WO2022262662A1 - 一种有机金属化合物及其应用 - Google Patents
一种有机金属化合物及其应用 Download PDFInfo
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- WO2022262662A1 WO2022262662A1 PCT/CN2022/098280 CN2022098280W WO2022262662A1 WO 2022262662 A1 WO2022262662 A1 WO 2022262662A1 CN 2022098280 W CN2022098280 W CN 2022098280W WO 2022262662 A1 WO2022262662 A1 WO 2022262662A1
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- WIPO (PCT)
- Prior art keywords
- substituted
- unsubstituted
- alkyl
- compound
- deuterium
- Prior art date
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- 150000002902 organometallic compounds Chemical class 0.000 title claims abstract description 32
- 239000002019 doping agent Substances 0.000 claims abstract description 9
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 46
- 229910052805 deuterium Inorganic materials 0.000 claims description 46
- -1 cyano, hydroxyl Chemical group 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 39
- 238000006467 substitution reaction Methods 0.000 claims description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 28
- 125000003118 aryl group Chemical group 0.000 claims description 27
- 229910052736 halogen Inorganic materials 0.000 claims description 26
- 150000002367 halogens Chemical class 0.000 claims description 26
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 21
- 150000002431 hydrogen Chemical class 0.000 claims description 21
- 239000003446 ligand Substances 0.000 claims description 21
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 20
- 229910052731 fluorine Inorganic materials 0.000 claims description 20
- 125000005104 aryl silyl group Chemical group 0.000 claims description 18
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 17
- 125000001072 heteroaryl group Chemical group 0.000 claims description 17
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- 229910052794 bromium Inorganic materials 0.000 claims description 15
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 150000002527 isonitriles Chemical class 0.000 claims description 12
- 150000002825 nitriles Chemical class 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 125000005865 C2-C10alkynyl group Chemical group 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 2
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 204
- 238000000859 sublimation Methods 0.000 abstract description 14
- 230000008022 sublimation Effects 0.000 abstract description 14
- 230000003287 optical effect Effects 0.000 abstract description 5
- 229920001621 AMOLED Polymers 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 description 134
- 238000003786 synthesis reaction Methods 0.000 description 133
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 64
- 238000000746 purification Methods 0.000 description 64
- 239000002994 raw material Substances 0.000 description 57
- 238000000034 method Methods 0.000 description 47
- 238000001819 mass spectrum Methods 0.000 description 44
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 239000007787 solid Substances 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 239000003208 petroleum Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000010408 film Substances 0.000 description 11
- 239000000741 silica gel Substances 0.000 description 11
- 229910002027 silica gel Inorganic materials 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000003480 eluent Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000008204 material by function Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- IQTHEAQKKVAXGV-UHFFFAOYSA-N 4-ditert-butylphosphanyl-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(P(C(C)(C)C)C(C)(C)C)C=C1 IQTHEAQKKVAXGV-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 101100457453 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) MNL1 gene Proteins 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 125000004306 triazinyl group Chemical group 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 1
- 125000004134 1-norbornyl group Chemical group [H]C1([H])C([H])([H])C2(*)C([H])([H])C([H])([H])C1([H])C2([H])[H] 0.000 description 1
- ZAZPDOYUCVFPOI-UHFFFAOYSA-N 2-methylpropylboronic acid Chemical compound CC(C)CB(O)O ZAZPDOYUCVFPOI-UHFFFAOYSA-N 0.000 description 1
- 125000004135 2-norbornyl group Chemical group [H]C1([H])C([H])([H])C2([H])C([H])([H])C1([H])C([H])([H])C2([H])* 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- PSCXEUSWZWRCMQ-UHFFFAOYSA-N F[S](F)F Chemical compound F[S](F)F PSCXEUSWZWRCMQ-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical group COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000003670 adamantan-2-yl group Chemical group [H]C1([H])C(C2([H])[H])([H])C([H])([H])C3([H])C([*])([H])C1([H])C([H])([H])C2([H])C3([H])[H] 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
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- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
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- 235000010290 biphenyl Nutrition 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- ORBBTCHHNMWMCP-UHFFFAOYSA-K cycloocta-1,5-diene trichloroiridium Chemical class [Ir](Cl)(Cl)Cl.C1=CCCC=CCC1 ORBBTCHHNMWMCP-UHFFFAOYSA-K 0.000 description 1
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 1
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- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical group CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
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- 125000003838 furazanyl group Chemical group 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000005968 oxazolinyl group Chemical group 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 125000004625 phenanthrolinyl group Chemical group N1=C(C=CC2=CC=C3C=CC=NC3=C12)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
Definitions
- the invention relates to the technical field of organic electroluminescence, in particular to an organic luminescent material suitable for organic electroluminescence devices, in particular to an organometallic compound and its application in organic electroluminescence devices.
- OLEDs organic electroluminescent devices
- the basic structure of an OLED device is a thin film of organic functional materials with various functions mixed between metal electrodes, like a sandwich structure. Driven by current, holes and electrons are injected from the cathode and anode, holes and electrons respectively After moving for a certain distance, the light-emitting layer is recombined and released in the form of light or heat, thereby producing the light emission of the OLED.
- organic functional materials are the core components of organic electroluminescent devices, and their thermal stability, photochemical stability, electrochemical stability, quantum yield, film formation stability, crystallinity, color saturation, etc. major factor in device performance.
- organic functional materials include fluorescent materials and phosphorescent materials.
- the fluorescent material is usually an organic small molecule material, and generally only 25% of the singlet state can be used to emit light, so the luminous efficiency is relatively low. Due to the spin-orbit coupling effect caused by the heavy atom effect, phosphorescent materials can use 75% of the energy of triplet excitons in addition to 25% of the singlet state, so the luminous efficiency can be improved.
- phosphorescent materials started relatively late, and the thermal stability, lifetime, and color saturation of materials need to be improved. This is a challenging subject.
- Various organometallic compounds have been developed as phosphorescent materials.
- patent document US20050123798 discloses a class of iridium-based complexes with indole as a ligand Although this type of material exhibits a better red light-emitting wavelength, the device luminous efficiency of this type of material is low and the color saturation needs to be further improved to meet the display requirements of DCIP3 or even BT2020;
- patent document CN107722062 discloses a class of acenaphthylene Iridium-platinum complexes constructed as units This type of material shows blue or green luminescence;
- patent document CN110317231 discloses a class of metal complexes constructed with acenaphthylene as a unit Such materials exhibit dark blue luminescence. In order to meet the market's demand for higher stability, longer life, more saturated color purity and higher luminous efficiency, more new materials need to be developed to meet the growing technical needs of the market.
- the present invention provides a high-performance organic electroluminescent device and an organometallic compound material capable of realizing such an organic electroluminescent device.
- the organometallic compound of the present invention has a general formula of Ir(La)(Lb)(Lc), wherein La is a structure represented by formula (1), and Lb is a structure represented by formula (2).
- the iridium complex provided by the invention has the advantages of high optical and electrical stability, low sublimation temperature, narrow emission half-maximum width, high color saturation, high luminous efficiency, long device life and the like, and can be used in organic electroluminescent devices. Especially as a red light-emitting dopant, it has the possibility of being applied to the AMOLED industry, especially for display, lighting and automobile taillights.
- X 1 is N or CR 1
- X 2 is N or CR 2
- X 3 is N or CR 3
- X 4 is N or CR 4
- X 5 is N or CR 5 ;
- At most one of X 1 -X 5 is N, and when X 1 -X 5 is CR 1 -CR 5 , at least one of R 1 -R 5 is not H;
- R 1 -R 10 are independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, mercapto, amino, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkane substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or Unsubstituted C2-C17 heteroaryl, substituted or unsubstituted tri-C1-C10 alkylsilyl, substituted or unsubstituted tri-C6-C12 arylsilyl, substituted or unsubstituted di-C1-C10 alkyl- C6-C30 aryl silyl, substituted or unsubstituted C
- heteroalkyl and heteroaryl contain at least one O, N or S heteroatom;
- Lb is the structure shown in formula (2)
- the dotted line position represents the position connected with metal Ir;
- Ra-Rg is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C10 hetero Alkyl, substituted or unsubstituted C3-C20 heterocycloalkyl; or Ra, Rb, and Rc are connected in pairs to form an alicyclic structure, and Re, Rf, and Rg are connected in pairs to form an alicyclic structure Structure; the substitution is amino, cyano, nitrile, Substituted by isonitrile or phosphino;
- heteroalkyl and heterocycloalkyl contain at least one O, N or S heteroatom;
- Lc is a monoanionic bidentate ligand, and Lc and Lb are not the same and are not OO ligands;
- Lc and La are the same or different, and the difference is that the core structure is different or the core structure is the same but the substituents are different or the core structure is the same and the substituents are the same but the positions of the substituents are different;
- two or three of La, Lb, and Lc are connected to each other to form a multidentate ligand.
- R 1 -R 10 are independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, mercapto, amino, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkane substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or Unsubstituted C2-C17 heteroaryl, substituted or unsubstituted tri-C1-C10 alkylsilyl, substituted or unsubstituted tri-C6-C12 arylsilyl, substituted or unsubstituted di-C1-C10 alkyl- C6-C30 aryl silyl, substituted or unsubstituted C
- two adjacent groups of R 1 -R 6 and R 7 -R 10 can be connected to each other to form an aliphatic ring or an aromatic ring structure;
- At least one of R 7 -R 10 is not hydrogen
- heteroalkyl and heteroaryl contain at least one O, N or S heteroatom;
- the substitution is deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl substituted amine, nitrile, isonitrile, phosphino, wherein the substitution is Single substitution to maximum number of substitutions.
- R 1 and/or R 4 and/or R 5 are not hydrogen.
- R 2 and R 3 are hydrogen.
- R 1 , R 4 , and R 5 are independently selected from deuterium, halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, The substitution is substituted by deuterium, F, Cl, Br or C1-C4 alkyl.
- R 6 is selected from deuterium, halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl; R 8 and/or R 10 is not hydrogen .
- R 8 and R 10 are independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, and the substitution is deuterium, F, Cl , Br or C1-C4 alkyl substituted.
- R 7 and R 9 are H.
- R 7 and R 8 , R 8 and R 9 , or R 9 and R 10 are connected to each other to form the structure shown in formula (4),
- Y 1 -Y 4 are independently CR 0 or N,
- Z1 is selected from O, S,
- R is independently hydrogen, deuterium , halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or Unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C30 heteroaryl, substituted or unsubstituted tri-C1-C10 alkylsilyl, substituted or unsubstituted Three C6-C30 aryl silicon groups, substituted or unsubstituted two C1-C10 alkyl-C6-C30 aryl silicon groups; the substitution is deuterium, F, Cl, Br, C1-C4 alkyl, C1 -C4 alkoxy, C3-C6 cycloalkyl, C1-C4 al
- Y 1 -Y 4 are independently CR 0 , Z1 is selected from O, and R 0 is independently hydrogen, deuterium, halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl; said substitution is substituted by deuterium, F, Cl, Br, C1-C4 alkyl.
- Lc is the same as La.
- Lc is the structure shown in formula (5)
- R 11 -R 18 are independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, amino, amino, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkane substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or Unsubstituted C2-C17 heteroaryl, substituted or unsubstituted tri-C1-C10 alkylsilyl, substituted or unsubstituted tri-C6-C12 arylsilyl, substituted or unsubstituted di-C1-C10 alkyl- C6-C30 aryl silyl, substituted or unsubstituted C1-C
- At least one group of two adjacent groups in R 11 -R 14 forms an aromatic ring structure as shown in the following formula (6);
- the dotted line represents the position connected with the pyridine ring
- R 19 -R 22 are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C17 hetero Aryl, substituted or unsubstituted tri-C1-C10 alkyl silyl, substituted or unsubstituted tri-C6-C12 aryl silyl, substituted or unsubstituted di-C1-C10 alkyl-C6-C30 aryl silyl , a substituted or unsubstituted C1-C10 alkyl,
- substitution is deuterium, F, Cl, Br, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 cycloalkyl, C1-C4 alkyl substituted amino, nitrile, isonitrile or phosphino replaced.
- R 15 and R 17 are deuterium, halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, wherein, R 11 -R 14 has a group of two adjacent
- the aromatic ring structure shown in formula (6) is formed between the groups, and the other two are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3- C10 cycloalkyl;
- R 19 -R 22 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl; the substitution is deuterium, F , Cl, Br, C1-C4 alkyl substituted.
- La is preferably one of the following structural formulas, or the corresponding partial or complete deuteration or fluorination
- Lb is preferably one of the following structural formulas, or the corresponding partial or complete deuteration or fluorination
- Lc is preferably one of the following structural formulas, or the corresponding partial or complete deuterium or fluorine
- the application is that the above-mentioned organometallic compound is used as a red light-emitting dopant material in the light-emitting layer of an organic electroluminescence device.
- the material of the invention not only has the advantages of high optical and electrical stability, low sublimation temperature, narrow emission half-peak width, high color saturation, high luminous efficiency, long device life and the like.
- the material of the invention can convert the triplet excited state into light, so the luminous efficiency of the organic electroluminescent device can be improved, thereby reducing energy consumption.
- a red light-emitting dopant it has the possibility of being applied to the AMOLED industry.
- the compound of the present invention a kind of organometallic compound, has the general formula of Ir(La)(Lb)(Lc), wherein La is the structure shown in formula (1),
- X 1 is N or CR 1
- X 2 is N or CR 2
- X 3 is N or CR 3
- X 4 is N or CR 4
- X 5 is N or CR 5 ;
- At most one of X 1 -X 5 is N, and when X 1 -X 5 is CR 1 -CR 5 , at least one of R 1 -R 5 is not H; at least one of R 7 -R 10 is not is hydrogen;
- R 1 -R 10 are independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, mercapto, amino, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkane substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or Unsubstituted C2-C17 heteroaryl, substituted or unsubstituted tri-C1-C10 alkylsilyl, substituted or unsubstituted tri-C6-C12 arylsilyl, substituted or unsubstituted di-C1-C10 alkyl- C6-C30 aryl silyl, substituted or unsubstituted C
- heteroalkyl and heteroaryl contain at least one O, N or S heteroatom;
- substitution is substituted by deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl substituted amino, nitrile, isonitrile, phosphino, wherein the substitution
- the number ranges from a single substitution to a maximum number of substitutions
- Lb is the structure shown in formula (2)
- the dotted line position represents the position connected with metal Ir;
- Ra-Rg is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C10 hetero Alkyl, substituted or unsubstituted C3-C20 heterocycloalkyl;
- Ra, Rb, Rc are connected in pairs to form an aliphatic ring structure, and Re, Rf, Rg are connected in pairs to form an aliphatic ring structure ;
- heteroalkyl and heterocycloalkyl contain at least one O, N or S heteroatom;
- substitution is amino, cyano, nitrile, Substituted by isonitrile and phosphino;
- Lc is a monoanionic bidentate ligand, and Lc and Lb are not the same and are not OO ligands;
- Lc and La are the same or different, and the difference is that the core structure is different or the core structure is the same but the substituents are different or the core structure is the same and the substituents are the same but the positions of the substituents are different;
- two or three of La, Lb, and Lc are connected to each other to form a multidentate ligand.
- carbon number a to b in the expression “substituted or unsubstituted X group with carbon number a to b" represents the carbon number when the X group is unsubstituted, The carbon number of the substituent when the X group is substituted is not included.
- the C1-C10 alkyl group is a straight-chain or branched-chain alkyl group, specifically methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl , tert-butyl, n-pentyl and its isomers, n-hexyl and its isomers, n-heptyl and its isomers, n-octyl and its isomers, n-nonyl and its isomers, n- Decyl and its isomers, etc., preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, more preferably propyl, isopropyl, Isobutyl, sec-butyl, tert-butyl.
- C3-C20 cycloalkyl examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl
- An alkyl group and the like are preferably cyclopentyl and cyclohexyl.
- C2-C10 alkenyl examples include vinyl, propenyl, allyl, 1-butadienyl, 2-butadienyl, 1-hexatrienyl, 2-hexatrienyl, 3 -hexatrienyl, etc., preferably propenyl and allyl.
- the C1-C10 heteroalkyl group is a straight-chain or branched-chain alkyl group, cycloalkyl group, etc. containing atoms other than carbon and hydrogen, such as mercaptomethylmethane group, methoxymethane group, ethyl Oxymethyl group, tert-butoxymethane group, N,N-dimethylmethane group, epoxybutyl group, epoxypentyl group, epoxyhexyl group, etc., preferably methoxymethyl group, ring Oxypentyl.
- aryl group examples include phenyl, naphthyl, anthracenyl, phenanthryl, naphthacene, pyrenyl, chrysyl, benzo[c]phenanthryl, benzo[g]chryl, fluorenyl, Benzofluorenyl, dibenzofluorenyl, biphenyl, terphenyl, quaterphenyl, fluoranthenyl, etc., preferably phenyl and naphthyl.
- heteroaryl examples include pyrrolyl, pyrazinyl, pyridyl, pyrimidinyl, triazinyl, indolyl, isoindolyl, imidazolyl, furyl, benzofuryl, isophenyl Dibenzofuryl, dibenzofuryl, dibenzothienyl, azadibenzofuryl, azadibenzothienyl, diazadibenzofuryl, diazadibenzothienyl, Quinolinyl, isoquinolinyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl, oxazolinyl, Oxadiazolyl, furazanyl, thienyl, benzothienyl, dihydroacridinyl, azacar
- La011-2 (25.20g, 74.68mmol), ammonium formate (47.09g, 746.84mmol), platinum dioxide (1.7g, 7.47mmol), tetrahydrofuran (500ml) were added in a 1000ml three-necked round-bottomed flask, and vacuum nitrogen replacement was carried out for 3 Once, stir at 65°C for 4 hours. TLC monitored the complete reaction of the raw material La011-2.
- La064-4 (16.21g, 46.60mmol), potassium tert-butoxide (10.46g, 93.19mmol), and deuterated dimethyl sulfoxide (80ml) into a 250ml three-necked round-bottomed flask, replace with vacuum nitrogen three times, and heat to The reaction was carried out overnight at 90°C for 15 hours, and the reaction of La064-4 was monitored by NMR.
- a 50mm*50mm*1.0mm glass substrate with an ITO (100nm) transparent electrode was ultrasonically cleaned in ethanol for 10 minutes, dried at 150°C and then treated with N 2 Plasma for 30 minutes. Install the washed glass substrate on the substrate holder of the vacuum evaporation device. First, the compound HATCN is evaporated on the side of the transparent electrode line to cover the transparent electrode to form a thin film with a film thickness of 5nm.
- the hetero compound (comparative compound X, compound of the present invention) has a film thickness of 30 nm, and the ratio of host material to dopant material is 90%:10%.
- An ETL film (25nm) and a LiQ film (1nm) were evaporated sequentially on the light-emitting layer, and finally a layer of metal Al (100nm) was evaporated as an electrode.
- the organic electroluminescent device using the compound of the present invention as a dopant has a narrower emission spectrum and a higher color saturation than the comparative compound. All show better performance.
- the sublimation temperature is defined as the temperature corresponding to an evaporation rate of 1 angstrom per second at a vacuum degree of 10 -7 Torr.
- the test results are as follows:
- the compound of the present invention has a lower sublimation temperature, which is beneficial to industrial application.
- the present invention unexpectedly provides better device luminous efficiency and improved lifetime, and at the same time provides unexpectedly lower sublimation temperature compared with the prior art.
- the above results show that the compound of the present invention has the advantages of low sublimation temperature, high optical and electrochemical stability, high color saturation, high luminous efficiency, long device life, etc., and can be used in organic electroluminescent devices. Especially as a red light-emitting dopant, it has the possibility of being applied to the OLED industry.
- the material of the invention not only has the advantages of high optical and electrical stability, low sublimation temperature, narrow emission half-peak width, high color saturation, high luminous efficiency, long device life and the like.
- the material of the invention can convert the triplet excited state into light, so the luminous efficiency of the organic electroluminescent device can be improved, thereby reducing energy consumption.
- a red light-emitting dopant it has the possibility of being applied to the AMOLED industry.
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Abstract
涉及一种具有Ir(La)(Lb)(Lc)通式的有机金属化合物及其应用,其中La为式(1)所示的结构,Lb为式(2)所示的结构。所述化合物具有光、电稳定性高,升华温度低,发射半峰宽窄,色饱和度高,发光效率高,器件寿命长等优点,可用于有机电致发光器件中。特别是作为红色发光掺杂体,具有应用于AMOLED产业的可能。
Description
本发明涉及有机电致发光技术领域,尤其涉及一种适合有机电致发光器件的有机发光材料,特别涉及一种有机金属化合物及其在有机电致发光器件上的应用。
目前,作为新一代显示技术的有机电致发光器件(OLED)在显示和照明技术方面都获得了越来越多的关注,应用前景十分广泛。但是,和市场应用要求相比,OLED器件的发光效率、驱动电压、使用寿命等性能还需要继续加强和改进。
一般来说,OLED器件基本结构为在金属电极中间夹杂各种不同功能的有机功能材料薄膜,犹如一个三明治的结构,在电流的驱动下,从阴阳两极分别注入空穴和电子,空穴和电子在移动一段距离后,在发光层得到复合,并以光或热的形式进行释放,从而产生了OLED的发光。然而,有机功能材料是有机电致发光器件的核心组成部分,材料的热稳定性、光化学稳定性、电化学稳定性、量子产率、成膜稳定性、结晶性、色饱和度等都是影响器件性能表现的主要因素。
一般地,有机功能材料包括荧光材料和磷光材料。荧光材料通常为有机小分子材料,一般只能利用25%单重态发光,所以发光效率比较低。而磷光材料由于重原子效应引起的自旋轨道耦合作用,除了利用25%单重态之外,还可以利用75%三重态激子的能量,所以发光效率可以得到提升。但是相较于荧光材料,磷光材料起步较晚,且材料的热稳定性、寿命、色饱和度等都有待提升,这是一个具有挑战性的课题。现已经有人开发各种有机金属化合物作为磷光材料。例如专利文献US20050123798公开了一类以吲哚为配体的铱基配合物
虽然该类材料体现出较好的红色发光波长,但是该类材料的器件发光效率较低和色饱和度也有待进一步改善以满足DCIP3甚至BT2020的显示需求;专利文献CN107722062公开了一类以苊烯为单元构筑的铱铂络合物
该类材料显示出蓝色或绿色的发光;专利文 献CN110317231公开了一类以苊烯为单元构筑的金属络合物
该类材料显示出深蓝色发光。为了满足市场对更高稳定性、更长寿命、更饱和色纯度色和更高发光效率的需求,需要开发更多的新材料以满足市场日益增长的技术需求。
发明内容
本发明为了解决上述缺陷,提供一种高性能的有机电致发光器件及可实现这样的有机电致发光器件的有机金属化合物材料。
本发明的有机金属化合物,具有Ir(La)(Lb)(Lc)的通式,其中La为式(1)所示的结构,Lb为式(2)所示的结构。本发明提供的铱络合物具有光、电稳定性高,升华温度低,发射半峰宽窄,色饱和度高,发光效率高,器件寿命长等优点,可用于有机电致发光器件中。特别是作为红色发光掺杂体,具有应用于AMOLED产业的可能,特别是用于显示、照明和汽车尾灯。
一种有机金属化合物,具有Ir(La)(Lb)(Lc)的通式,其中La为式(1)所示的结构,
其中,虚线表示与金属Ir连接的位置;
其中,X
1为N或CR
1,X
2为N或CR
2,X
3为N或CR
3,X
4为N或CR
4,X
5为N或CR
5;
其中,X
1-X
5至多之一为N,且当X
1-X
5为CR
1-CR
5时,其中R
1-R
5至少之一不为H;
其中,R
1-R
10独立地选自氢、氘、卤素、氰基、羟基、巯基、胺基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基,或者R
1-R
6、R
7-R
10两个相邻的基团之间可以相互连接形成脂肪族环或芳香族环状结构;且R
7-R
10至少之一不为氢;所述取代为被氘、F、Cl、Br、C1-C6烷基、C3-C6环烷基、C1-C6 烷基取代的胺基、腈、异腈或膦基所取代,其中取代数目为单取代到最大数目取代;
其中,所述杂烷基和杂芳基中至少含有一个O、N或S杂原子;
其中Lb为式(2)所示的结构,
其中,虚线位置表示与金属Ir连接的位置;
其中,Ra-Rg独立地选自氢、氘、卤素、取代的或未取代的C1-C10烷基、取代的或未取代的C3-C20环烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20杂环烷基;或者Ra、Rb、Rc之间两两连接以形成脂肪环状结构,Re、Rf、Rg之间两两连接以形成脂肪环状结构;所述取代为被氘、F、Cl、Br、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C1-C4烷基取代的胺基、氰基、腈、异腈或膦基所取代;
其中,所述杂烷基和杂环烷基中至少含有一个O、N或S杂原子;
其中,Lc为单阴离子型双齿配体,Lc与Lb不相同且不为OO型配体;
其中,Lc与La相同或不相同,所述不相同为母核结构不相同或母核结构相同但取代基不同或母核结构相同取代基相同但取代基位置不相同;
其中,La、Lb、Lc之间两两或三者相互连接形成多齿配体。
作为优选的有机金属化合物,其中La为式(3)所示的结构,
其中,虚线表示与金属Ir连接的位置;
其中,R
1-R
10独立地选自氢、氘、卤素、氰基、羟基、巯基、胺基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基;
或者,R
1-R
6、R
7-R
10两个相邻的基团之间可以相互连接形成脂肪族环或芳香族环状结构;
其中,R
7-R
10至少之一不为氢;
其中,所述杂烷基和杂芳基中至少含有一个O、N或S杂原子;
其中,所述取代为氘、F、Cl、Br、C1-C6烷基、C3-C6环烷基、C1-C6烷基取代的胺基、腈、异腈、膦基,其中所述取代为单取代到最大数目取代。
其中式(3)中,R
1和/或R
4和/或R
5不为氢。
其中式(3)中,R
2和R
3为氢。
其中式(3)中,其中所述R
1、R
4、R
5独立选自氘、卤素、取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基,所述取代为被氘、F、Cl、Br或C1-C4烷基所取代。
其中式(3)中,R
6选自氘、卤素、取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基;R
8和/或R
10不为氢。
其中式(3)中,R
8、R
10独立选自取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基,所述取代为被氘、F、Cl、Br或C1-C4烷基所取代。
其中式(3)中,R
7、R
9为H。
其中R
7和R
8、R
8和R
9、或者R
9和R
10之间相互连接以形成式(4)所示的结构,
其中*表示连接的位置,
Y
1-Y
4独立地为CR
0或N,
Z1选自O、S,
R
0独立地为氢、氘、卤素、氰基、取代或未取代的C1-C10烷基、取代或未取代的C3-C20环烷基、取代或未取代的C2-C30烯基、取代或未取代的C2-C30炔基、取代或未取代的C6-C30芳基、取代或未取代的C1-C30杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C30芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基;所述取代为被氘、F、Cl、Br、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C1-C4烷基取代的胺基、腈、异腈或膦基所取代。
其中式(4)中,Y
1-Y
4独立地为CR
0,Z1选自O,R
0独立地为氢、氘、卤素、取代或未取代的C1-C6烷基、取代或未取代的C3-C10环烷基;所述取代为被氘、F、Cl、Br、C1-C4烷基所取代。
其中Lc与La相同。
其中Lc为式(5)所示的结构,
其中,虚线表示与金属Ir连接的位置;
其中,R
11-R
18独立地选自氢、氘、卤素、氰基、羟基、氨基、胺基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基;其中,R
15-R
18中至少两个不为氢;
其中,R
11-R
14中至少一组两个相邻的基团之间形成如下式(6)所示芳香族环状结构;
其中,虚线表示与吡啶环连接的位置;
其中,R
19-R
22独立地选自氢、氘、卤素、氰基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基、或者R
19-R
22两个相邻的基团之间相互连接形成脂肪族环或芳香族环状结构;
所述取代为被氘、F、Cl、Br、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C1-C4烷基取代的胺基、腈、异腈或膦基所取代。
其中R
15、R
17为氘、卤素、取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基,其中,R
11-R
14中有一组两个相邻的基团之间形成式(6)所示芳香族环状结构,其它两个独立选自氢、氘、卤素、取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基;
其中,R
19-R
22独立地选自氢、氘、卤素、取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基;所述取代为被氘、F、Cl、Br、C1-C4烷基所取代。
作为优选的有机金属化合物,其中La优选为以下结构式之一,或者对应的部分或完全氘代或者氟代,
作为优选的有机金属化合物,其中Lb优选为以下结构式之一,或者对应的部分或完全氘代或者氟代,
作为优选的有机金属化合物,其中Lc优选为以下结构式之一,或者对应的部分或完全氘 代或者氟代,
上述有机金属化合物在有机电致发光器件中的应用。
所述的应用,为上述有机金属化合物作为有机电致发光器件中发光层中的红色发光掺杂材料。
本发明的材料不但具有光、电稳定性高,升华温度低,发射半峰宽窄,色饱和度高,发光效率高,器件寿命长等优点。本发明的材料作为磷光材料,可以将三重激发态转换成光,所以能够提高有机电致发光器件的发光效率,从而降低能耗。特别是作为红色发光掺杂体,具有应用于AMOLED产业的可能。
下面结合实施例对本发明做进一步的详细说明。
本发明的化合物,一种有机金属化合物,具有Ir(La)(Lb)(Lc)的通式,其中La为式(1)所示的结构,
其中,虚线表示与金属Ir连接的位置;
其中,X
1为N或CR
1,X
2为N或CR
2,X
3为N或CR
3,X
4为N或CR
4,X
5为N或CR
5;
其中,X
1-X
5至多之一为N,且当X
1-X
5为CR
1-CR
5时,其中R
1-R
5至少之一不为H;R
7-R
10至少之一不为氢;
其中,R
1-R
10独立地选自氢、氘、卤素、氰基、羟基、巯基、胺基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基;R
1-R
6、R
7-R
10两个相邻的基团之间可以相互连接形成脂肪族环或芳香族环状结构;
其中,所述杂烷基和杂芳基中至少含有一个O、N或S杂原子;
其中,所述取代为被氘、F、Cl、Br、C1-C6烷基、C3-C6环烷基、C1-C6烷基取代的胺基、腈、异腈、膦基所取代,其中取代数目为单取代到最大数目取代;
其中Lb为式(2)所示的结构,
其中,虚线位置表示与金属Ir连接的位置;
其中,Ra-Rg独立地选自氢、氘、卤素、取代的或未取代的C1-C10烷基、取代的或未取代的C3-C20环烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20杂环烷基;Ra、Rb、Rc之间两两连接以形成脂肪环状结构、Re、Rf、Rg之间两两连接以形成脂肪环状结构;
其中,所述杂烷基和杂环烷基中至少含有一个O、N或S杂原子;
其中,所述取代为被氘、F、Cl、Br、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C1-C4烷基取代的胺基、氰基、腈、异腈、膦基所取代;
其中,Lc均为单阴离子型双齿配体,Lc与Lb不相同且不为OO型配体;
其中,Lc与La相同或不相同,所述不相同为母核结构不相同或母核结构相同但取代基不同或母核结构相同取代基相同但取代基位置不相同;
其中,La、Lb、Lc之间两两或三者相互连接形成多齿配体。
以下,对于式(1)-式(5)所表示的化合物的各基团的例子进行说明。
需要说明的是,本说明书中,“取代或未取代的碳数a~b的X基”这一表述中的“碳数a~b”表示的是X基未取代的情况下的碳数,不包括X基被取代时的取代基的碳数。
作为C1~C10的烷基,为直链状或支链状的烷基,具体来说,为甲基、乙基、丙基、、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基及其异构体、正己基及其异构体、正庚基及其异构体、正辛基及其异构体、正壬基及其异构体、正癸基及其异构体等,优选为甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基,更优选为丙基、异丙基、异丁基、仲丁基、叔丁基。
作为C3~C20的环烷基,可举出环丙基、环丁基、环戊基、环己基、1-金刚烷基、2-金刚烷基、1-降冰片烷基、2-降冰片烷基等,优选为环戊基、环己基。
作为C2~C10的烯基,可举出乙烯基、丙烯基、烯丙基、1-丁二烯基、2-丁二烯基、1- 己三烯基、2-己三烯基、3-己三烯基等,优选为丙烯基、烯丙基。
作为C1-C10杂烷基,为含有除碳氢以外的原子构成的直链状或支链状的烷基、环烷基等,可举出巯甲基甲烷基、甲氧基甲烷基、乙氧基甲烷基、叔丁氧基甲烷基、N,N-二甲基甲烷基、环氧丁烷基、环氧戊烷基、环氧己烷基等,优选为甲氧基甲烷基、环氧戊烷基。
作为芳基的具体例,为苯基、萘基、蒽基、菲基、并四苯基、芘基、屈基、苯并[c]菲基、苯并[g]屈基、芴基、苯并芴基、二苯并芴基、联苯基、三联苯基、四联苯基、荧蒽基等,优选为苯基、萘基。
作为杂芳基的具体例,可举出吡咯基、吡嗪基、吡啶基、嘧啶基、三嗪基、吲哚基、异吲哚基、咪唑基、呋喃基、苯并呋喃基、异苯并呋喃基、二苯并呋喃基、二苯并噻吩基、氮杂二苯并呋喃基、氮杂二苯并噻吩基、二氮杂二苯并呋喃基、二氮杂二苯并噻吩基、喹啉基、异喹啉基、喹喔啉基、咔唑基、菲啶基、吖啶基、菲咯啉基、吩嗪基、吩噻嗪基、吩噁嗪基、噁唑啉基、噁二唑基、呋咱基、噻吩基、苯并噻吩基、二氢吖啶基、氮杂咔唑基、二氮杂咔唑基、喹唑啉基等,优选为吡啶基、嘧啶基、三嗪基、二苯并呋喃基、二苯并噻吩基、氮杂二苯并呋喃基、氮杂二苯并噻吩基、二氮杂二苯并呋喃基、二氮杂二苯并噻吩基、咔唑基、氮杂咔唑基、二氮杂咔唑基。
下述实施例仅仅是为了便于理解技术发明,不应视为本发明的具体限制。
本发明中的化合物合成中涉及的原物料和溶剂等均购自于Alfa、Acros等本领域技术人员熟知的供应商
配体La004的合成
化合物La004-3的合成
将化合物La004-1(20.00g,77.47mmol)、La004-2(21.45g,77.47mmol)、[1,1'-双(二苯基膦)二茂铁]二氯化钯(1.42g,1.55mmol)、碳酸钾(21.41g,154.94mmol)、1,4-二氧六环(200ml)、去离子水(80ml)加入1000ml的三口圆底烧瓶中,真空氮气置换3次,在氮气保护下,80℃搅拌2小时。TLC监控(展开剂为乙酸乙酯:石油醚=1:10),原料La004-1反应完全。
冷却到室温,减压浓缩除去有机溶剂,加入二氯甲烷(500ml)去离子水洗涤(3*150ml),分液,有机相浓缩后进行硅胶柱层析(200-300目硅胶,洗脱剂为乙酸乙酯:石油醚=1:20), 洗脱后浓缩得到浅黄色固体为化合物La004-3(20.10g,纯度:99.10%,收率:79.05%),质谱:328.26(M+H)。
化合物La004-4的合成
将化合物La004-3(18.50g,56.36mmol)、醋酸钯(253.06mg,1.13mmol)、三(邻甲基苯基)磷(687.87mg,2.26mmol)、三水合醋酸钠(15.34g,112.72mmol)、N,N-二甲基甲酰胺(185ml)加入500ml的三口圆底烧瓶中,真空氮气置换3次,在氮气保护下,100℃搅拌6小时。TLC监控(展开剂为乙酸乙酯:石油醚=1:15)原料La004-3反应完全。
直接浓缩除去N,N-二甲基甲酰胺,加入乙酸乙酯(500ml),加入去离子水洗涤(3*200ml),分液,有机相浓缩后进行硅胶柱层析(200-300目硅胶,洗脱剂为乙酸乙酯:石油醚=1:25),浓缩后得到浅黄色糖状固体为化合物La004-4(12.37g,纯度:99.53%,收率:75.21%),质谱:292.06(M+H)。
化合物La004的合成
将化合物La004-4(12.00g,41.13mmol)、异丁基硼酸(6.29g,61.69mmol)、三(二亚苄基丙酮)二钯(753mg,0.82mmol)、2-二环己基膦-2′,6′-二甲氧基-联苯(675.73mg,1.64mmol)、磷酸钾(18.94g,82.26mmol)、甲苯(120ml)加入500ml的三口圆底烧瓶中,真空氮气置换3次,在氮气保护下,105℃搅拌4小时。TLC监控(展开剂为乙酸乙酯:石油醚=1:12),原料La004-4反应完全。
降至室温,加入乙酸乙酯(400ml),去离子水洗涤(3*250ml),分液,有机相浓缩后进行硅胶柱层析(200-300目硅胶,洗脱剂为乙酸乙酯:石油醚=1:25),浓缩后得到白色糖状固体为化合物La004(9.02g,纯度:99.83%,收率:70.00%),质谱:314.14(M+H)。
化合物Ir(La004)
2(Lb005)的合成
化合物Ir(La004)-1的合成
将化合物Lb004(18.61g,59.37mmol)、IrCl
3·3H
2O(5.98g,16.96mmol)加入1000ml的三口圆底烧瓶中,加入乙二醇乙醚(120ml)及去离子水(40ml),真空氮气置换3次,接着加热至105℃搅拌回流24小时。
冷却到室温后,加入甲醇(200ml),室温打浆1h,抽滤,滤饼用甲醇(50ml)洗涤,固 体在80℃真空干燥得到化合物Ir(La004)-1(10.84g,收率:75.00%)。得到的化合物不经纯化直接使用于下一步。
化合物Ir(La004)
2(Lb005)的合成
将化合物Ir(La004)-1(6.54g,3.84mmol)、Lb005(4.08g,19.20mmol)、碳酸钠(4.07g,38.40mmol)、乙二醇乙醚(66ml)加入250ml的单口圆底烧瓶中,真空氮气置换3次,50℃搅拌24小时,TLC监控(展开剂为甲醇:二氯甲烷=1:100),Ir(La004)-1反应完全。
冷却到室温后,加入甲醇(132ml)室温打浆2h,抽滤,滤饼使用二氯甲烷(200ml)溶解滤200-300目硅胶(50g),滤液使用去离子水洗涤(3*80ml),50℃浓缩得到暗红色固体,使用四氢呋喃与甲醇重结晶两次得到红色固体为化合物Ir(La004)
2(Lb005)(3.57g,纯度:99.83%,收率:45.17%)。将3.57克Ir(La004)
2(Lb005)粗品升华纯化后得到升华纯Ir(La004)
2(Lb005)(2.22g,纯度:99.80%,收率:62.16%),质谱:1029.36(M+H)。
1H NMR(400MHz,CDCl3)δ8.44(d,J=15.0Hz,2H),8.05(m,4H),7.68(s,2H),7.63-7.51(m,2H),7.44-7.42(s,4H),4.60(s,1H),2.70(m,4H),2.27(s,12H),1.99-1.57(m,4H),1.11-1.04(m,12H),0.83-0.77(m,8H),0.67(m,6H),0.94(m,6H).
配体La008的合成:
化合物La008的合成
参照化合物La004的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物La008(15.40g,纯度:99.75%,收率:70.15%),质谱:368.15(M+H)
化合物Ir(La008)
2(Lb005)的合成
化合物Ir(La008)-1的合成
参照化合物Ir(La004)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La008)-1(7.31g,收率:70.52%)。不经纯化直接使用于下一步。
化合物Ir(La008)
2(Lb005)的合成
参照化合物Ir(La004)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La008)
2(Lb005)(3.78g,纯度:99.86%,收率:42.36%)。将3.78克Ir(La008)
2(Lb005)粗品升华纯化后得到升华纯Ir(La008)
2(Lb005)(2.27g,纯度:99.82%,收率:60.25%),质谱:1137.26(M+H)。
1H NMR(400MHz,CDCl3)δ8.43(d,J=15.1Hz,2H),8.03(m,4H),7.66(s,2H),7.63-7.53(m,2H),7.42-7.41(s,4H),4.59(s,1H),2.80-2.73(m,2H),2.70(m,2H),1.96-1.82(m,8H),1.75-1.68(m,8H),1.65-1.61(m,24H),1.52-1.43(m,8H),1.11-0.97(m,6H),0.94(m,6H).
配体La009的合成
化合物La009的合成
参照化合物La004的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物La009(20.14g,纯度:99.81%,收率:68.22%),质谱:340.10(M+H)
化合物Ir(La009)
2(Lb005)的合成
化合物Ir(La009)-1的合成:
参照化合物Ir(La004)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La009)-1(10.53g,收率:68.72%)。不经纯化直接使用于下一步。
化合物Ir(La009)
2(Lb005)的合成
参照化合物Ir(La004)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La009)
2(Lb005)(4.14g,纯度:99.89%,收率:38.58%)。将4.14克 Ir(La009)
2(Lb005)粗品升华纯化后得到升华纯Ir(La009)
2(Lb005)(2.67g,纯度:99.87%,收率:64.49%),质谱:1081.52(M+H)。
1H NMR(400MHz,CDCl3)δ8.44(d,J=15.12Hz,2H),8.06(m,4H),7.69(s,2H),7.68-7.54(m,2H),7.47-7.42(s,4H),4.58(s,1H),2.80(m,4H),2.27(s,12H),2.20(m,4H),1.73-1.62(m,16H),1.52-1.43(m,8H),1.11-0.97(m,6H),0.94(m,6H).
化合物Ir(La009)
2(Lb007)的合成
化合物Ir(La009)
2(Lb007)的合成
参照化合物Ir(La004)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La009)
2(Lb007)(3.53g,纯度:99.79%,收率:41.37%)。将3.53克Ir(La009)
2(Lb007)粗品升华纯化后得到升华纯Ir(La009)
2(Lb007)(2.15g,纯度:99.75%,收率:60.90%),质谱:1109.52(M+H)。
1H NMR(400MHz,CDCl3)δ8.47(d,J=15.20Hz,2H),8.10(m,4H),7.69(s,2H),7.67-7.53(m,2H),7.45-7.40(s,4H),4.57(s,1H),2.57(m,4H),2.26(s,12H),2.20-1.93(m,2H),1.73-1.22(m,16H),1.42-1.16(m,8H),0.99-0.89(m,18H).
化合物Ir(La009)
2(Lb031)的合成
化合物Ir(La009)
2(Lb031)的合成
参照化合物Ir(La004)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La009)
2(Lb031)(2.21g,纯度:99.80%,收率:38.78%)。将2.21克Ir(La009)
2(Lb031)粗品升华纯化后得到升华纯Ir(La009)
2(Lb031)(1.32g,纯度:99.78%,收率:59.72%),质谱:1105.54(M+H)。
1H NMR(400MHz,CDCl3)δ8.45(d,J=15Hz,2H),8.08(m,4H),7.69(s,2H),7.60-7.51(m,2H),7.47-7.42(s,4H),4.57(s,1H),3.06(m,4H),2.57(m,4H),2.26(s,12H),2.20-1.93(m,4H),1.73-1.22(m,32H).
配体La011的合成
化合物La011-2的合成
将La004-4(30g,102.82mmol)、La011-1(25.67g,123.38mmol)、双(4-二甲氨基苯基二叔丁基膦)二氯化钯(730mg,1.03mmol)、碳酸钾(28.40g,205.64mmol)、1,4-二氧六环(300ml)、去离子水(100ml)加入1000ml的单口圆底烧瓶中,真空氮气置换3次,80℃搅拌1小时。TLC监控(展开剂为乙酸乙酯:石油醚=1:5)原料La004-4反应完全。
降至室温,浓缩除去溶剂,加入二氯甲烷(500ml),去离子水洗涤(3*150ml),分液,有机相浓缩后进行硅胶柱层析(200-300目硅胶,洗脱剂为乙酸乙酯:石油醚=1:10),浓缩后得到白色固体为化合物La011-2(29.91g,纯度:99.62%,收率:86.21%),质谱:338.24(M+H)。
化合物La011-3的合成
将La011-2(25.20g,74.68mmol)、甲酸铵(47.09g,746.84mmol)、二氧化铂(1.7g,7.47mmol)、四氢呋喃(500ml)加入1000ml的三口圆底烧瓶中,真空氮气置换3次,65℃搅拌4小时。TLC监控原料La011-2反应完全。
降至室温,浓缩除去溶剂,加入二氯甲烷(700ml),去离子水洗涤(3*250ml),分液,有机相浓缩后进行硅胶柱层析(200-300目硅胶,洗脱剂为乙酸乙酯:石油醚=1:12),浓缩后得到白色糖状固体为化合物La011-3(17.77g,纯度:99.58%,收率:70.11%),质谱:340.06(M+H)。
化合物La011的合成
将La011-3(17.70g,52.15mmol)、二氯甲烷(200ml)加入500ml的三口圆底烧瓶中,抽真空氮气置换3次,室温搅拌下滴加双(2-甲氧基乙基)氨基三氟化硫(23.07g,104.30mmol),室温搅拌过夜。TLC监控(展开剂为乙酸乙酯:石油醚=1:10)原料La011-3反应完全。
将反应液滴加至饱和碳酸氢钠水溶液中淬灭反应,调节体系pH值为8,浓缩除去四氢呋喃,加入二氯甲烷(600ml),分液,去离子水洗涤(3*230ml),分液,有机相浓缩后进行硅 胶柱层析(200-300目硅胶,洗脱剂为乙酸乙酯:石油醚=1:20),浓缩后得到白色糖状固体为化合物La011(13.68g,纯度:99.69%,收率:72.56%),质谱:362.14(M+H)。
化合物Ir(La011)
2(Lb005)的合成
化合物Ir(La011)-1的合成
参照化合物Ir(La004)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La011)-1(6.92g,收率:68.33%)。不经纯化直接使用于下一步。
化合物Ir(La011)
2(Lb005)的合成
参照化合物Ir(La004)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La011)
2(Lb005)(2.73g,纯度:99.75%,收率:32.81%)。将2.73克Ir(La011)
2(Lb005)粗品升华纯化后得到升华纯Ir(La011)
2(Lb005)(1.64g,纯度:99.68%,收率:60.04%),质谱:1125.45(M+H)。
1H NMR(400MHz,CDCl3)δ8.40(d,J=15.0Hz,2H),8.13(t,J=3.0Hz,2H),7.89-7.79(m,4H),7.55-7.51(m,2H),7.21(d,J=1.4Hz,2H),7.03(d,J=4.58Hz,2H),4.60(s,1H),3.30(m,2H),2.27(s,12H),2.20(m,2H),1.96-1.76(m,12H),1.52-1.43(m,8H),1.11-0.98(m,6H),0.97(m,6H).
配体La020的合成
化合物La020-3的合成
参照化合物La004-3的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La020-3(24.87g,纯度:99.36%,收率:80.11%),质谱:342.28(M+H)。
化合物La020-4的合成
参照化合物La004-4的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La020-4(17.47g,纯度:99.50%,收率:78.62%),质谱:306.88(M+H)。
化合物La020的合成
参照化合物La004的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La020(14.24g,纯度:99.74%,收率:68.75%),质谱:382.15(M+H)。
化合物Ir(La020)
2(Lb005)的合成
化合物Ir(La020)-1的合成
参照化合物Ir(La004)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La020)-1(8.03g,收率:66.54%)。不经纯化直接使用于下一步。
化合物Ir(La020)
2(Lb005)的合成
参照化合物Ir(La004)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La020)
2(Lb005)(2.51g,纯度:99.79%,收率:33.72%)。将2.51克Ir(La020)
2(Lb005)粗品升华纯化后得到升华纯Ir(La020)
2(Lb005)(1.41g,纯度:99.74%,收率:56.17%),质谱:1165.74(M+H)。
1H NMR(400MHz,CDCl3)δ8.40(d,J=7.5Hz,2H),8.12-8.06(m,4H),7.68(d,J=1.4Hz,2H),7.53(m,2H),6.92(s,2H),4.56(s,1H),2.80-2.73(m,2H),2.71(m,12H),2.43(m,8H),1.75-1.68(m,8H),1.65-1.61(m,8H),1.52-1.43(m,8H),1.11-0.97(m,12H),0.94(m,12H).
配体La026的合成
化合物La026-3的合成
将化合物La026-1(33.00g,114.89mmol)、La026-2(21.23g,137.87mmol)、双(4-二甲氨基苯基二叔丁基膦)二氯化钯(807.20mg,1.14mmol)、碳酸钾(31.78g,229.96mmol)、甲 苯(360ml)、乙醇(120ml)、去离子水(120ml)加入1000ml的三口圆底烧瓶中,抽真空氮气置换3次,在氮气保护下,75℃搅拌2小时。TLC监控(展开剂为乙酸乙酯:石油醚=1:10)原料La026-1反应完全。
加入乙酸乙酯(300ml),分液,加入去离子水洗涤(3*250ml),分液,有机相浓缩后进行硅胶柱层析(200-300目硅胶,洗脱剂为乙酸乙酯:石油醚=1:20),浓缩后得到白色固体为化合物La026-3(20.10g,纯度:99.52%,收率:84.00%),质谱:209.08(M+H)。
化合物La026-4的合成
将化合物La026-3(19.16g,91.99mmol)、La004-2(30.57g,110.39mmol)、醋酸钯(413.05mg,1.84mmol)、1,3-双(二苯基膦)丙烷(1.52g,3.68mmol)、三水合醋酸钠(25.03g,183.98mmol)、N,N-二甲基甲酰胺(250ml)加入1000ml的三口圆底烧瓶中,真空氮气置换3次,80℃搅拌8小时。TLC监控(展开剂为乙酸乙酯:石油醚=1:7)原料La026-3反应完全。
直接浓缩除去N,N-二甲基甲酰胺,加入乙酸乙酯(800ml),加入去离子水洗涤(3*350ml),分液,有机相浓缩后进行硅胶柱层析(200-300目硅胶,洗脱剂为乙酸乙酯:石油醚=1:15),浓缩后得到浅黄色糖状固体为化合物La026-4(26.09g,纯度:99.55%,收率:70.14%),质谱:404.06(M+H)。
化合物La026-5的合成
参照化合物La004-4的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La026-5(19.23g,纯度:99.45%,收率:76.92%),质谱:368.18(M+H)。
化合物La026的合成
参照化合物La004的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La026(10.15g,纯度:99.65%,收率:67.73%),质谱:376.26(M+H)。
化合物Ir(La026)
2(Lb005)的合成
化合物Ir(La026)-1的合成
参照化合物Ir(La004)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La026)-1(7.66g,收率:45.72%)。不经纯化直接使用于下一步。
化合物Ir(La026)
2(Lb005)的合成
参照化合物Ir(La004)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得 到红色固体为化合物Ir(La026)
2(Lb005)(2.10g,纯度:99.90%,收率:35.86%)。将2.10克Ir(La026)
2(Lb005)粗品升华纯化后得到升华纯Ir(La026)
2(Lb005)(1.22g,纯度:99.85%,收率:58.09%),质谱:1153.36(M+H)。
1H NMR(400MHz,CDCl3)δ8.40(d,J=7.5Hz,2H),8.12(dt,J=10.4,1.3Hz,4H),7.98(dd,J=7.4,1.5Hz,2H),7.82(s,2H),7.56-7.50(m,4H),7.41-7.36(m,4H),7.31(td,J=7.5,1.5Hz,2H),4.70(s,1H),2.87(m,2H),2.47(s,6H),2.03-2.01(m,2H),1.68-1.46(m,8H),1.21-1.13(m,12H),0.98-0.85(m,12H).
配体La033的合成
化合物La033的合成
参照化合物La004的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La033(16.54g,纯度:99.50%,收率:62.53%),质谱:416.06(M+H)。
化合物Ir(La033)
2(Lb005)的合成
化合物Ir(La033)-1的合成
参照化合物Ir(La004)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La033)-1(9.01g,收率:47.31%)。不经纯化直接使用于下一步。
化合物Ir(La033)
2(Lb005)的合成
参照化合物Ir(La004)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La033)
2(Lb005)(4.02g,纯度:99.76%,收率:46.27%)。将4.02克Ir(La033)
2(Lb005)粗品升华纯化后得到升华纯Ir(La033)
2(Lb005)(2.41g,纯度:99.68%,收率:59.95%),质谱:1233.58(M+H)。
1H NMR(400MHz,CDCl3)δ8.44(d,J=7.5Hz,2H),8.09(t,J=1.3Hz,4H),7.98(dd,J=7.4,1.5Hz,2H),7.82(s,2H),7.58-7.53(m,4H),7.39(td,J=7.5,1.5Hz,2H),7.35(d,J=1.3Hz, 2H),7.31(td,J=7.5,1.5Hz,2H),4.58(s,1H),2.57(m,4H),2.27(s,6H),2.10-1.99(m,4H),1.76-1.62(m,16H),1.52-1.43(m,8H),1.11-0.97(m,6H),0.94(m,6H).
配体La051的合成
化合物La051-3的合成
参照化合物La004-3的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La051-3(19.11g,纯度:99.63%,收率:67.44%),质谱:384.02(M+H)。
化合物La051-4的合成
参照化合物La004-4的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La051-4(12.34g,纯度:99.30%,收率:75.05%),质谱:348.52(M+H)。
化合物La051的合成
参照化合物La004的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La051(9.16g,纯度:99.86%,收率:68.07%),质谱:370.45(M+H)。
化合物Ir(La051)
2(Lb005)的合成
化合物Ir(La051)-1的合成
参照化合物Ir(La004)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La051)-1(6.01g,收率:75.66%)。不经纯化直接使用于下一步。
化合物Ir(La051)
2(Lb005)的合成
参照化合物Ir(La004)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La051)
2(Lb005)(3.35g,纯度:99.88%,收率:52.52%)。将3.35克Ir(La051)
2(Lb005)粗品升华纯化后得到升华纯Ir(La051)
2(Lb005)(2.13g,纯度:99.86%,收率:63.58%),质谱:1141.43(M+H)。
1H NMR(400MHz,CDCl3)δ8.39(d,J=14.8Hz,2H),8.08-8.07(m,2H),8.04(t,J=3.0Hz,2H),7.66(d,J=3.1Hz,2H),7.52(dd,J=15.0,2.9Hz,2H),7.21(d,J=1.4Hz,2H),7.06(d,J=3.1Hz,2H),4.58(s,1H),2.87(m,4H),2.27(m,2H),1.32-1.30(m,42H),1.63-1.22(m,8H),0.94-0.85(m,12H).
配体La064的合成
化合物La064-1的合成
参照化合物La004-3的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La064-3(15.24g,纯度:99.43%,收率:65.35%),质谱:384.02(M+H)。
化合物La064-4的合成
参照化合物La004-4的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La064-4(11.85g,纯度:99.30%,收率:73.16%),质谱:348.52(M+H)。
化合物La064的合成
参照化合物La004的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La064(8.86g,纯度:99.61%,收率:65.95%),质谱:370.45(M+H)。
化合物Ir(La064)
2(Lb005)的合成
化合物Ir(La064)-1的合成
参照化合物Ir(La004)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La064)-1(5.73g,收率:74.21%)。不经纯化直接使用于下一步。
化合物Ir(La064)
2(Lb005)的合成
参照化合物Ir(La004)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La064)
2(Lb005)(1.80g,纯度:99.83%,收率:56.71%)。将1.80克Ir(La064)
2(Lb005)粗品升华纯化后得到升华纯Ir(La064)
2(Lb005)(1.10g,纯度:99.79%,收 率:61.11%),质谱:1141.43(M+H)。
1H NMR(400MHz,CDCl3),δ8.44(d,J=15.0Hz,2H),8.10-8.01(m,4H),7.57(dd,J=15.0,3.0Hz,2H),7.51(d,J=3.1Hz,2H),6.75(d,J=2.9Hz,2H),4.60(s,1H),2.47-2.43(m,8H),2.33-2.15(m,12H),1.82-1.80(m,6H),1.31-1.24(m,8H),0.94-0.86(m,36H).
配体La080的合成
化合物La080-4的合成
将La064-4(16.21g,46.60mmol)、叔丁醇钾(10.46g,93.19mmol)、氘代二甲基亚砜(80ml)加入250ml的三口圆底烧瓶中,真空氮气置换三次,加热至90℃反应过夜15h,核磁监控La064-4反应完毕。
将反应液滴加至去离子水中(250ml),加入乙酸乙酯(500ml),室温搅拌30分钟,分液,有机相去离子水洗涤(3*150ml),分液,有机相浓缩进行硅胶柱层析(200-300目硅胶,洗脱剂为乙酸乙酯:石油醚=1:15),浓缩后得到白色糖状固体为化合物La080-4(15.44g,纯度:99.60%,氘代率:99.12%,收率:95.00%),质谱:349.05(M+H)。
化合物La080的合成
参照化合物La004的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La080(10.16g,纯度:99.51%,收率:67.05%),质谱:425.35(M+H)。
化合物Ir(La080)
2(Lb005)的合成
化合物Ir(La080)-1的合成
参照化合物Ir(La004)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La080)-1(6.10g,收率:75.27%)。不经纯化直接使用于下一步。
化合物Ir(La080)
2(Lb005)的合成
参照化合物Ir(La004)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La080)
2(Lb005)(1.98g,纯度:99.77%,收率:54.38%)。将1.98克Ir(La080)
2(Lb005)粗品升华纯化后得到升华纯Ir(La080)
2(Lb005)(1.33g,收率:67.17%),质谱:1251.62(M+H)。
1H NMR(400MHz,CDCl3)δ8.79(d,J=2.7Hz,2H),8.64-8.62(m,4H),7.70(d,J=2.9Hz,2H),6.94(d,J=2.9Hz,2H),4.84(s,1H),2.73-2.47(m,6H),2.40(s,12H),2.31(m,2H),1.83-1.63(m,18H),1.44-1.31(m,8H),0.94-0.86(m,36H).
配体La102的合成
化合物La102-3的合成
参照化合物La026-3的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La102-3(25.86g,纯度:99.61%,收率:85.14%),质谱:265.27(M+H)。
化合物La102-4的合成
参照化合物La026-4的合成和纯化方法,只需要将对应的原物料变更即可,得到浅黄色糖状固体为化合物La102-4(30.19g,纯度:99.34%,收率:71.28%),质谱:460.32(M+H)。化合物La102-5的合成
参照化合物La004-4的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La102-5(17.44g,纯度:99.51%,收率:78.80%),质谱:424.26(M+H)。
化合物La102的合成
参照化合物La004的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物La102(11.71g,纯度:99.65%,收率:71.02%),质谱:460.28(M+H)。
化合物Ir(La102)
2(Lb005)的合成
化合物Ir(La102)-1的合成
参照化合物Ir(La004)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合 物Ir(La102)-1(7.00g,收率:78.66%)。不经纯化直接使用于下一步。
化合物Ir(La102)
2(Lb005)的合成
参照化合物Ir(La004)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La102)
2(Lb005)(3.28g,纯度:99.76%,收率:48.58%)。将3.28克Ir(La102)
2(Lb005)粗品升华纯化后得到升华纯Ir(La102)
2(Lb005)(2.04g,纯度:99.76%,收率:62.19%),质谱:1321.26(M+H)。
1H NMR(400MHz,CDCl
3)δ8.44(d,J=15.0Hz,2H),8.12-8.04(m,4H),7.98(dd,J=14.6,3.4Hz,2H),7.78(s,2H),7.59-7.52(m,4H),7.42-7.28(m,4H),4.79(s,1H),2.47-2.43(m,8H),2.35(s,6H),2.31(m,2H),1.83-1.73(m,2H),1.31-1.24(m,8H),0.94-0.86(m,42H).
化合物Ir(La004)(Lb005)(Lc004)的合成
化合物[Ir(La004)(COD)]-1的合成
将La004(14.27g,45.52mmol)、氧化银(5.27g,22.76mmol)、4A粉末分子筛(15g)、二氯甲烷(300ml)加入1000ml的单口圆底烧瓶中,真空氮气置换3次,室温搅拌反应2h,反应液变为棕黑色浑浊液。TLC监控(展开剂为乙酸乙酯:石油醚=1:8)原料La004消耗完毕。接着往反应液中加入1,5-环辛二烯氯化铱二聚体(15.28g,22.76mmol),室温搅拌过夜12h,溶液变成红棕色,TLC监控(展开剂为甲醇:二氯甲烷=1:100),有大量大极性红色产物生成,停止反应。
过滤,用少量二氯甲烷淋洗滤饼,收集滤液浓缩至30ml溶剂,加入正己烷(200ml),室温打浆1小时,抽滤,滤饼干燥得到橙红色固体为[Ir(La004)(COD)]-1(13.31g,收率:88.21%),质谱:648.19(M+H)
化合物[Ir(La004)(Lc004)]-1的合成
将化合物[Ir(La004)(COD)]-1(10.00g,15.45mmol)、Lc004(13.40g,46.35mmol)、乙二醇乙醚(150ml)加入500ml的三口圆底烧瓶中,真空置换3次,加热至120℃搅拌16小时。TLC监控(展开剂为甲醇:二氯甲烷=1:100)原料[Ir(La004)(COD)]-1消耗完毕。
冷却到室温后,加入甲醇(300ml),过滤,滤饼用甲醇(50ml)洗涤,固体在80℃真空干燥得到化合物[Ir(La004)(Lc004)]-1(6.82g,收率:53.60%)。得到的化合物不经纯化直接 使用于下一步。
化合物Ir(La004)(Lb005)(Lc004)的合成
参照化合物Ir(La004)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La004)(Lb005)(Lc004)(2.50g,纯度:99.83%,收率:48.58%)。将2.50克Ir(La004)(Lb005)(Lc004)粗品升华纯化后得到升华纯Ir(La004)(Lb005)(Lc004)(1.44g,纯度:99.81%,收率:57.60%),质谱:1005.68(M+H)
1H NMR(400MHz,CDCl
3)δ8.42(dd,J=19.9,15.0Hz,2H),8.13-8.05(m,3H),8.03(d,J=3.1Hz,1H),7.78(d,J=15.0Hz,1H),7.64(d,J=3.1Hz,1H),7.55-7.49(m,4H),6.96(d,J=2.9Hz,2H),4.76(s,1H),2.54-2.40(s,12H),2.38-2.30(m,4H),2.28(m,2H),1.81-1.24(m,10H),1.01-0.86(m,24H).
化合物Ir(La004)(Lb005)(Lc011)的合成
化合物[Ir(La004)(Lc011)]-1的合成
参照化合物[Ir(La004)(Lc004)]-1的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物[Ir(La004)(Lc011)]-1(6.48g,收率:51.35%)。得到的化合物不经纯化直接使用于下一步。
化合物Ir(La004)(Lb005)(Lc011)的合成
参照化合物Ir(La004)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La004)(Lb005)(Lc011)(2.1g,纯度:99.78%,收率:45.25%)。将3.1克Ir(La004)(Lb005)(Lc011)粗品升华纯化后得到升华纯Ir(La004)(Lb005)(Lc011)(1.09g,纯度:99.75%,收率:51.90%),质谱:1005.68(M+H)。
1H NMR(400MHz,CDCl
3)δ8.60(d,J=7.5Hz,1H),8.44(d,J=7.5Hz,1H),8.05-8.01(m,3H),7.95(dd,J=7.5,1.4Hz,1H),7.71-7.62(m,2H),7.57(d,J=7.5Hz,1H),7.35(d,J=7.5Hz,1H),7.19(dd,J=7.5,1.4Hz,1H),7.08(s,1H),6.96(d,J=1.4Hz,2H),4.79(s,1H),2.57-2.43(s,12H),2.40-2.31(m,4H),2.31(m,2H),1.83-1.53(m,2H),1.31-1.24(m,8H),0.99-0.86(m,24H).
化合物Ir(La004)(Lb005)(Lc023)的合成
化合物[Ir(La004)(Lc023)]-1的合成
参照化合物[Ir(La004)(Lc004)]-1的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物[Ir(La004)(Lc023)]-1(7.56g,收率:54.52%)。得到的化合物不经纯化直接使用于下一步。
化合物Ir(La004)(Lb005)(Lc023)的合成
参照化合物Ir(La004)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La004)(Lb005)(Lc023)(2.55g,纯度:99.86%,收率:46.74%)。将2.55克Ir(La004)(Lb005)(Lc023)粗品升华纯化后得到升华纯Ir(La004)(Lb005)(Lc023)(1.46g,纯度:99.81%,收率:57.25%),质谱:1066.26(M+H)。
1H NMR(400MHz,CDCl
3)δ8.44(d,J=15.0Hz,1H),8.36(d,J=15.0Hz,1H),8.14(dd,J=3.0,1.5Hz,1H),8.04(t,J=3.0Hz,1H),7.98(dd,J=14.6,3.5Hz,1H),7.80-7.76(m,3H),7.67-7.64(m,3H),7.59-7.52(m,2H),7.49-7.45(m,1H),7.47-7.27(m,2H),6.96(d,J=3.1Hz,1H),4.79(s,1H),2.87-2.43(m,3H),2.40-2.31(s,9H),2.31(m,2H),1.83-1.53(m,9H),1.31-0.86(m,24H).
应用例:有机电致发光器件的制作
将50mm*50mm*1.0mm的具有ITO(100nm)透明电极的玻璃基板在乙醇中超声清洗10分钟,再150度烘干后经过N
2Plasma处理30分钟。将洗涤后的玻璃基板安装在真空蒸镀装置的基板支架上,首先再有透明电极线一侧的面上按照覆盖透明电极的方式蒸镀化合物HATCN,形成膜厚为5nm的薄膜,紧接着蒸镀一层HTM1形成膜厚为60nm的薄膜,再在HTM1薄膜上蒸镀一层HTM2形成膜厚为10nm的薄膜,然后,在HTM2膜层上再采用共蒸镀的模式蒸镀主体材料和掺杂化合物(对比化合物X、本发明的化合物),膜厚为30nm,主体材料和掺杂材料比例为90%:10%。在发光层上再依次蒸镀ETL膜层(25nm)LiQ膜层(1nm),最后蒸镀一层金属Al(100nm)作为电极。
评价:
将上述器件进行器件性能测试,在各实施例和比较例中,使用恒定电流电源(Keithley 2400),使用固定的电流密度流过发光元件,使用分光辐射计(CS 2000)测试发光波谱。同时测定电压值以及测试亮度为初始亮度的90%的时间(LT90)。结果如下:
由上面表格中的数据对比可知,使用本发明的化合物作为掺杂剂的有机电致发光器件,相较于对比化合物发射光谱较窄,色彩饱和度较高,在驱动电压、发光效率、器件寿命都表现出更加优越的性能。
升华温度对比:升华温度的定义为:在10
-7Torr的真空度,蒸镀速率为1埃每秒对应的温度。测试结果如下:
掺杂材料 | 升华温度 |
Ir(La004) 2(Lb005) | 266 |
Ir(La009) 2(Lb005) | 269 |
Ir(La026) 2(Lb005) | 272 |
Ir(La033) 2(Lb005) | 270 |
Ir(La102) 2(Lb005) | 256 |
Ir(La004)(Lb005)(Lc004) | 262 |
对比化合物1 | 280 |
对比化合物2 | 288 |
对比化合物3 | 286 |
对比化合物4 | 276 |
由上面表格中的数据对比可知,本发明化合物具有较低的升华温度,有利于产业化应用。
本发明通过对取代基的特殊搭配,出乎意料地提供了更好的器件发光效率和改善的寿命,同时相对于现有技术,出乎意料地提供了较低的升华温度。上述结果表明本发明的化合物具有升华温度较低,光、电化学稳定性高,色饱和度高,发光效率高,器件寿命长等优点,可用于有机电致发光器件中。特别是作为红色发光掺杂体,具有应用于OLED产业的可能。
本发明的材料不但具有光、电稳定性高,升华温度低,发射半峰宽窄,色饱和度高,发光效率高,器件寿命长等优点。本发明的材料作为磷光材料,可以将三重激发态转换成光,所以能够提高有机电致发光器件的发光效率,从而降低能耗。特别是作为红色发光掺杂体,具有应用于AMOLED产业的可能。
Claims (18)
- 一种有机金属化合物,具有Ir(La)(Lb)(Lc)的通式,其中La为式(1)所示的结构,其中,虚线表示与金属Ir连接的位置;其中,X 1为N或CR 1,X 2为N或CR 2,X 3为N或CR 3,X 4为N或CR 4,X 5为N或CR 5;其中,X 1-X 5至多之一为N,且当X 1-X 5为CR 1-CR 5时,其中R 1-R 5至少之一不为H;其中,R 1-R 10独立地选自氢、氘、卤素、氰基、羟基、巯基、胺基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基,或者R 1-R 6、R 7-R 10两个相邻的基团之间可以相互连接形成脂肪族环或芳香族环状结构;且R 7-R 10至少之一不为氢;所述取代为被氘、F、Cl、Br、C1-C6烷基、C3-C6环烷基、C1-C6烷氧基、C1-C6烷基取代的胺基、腈、异腈或膦基所取代,其中取代数目为单取代到最大数目取代;其中,所述杂烷基和杂芳基中至少含有一个O、N或S杂原子;其中Lb为式(2)所示的结构,其中,虚线位置表示与金属Ir连接的位置;其中,Ra-Rg独立地选自氢、氘、卤素、取代的或未取代的C1-C10烷基、取代的或未取代的C3-C20环烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20杂环烷基;或者Ra、Rb、Rc之间两两连接以形成脂肪环状结构,Re、Rf、Rg之间两两连接以形成脂肪环状结构;所述取代为被氘、F、Cl、Br、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C1-C4烷基取代的胺基、氰基、腈、异腈或膦基所取代;其中,所述杂烷基和杂环烷基中至少含有一个O、N或S杂原子;其中,Lc为单阴离子型双齿配体,Lc与Lb不相同且不为OO型配体;其中,Lc与La相同或不相同,所述不相同为母核结构不相同或母核结构相同但取代基不同或母核结构相同取代基相同但取代基位置不相同;或者,La、Lb、Lc之间两两或三者相互连接形成多齿配体。
- 根据权利要求1所述的有机金属化合物,其中La为式(3)所示的结构,其中,虚线表示与金属Ir连接的位置;其中,R 1-R 10独立地选自氢、氘、卤素、氰基、羟基、巯基、胺基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基;或者,R 1-R 6、R 7-R 10两个相邻的基团之间相互连接形成脂肪族环或芳香族环状结构;其中,R 7-R 10至少之一不为氢;其中,所述杂烷基和杂芳基中至少含有一个O、N或S杂原子;其中,所述取代为被氘、F、Cl、Br、C1-C6烷基、C3-C6环烷基、C1-C6烷氧基、C1-C6烷基取代的胺基、腈、异腈、膦基所取代,其中所述取代为单取代到最大数目取代。
- 根据权利要求2所述的有机金属化合物,其中式(3)中,R 1和/或R 4和/或R 5不为氢。
- 根据权利要求3所述的有机金属化合物,其中式(3)中,R 2和R 3为氢。
- 根据权利要求4所述的有机金属化合物,其中式(3)中,其中所述R 1、R 4、R 5独立选自氘、卤素、取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基,所述取代为被氘、F、Cl、Br或C1-C4烷基所取代。
- 根据权利要求2所述的有机金属化合物,其中式(3)中,R 6选自氘、卤素、取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基;R 8和/或R 10不为氢。
- 根据权利要求6所述的有机金属化合物,其中式(3)中,R 8、R 10独立选自取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基,所述取代为被氘、F、Cl、Br或C1-C4烷基所取代。
- 根据权利要求2所述的有机金属化合物,其中式(3)中,R 7、R 9为H。
- 根据权利要求2所述的有机金属化合物,其中R 7和R 8、R 8和R 9、或者R 9和R 10之间相互连接以形成式(4)所示的结构,其中*表示连接的位置,Y 1-Y 4独立地为CR 0或N,Z1选自O、S,R 0独立地为氢、氘、卤素、氰基、取代或未取代的C1-C10烷基、取代或未取代的C3-C20环烷基、取代或未取代的C2-C30烯基、取代或未取代的C2-C30炔基、取代或未取代的C6-C30芳基、取代或未取代的C1-C30杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C30芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基;所述取代为被氘、F、Cl、Br、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C1-C4烷基取代的胺基、腈、异腈或膦基所取代。
- 根据权利要求9所述的有机金属化合物,其中式(4)中,Y 1-Y 4独立地为CR 0,Z1选自O,R 0独立地为氢、氘、卤素、取代或未取代的C1-C6烷基、取代或未取代的C3-C10环烷基;所述取代为被氘、F、Cl、Br、C1-C4烷基所取代。
- 根据权利要求1-10任一所述的有机金属化合物,其中Lc与La相同。
- 根据权利要求1-10任一所述的有机金属化合物,其中Lc为式(5)所示的结构,其中,虚线表示与金属Ir连接的位置;其中,R 11-R 18独立地选自氢、氘、卤素、氰基、羟基、氨基、胺基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基 二C6-C30芳基硅基;其中,R 15-R 18中至少两个不为氢;其中,R 11-R 14中至少一组两个相邻的基团之间形成如下式(6)所示芳香族环状结构;其中,虚线表示与吡啶环连接的位置;其中,R 19-R 22独立地选自氢、氘、卤素、氰基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基、或者R 19-R 22两个相邻的基团之间相互连接形成脂肪族环或芳香族环状结构;所述取代为被氘、F、Cl、Br、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C1-C4烷基取代的胺基、腈、异腈或膦基所取代。
- 根据权利要求12所述的有机金属化合物,其中R 15、R 17为氘、卤素、取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基,其中,R 11-R 14中有一组两个相邻的基团之间形成式(6)所示芳香族环状结构,其它两个独立选自氢、氘、卤素、取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基;其中,R 19-R 22独立地选自氢、氘、卤素、取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基;所述取代为被氘、F、Cl、Br、C1-C4烷基所取代。
- 权利要求1-16任一所述有机金属化合物在有机电致发光器件中的应用。
- 权利要求17所述的应用,为权利要求1-16任一所述有机金属化合物作为有机电致发光器件的发光层中的红色发光掺杂材料。
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