202的材料为ITO、电洞传输层204的材料为4,4”-环己基二[N,N-二(4-甲基苯基)]苯胺(TAPC)、发光层206的材料为掺杂了本发明的化合物的1,3-双(N-咔唑基)苯(mCP)、电子传输层208的材料为1,3,5-三[(3-吡啶基)-苯-3-基]苯(TmPyPB),且阴极210的材料为LiF/Al。
综上所述,本发明的铱错合物亦具有强的配位键,其能推高金属中心dd激发态的跃迁能阶,进而降低磷光的无辐射淬熄,使发光效率和色纯度提高。此外,本发明的铱错合物具有强场配体碳烯,其与铱金属生成的键结更强,因此,生成的错合物稳定性更高。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (11)
1.一种铱错合物,由通式(I)所表示:
其中
n为1、2、3或4;
R1为经取代或未经取代的C1-C12烷基或经取代或未经取代的C6-C12芳基;
R2为氢、氟或-CmF2m+1、经取代或未经取代的C1-C12烷基或经取代或未经取代的C6-C12芳基,m为1、2或3;
R3为氢、氟、-CmF2m+1、经取代或未经取代的C1-C6烷基或经取代或未经取代的C1-C6烷氧基,m为1、2或3;
各R4独立为氢或经取代或未经取代的C1-C12烷基,或多个R4可键结而形成C3-C8含氮芳香杂环或芳香环,且多个R4可相同或不同;
X1、X2、X3、X4各自独立为碳或氮;
Y1、Y2、Y3各自为碳或氮,但Y1、Y2及Y3中至少一者为氮,且所述Y1^Y2^Y3三牙配基为负二价。
2.根据权利要求1所述的铱错合物,其中所述Y1^Y2^Y3三牙配基上也有至少一个拉电子基。
3.根据权利要求1所述的铱错合物,其中Y1与Y2为氮且Y3为碳,且其结构由通式(I-1)表示:
其中R1、R2、R3、R4、n、X1、X2、X3及X4的定义与通式(I)的相同。
4.根据权利要求1所述的铱错合物,其中X1、X2、X3、X4皆为碳。
5.根据权利要求4所述的铱错合物,其结构由式(I-1-1)至式(I-1-24)中任一者所表示:
6.根据权利要求1所述的铱错合物,其中X1、X2、X3、X4中至少有一者为氮。
7.根据权利要求6所述的铱错合物,其结构由式(I-1-25)至式(I-1-31)中任一者所表示:
8.根据权利要求1所述的铱错合物,其结构由式(I-a)至式(I-f)中任一者所表示:
9.一种有机发光二极管,包括二电极及配置在所述二电极之间的一发光层,所述发光层含有如权利要求1-8项中任一项所述的铱错合物。
10.根据权利要求9所述的有机发光二极管,其中所述铱错合物是作为掺杂剂,掺入所述发光层的一主体材料中。
11.一种具碳烯结构的含氮三牙配基,由通式(1)表示:
其中
n为1、2、3或4;
R1为经取代或未经取代的C1-C12烷基或经取代或未经取代的C6-C12芳基;
R2为氢、氟、-CmF2m+1、经取代或未经取代的C1-C12烷基或经取代或未经取代的C6-C12芳基,m为1、2或3;
R3为氢、氟、-CmF2m+1、经取代或未经取代的C1-C6烷基或经取代或未经取代的C1-C6烷氧基,m为1、2或3;
各R4独立为氢或经取代或未经取代的C1-C12烷基,或多个R4可键结而形成C3-C8含氮芳香杂环或芳香环,且多个R4可相同或不同;以及
X1、X2、X3、X4各自独立为碳或氮。
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