CN116041243A - A fluorene-based triarylamine compound and its application in organic electroluminescent devices - Google Patents
A fluorene-based triarylamine compound and its application in organic electroluminescent devices Download PDFInfo
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- CN116041243A CN116041243A CN202310060201.XA CN202310060201A CN116041243A CN 116041243 A CN116041243 A CN 116041243A CN 202310060201 A CN202310060201 A CN 202310060201A CN 116041243 A CN116041243 A CN 116041243A
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- -1 triarylamine compound Chemical class 0.000 title claims abstract description 128
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 125000001424 substituent group Chemical group 0.000 claims abstract description 45
- 239000000126 substance Substances 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims description 93
- 150000001875 compounds Chemical class 0.000 claims description 87
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 62
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 55
- 229910052805 deuterium Inorganic materials 0.000 claims description 55
- 125000003118 aryl group Chemical group 0.000 claims description 54
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 51
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 50
- 229910052801 chlorine Inorganic materials 0.000 claims description 50
- 239000000460 chlorine Substances 0.000 claims description 50
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 50
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 47
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 47
- 229910052731 fluorine Inorganic materials 0.000 claims description 47
- 239000011737 fluorine Substances 0.000 claims description 47
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 41
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 38
- 125000001072 heteroaryl group Chemical group 0.000 claims description 36
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 35
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 35
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 35
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 35
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 35
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 35
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 35
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 35
- 125000001624 naphthyl group Chemical group 0.000 claims description 33
- 235000010290 biphenyl Nutrition 0.000 claims description 31
- 239000004305 biphenyl Substances 0.000 claims description 31
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 29
- 230000005525 hole transport Effects 0.000 claims description 28
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 27
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 22
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 21
- 125000004414 alkyl thio group Chemical group 0.000 claims description 21
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 21
- 229910052794 bromium Inorganic materials 0.000 claims description 21
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 21
- 239000012044 organic layer Substances 0.000 claims description 21
- 125000004076 pyridyl group Chemical group 0.000 claims description 21
- 238000002347 injection Methods 0.000 claims description 20
- 239000007924 injection Substances 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 18
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 17
- 125000003944 tolyl group Chemical group 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 10
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229910052722 tritium Inorganic materials 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 claims description 6
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 6
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 6
- 125000006835 (C6-C20) arylene group Chemical group 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001555 benzenes Chemical group 0.000 claims description 4
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 229930194542 Keto Natural products 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 2
- 125000005566 carbazolylene group Chemical group 0.000 claims description 2
- 125000005567 fluorenylene group Chemical group 0.000 claims description 2
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 238000013086 organic photovoltaic Methods 0.000 claims description 2
- 108091008695 photoreceptors Proteins 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000005551 pyridylene group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 125000005493 quinolyl group Chemical group 0.000 claims description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 2
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005556 thienylene group Chemical group 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 125000004306 triazinyl group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 40
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000000903 blocking effect Effects 0.000 abstract description 5
- 239000003086 colorant Substances 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 230000032258 transport Effects 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 9
- 230000008020 evaporation Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 125000002950 monocyclic group Chemical group 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000002619 bicyclic group Chemical group 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 125000002541 furyl group Chemical group 0.000 description 4
- 239000002346 layers by function Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- 125000003367 polycyclic group Chemical group 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000003003 spiro group Chemical group 0.000 description 4
- 125000003107 substituted aryl group Chemical group 0.000 description 4
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000001544 thienyl group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- 125000005259 triarylamine group Chemical group 0.000 description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 2
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 2
- AEBWATHAIVJLTA-UHFFFAOYSA-N 1,2,3,3a,4,5,6,6a-octahydropentalene Chemical compound C1CCC2CCCC21 AEBWATHAIVJLTA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 125000004350 aryl cycloalkyl group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 150000001934 cyclohexanes Chemical class 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 150000001940 cyclopentanes Chemical class 0.000 description 2
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 2
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000005509 dibenzothiophenyl group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000008376 fluorenones Chemical class 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- BNRNAKTVFSZAFA-UHFFFAOYSA-N hydrindane Chemical compound C1CCCC2CCCC21 BNRNAKTVFSZAFA-UHFFFAOYSA-N 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 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 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 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 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WTAPZWXVSZMMDG-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 WTAPZWXVSZMMDG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- IVDFJHOHABJVEH-UHFFFAOYSA-N HOCMe2CMe2OH Natural products CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 1
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- 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 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000001691 aryl alkyl amino group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000005620 boronic acid group Chemical group 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 125000004367 cycloalkylaryl group Chemical group 0.000 description 1
- 150000001930 cyclobutanes Chemical class 0.000 description 1
- 150000001932 cycloheptanes Chemical class 0.000 description 1
- 150000001942 cyclopropanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004773 frontier orbital Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005241 heteroarylamino group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
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- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
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- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
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- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
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Abstract
Description
技术领域Technical Field
本发明涉及有机电致发光材料领域，特别是涉及一种基于芴的三芳胺类化合物及其在有机电致发光器件中的应用。The invention relates to the field of organic electroluminescent materials, in particular to a fluorene-based triarylamine compound and application thereof in an organic electroluminescent device.
背景技术Background Art
有机电致发光器件(又被称为OLED，即有机发光二极管)是一类自发光的电子元器件。与现有的液晶显示(LCD)、等离子显示(PDP)和场发射显示(FED)等其他平板显示技术相比，有机电致发光显示具有对比度高，可视角宽，响应速度快，色彩表现力优异等特点，并且OLED器件能够在柔性基底上制备成为可卷曲或可弯折的柔性显示器产品。因此，近年来OLED显示器被广泛应用于手机、平板电脑、挂壁电视机等消费电子领域，以及车载显示领域中。Organic electroluminescent devices (also known as OLEDs, i.e. organic light-emitting diodes) are a type of self-luminous electronic components. Compared with other existing flat panel display technologies such as liquid crystal display (LCD), plasma display (PDP) and field emission display (FED), organic electroluminescent displays have the characteristics of high contrast, wide viewing angle, fast response speed, excellent color expression, etc., and OLED devices can be prepared on flexible substrates to become rollable or bendable flexible display products. Therefore, in recent years, OLED displays have been widely used in consumer electronics such as mobile phones, tablet computers, wall-mounted TVs, as well as in the field of vehicle-mounted displays.
OLED器件主要由电极，有机发光层和有机功能层三部分组成类似“三明治”的结构。在器件两端的电极施加正向的电压，电子和空穴分别从器件的阳极和阴极注入，经有机功能层的传输，两种载流子在有机发光层中复合，形成结合紧密的电子-空穴对，即激子。随着激子的能量传递到发光材料并以光子的形式释放，器件即实现发光。为了提升器件的发光效率，降低驱动电压，通常还会引入合适的功能层材料，例如载流子注入层，载流子传输层等。例如，一种典型的有机电致发光器件结构包括：阳极/空穴注入层(HIL)/空穴传输层(HTL)/发光层(EML,发光主体材料:发光客体材料)/电子传输层(ETL)/电子注入层(EIL)/阴极。其中，其中空穴传输层材料负责将空穴传递至发光层，具有十分重要的作用。OLED devices are mainly composed of three parts: electrodes, organic light-emitting layers and organic functional layers, which are similar to a "sandwich" structure. A positive voltage is applied to the electrodes at both ends of the device, and electrons and holes are injected from the anode and cathode of the device respectively. After being transmitted by the organic functional layer, the two carriers recombine in the organic light-emitting layer to form a tightly bound electron-hole pair, i.e., an exciton. As the energy of the exciton is transferred to the light-emitting material and released in the form of photons, the device emits light. In order to improve the luminous efficiency of the device and reduce the driving voltage, suitable functional layer materials such as carrier injection layer and carrier transport layer are usually introduced. For example, a typical organic electroluminescent device structure includes: anode/hole injection layer (HIL)/hole transport layer (HTL)/light-emitting layer (EML, light-emitting host material: light-emitting guest material)/electron transport layer (ETL)/electron injection layer (EIL)/cathode. Among them, the hole transport layer material is responsible for transferring holes to the light-emitting layer, which plays a very important role.
近年来，基于OLED技术的显示器在消费电子领域的占比逐年增加，这要求其在驱动功率，发光效率和使用寿命方面不低于其他常规的显示器。因此，开发化学结构稳定，性能优异的功能层材料是十分有必要的。具体来说，材料应具有适当的分子量和溶解性，从而易于提纯，以及在高真空的环境下热沉积；同时也需要有良好的热稳定性和电化学稳定性，确保器件的使用寿命延长。而现有材料的效率和稳定性均有待进一步提升。In recent years, the proportion of displays based on OLED technology in the consumer electronics field has increased year by year, which requires that its driving power, luminous efficiency and service life are not lower than other conventional displays. Therefore, it is necessary to develop functional layer materials with stable chemical structure and excellent performance. Specifically, the material should have an appropriate molecular weight and solubility, so that it is easy to purify and thermally deposit in a high vacuum environment; it also needs to have good thermal stability and electrochemical stability to ensure that the service life of the device is extended. The efficiency and stability of existing materials need to be further improved.
发明内容Summary of the invention
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种基于芴的三芳胺类化合物及其在有机电致发光器件中的应用，用于解决现有技术中的问题。In view of the above-mentioned shortcomings of the prior art, the object of the present invention is to provide a fluorene-based triarylamine compound and its application in an organic electroluminescent device, so as to solve the problems in the prior art.
为实现上述目的及其他相关目的，本发明一方面提供一种基于芴的三芳胺类化合物，所述三芳胺类化合物的化学结构如式(1)所示：To achieve the above-mentioned object and other related objects, the present invention provides a triarylamine compound based on fluorene, wherein the chemical structure of the triarylamine compound is shown in formula (1):
式(1)中，R1，R2彼此相同或不同，独立地选自取代或未取代的C1～C12的直链或支链烷基、取代或未取代的C3～C12的环烷基、取代或未取代的C6～C30的芳基、取代或未取代的C2～C30的杂芳基，或R1、R2键合成环；In formula (1), R 1 and R 2 are the same or different and are independently selected from substituted or unsubstituted C1-C12 straight or branched alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or R 1 and R 2 are bonded to form a ring;
Rm、Rn每一次出现，各自独立地选自氘、氚、氟、氯、氰基、三氟甲基、C1～C10的烷基、C3～C10的环烷基、C1～C10的烷氧基、C1～C10的烷硫基、C6～C20的芳基、C2～C20的杂芳基中的一个，或位于相邻位置的两个Rm基团彼此连接形成取代或未取代的苯环；m和n分别独立地选自0、1、2、3、或4；Each occurrence of R m and R n is independently selected from one of deuterium, tritium, fluorine, chlorine, cyano, trifluoromethyl, C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C20 aryl, C2-C20 heteroaryl, or two R m groups at adjacent positions are connected to form a substituted or unsubstituted benzene ring; m and n are independently selected from 0, 1, 2, 3, or 4;
L0、L1、L2彼此相同或不同，各自独立地选自单键、取代或未取代的C6～C20的亚芳基、或取代或未取代的C2～C20的亚杂芳基；L 0 , L 1 , and L 2 are the same as or different from each other, and are each independently selected from a single bond, a substituted or unsubstituted C6-C20 arylene group, or a substituted or unsubstituted C2-C20 heteroarylene group;
Ar1、Ar2彼此相同或不同，各自独立地选自取代或未取代的C6～C40的芳基、或取代或未取代的C2～C40的杂芳基；Ar 1 and Ar 2 are the same or different, and are each independently selected from a substituted or unsubstituted C6-C40 aryl group, or a substituted or unsubstituted C2-C40 heteroaryl group;
A选自取代或未取代的苊基，或取代或未取代的式(2)～式(4)所示基团：A is selected from substituted or unsubstituted acenaphthenyl, or substituted or unsubstituted groups represented by formula (2) to formula (4):
式(2)～式(4)中，Z1～Z12相同或不同，各自独立地选自-N(Rd)-、-C(Re)(Rf)-、-O-或-S-；其中，所述Rd、Re、Rf，彼此相同或不同，各自独立地选自氢、氘、取代或未取代的C1～C10的烷基、取代或未取代的C3～C10的环烷基、取代或未取代的C6～C18的芳基、或取代或未取代的C2～C18的杂芳基；*表示键合位点。In formula (2) to formula (4), Z 1 to Z 12 are the same or different, and are each independently selected from -N(R d )-, -C( Re )(R f )-, -O- or -S-; wherein R d , Re , and R f are the same or different, and are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C18 aryl, or substituted or unsubstituted C2-C18 heteroaryl; * represents a bonding site.
本发明另一方面提供一种有机层，包括前述的基于芴的三芳胺类化合物。Another aspect of the present invention provides an organic layer, comprising the aforementioned fluorene-based triarylamine compound.
本发明另一方面提供如本发明前述的基于芴的三芳胺类化合物、和/或前述的有机层在有机电致发光器件中的应用。Another aspect of the present invention provides use of the aforementioned fluorene-based triarylamine compound and/or the aforementioned organic layer in an organic electroluminescent device.
本发明另一方面提供一种有机电致发光器件，包括第一电极、第二电极和有机层，其中所述有机层为空穴注入层、空穴传输层、发光层、电子注入层或电子传输层中至少一层，且所述有机层包括前述的基于芴的三芳胺类化合物。Another aspect of the present invention provides an organic electroluminescent device, comprising a first electrode, a second electrode and an organic layer, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron injection layer or an electron transport layer, and the organic layer comprises the aforementioned triarylamine compound based on fluorene.
本发明另一方面提供一种显示或照明装置，包括如本发明前述的有机电致发光器件。Another aspect of the present invention provides a display or lighting device, comprising the organic electroluminescent device as described above in the present invention.
与现有技术相比，本发明的有益效果为：Compared with the prior art, the present invention has the following beneficial effects:
本发明提供的三芳胺类化合物，具有良好的溶解性，空穴传输特性和化学稳定性；此外，分子内引入环烷基并芳基或杂环烷基并芳基，有利于获得热稳定性优良的连续均匀的无定形态薄膜。将本发明提供的化合物作为空穴传输材料应用于有机电致发光器件，具有工作电压低、发光效率和使用寿命高的优势，同时可以降低器件的生产成本。The triarylamine compound provided by the present invention has good solubility, hole transport properties and chemical stability; in addition, the introduction of a cycloalkyl aryl group or a heterocycloalkyl aryl group into the molecule is conducive to obtaining a continuous and uniform amorphous film with excellent thermal stability. The compound provided by the present invention is used as a hole transport material in an organic electroluminescent device, which has the advantages of low operating voltage, high luminous efficiency and service life, and can also reduce the production cost of the device.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1是实施例中有机电致发光器件的一种结构示意图。FIG. 1 is a schematic structural diagram of an organic electroluminescent device in an embodiment.
图2是实施例中有机电致发光器件的另一种结构示意图。FIG. 2 is another schematic diagram of the structure of an organic electroluminescent device in an embodiment.
图中：In the figure:
101 基底101 Base
102 第一电极102 first electrode
103 空穴注入层103 Hole injection layer
104 第一层空穴传输层104 First hole transport layer
105 第二层空穴传输层105 Second hole transport layer
106 发光层106 Luminescent Layer
107 空穴阻挡层107 Hole blocking layer
108 电子传输层108 Electron transport layer
109 第二电极109 second electrode
110 覆盖层110 Overlay
具体实施方式DETAILED DESCRIPTION
以下，详细说明具体公开的芴类化合物及其在有机电致发光器件中的应用的实施方式。本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。The following is a detailed description of the specific disclosed fluorene compounds and the embodiments of their application in organic electroluminescent devices. Those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention.
在进一步描述本发明具体实施方式之前，应理解，本发明的保护范围不局限于下述特定的具体实施方案；还应当理解，本发明实施例中使用的术语是为了描述特定的具体实施方案，而不是为了限制本发明的保护范围；在本发明说明书和权利要求书中，除非文中另外明确指出，单数形式“一个”、“一”和“这个”包括复数形式。Before further describing the specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific specific embodiments described below; it should also be understood that the terms used in the examples of the present invention are for describing the specific specific embodiments rather than for limiting the scope of protection of the present invention; in the present specification and claims, unless otherwise expressly stated herein, the singular forms "a", "an" and "the" include plural forms.
当实施例给出数值范围时，应理解，除非本发明另有说明，每个数值范围的两个端点以及两个端点之间任何一个数值均可选用。除非另外定义，本发明中使用的所有技术和科学术语与本技术领域技术人员通常理解的意义相同。除实施例中使用的具体方法、设备、材料外，根据本技术领域的技术人员对现有技术的掌握及本发明的记载，还可以使用与本发明实施例中所述的方法、设备、材料相似或等同的现有技术的任何方法、设备和材料来实现本发明。When the embodiments give numerical ranges, it should be understood that, unless otherwise specified in the present invention, both endpoints of each numerical range and any numerical value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those generally understood by those skilled in the art. In addition to the specific methods, equipment, and materials used in the embodiments, according to the grasp of the prior art by those skilled in the art and the record of the present invention, any methods, equipment, and materials of the prior art similar or equivalent to the methods, equipment, and materials described in the embodiments of the present invention can also be used to realize the present invention.
本发明发明人经过大量探索研究，目的在于提供一类基于芴的三芳胺类化合物。首先，芴及其衍生物具有特殊的平面型联苯类结构，分子结构稳定，热稳定性和化学稳定性良好，将这类片段引入三芳胺类体系，有利于获得高空穴迁移率的材料；其次，芳基并环烷基或芳基并杂环烷基这类特殊片段的引入，能够形成一定的分子间空间位阻，不仅能够提高分子的溶解度，降低升华温度，有助于材料提纯，而且在成膜过程中有利于抑制分子间堆积，倾向于形成缺陷少的均匀的无定形薄膜，受器件工作过程中产生的焦耳热的影响较小，使得器件的使用寿命得以延长；另一方面，在芳基并环烷基或芳基并杂环烷基基团与芴基团之间引入亚苯基，可以起到延长共轭的作用，使分子的载流子传输特性不至于牺牲太多。此外，通过在三芳胺上连接不同的芳香基团，较容易地实现分子的前线轨道能级和单线态、三线态能级的调控，从而满足不同色光(例如红，绿，蓝光)器件对空穴传输层材料的要求。在此基础上，完成了本申请。After extensive exploration and research, the inventors of the present invention aim to provide a class of triarylamine compounds based on fluorene. First, fluorene and its derivatives have a special planar biphenyl structure, stable molecular structure, good thermal stability and chemical stability. Introducing such fragments into the triarylamine system is conducive to obtaining materials with high hole mobility; secondly, the introduction of special fragments such as aryl cycloalkyl or aryl heterocycloalkyl can form a certain intermolecular steric hindrance, which can not only improve the solubility of the molecule, reduce the sublimation temperature, and help purify the material, but also help to inhibit intermolecular accumulation during the film formation process, tend to form a uniform amorphous film with few defects, and are less affected by the Joule heat generated during the operation of the device, so that the service life of the device can be extended; on the other hand, the introduction of a phenylene group between the aryl cycloalkyl or aryl heterocycloalkyl group and the fluorene group can play a role in extending the conjugation, so that the carrier transport properties of the molecule will not be sacrificed too much. In addition, by connecting different aromatic groups to the triarylamine, it is easier to achieve the regulation of the frontier orbital energy level and the singlet and triplet energy levels of the molecule, thereby meeting the requirements of different color light (such as red, green, and blue light) devices for hole transport layer materials. On this basis, this application is completed.
本发明第一方面提供一种基于芴的三芳胺类化合物，所述基于芴的三芳胺类化合物的化学结构如式(1)所示：The first aspect of the present invention provides a fluorene-based triarylamine compound, wherein the chemical structure of the fluorene-based triarylamine compound is shown in formula (1):
式(1)中，R1，R2彼此相同或不同，独立地选自取代或未取代的C1～C12的直链或支链烷基、取代或未取代的C3～C12的环烷基、取代或未取代的C6～C30的芳基、取代或未取代的C2～C30的杂芳基，或R1、R2键合成环；In formula (1), R 1 and R 2 are the same or different and are independently selected from substituted or unsubstituted C1-C12 straight or branched alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or R 1 and R 2 are bonded to form a ring;
Rm、Rn每一次出现，各自独立地选自氘、氚、氟、氯、氰基、三氟甲基、C1～C10的烷基、C3～C10的环烷基、C1～C10的烷氧基、C1～C10的烷硫基、C6～C20的芳基、C2～C20的杂芳基中的一个，或位于相邻位置的两个Rm基团彼此连接形成取代或未取代的苯环；m和n分别独立地选自0、1、2、3、或4；Each occurrence of R m and R n is independently selected from one of deuterium, tritium, fluorine, chlorine, cyano, trifluoromethyl, C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C20 aryl, C2-C20 heteroaryl, or two R m groups at adjacent positions are connected to form a substituted or unsubstituted benzene ring; m and n are independently selected from 0, 1, 2, 3, or 4;
L0、L1、L2彼此相同或不同，各自独立地选自单键、取代或未取代的C6～C20的亚芳基、或取代或未取代的C2～C20的亚杂芳基；L 0 , L 1 , and L 2 are the same as or different from each other, and are each independently selected from a single bond, a substituted or unsubstituted C6-C20 arylene group, or a substituted or unsubstituted C2-C20 heteroarylene group;
Ar1、Ar2彼此相同或不同，各自独立地选自取代或未取代的C6～C40的芳基、或取代或未取代的C2～C40的杂芳基；Ar 1 and Ar 2 are the same or different, and are each independently selected from a substituted or unsubstituted C6-C40 aryl group, or a substituted or unsubstituted C2-C40 heteroaryl group;
A选自取代或未取代的苊基，或取代或未取代的式(2)～式(4)所示基团：A is selected from substituted or unsubstituted acenaphthenyl, or substituted or unsubstituted groups represented by formula (2) to formula (4):
式(2)～式(4)中，Z1～Z12相同或不同，各自独立地选自-N(Rd)-、-C(Re)(Rf)-、-O-或-S-；其中，所述Rd、Re、Rf，彼此相同或不同，各自独立地选自氢、氘、取代或未取代的C1～C10的烷基、取代或未取代的C3～C10的环烷基、取代或未取代的C6～C18的芳基、或取代或未取代的C2～C18的杂芳基；*表示键合位点。In formula (2) to formula (4), Z 1 to Z 12 are the same or different, and are each independently selected from -N(R d )-, -C( Re )(R f )-, -O- or -S-; wherein R d , Re , and R f are the same or different, and are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C18 aryl, or substituted or unsubstituted C2-C18 heteroaryl; * represents a bonding site.
本发明所提供的化合物中，可选的，所述化合物的化学结构如式(5)～(16)所示：Among the compounds provided by the present invention, optionally, the chemical structures of the compounds are shown in formulas (5) to (16):
式(5)～(16)中，R1～R2、Rm～Rn、A、L0、L1、L2、Ar1、Ar2、m和n如式(1)所定义。In formulae (5) to (16), R 1 to R 2 , R m to R n , A, L 0 , L 1 , L 2 , Ar 1 , Ar 2 , m and n are as defined in formula (1).
本发明所提供的化合物中，式(1)中，R1、R2、Ra～Rf、L0、L1、L2、A、Z1～Z12、Ar1和Ar2中，所述“取代或未取代的”中的“取代的”取代基独立选自氘、氟、氯、溴、氰基、硝基、三氟甲基、-CD3、C1～C10的烷基、C3～C10的环烷基、C1～C10的烷氧基、C1～C10的烷硫基、C6～C20的芳基、C2～C20的杂芳基中的一个或多个；且，R1～R2、Ra～Rf、L0、L1、L2、A、Z1～Z12、Ar1和Ar2的取代基彼此相同或不相同。In the compounds provided by the present invention, in formula (1), in R 1 , R 2 , Ra to R f , L 0 , L 1 , L 2 , A, Z 1 to Z 12 , Ar 1 and Ar 2 , the “substituted” substituent in the “substituted or unsubstituted” is independently selected from one or more of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, -CD 3 , C1 to C10 alkyl, C3 to C10 cycloalkyl, C1 to C10 alkoxy, C1 to C10 alkylthio, C6 to C20 aryl, and C2 to C20 heteroaryl; and the substituents of R 1 to R 2 , Ra to R f , L 0 , L 1 , L 2 , A, Z 1 to Z 12 , Ar 1 and Ar 2 are the same or different.
本发明所提供的化合物中，式(2)～式(4)中芳香环上的氢未被取代，或芳香环上的任意氢原子可以被以下基团中的一个所取代：氘、氚、氟、氯、氰基、三氟甲基、-CD3、取代或未取代的C1～C10的烷基、取代或未取代C3～C10的环烷基、取代或未取代的C1～C10的烷氧基、取代或未取代的C1～C10的烷硫基、取代或未取代的C6～C18的芳基、取代或未取代的C2～C18的杂芳基、取代或未取代的C1～C18的酮基、取代或未取代的C2～C18的烷氧基羰基、取代或未取代的C6～C18的芳氧基羰基。In the compounds provided by the present invention, the hydrogen atoms on the aromatic rings in formulae (2) to (4) are not substituted, or any hydrogen atoms on the aromatic rings may be substituted by one of the following groups: deuterium, tritium, fluorine, chlorine, cyano, trifluoromethyl, -CD 3 , substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C10 alkylthio, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C18 heteroaryl, substituted or unsubstituted C1-C18 keto, substituted or unsubstituted C2-C18 alkoxycarbonyl, substituted or unsubstituted C6-C18 aryloxycarbonyl.
本发明所提供的化合物中，式(1)、(5)～(16)中，当R1，R2彼此相同或不同，独立地选自取代或未取代的C1～C12的直链或支链烷基时，例如可以是C1～C10、C1～C8、C1～C6、C1～C5等。可选的选自甲基、乙基、丙基、正丙基、异丙基、丁基、正丁基、异丁基、叔丁基、仲丁基、1-甲基-丁基、1-乙基-丁基、戊基、正戊基、异戊基、新戊基、叔戊基、己基、正己基、1-甲基戊基、2-甲基戊基、4-甲基-2-戊基、3，3-二甲基丁基、2-乙基丁基、庚基、正庚基、1-甲基己基、环戊基甲基、环己基甲基、辛基、正辛基、叔辛基、1-甲基庚基、2-乙基己基、2-丙基戊基、正壬基、2，2-二甲基庚基、1-乙基-丙基、1，1-二甲基-丙基、异己基、4-甲基己基、5-甲基己基等。烷基上的氢可以是进一步被如下取代基中的一个或多个进一步取代。所述“取代或未取代的”中的“取代的”取代基独立选自氘、氟、氯、溴、氰基、硝基、三氟甲基、-CD3、C1～C10的烷基、C3～C10的环烷基、C1～C10的烷氧基、C1～C10的烷硫基、C6～C20的芳基、C2～C20的杂芳基中的一个或多个。优选的，取代基选自氘、氟、氯、氰基、硝基、三氟甲基、-CD3、甲氧基、甲硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、二联苯基、萘基、吡啶基，或任意组合。In the compounds provided by the present invention, in formulas (1), (5) to (16), when R 1 and R 2 are the same or different and are independently selected from substituted or unsubstituted C1 to C12 straight or branched alkyl groups, for example, they can be C1 to C10, C1 to C8, C1 to C6, C1 to C5, etc. The alkyl radicals may be selected from methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc. The hydrogen on the alkyl radical may be further substituted by one or more of the following substituents. The "substituted" substituent in the "substituted or unsubstituted" is independently selected from one or more of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, -CD 3 , C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C20 aryl, C2-C20 heteroaryl. Preferably, the substituent is selected from deuterium, fluorine, chlorine, cyano, nitro, trifluoromethyl, -CD 3 , methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, biphenyl, naphthyl, pyridyl, or any combination thereof.
本发明所提供的化合物中，式(1)、(5)～(16)中，当R1，R2彼此相同或不同，独立地选自取代或未取代的C3～C12的环烷基。其在一些实施方案中具有3至11个碳原子(即C3-C11环烷基)，或者3至10个碳原子(即C3-C10环烷基)，或者3至8个碳原子(即C3-C8环烷基)，或者3至7个碳原子(即C3-C7环烷基)，或者3至6个碳原子(即C3-C6环烷基)。可选的“环烷基”包括单环、双环或三环环烷基。双环和三环环烷基包括桥环烷基、稠环和螺环烷基。进一步可选的，环烷基包括但不限于环丙基、环丁基、环戊基、环戊烯基、环己基、环己烯基、环庚基、环辛基、十氢萘、八氢并环戊二烯、八氢-1H-茚、螺环基。所述“环烷基”是可选地未取代或经取代的，取代基优选是一或多个(例如1-5、1-4、1-3、1-2、或1个)选自氘、氟、氯、溴、氰基、硝基、三氟甲基、-CD3、C1～C10的烷基、C3～C10的环烷基、C1～C10的烷氧基、C1～C10的烷硫基、C6～C20的芳基、C2～C20的杂芳基中的一个或多个。优选的，取代基选自氘、氟、氯、氰基、硝基、三氟甲基、-CD3、甲氧基、甲硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、二联苯基、萘基、吡啶基，或任意组合。In the compounds provided by the present invention, in formulas (1), (5) to (16), when R 1 and R 2 are the same or different from each other, they are independently selected from substituted or unsubstituted C3 to C12 cycloalkyl groups. In some embodiments, they have 3 to 11 carbon atoms (i.e., C3-C11 cycloalkyl groups), or 3 to 10 carbon atoms (i.e., C3-C10 cycloalkyl groups), or 3 to 8 carbon atoms (i.e., C3-C8 cycloalkyl groups), or 3 to 7 carbon atoms (i.e., C3-C7 cycloalkyl groups), or 3 to 6 carbon atoms (i.e., C3-C6 cycloalkyl groups). Optional "cycloalkyl groups" include monocyclic, bicyclic or tricyclic cycloalkyl groups. Bicyclic and tricyclic cycloalkyl groups include bridged cycloalkyl groups, condensed rings and spirocycloalkyl groups. Further optionally, cycloalkyl includes but is not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, decahydronaphthalene, octahydropentalene, octahydro-1H-indene, spirocyclyl. The "cycloalkyl" is optionally unsubstituted or substituted, and the substituent is preferably one or more (e.g., 1-5, 1-4, 1-3, 1-2, or 1) selected from deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, -CD3 , C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C20 aryl, C2-C20 heteroaryl. Preferably, the substituent is selected from deuterium, fluorine, chlorine, cyano, nitro, trifluoromethyl, -CD 3 , methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, biphenyl, naphthyl, pyridyl, or any combination thereof.
本发明所提供的化合物中，式(1)、(5)～(16)中，当R1，R2彼此相同或不同，独立地选自取代或未取代的C6～C30的芳基，是指含有6至30个环原子并且可选地包含一个或多个稠合环的一价碳环芳族基团，例如C6～C30、C6～C25、C6～C20、C6～C15芳基、C6～C12芳基等。芳基可为单环芳基或多环芳基。在一些实施例中，单环芳基包括但不限于苯基、联苯基、三联苯基、四联苯基、五联苯基等。多环芳基包括但不限于萘基、蒽基、菲基、芘基、苝基、芴基等。芴基可为经取代的，例如9，9’-二甲基芴基、9，9’-二苯并芴基等。此外，取代基中的两个可彼此结合形成螺环结构，例如9，9’-螺二芴基等。所述“芳基”是可选地经取代的芳基。经取代的芳基是指经取代基取代一或多次(例如1-4、1-3次或1-2次)的芳基，例如芳基被取代基单取代、双取代或三取代，其中取代基可选地例如选自氘、氟、氯、溴、氰基、硝基、三氟甲基、-CD3、C1～C10的烷基、C3～C10的环烷基、C1～C10的烷氧基、C1～C10的烷硫基、C6～C20的芳基、C2～C20的杂芳基中的一个或多个。优选的，取代基选自氘、氟、氯、氰基、硝基、三氟甲基、-CD3、甲氧基、甲硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、二联苯基、萘基、吡啶基，或任意组合。In the compounds provided by the present invention, in formulas (1), (5) to (16), when R 1 and R 2 are the same or different from each other and are independently selected from substituted or unsubstituted C6 to C30 aryl groups, it refers to a monovalent carbocyclic aromatic group containing 6 to 30 ring atoms and optionally containing one or more fused rings, such as C6 to C30, C6 to C25, C6 to C20, C6 to C15 aryl, C6 to C12 aryl, etc. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. In some embodiments, the monocyclic aryl group includes but is not limited to phenyl, biphenyl, terphenyl, quaterphenyl, pentaphenyl, etc. The polycyclic aryl group includes but is not limited to naphthyl, anthracenyl, phenanthrenyl, pyrenyl, peryl, fluorenyl, etc. The fluorenyl group may be substituted, such as 9,9'-dimethylfluorenyl, 9,9'-dibenzofluorenyl, etc. In addition, two of the substituents may be combined with each other to form a spiro ring structure, such as 9,9'-spirobifluorenyl, etc. The "aryl" is an optionally substituted aryl. The substituted aryl refers to an aryl substituted one or more times (e.g., 1-4, 1-3 or 1-2 times) by a substituent, for example, the aryl is monosubstituted, disubstituted or trisubstituted by a substituent, wherein the substituent is optionally selected from one or more of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, -CD 3 , C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C20 aryl, C2-C20 heteroaryl. Preferably, the substituent is selected from deuterium, fluorine, chlorine, cyano, nitro, trifluoromethyl, -CD 3 , methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, biphenyl, naphthyl, pyridyl, or any combination thereof.
本发明所提供的化合物中，式(1)、(5)～(16)中，当R1，R2彼此相同或不同，独立地选自取代或未取代的C2～C30的杂芳基。例如C2～C20的杂芳基、C2～C15的杂芳基、C2～C12的杂芳基、C2～C10的杂芳基等。可选的，例如选自吡啶基、呋喃基、噻吩基、苯并呋喃基、苯并噻吩基、二苯并呋喃基、二苯并噻吩基、咔唑基等。所述杂芳基基团可未被取代或被取代。经取代的杂芳基是指经取代基取代一或多次(例如1-4、1-3次或1-2次)的杂芳基，其中取代基可选地选自氘、氟、氯、溴、氰基、硝基、三氟甲基、-CD3、C1～C10的烷基、C3～C10的环烷基、C1～C10的烷氧基、C1～C10的烷硫基、C6～C20的芳基、C2～C20的杂芳基中的一个或多个。优选的，取代基选自氘、氟、氯、氰基、硝基、三氟甲基、-CD3、甲氧基、甲硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、二联苯基、萘基、吡啶基，或任意组合。In the compounds provided by the present invention, in formulas (1), (5) to (16), when R 1 and R 2 are the same or different, they are independently selected from substituted or unsubstituted C2 to C30 heteroaryl groups. For example, C2 to C20 heteroaryl groups, C2 to C15 heteroaryl groups, C2 to C12 heteroaryl groups, C2 to C10 heteroaryl groups, etc. Optionally, for example, selected from pyridyl, furyl, thienyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, etc. The heteroaryl group may be unsubstituted or substituted. Substituted heteroaryl refers to heteroaryl substituted one or more times (e.g., 1-4, 1-3 or 1-2 times) by substituents, wherein the substituents are optionally selected from one or more of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, -CD 3 , C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C20 aryl, C2-C20 heteroaryl. Preferably, the substituents are selected from deuterium, fluorine, chlorine, cyano, nitro, trifluoromethyl, -CD 3 , methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, biphenyl, naphthyl, pyridyl, or any combination thereof.
可选的，式(1)、(5)～(16)中，R1，R2彼此相同或不同，独立地选自取代或未取代的C1～C10的直链或支链烷基、取代或未取代的C3～C10的环烷基、取代或未取代的C6～C20的芳基、取代或未取代的C2～C20的杂芳基。Optionally, in formulas (1), (5) to (16), R 1 and R 2 are the same or different and are independently selected from substituted or unsubstituted C1 to C10 straight or branched alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C2 to C20 heteroaryl.
本发明所提供的化合物中，式(1)、(5)～(16)中，当R1，R2彼此相同或不同，R1、R2键合成环，可选的成环方式例如：R1～R2同时选自C1～C12的直链或支链烷基，且彼此通过单键连接形成取代或未取代的环烷基。再例如，R1～R2同时选自取代或未取代的C6～C30的芳基，且彼此通过单键、-O-、-S-、-N(Ra)-、-C(Rb)(Rc)-中的其中一种连接形成取代或未取代的芳环或取代或未取代的杂芳环。所述Ra，Rb，Rc彼此相同或不同，独立地选自取代或未取代的C1～C10的直链或支链烷基，取代或未取代的C3～C10的环烷基，取代或未取代的C6～C20的芳基，或取代或未取代的C2～C20的杂芳基。In the compounds provided by the present invention, in formulas (1), (5) to (16), when R 1 and R 2 are the same or different, R 1 and R 2 are bonded to form a ring, and the optional ring formation method is, for example: R 1 to R 2 are simultaneously selected from C1 to C12 straight chain or branched alkyl groups, and are connected to each other through a single bond to form a substituted or unsubstituted cycloalkyl group. For another example, R 1 to R 2 are simultaneously selected from substituted or unsubstituted C6 to C30 aryl groups, and are connected to each other through a single bond, -O-, -S-, -N(R a )-, -C(R b )(R c )- to form a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heteroaromatic ring. The Ra , Rb and Rc are the same as or different from each other and are independently selected from substituted or unsubstituted C1-C10 straight or branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, or substituted or unsubstituted C2-C20 heteroaryl.
可选的，R1～R2同时选自C1～C12的直链或支链烷基，且彼此通过单键连接形成取代或未取代的环丙烷、取代或未取代的环丁烷、取代或未取代的环戊烷、取代或未取代的环己烷、取代或未取代的环庚烷等。取代的取代基例如可以为氘、氟、氯、氰基、硝基、三氟甲基、-CD3、甲氧基、甲硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、二联苯基、萘基、吡啶基，或任意组合。取代的环戊烷例如为
可选的，R1～R2同时选自取代或未取代的苯基，且彼此通过单键、-C(Rb)(Rc)-连接形成取代或未取代的芳环结构。R1～R2通过单键连接例如形成
可选的，R1～R2同时选自取代或未取代的苯基，且彼此通过-O-、-S-、-N(Ra)-中的其中一种连接形成取代或未取代的杂芳环结构。例如R1～R2通过-O-连接形成
进一步的，为了方便描述，将R1～R2彼此键合形成的基团定义为基团E，基团E选自如下基团的任一个：Further, for the convenience of description, the group formed by R 1 to R 2 bonding to each other is defined as group E, and group E is selected from any one of the following groups:
基团E中，*表示键合位点，与式(1)或式(5)～式(16)中的芴基团的9,9’-位键合形成螺环结构。举例，例如基团E为
所述Ra、Rb、Rc定义同前。优选的，所述Ra、Rb、Rc彼此相同或不同，独立地选甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丁基、环戊基、环己基、苯基、特丁基苯基、萘基、或二联苯基。The Ra , Rb and Rc are as defined above. Preferably, the Ra , Rb and Rc are the same or different from each other and are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tert-butylphenyl, naphthyl or biphenyl.
基团E所述的每一个结构中，任意一个苯环上的氢原子均可以被氘、氟、氯、氰基、硝基、三氟甲基、-CD3、甲氧基、甲硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、乙苯基、叔丁基苯基、萘基、吡啶基中的一个所取代；任意一个环烷基上的氢原子均可以被氘、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基中的一个所取代。In each structure of group E, any hydrogen atom on the benzene ring may be replaced by one of deuterium, fluorine, chlorine, cyano, nitro, trifluoromethyl, -CD 3 , methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, ethylphenyl, tert-butylphenyl, naphthyl and pyridyl; any hydrogen atom on the cycloalkyl group may be replaced by one of deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
优选的，所述R1～R2彼此相同或不同，各自独立地选自取代或未取代的下述基团之一：甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丁基、环戊基、环己基、苯基、萘基、二联苯基、苯并呋喃基、苯并噻吩基、二苯并呋喃基、二苯并噻吩基、咔唑基，芴基；或R1～R2彼此键合形成基团E，基团E选自如下基团的任一个：Preferably, the R 1 to R 2 are the same as or different from each other, and are independently selected from one of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, biphenyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, fluorenyl; or R 1 to R 2 are bonded to each other to form a group E, and the group E is selected from any one of the following groups:
其中，Ra,Rb,Rc的定义同前。Wherein, Ra , Rb and Rc are defined as above.
R1～R2中，所述“取代或未取代的”中的“取代的”取代基独立选自氘、氟、氯、氰基、硝基、三氟甲基、-CD3、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、甲氧基、乙氧基、甲硫基、乙硫基、环丁基、环戊基、环己基、苯基、萘基、二联苯基、二苯并呋喃基、二苯并噻吩基、咔唑基、芴基中的一个或多个，其中取代基彼此相同或不同。例如取代的甲基为-CD3。再例如取代的苯基为苯甲基。In R 1 to R 2 , the "substituted" substituent in the "substituted or unsubstituted" is independently selected from one or more of deuterium, fluorine, chlorine, cyano, nitro, trifluoromethyl, -CD 3 , methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, methylthio, ethylthio, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, carbazolyl, fluorenyl, and the substituents are the same or different. For example, the substituted methyl is -CD 3 . For another example, the substituted phenyl is benzyl.
本发明所提供的化合物中，所述Rm,Rn每一次出现，各自独立地选自氘、氚、氟、氯、氰基、三氟甲基、C1～C10的烷基、C3～C10的环烷基、C1～C10的烷氧基、C1～C10的烷硫基、C6～C20的芳基、C2～C20的杂芳基中的一个，或位于相邻位置的两个Rm基团彼此连接形成取代或未取代的苯环；m和n分别为基团Rm和Rn的数量，独立地选自0,1,2,3,4。m为0时，代表不存在Rm，即Rm连接的苯环上的氢未被取代。n为0时，代表不存在Rn，即与Rn连接的苯环上的氢未被取代。In the compounds provided by the present invention, each occurrence of R m and R n is independently selected from one of deuterium, tritium, fluorine, chlorine, cyano, trifluoromethyl, C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C20 aryl, C2-C20 heteroaryl, or two R m groups located at adjacent positions are connected to each other to form a substituted or unsubstituted benzene ring; m and n are the number of groups R m and R n , respectively, independently selected from 0, 1, 2, 3, 4. When m is 0, it means that R m does not exist, that is, the hydrogen on the benzene ring connected to R m is not replaced. When n is 0, it means that R n does not exist, that is, the hydrogen on the benzene ring connected to R n is not replaced.
具体实施例中，Rm选自氢、氘、氚、氟、氯、氰基、三氟甲基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丁基、环戊基、环己基、苯基、萘基、或二联苯基；或当m>1时，位于相邻位置的两个Rm彼此连接形成苯环。当相邻的位置的两个Ra彼此连接形成苯环是的结构为
具体实施例中，Rn选自氢、氘、氚、氟、氯、氰基、三氟甲基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丁基、环戊基、环己基、苯基、萘基、或二联苯基。In a specific embodiment, Rn is selected from hydrogen, deuterium, tritium, fluorine, chlorine, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, or biphenyl.
本发明所提供的化合物中，所述L0，L1，L2彼此相同或不同，各自独立地选自单键、取代或未取代的C6～C20的亚芳基、或取代或未取代的C2～C20的亚杂芳基。具体实施例中，所述L0、L1、L2各自独立地选自单键，或当不选自单键时，彼此相同或不同，各自独立地选自取代或未取代的如下基团之一：亚苯基、亚萘基、亚吡啶基、亚噻吩基、亚硒吩基、亚呋喃基、亚吡咯基、亚苯并噻吩基、亚苯并呋喃基、亚吲哚基、亚二苯并噻吩基、亚二苯并呋喃基、亚芴基、亚咔唑基。L0、L1、L2中，所述“取代或未取代的”中“取代”的取代基，独立选自下述基团中的任意一个或其组合：氘、氟、氯、氰基、硝基、三氟甲基、-CD3、甲氧基、甲硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、二联苯基、萘基、吡啶基。In the compounds provided by the present invention, L 0 , L 1 , and L 2 are the same or different from each other, and are independently selected from a single bond, a substituted or unsubstituted C6-C20 arylene group, or a substituted or unsubstituted C2-C20 heteroarylene group. In a specific embodiment, L 0 , L 1 , and L 2 are independently selected from a single bond, or when not selected from a single bond, are the same or different from each other, and are independently selected from one of the following substituted or unsubstituted groups: phenylene, naphthylene, pyridylene, thienylene, selenophene, furanylene, pyrrolylene, benzothienylene, benzofuranylene, indolylene, dibenzothienylene, dibenzofuranylene, fluorenylene, and carbazolylene. In L 0 , L 1 and L 2 , the substituent of “substituted” in the “substituted or unsubstituted” is independently selected from any one or a combination of the following groups: deuterium, fluorine, chlorine, cyano, nitro, trifluoromethyl, -CD 3 , methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, biphenyl, naphthyl and pyridyl.
本发明所提供的化合物中，所述基团A选自取代或未取代的苊基，或取代或未取代的式(2)～式(4)所示基团：In the compounds provided by the present invention, the group A is selected from substituted or unsubstituted acenaphthene groups, or substituted or unsubstituted groups represented by formula (2) to formula (4):
式(2)～式(4)中，*表示键合位点；Z1～Z12相同或不同，各自独立地选自-N(Rd)-、-C(Re)(Rf)-、-O-或-S-；其中，所述Rd、Re、Rf，彼此相同或不同，各自独立地选自氢、氘、取代或未取代的C1～C10的烷基、取代或未取代的C3～C10的环烷基、取代或未取代的C6～C18的芳基、或取代或未取代的C2～C18的杂芳基。In formula (2) to formula (4), * represents a bonding site; Z 1 to Z 12 are the same or different, and are each independently selected from -N(R d )-, -C( Re )(R f )-, -O- or -S-; wherein R d , Re , and R f are the same or different, and are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C18 aryl, or substituted or unsubstituted C2-C18 heteroaryl.
本发明式(2)～式(4)中，所述Rd、Re、Rf，彼此相同或不同，各自独立地选自氢。In formula (2) to formula (4) of the present invention, R d , Re , and R f are the same or different from each other and are independently selected from hydrogen.
本发明式(2)～式(4)中，所述Rd、Re、Rf，彼此相同或不同，各自独立地选自氘。In formula (2) to formula (4) of the present invention, R d , Re , and R f are the same as or different from each other and are independently selected from deuterium.
本发明式(2)～式(4)中，所述Rd、Re、Rf，彼此相同或不同，各自独立地选自取代或未取代的C1～C10的烷基。例如可以是C1～C10、C1～C8、C1～C6、C1～C5等。可选的选自甲基、乙基、丙基、正丙基、异丙基、丁基、正丁基、异丁基、叔丁基、仲丁基、1-甲基-丁基、1-乙基-丁基、戊基、正戊基、异戊基、新戊基、叔戊基、己基、正己基、1-甲基戊基、2-甲基戊基、4-甲基-2-戊基、3，3-二甲基丁基、2-乙基丁基、庚基、正庚基、1-甲基己基、环戊基甲基、环己基甲基、辛基、正辛基、叔辛基、1-甲基庚基、2-乙基己基、2-丙基戊基、正壬基、2，2-二甲基庚基、1-乙基-丙基、1，1-二甲基-丙基、异己基、4-甲基己基、5-甲基己基等。烷基上的氢可以是进一步被如下取代基中的一个或多个进一步取代。所述“取代或未取代的”中的“取代的”取代基独立选自氘、氟、氯、溴、氰基、硝基、三氟甲基、-CD3、C1～C10的烷基、C3～C10的环烷基、C1～C10的烷氧基、C1～C10的烷硫基、C6～C20的芳基、C2～C20的杂芳基中的一个或多个。优选的，取代基选自氘、氟、氯、氰基、硝基、三氟甲基、-CD3、甲氧基、甲硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、二联苯基、萘基、吡啶基，或任意组合。In formula (2) to formula (4) of the present invention, R d , Re , and R f are the same or different and are independently selected from substituted or unsubstituted C1-C10 alkyl groups, for example, C1-C10, C1-C8, C1-C6, C1-C5, etc. The alkyl radicals may be selected from methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc. The hydrogen on the alkyl radical may be further substituted by one or more of the following substituents. The "substituted" substituent in the "substituted or unsubstituted" is independently selected from one or more of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, -CD 3 , C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C20 aryl, C2-C20 heteroaryl. Preferably, the substituent is selected from deuterium, fluorine, chlorine, cyano, nitro, trifluoromethyl, -CD 3 , methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, biphenyl, naphthyl, pyridyl, or any combination thereof.
本发明式(2)～式(4)中，所述Rd、Re、Rf，彼此相同或不同，独立选自取代或未取代的C3～C10的环烷基。其在一些实施方案中具有3至8个碳原子(即C3-C8环烷基)，或者3至7个碳原子(即C3-C7环烷基)，或者3至6个碳原子(即C3-C6环烷基)。可选的“环烷基”包括单环、双环或三环环烷基。双环和三环环烷基包括桥环烷基、稠环和螺环烷基。进一步可选的，环烷基包括但不限于环丙基、环丁基、环戊基、环戊烯基、环己基、环己烯基、环庚基、环辛基、十氢萘、八氢并环戊二烯、八氢-1H-茚、螺环基。所述“环烷基”是可选地未取代或经取代的，取代基优选是一或多个(例如1-5、1-4、1-3、1-2、或1个)选自氘、氟、氯、溴、氰基、硝基、三氟甲基、-CD3、C1～C10的烷基、C3～C10的环烷基、C1～C10的烷氧基、C1～C10的烷硫基、C6～C20的芳基、C2～C20的杂芳基中的一个或多个。优选的，取代基选自氘、氟、氯、氰基、硝基、三氟甲基、-CD3、甲氧基、甲硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、二联苯基、萘基、吡啶基，或任意组合。In formula (2) to formula (4) of the present invention, R d , Re , and R f are identical or different from each other and are independently selected from substituted or unsubstituted C3 to C10 cycloalkyl groups. In some embodiments, they have 3 to 8 carbon atoms (i.e., C3-C8 cycloalkyl groups), or 3 to 7 carbon atoms (i.e., C3-C7 cycloalkyl groups), or 3 to 6 carbon atoms (i.e., C3-C6 cycloalkyl groups). Optional "cycloalkyl groups" include monocyclic, bicyclic or tricyclic cycloalkyl groups. Bicyclic and tricyclic cycloalkyl groups include bridged cycloalkyl groups, condensed rings, and spirocyclic alkyl groups. Further optional, cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, decahydronaphthalene, octahydropentalene, octahydro-1H-indene, and spirocyclic groups. The "cycloalkyl" is optionally unsubstituted or substituted, and the substituent is preferably one or more (e.g., 1-5, 1-4, 1-3, 1-2, or 1) selected from deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, -CD 3 , C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C20 aryl, C2-C20 heteroaryl. Preferably, the substituent is selected from deuterium, fluorine, chlorine, cyano, nitro, trifluoromethyl, -CD 3 , methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, biphenyl, naphthyl, pyridyl, or any combination thereof.
本发明式(2)～式(4)中，所述Rd、Re、Rf，彼此相同或不同，独立选自取代或未取代的C6～C18的芳基。芳基可为单环芳基或多环芳基。在一些实施例中，单环芳基包括但不限于苯基、联苯基、三联苯基等。多环芳基包括但不限于萘基、蒽基、芴基等。芴基可为经取代的，例如9，9’-二甲基芴基、9，9’-二苯并芴基等。此外，取代基中的两个可彼此结合形成螺环结构，例如9，9’-螺二芴基等。所述“芳基”是可选地经取代的芳基。经取代的芳基是指经取代基取代一或多次(例如1-4、1-3次或1-2次)的芳基，例如芳基被取代基单取代、双取代或三取代，其中取代基可选地例如选自氘、氟、氯、溴、氰基、硝基、三氟甲基、-CD3、C1～C10的烷基、C3～C10的环烷基、C1～C10的烷氧基、C1～C10的烷硫基、C6～C20的芳基、C2～C20的杂芳基中的一个或多个。优选的，取代基选自氘、氟、氯、氰基、硝基、三氟甲基、-CD3、甲氧基、甲硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、二联苯基、萘基、吡啶基，或任意组合。In formula (2) to formula (4) of the present invention, the R d , Re , and R f are the same or different from each other and are independently selected from substituted or unsubstituted C6 to C18 aryl groups. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. In some embodiments, the monocyclic aryl group includes, but is not limited to, phenyl, biphenyl, terphenyl, and the like. The polycyclic aryl group includes, but is not limited to, naphthyl, anthracenyl, fluorenyl, and the like. The fluorenyl group may be substituted, such as 9,9'-dimethylfluorenyl, 9,9'-dibenzofluorenyl, and the like. In addition, two of the substituents may be combined with each other to form a spiro ring structure, such as 9,9'-spirobifluorenyl, and the like. The "aryl group" is an optionally substituted aryl group. Substituted aryl refers to aryl substituted one or more times (e.g. 1-4, 1-3 or 1-2 times) by substituents, for example, aryl is mono-substituted, di-substituted or tri-substituted by substituents, wherein the substituents are optionally selected from one or more of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, -CD 3 , C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C20 aryl, C2-C20 heteroaryl. Preferably, the substituent is selected from deuterium, fluorine, chlorine, cyano, nitro, trifluoromethyl, -CD 3 , methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, biphenyl, naphthyl, pyridyl, or any combination thereof.
本发明式(2)～式(4)中，所述Rd、Re、Rf，彼此相同或不同，取代或未取代的C2～C18的杂芳基。例如取代或未取代的C2～C15的杂芳基、取代或未取代的C2～C12的杂芳基、或取代或未取代的C2～C10的杂芳基等。例如选自吡啶基、呋喃基、噻吩基、苯并呋喃基、苯并噻吩基、二苯并呋喃基、二苯并噻吩基、咔唑基等。所述杂芳基基团可未被取代或被取代。经取代的杂芳基是指经取代基取代一或多次(例如1-4、1-3次或1-2次)的杂芳基，其中取代基可选地选自氘、氟、氯、溴、氰基、硝基、三氟甲基、-CD3、C1～C10的烷基、C3～C10的环烷基、C1～C10的烷氧基、C1～C10的烷硫基、C6～C20的芳基、C2～C20的杂芳基中的一个或多个。优选的，取代基选自氘、氟、氯、氰基、硝基、三氟甲基、-CD3、甲氧基、甲硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、二联苯基、萘基、吡啶基，或任意组合。In formula (2) to formula (4) of the present invention, R d , Re , and R f are the same or different from each other, and are substituted or unsubstituted C2-C18 heteroaryl groups. For example, substituted or unsubstituted C2-C15 heteroaryl groups, substituted or unsubstituted C2-C12 heteroaryl groups, or substituted or unsubstituted C2-C10 heteroaryl groups. For example, they are selected from pyridyl, furyl, thienyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, etc. The heteroaryl group may be unsubstituted or substituted. Substituted heteroaryl refers to heteroaryl substituted one or more times (e.g., 1-4, 1-3 or 1-2 times) by substituents, wherein the substituents are optionally selected from one or more of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, -CD 3 , C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C20 aryl, C2-C20 heteroaryl. Preferably, the substituents are selected from deuterium, fluorine, chlorine, cyano, nitro, trifluoromethyl, -CD 3 , methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, biphenyl, naphthyl, pyridyl, or any combination thereof.
本发明式(2)～式(4)中，A选自取代或未取代的苊基，或者选自基团G与苯环形成的并环结构；所述基团G选自如下任一结构：In formula (2) to formula (4) of the present invention, A is selected from substituted or unsubstituted acenaphthene groups, or selected from the ring structure formed by group G and a benzene ring; the group G is selected from any of the following structures:
其中，*碳代表与苯环上碳对应连接的碳；Rd定义同前。例如
具体实施例中，基团A包括但不限于如下基团：In a specific embodiment, group A includes but is not limited to the following groups:
本发明所提供的化合物中，Ar1、Ar2彼此相同或不同，各自独立地选自取代或未取代的C6～C40的芳基、或取代或未取代的C2～C40的杂芳基。可选的，所述Ar1和Ar2彼此相同或不同，各自独立地选自如下基团的任一个：In the compounds provided by the present invention, Ar 1 and Ar 2 are the same or different from each other, and are independently selected from substituted or unsubstituted C6-C40 aryl groups, or substituted or unsubstituted C2-C40 heteroaryl groups. Optionally, Ar 1 and Ar 2 are the same or different from each other, and are independently selected from any one of the following groups:
其中，X独立地选自-N-、-CH-、-C(R3)-或-C*a-；R3独立地选自氘、氟、氯、溴、氰基、硝基、取代或未取代的C1～C10的烷基、取代或未取代的C3～C10的环烷基、取代或未取代的C1～C10的烷氧基、取代或未取代的C1～C10的烷硫基、取代或未取代的C6～C20的芳基、C2～C20的取代或未取代的杂芳基；*a为键合位点。可选的，R3独立地选自氘、氟、氯、溴、氰基、硝基、或取代或未取代的下述基团之一：甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、甲氧基、乙氧基、甲硫基、乙硫基、环丁基、环戊基、环己基、苯基、萘基、二联苯基、吡啶基、呋喃基、噻吩基、苯并呋喃基、苯并噻吩基、二苯并呋喃基、二苯并噻吩基、咔唑基、芴基等。“取代的”取代基独立选自氘、氟、氯、氰基、硝基、三氟甲基、-CD3、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、甲氧基、乙氧基、甲硫基、乙硫基、环丁基、环戊基、环己基、苯基、萘基、二联苯基、二苯并呋喃基、二苯并噻吩基、咔唑基、芴基中的一个或多个，其中取代基彼此相同或不同。Wherein, X is independently selected from -N-, -CH-, -C(R 3 )- or -C *a -; R 3 is independently selected from deuterium, fluorine, chlorine, bromine, cyano, nitro, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C10 alkylthio, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C20 heteroaryl; * a is a bonding site. Optionally, R3 is independently selected from deuterium, fluorine, chlorine, bromine, cyano, nitro, or one of the following groups which are substituted or unsubstituted: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, methylthio, ethylthio, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, biphenyl, pyridyl, furyl, thienyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, fluorenyl, etc. "Substituted" substituents are independently selected from one or more of deuterium, fluorine, chlorine, cyano, nitro, trifluoromethyl, -CD3 , methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, methylthio, ethylthio, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, fluorenyl, wherein the substituents are the same or different from each other.
Y选自-O-、-S-、-Se-、-N(R4)-、-C(R5)(R6)、-Si(R7)(R8)-；R4～R8各自独立地选自取代或未取代的C1～C10的烷基、取代或未取代的C3～C10的环烷基、取代或未取代的C6～C20的芳基、取代或未取代的C2～C20的杂芳基；或者，R5、R6独立选自取代或未取代的C1～C6的直链或支链烷基且R5、R6彼此键合形成取代或未取代的C5～C12的脂肪族环；或者R7、R8独立选自取代或未取代的C6～C12的芳基或取代或未取代的C2～C12的杂芳基，且R7、R8彼此通过单键、-O-、-S-、-N(R9)-、-C(R10)(R11)-中的其中一种连接形成取代或未取代的芳环或取代或未取代的杂芳环；所述R9～R11独立地选自氘、氟、氯、溴、氰基、硝基、取代或未取代的C1～C10的烷基、取代或未取代的C3～C10的环烷基、取代或未取代的C1～C10的烷氧基、取代或未取代的C1～C10的烷硫基、取代或未取代的C6～C20的芳基、或C2～C20的取代或未取代的杂芳基。Y is selected from -O-, -S-, -Se-, -N(R 4 )-, -C(R 5 )(R 6 ), -Si(R 7 )(R 8 )-; R 4 to R 8 are each independently selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C20 heteroaryl; or, R 5 and R 6 are independently selected from substituted or unsubstituted C1-C6 straight or branched alkyl, and R 5 and R 6 are bonded to each other to form a substituted or unsubstituted C5-C12 aliphatic ring; or R 7 and R 8 are independently selected from substituted or unsubstituted C6-C12 aryl or substituted or unsubstituted C2-C12 heteroaryl, and R 7 , R 8 are connected to each other by a single bond, -O-, -S-, -N(R 9 )-, or -C(R 10 )(R 11 )- to form a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heteroaromatic ring; and R 9 to R 11 are independently selected from deuterium, fluorine, chlorine, bromine, cyano, nitro, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C10 alkylthio, substituted or unsubstituted C6-C20 aryl, or C2-C20 substituted or unsubstituted heteroaryl.
可选的，R4～R8独立地选自氘、氟、氯、溴、氰基、硝基、或取代或未取代的下述基团之一：甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、甲氧基、乙氧基、甲硫基、乙硫基、环丁基、环戊基、环己基、苯基、萘基、二联苯基、吡啶基、呋喃基、噻吩基、苯并呋喃基、苯并噻吩基、二苯并呋喃基、二苯并噻吩基、咔唑基、芴基等。“取代的”取代基独立选自氘、氟、氯、氰基、硝基、三氟甲基、-CD3、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、甲氧基、乙氧基、甲硫基、乙硫基、环丁基、环戊基、环己基、苯基、萘基、二联苯基、二苯并呋喃基、二苯并噻吩基、咔唑基、芴基中的一个或多个，其中取代基彼此相同或不同。Optionally, R 4 to R 8 are independently selected from deuterium, fluorine, chlorine, bromine, cyano, nitro, or one of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, methylthio, ethylthio, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, biphenyl, pyridyl, furyl, thienyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, fluorenyl, etc. "Substituted" substituents are independently selected from one or more of deuterium, fluorine, chlorine, cyano, nitro, trifluoromethyl, -CD3 , methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, methylthio, ethylthio, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, fluorenyl, wherein the substituents are the same or different from each other.
或者，R5、R6彼此键合形成环丙烷、环丁烷、环戊烷、环己烷或环庚烷等。Alternatively, R 5 and R 6 are bonded to each other to form cyclopropane, cyclobutane, cyclopentane, cyclohexane or cycloheptane.
R7～R8同时选自取代或未取代的苯基，且彼此通过单键、-C(R10)(R11)-连接形成取代或未取代的芳环基结构。R7～R8通过单键连接例如形成
或者R7、R8同时选自取代或未取代的苯基，且彼此通过-O-、-S-、-N(R9)-中的其中一种连接形成取代或未取代的杂芳环基结构。例如R7、R8通过-O-连接形成
X、Y中，所述“取代或未取代的”中“取代的”的取代基独立选自下述基团中的任意一个：氘、氟、氯、氰基、硝基、三氟甲基、甲氧基、甲硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、二联苯基、萘基、吡啶基。In X and Y, the substituent of "substituted" in the "substituted or unsubstituted" is independently selected from any one of the following groups: deuterium, fluorine, chlorine, cyano, nitro, trifluoromethyl, methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, biphenyl, naphthyl, and pyridyl.
具体实施例中，所述Ar1和Ar2彼此相同或不同，各自独立地选自如下基团：In a specific embodiment, Ar 1 and Ar 2 are the same or different from each other, and are independently selected from the following groups:
所述任意基团中，任意一个且仅有一个芳香环上的碳是键合位点，或任意一个氢原子均可以被氘、氟、氯、溴、氰基、硝基、三氟甲基、-CD3、甲氧基、乙氧基、甲硫基、乙硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、萘基、吡啶基、吡嗪基、嘧啶基、三嗪基、喹啉基、异喹啉基、喹喔啉基中的一个所取代。In any of the above groups, any and only one carbon on the aromatic ring is a bonding site, or any hydrogen atom may be substituted by deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, -CD 3 , methoxy, ethoxy, methylthio, ethylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, naphthyl, pyridyl, pyrazinyl, pyrimidinyl, triazinyl, quinolyl, isoquinolyl, quinoxalinyl.
例如
本发明所提供的化合物中，可选的，m选自0、1、2、或3；进一步可选的，m选自0、1、或2。进一步可选的，m选自0、或1等。可选的，n选自0、1、2、或3；进一步可选的，n选自0、1、或2。进一步可选的，n选自0、或1等。In the compounds provided by the present invention, m is optionally selected from 0, 1, 2, or 3; further optionally, m is selected from 0, 1, or 2. Further optionally, m is selected from 0, or 1, etc. Optionally, n is selected from 0, 1, 2, or 3; further optionally, n is selected from 0, 1, or 2. Further optionally, n is selected from 0, or 1, etc.
本发明所提供的化合物中，所述化合物选自以下化学结构中的一种或多种：Among the compounds provided by the present invention, the compounds are selected from one or more of the following chemical structures:
具体的，上述结构可为未取代或者选自以下的一个或多个取代基取代。例如可以是氘、卤素基团、腈基、硝基、羟基、羰基、酯基、酰亚胺基、氧化膦基团、烷氧基、芳氧基、烷基硫基、芳基硫基、烷基磺酰基、芳基磺酰基、甲硅烷基、硼基、烷基、环烷基、烯基、芳基、芳烷基、芳烯基、烷基芳基、烷基氨基、芳烷基氨基、杂芳基氨基、芳基氨基、芳基杂芳基氨基、芳基膦基和杂芳基等。Specifically, the above structure may be unsubstituted or substituted with one or more substituents selected from the following. For example, it may be deuterium, a halogen group, a nitrile group, a nitro group, a hydroxyl group, a carbonyl group, an ester group, an imide group, a phosphine oxide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a silyl group, a boron group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an aralkenyl group, an alkylaryl group, an alkylamino group, an aralkylamino group, a heteroarylamino group, an arylamino group, an arylheteroarylamino group, an arylphosphino group, and a heteroaryl group.
本发明第二方面提供一种有机层，包括本发明第一方面所述的基于芴的三芳胺类化合物。The second aspect of the present invention provides an organic layer, comprising the fluorene-based triarylamine compound according to the first aspect of the present invention.
本发明第三方面提供如本发明第一方面所述的基于芴的三芳胺类化合物、和/或本发明第二方面所述的有机层在有机电致发光器件中的应用。The third aspect of the present invention provides use of the fluorene-based triarylamine compound as described in the first aspect of the present invention and/or the organic layer as described in the second aspect of the present invention in an organic electroluminescent device.
本发明第四方面提供一种有机电致发光器件，包括第一电极、第二电极、以及设置在第一电极和第二电极之间的一个或多个有机层，为底部或顶部发光器件结构，其有机层可为单层结构，也可为层合有两个或多个有机层的多层串联结构，所述有机层如具有包括空穴注入层、空穴传输层、发光层、电子注入层或电子传输层中至少一层。可使用制备有机电致发光器件的常见方法和材料来制备。所述有机层包括如本发明第一方面所述的基于芴的三芳胺类化合物。The fourth aspect of the present invention provides an organic electroluminescent device, comprising a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode, which is a bottom or top light-emitting device structure, wherein the organic layer may be a single-layer structure, or a multilayer tandem structure having two or more organic layers laminated thereon, wherein the organic layer may include at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron injection layer, or an electron transport layer. The organic layer may be prepared using common methods and materials for preparing organic electroluminescent devices. The organic layer includes a triarylamine compound based on fluorene as described in the first aspect of the present invention.
本发明所提供的有机电致发光器件中，第一电极作为阳极层，阳极材料例如可以是具有大功函数的材料，使得空穴顺利地注入有机层。更例如可以是金属、金属氧化物、金属和氧化物的组合、导电聚合物等。金属氧化物例如可以是氧化铟锡(ITO)、氧化锌、氧化铟、和氧化铟锌(IZO)等。In the organic electroluminescent device provided by the present invention, the first electrode serves as an anode layer, and the anode material may be, for example, a material having a large work function, so that holes are smoothly injected into the organic layer. For example, it may be a metal, a metal oxide, a combination of a metal and an oxide, a conductive polymer, etc. The metal oxide may be, for example, indium tin oxide (ITO), zinc oxide, indium oxide, and indium zinc oxide (IZO).
本发明所提供的有机电致发光器件中，第二电极作为阴极层，阴极材料例如可以是具有小功函数的材料，使得电子顺利地注入有机层。阴极材料例如可以是金属或多层结构材料。金属例如可以是镁、银、钙、钠、钾、钛、铟、钇、锂、钆、铝、锡和铅、或其合金。阴极材料优选选自镁和银。In the organic electroluminescent device provided by the present invention, the second electrode serves as a cathode layer, and the cathode material may be, for example, a material having a small work function, so that electrons are smoothly injected into the organic layer. The cathode material may be, for example, a metal or a multilayer structure material. The metal may be, for example, magnesium, silver, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, tin and lead, or an alloy thereof. The cathode material is preferably selected from magnesium and silver.
本发明所提供的有机电致发光器件中，空穴注入层的材料，优选最高占据分子轨道(HOMO)介于阳极材料的功函数与周围有机层的HOMO之间的材料作为在低电压下有利地从阳极接收空穴的材料。In the organic electroluminescent device provided by the present invention, the material of the hole injection layer is preferably a material whose highest occupied molecular orbital (HOMO) is between the work function of the anode material and the HOMO of the surrounding organic layer as a material that is advantageous for receiving holes from the anode at low voltage.
本发明所提供的有机电致发光器件中，空穴传输层的材料是对空穴具有高迁移率的材料适合作为接收来自阳极或空穴注入层的空穴并将空穴传输至发光层的材料。空穴传输层的材料包括但不限于芳基胺的有机材料、导电聚合物、同时具有共轭部分和非共轭部分的嵌段共聚物等。In the organic electroluminescent device provided by the present invention, the material of the hole transport layer is a material having high mobility for holes and is suitable as a material for receiving holes from the anode or the hole injection layer and transporting the holes to the light-emitting layer. The material of the hole transport layer includes, but is not limited to, an organic material of arylamine, a conductive polymer, a block copolymer having both a conjugated part and a non-conjugated part, and the like.
本发明所提供的有机电致发光器件中，发光层的材料通常可以选自对荧光或磷光具有良好量子效率的材料作为能够通过接收分别来自空穴传输层和来自电子传输层的空穴和电子并使空穴与电子结合而在可见光区域内发光的材料。In the organic electroluminescent device provided by the present invention, the material of the light-emitting layer can generally be selected from materials with good quantum efficiency for fluorescence or phosphorescence as materials that can emit light in the visible light region by receiving holes and electrons from the hole transport layer and the electron transport layer respectively and combining the holes with the electrons.
本发明所提供的有机电致发光器件中，电子传输层的材料是对电子具有高迁移率的材料适合作为有利地接收来自阴极的电子并将电子传输至发光层的材料。In the organic electroluminescent device provided by the present invention, the material of the electron transport layer is a material having high electron mobility, which is suitable as a material that advantageously receives electrons from the cathode and transports the electrons to the light-emitting layer.
本发明所提供的有机电致发光器件中，覆盖层的材料通常具有高折射率，因此可有助于有机发光器件的光效率提高，尤其是有助于外部发光效率提高。In the organic electroluminescent device provided by the present invention, the material of the cover layer generally has a high refractive index, and thus can help improve the light efficiency of the organic light-emitting device, especially help improve the external light-emitting efficiency.
本发明所提供的有机电致发光器件中，所述有机电致发光器件为有机光伏器件、有机发光器件、有机太阳电池、电子纸、有机感光体、有机薄膜晶体管等。In the organic electroluminescent device provided by the present invention, the organic electroluminescent device is an organic photovoltaic device, an organic light-emitting device, an organic solar cell, an electronic paper, an organic photoreceptor, an organic thin film transistor, etc.
本发明另一方面提供一种显示或照明装置，包括本发明所述的有机电致发光器件。Another aspect of the present invention provides a display or lighting device, comprising the organic electroluminescent device of the present invention.
除特别说明外，本发明中未提及合成方法的化合物均为市售商品；本发明中质谱采用ZABHS型质谱仪测定(英国Micromass公司制造)，核磁采用Bruker 400MHz型核磁共振仪(德国Bruker公司制造)。Unless otherwise specified, the compounds not mentioned in the present invention are all commercially available products; the mass spectrum in the present invention is measured by a ZABHS mass spectrometer (manufactured by Micromass, UK), and the nuclear magnetic resonance is measured by a Bruker 400 MHz nuclear magnetic resonance instrument (manufactured by Bruker, Germany).
合成实施例：Synthesis Example:
本发明中所涉及的化合物可通过下述通用的合成路线制备，但并不局限于此。本领域技术人员可以在其基础上在不悖离本发明原则的前提下进行任何修改、等同替换、改进等，而将该方法扩展到本发明的权利要求书要求保护的技术方案的范围之内。The compounds involved in the present invention can be prepared by the following general synthetic routes, but are not limited thereto. Those skilled in the art can make any modifications, equivalent substitutions, improvements, etc. on the basis of the general synthetic routes without departing from the principles of the present invention, and expand the method to the scope of the technical solutions claimed in the claims of the present invention.
其中，对于化合物i,iii和v，X1,X2和X3彼此独立地选自碘，溴或氯。优选地，当X2选自溴时，X1选自氯；优选地，X3选自溴或氯。Wherein, for compounds i, iii and v, X 1 , X 2 and X 3 are independently selected from iodine, bromine or chlorine. Preferably, when X 2 is selected from bromine, X 1 is selected from chlorine; preferably, X 3 is selected from bromine or chlorine.
对于化合物iv，当L0选自单键时，X3为氢；当L0不选自单键时，X3选自硼酸基或频那醇硼酯基。For compound iv, when L 0 is selected from a single bond, X 3 is hydrogen; when L 0 is not selected from a single bond, X 3 is selected from a boronic acid group or a pinacol boronate group.
R1～R2、Rm～Rn、A、L0、L1、L2、Ar1、Ar2、m和n如式(1)、式(5)～(16)所定义。R 1 to R 2 , R m to R n , A, L 0 , L 1 , L 2 , Ar 1 , Ar 2 , m and n are as defined in formula (1) and formulas (5) to (16).
本发明提供的化合物，总体上可通过本领域常见的铃木偶联反应和乌尔曼偶联反应合成，制备操作成熟简便，能够实现低成本大规模地合成生产。The compounds provided by the present invention can generally be synthesized through the common Suzuki coupling reaction and Ullmann coupling reaction in the art, and the preparation operation is mature and simple, and can achieve low-cost large-scale synthetic production.
化合物iii的合成：Synthesis of compound iii:
在氮气氛围下，向干燥的三口烧瓶中依次加入化合物i(40.0mmol,1eq)、化合物ii(40.0mmol,1eq)和脱气甲苯(200mL)，搅拌均匀后，再依次加入四三苯基膦钯(924.4mg，0.8mmol，2％eq)，碳酸钾(13.8g,100mmol,2.5eq)，脱气的乙醇(120mL)以及去离子水(80mL)。充分搅拌后，将反应体系在氮气氛围下升温至回流，通过薄层色谱法分析基本无原料剩余，停止加热。当反应液降温至室温时，向反应体系加入100mL甲苯，搅拌5分钟后静置分层，用分液漏斗分液，保留有机相，水相用甲苯(3×40mL)萃取，与前述保留有机相合并，使用无水硫酸镁干燥，过滤，减压蒸馏去除溶剂，粗产品经快速硅胶柱色谱纯化(流动相为正己烷/二氯甲烷混合溶剂)，得到化合物iii。In a nitrogen atmosphere, compound i (40.0mmol, 1eq), compound ii (40.0mmol, 1eq) and degassed toluene (200mL) were added to a dry three-necked flask in sequence, and after stirring evenly, tetrakistriphenylphosphine palladium (924.4mg, 0.8mmol, 2%eq), potassium carbonate (13.8g, 100mmol, 2.5eq), degassed ethanol (120mL) and deionized water (80mL) were added in sequence. After sufficient stirring, the reaction system was heated to reflux under a nitrogen atmosphere. After thin layer chromatography analysis, there was basically no raw material remaining, and heating was stopped. When the reaction solution was cooled to room temperature, 100 mL of toluene was added to the reaction system, and the mixture was stirred for 5 minutes and then allowed to stand to separate the layers. The liquids were separated using a separatory funnel, and the organic phase was retained. The aqueous phase was extracted with toluene (3×40 mL), combined with the above-retained organic phase, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was purified by flash silica gel column chromatography (the mobile phase was a mixed solvent of n-hexane/dichloromethane) to obtain compound iii.
目标化合物的合成：Synthesis of target compound:
在氮气氛围下，向三口烧瓶中依次加入化合物iii(20.0mmol,1eq)，化合物iv(20.0mmol,1eq)和无水甲苯(120mL)，充分搅拌，再分别加入叔丁醇钠(2.9g,30.0mmol,1.5eq)，双二亚苄基丙酮钯(113.2mg,0.2mmol,1％eq)，和三叔丁基膦(10％正己烷溶液,1.0mL,0.4mmol,2％eq)。开启搅拌，将上述体系充分混合，并在氮气氛围下升温至回流，通过薄层色谱法分析基本无原料剩余，停止加热。待反应体系温度降至室温，向其加入5mL浓盐酸(37％的水溶液)和100mL去离子水的混合溶液，静置分层，用分液漏斗分液，保留有机相，水相用甲苯(3×30mL)萃取，与前述保留有机相合并，减压蒸馏去除溶剂，粗产品依次经过硅胶柱层析分离(流动相为正己烷/甲苯混合溶剂)，以及甲苯/乙醇/正己烷的混合溶剂重结晶，得到目标化合物。In a nitrogen atmosphere, compound iii (20.0 mmol, 1 eq), compound iv (20.0 mmol, 1 eq) and anhydrous toluene (120 mL) were added to a three-necked flask in sequence, and stirred thoroughly. Sodium tert-butoxide (2.9 g, 30.0 mmol, 1.5 eq), bis(dibenzylideneacetone palladium) (113.2 mg, 0.2 mmol, 1% eq), and tri-tert-butylphosphine (10% n-hexane solution, 1.0 mL, 0.4 mmol, 2% eq) were added respectively. Stirring was started, the above system was fully mixed, and the temperature was raised to reflux under a nitrogen atmosphere. There was basically no raw material left by thin layer chromatography analysis, and heating was stopped. After the temperature of the reaction system drops to room temperature, add a mixed solution of 5 mL of concentrated hydrochloric acid (37% aqueous solution) and 100 mL of deionized water, let stand to separate the layers, separate the layers with a separatory funnel, retain the organic phase, extract the aqueous phase with toluene (3×30 mL), combine with the above-retained organic phase, and distill under reduced pressure to remove the solvent. The crude product is successively separated by silica gel column chromatography (the mobile phase is a mixed solvent of n-hexane/toluene) and recrystallized from a mixed solvent of toluene/ethanol/n-hexane to obtain the target compound.
化合物ii的合成是通过铃木偶联反应实现的，具体可参照化合物iii的制备方法，不同之处在于，分别将原料化合物i和ii等当量地替换为化合物v和vi。The synthesis of compound ii is achieved through Suzuki coupling reaction, which can be specifically referred to the preparation method of compound iii, except that the raw material compounds i and ii are replaced by compounds v and vi in equivalent amounts, respectively.
化合物iv的合成可参照现有技术文献WO2016064110A1提供的方法。The synthesis of compound iv can refer to the method provided in the prior art document WO2016064110A1.
进一步地，化合物i可以9,9’-二氢芴的衍生物或9-芴酮的衍生物为起始原料进行合成，具体合成路线如下。Furthermore, compound i can be synthesized using a derivative of 9,9'-dihydrofluorene or a derivative of 9-fluorenone as a starting material, and the specific synthesis route is as follows.
a.当R1,R2各自独立地选自取代或未取代的烷基，或取代或未取代的芳基，或取代或未取代的杂芳基时：a. When R 1 and R 2 are each independently selected from substituted or unsubstituted alkyl, or substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl:
在氮气氛围下，向反应瓶中依次加入9,9’-二氢芴的衍生物(化合物v,50.0mmol,1eq)和无水四氢呋喃(100mL)，搅拌均匀后，将溶液降温至0℃，在氮气氛围下分批次加入叔丁醇钾(5.7g,50.0mmol,1eq)。加料完成后，将反应体系缓慢恢复至室温，继续搅拌1.5小时。随后，缓慢加入碘代烷烃R1-I(50.0mmol,1eq)，观察到反应体系变为乳白色浊液。在室温下，将所述悬浊液在氮气氛围搅拌2小时，随后过滤，收集滤液，减压蒸馏去除溶剂。将所得中间体化合物进一步作为反应底物，重复上述实验流程，不同之处在于，将碘代烷烃等当量地替换为R2-I，从而得到目标化合物i。Under a nitrogen atmosphere, a derivative of 9,9'-dihydrofluorene (compound v, 50.0mmol, 1eq) and anhydrous tetrahydrofuran (100mL) were added to the reaction bottle in sequence. After stirring evenly, the solution was cooled to 0°C, and potassium tert-butoxide (5.7g, 50.0mmol, 1eq) was added in batches under a nitrogen atmosphere. After the addition was completed, the reaction system was slowly restored to room temperature and continued to stir for 1.5 hours. Subsequently, iodoalkane R 1 -I (50.0mmol, 1eq) was slowly added, and it was observed that the reaction system became a milky white turbid liquid. At room temperature, the suspension was stirred in a nitrogen atmosphere for 2 hours, then filtered, the filtrate was collected, and the solvent was removed by distillation under reduced pressure. The obtained intermediate compound was further used as a reaction substrate, and the above experimental process was repeated, except that the iodoalkane was replaced equivalently with R 2 -I to obtain the target compound i.
b.当R1,R2均选自取代或未取代的烷基，并彼此通过单键相连接形成环烷基时：b. When R 1 and R 2 are both selected from substituted or unsubstituted alkyl groups and are connected to each other via a single bond to form a cycloalkyl group:
采用与情况a相类似的方法进行化合物i的合成，不同之处在于，将碘代烷烃等当量地替换为双碘代的烷烃I-R2-R1-I，经由一步反应得到目标化合物i。The synthesis of compound i is carried out in a similar manner to case a, except that the iodinated alkane is replaced by a diiodinated alkane IR 2 -R 1 -I in equivalent amounts, and the target compound i is obtained through a one-step reaction.
c.当R1,R2均选自取代或未取代的芳基，或取代或未取代的杂芳基，并彼此键合形成螺环结构时：c. When R 1 and R 2 are both selected from substituted or unsubstituted aryl groups, or substituted or unsubstituted heteroaryl groups, and are bonded to each other to form a spiro ring structure:
其中，Z’选自单键、-O-、-S-、-N(Ra)-、-C(Rb)(Rc)-中的其中一种连接形成螺环结构。所述Ra,Rb,Rc彼此相同或不同，独立地选自取代或未取代的C1～C10的直链或支链烷基，取代或未取代的C3～C10的环烷基，取代或未取代的C6～C20的芳基，取代或未取代的C2～C20的杂芳基。Wherein, Z' is selected from a single bond, -O-, -S-, -N(R a )-, -C(R b )(R c )-, connected to form a spirocyclic structure. Said R a , R b , and R c are the same or different from each other, and are independently selected from substituted or unsubstituted C1-C10 straight or branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C20 heteroaryl.
在氮气氛围下，向三口烧瓶中依次加入溴代芳基化合物vi(50.0mmol,1eq)和无水四氢呋喃(150mL)，搅拌均匀后将其冷却至-78℃，逐滴加入正丁基锂(22mL,2.5M的正己烷溶液,55.0mmol,1.1eq)。滴加完毕后，在-78℃下继续搅拌1小时，接着分批次加入无水三氯化铝(6.7g,50.0mmol,1eq)，并继续搅拌30分钟。随后逐滴加入芴酮衍生物(化合物v,50.0mmol,1eq)的无水四氢呋喃(100mL)溶液，滴加完成后在-78℃下继续反应30分钟。随后将反应体系缓慢恢复至室温，并在室温下反应10小时。通过薄层色谱法分析基本无原料剩余，加入浓度为1M的稀盐酸(100mL)，淬灭反应。随后加入100mL乙酸乙酯，搅拌3分钟后静置分层，用分液漏斗分液，保留有机相，水相用乙酸乙酯(3×40mL)萃取，与前述保留有机相合并，使用无水硫酸镁干燥，过滤，减压蒸馏去除溶剂，粗产品经快速硅胶柱色谱纯化(流动相为正己烷/乙酸乙酯混合溶剂)，得到目标化合物i。Under nitrogen atmosphere, bromoaryl compound vi (50.0mmol, 1eq) and anhydrous tetrahydrofuran (150mL) were added to a three-necked flask in sequence, stirred evenly, and cooled to -78°C. n-Butyl lithium (22mL, 2.5M n-hexane solution, 55.0mmol, 1.1eq) was added dropwise. After the addition was completed, stirring was continued at -78°C for 1 hour, and then anhydrous aluminum chloride (6.7g, 50.0mmol, 1eq) was added in batches, and stirring was continued for 30 minutes. Then, a solution of anhydrous tetrahydrofuran (100mL) of a fluorenone derivative (compound v, 50.0mmol, 1eq) was added dropwise, and the reaction was continued at -78°C for 30 minutes after the addition was completed. The reaction system was then slowly restored to room temperature and reacted at room temperature for 10 hours. According to thin layer chromatography analysis, there was basically no raw material remaining, and dilute hydrochloric acid (100mL) with a concentration of 1M was added to quench the reaction. Subsequently, 100 mL of ethyl acetate was added, and the mixture was stirred for 3 minutes and allowed to stand to separate the layers. The organic phase was retained, and the aqueous phase was extracted with ethyl acetate (3×40 mL), combined with the above-retained organic phase, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was purified by flash silica gel column chromatography (the mobile phase was a mixed solvent of n-hexane/ethyl acetate) to obtain the target compound i.
参照上述制备方法合成表1所列举的化合物，对于每一个化合物Hx，在上述制备方法中所涉及的原料或中间体化合物i,ii,iv分别以i-x,ii-x,iv-x表示。其中，使用的主要原料、合成的中间体、收率以及质谱表征数据如表1所示。The compounds listed in Table 1 were synthesized by referring to the above preparation method. For each compound Hx, the raw materials or intermediate compounds i, ii, iv involved in the above preparation method are represented by i-x, ii-x, iv-x, respectively. The main raw materials used, the synthesized intermediates, the yields and the mass spectrometry characterization data are shown in Table 1.
表1Table 1
合成实施例中所涉及代表性化合物的核磁数据如表2所示。The NMR data of the representative compounds involved in the synthesis examples are shown in Table 2.
表2Table 2
器件实施例：Device Example:
器件所用的本发明的化合物均经过升华提纯，纯度均大于99.98％。The compounds used in the device are all purified by sublimation, and the purity is greater than 99.98%.
本发明所涉及的化合物，可作为蓝光，红光，绿光等多种色光OLED器件的空穴传输材料使用。下面给出具体的器件制作方法和测试结果。The compound involved in the present invention can be used as a hole transport material for OLED devices with multiple colors such as blue light, red light, green light, etc. The specific device manufacturing method and test results are given below.
蓝色有机电致发光器件的制备Preparation of blue organic electroluminescent devices
蓝光器件实施例1：Blue light device embodiment 1:
按照如图1所示的结构制作蓝色顶部发光有机电致发光器件，制备工艺为：在玻璃材质的基底101上，通过磁控溅射工艺形成透明的ITO膜层(厚度150nm)，得到第一电极102作为阳极。在阳极表面蒸镀化合物1与本发明化合物H13的混合材料作为空穴注入层103，混合比例为3:97(质量比)，厚度为10nm；随后在空穴注入层表面依次蒸镀本发明化合物H13(厚度100nm)和化合物1-2(厚度20nm)，分别得到第一层空穴传输层104和第二层空穴传输层105。接下来，在第二空穴传输层105的表面，将化合物3和化合物4以95:5的质量比进行共蒸镀，形成有机发光层106(厚度30nm)。随后，在有机发光层表面依次蒸镀化合物5形成空穴阻挡层107(厚度10nm)，以及混合比例为4:6(质量比)的化合物6和LiQ形成电子传输层108(厚度30nm)。随后，将镁(Mg)和银(Ag)以1∶9的蒸镀速率混合沉积在电子传输层108的表面，形成厚度为10nm的第二电极109作为阴极。最后，蒸镀厚度为70nm的化合物7作为覆盖层，完成有机发光器件的制造。A blue top-emitting organic electroluminescent device was prepared according to the structure shown in FIG1 . The preparation process was as follows: On a glass substrate 101 , a transparent ITO film layer (thickness 150 nm) was formed by magnetron sputtering to obtain a first electrode 102 as an anode. A mixed material of compound 1 and compound H13 of the present invention was evaporated on the surface of the anode as a hole injection layer 103, with a mixing ratio of 3:97 (mass ratio) and a thickness of 10 nm; then, compound H13 of the present invention (thickness 100 nm) and compound 1-2 (thickness 20 nm) were sequentially evaporated on the surface of the hole injection layer to obtain a first hole transport layer 104 and a second hole transport layer 105 , respectively. Next, on the surface of the second hole transport layer 105 , compound 3 and compound 4 were co-evaporated at a mass ratio of 95:5 to form an organic light-emitting layer 106 (thickness 30 nm). Subsequently, compound 5 was sequentially evaporated on the surface of the organic light-emitting layer to form a hole blocking layer 107 (thickness 10 nm), and compound 6 and LiQ with a mixing ratio of 4:6 (mass ratio) formed an electron transport layer 108 (thickness 30 nm). Subsequently, magnesium (Mg) and silver (Ag) were mixed and deposited on the surface of the electron transport layer 108 at an evaporation rate of 1:9 to form a second electrode 109 with a thickness of 10 nm as a cathode. Finally, compound 7 with a thickness of 70 nm was evaporated as a covering layer to complete the manufacture of the organic light-emitting device.
在上述器件制备过程中，真空度全程保持在2×10-7Torr至5×10-6Torr之间；有机物的蒸镀速率在
所述化合物1,1-2,1-3,1-4,5,6,7和LiQ的化学结构如表3所示The chemical structures of the compounds 1, 1-2, 1-3, 1-4, 5, 6, 7 and LiQ are shown in Table 3
表3Table 3
蓝光器件实施例2～10Blue light device embodiments 2 to 10
除了在形成空穴注入层和空穴传输层时，分别以下表4中化合物(H20、H46、H78、H108、H113、H132、H157、H214、H283)替代化合物H13外，采用与蓝光器件实施例1相同的方法制作有机电致发光器件。An organic electroluminescent device was prepared by the same method as in Example 1 of the blue light device, except that the compounds in Table 4 (H20, H46, H78, H108, H113, H132, H157, H214, and H283) were used to replace compound H13 when forming the hole injection layer and the hole transport layer.
对比例1～4Comparative Examples 1 to 4
除了在形成空穴注入层和空穴传输层时，分别以化合物HTA,HTB,HTC和HTD替代化合物H13外，采用与蓝光器件实施例1相同的方法制作有机电致发光器件。The organic electroluminescent device was prepared in the same manner as in Example 1 of the blue light device, except that the compound HTA, HTB, HTC and HTD were used to replace the compound H13 when forming the hole injection layer and the hole transport layer.
所述化合物HTA,HTB,HTC和HTD的化学结构如下所示：The chemical structures of the compounds HTA, HTB, HTC and HTD are shown below:
对如上制得的有机电致发光器件，其工作电压和效率通过计算机控制的Keithley2400测试系统计算得到。黑暗条件下的器件寿命使用配备电源和光电二极管作为检测单元的Polaronix(McScience Co.)寿命测量系统得到，LT95表示器件亮度衰减至初始亮度的95％时所需的时间。测试结果如表4所示。For the organic electroluminescent device prepared as above, its operating voltage and efficiency were calculated by a computer-controlled Keithley 2400 test system. The device life under dark conditions was obtained using a Polaronix (McScience Co.) life measurement system equipped with a power supply and a photodiode as a detection unit, and LT95 represents the time required for the device brightness to decay to 95% of the initial brightness. The test results are shown in Table 4.
表4Table 4
红色有机电致发光器件的制备Preparation of red organic electroluminescent devices
红光器件实施例1：Red light device embodiment 1:
按照如图2所示的结构制作红色底部发光有机电致发光器件，制备工艺为：在玻璃材质的基底101上，通过磁控溅射工艺形成透明的ITO膜层(厚度150nm)，得到第一电极102作为阳极。在阳极表面蒸镀化合物1与化合物2的混合材料作为空穴注入层103，混合比例为3:97(质量比)，厚度为10nm；随后在空穴注入层表面依次蒸镀化合物2(厚度100nm)和本发明化合物H10(厚度20nm)，分别得到第一层空穴传输层104和第二层空穴传输层105。接下来，在第二空穴传输层105的表面，将化合物2-3和化合物2-4以95:5的质量比进行共蒸镀，形成有机发光层106(厚度40nm)。随后，在有机发光层表面依次蒸镀化合物5形成空穴阻挡层107(厚度10nm)，以及混合比例为4:6(质量比)的化合物6和LiQ形成电子传输层108(厚度30nm)。最后，将镁(Mg)和银(Ag)以1∶9的蒸镀速率混合沉积在电子传输层108的表面，形成厚度为10nm的第二电极109作为阴极，完成有机发光器件的制造。A red bottom-emitting organic electroluminescent device was prepared according to the structure shown in FIG2. The preparation process was as follows: On a glass substrate 101, a transparent ITO film layer (thickness 150 nm) was formed by magnetron sputtering to obtain a first electrode 102 as an anode. A mixed material of compound 1 and compound 2 was evaporated on the surface of the anode as a hole injection layer 103, with a mixing ratio of 3:97 (mass ratio) and a thickness of 10 nm; then compound 2 (thickness 100 nm) and compound H10 of the present invention (thickness 20 nm) were sequentially evaporated on the surface of the hole injection layer to obtain a first hole transport layer 104 and a second hole transport layer 105, respectively. Next, on the surface of the second hole transport layer 105, compound 2-3 and compound 2-4 were co-evaporated at a mass ratio of 95:5 to form an organic light-emitting layer 106 (thickness 40 nm). Subsequently, compound 5 is sequentially evaporated on the surface of the organic light-emitting layer to form a hole blocking layer 107 (thickness 10 nm), and compound 6 and LiQ with a mixing ratio of 4:6 (mass ratio) are formed into an electron transport layer 108 (thickness 30 nm). Finally, magnesium (Mg) and silver (Ag) are mixed and deposited on the surface of the electron transport layer 108 at an evaporation rate of 1:9 to form a second electrode 109 with a thickness of 10 nm as a cathode, completing the manufacture of the organic light-emitting device.
在上述器件制备过程中，真空度全程保持在2×10-7Torr至5×10-6Torr之间；有机物的蒸镀速率在
化合物1,5,6,7和LiQ的化学结构如前所述，化合物2,2-3,2-4的化学结构如表5所示。The chemical structures of compounds 1, 5, 6, 7 and LiQ are described above, and the chemical structures of compounds 2, 2-3, 2-4 are shown in Table 5.
表5Table 5
红光器件实施例2～10Red light device embodiments 2 to 10
除了在形成发光层时，分别以下表6中化合物(H21、H60、H89、H111、H142、H165、H180、H245、H325)替代化合物H10外，采用与红光器件实施例1相同的方法制作有机电致发光器件。The organic electroluminescent device was prepared by the same method as in Example 1 of the red light device, except that the compounds in Table 6 below (H21, H60, H89, H111, H142, H165, H180, H245, H325) were used to replace the compound H10 when forming the light-emitting layer.
对比例5～7Comparative Examples 5 to 7
除了在形成发光层时，分别以化合物HTE,HTF和HTG替代化合物H10外，采用与红光器件实施例1相同的方法制作有机电致发光器件。化合物HTE,HTF和HTG的化学结构如下所示：The organic electroluminescent device was prepared in the same manner as in Example 1 of the red light device, except that the compound HTE, HTF and HTG were used to replace the compound H10 when forming the light-emitting layer. The chemical structures of the compounds HTE, HTF and HTG are shown below:
对如上制得的有机电致发光器件，其工作电压和效率通过计算机控制的Keithley2400测试系统计算得到。黑暗条件下的器件寿命使用配备电源和光电二极管作为检测单元的Polaronix(McScience Co.)寿命测量系统得到，LT95表示器件亮度衰减至初始亮度的95％时所需的时间。测试结果如表6所示。For the organic electroluminescent device prepared as above, its operating voltage and efficiency were calculated by a computer-controlled Keithley 2400 test system. The device life under dark conditions was obtained using a Polaronix (McScience Co.) life measurement system equipped with a power supply and a photodiode as a detection unit, and LT95 represents the time required for the device brightness to decay to 95% of the initial brightness. The test results are shown in Table 6.
表6Table 6
绿色有机电致发光器件的制备Preparation of green organic electroluminescent devices
绿光器件实施例1：Green light device embodiment 1:
按照如图2所示的结构制作绿色底部发光有机电致发光器件，制备工艺为：在玻璃材质的基底101上，通过磁控溅射工艺形成透明的ITO膜层(厚度150nm)，得到第一电极102作为阳极。在阳极表面蒸镀化合物1与化合物2的混合材料作为空穴注入层103，混合比例为3:97(质量比)，厚度为10nm；随后在空穴注入层表面依次蒸镀化合物2(厚度100nm)和本发明化合物H17(厚度40nm)，分别得到第一层空穴传输层104和第二层空穴传输层105。接下来，在第二空穴传输层105的表面，将化合物3-3A，化合物3-3B和化合物3-4以45:45:10的质量比进行共蒸镀，形成有机发光层106(厚度40nm)。随后，在有机发光层表面依次蒸镀化合物5形成空穴阻挡层107(厚度10nm)，以及混合比例为4:6(质量比)的化合物6和LiQ形成电子传输层108(厚度30nm)。最后，将镁(Mg)和银(Ag)以1∶9的蒸镀速率混合沉积在电子传输层108的表面，形成厚度为10nm的第二电极109作为阴极，完成有机发光器件的制造。A green bottom-emitting organic electroluminescent device was prepared according to the structure shown in FIG2. The preparation process was as follows: On a glass substrate 101, a transparent ITO film layer (thickness 150 nm) was formed by magnetron sputtering to obtain a first electrode 102 as an anode. A mixed material of compound 1 and compound 2 was evaporated on the surface of the anode as a hole injection layer 103, with a mixing ratio of 3:97 (mass ratio) and a thickness of 10 nm; then compound 2 (thickness 100 nm) and compound H17 of the present invention (thickness 40 nm) were sequentially evaporated on the surface of the hole injection layer to obtain a first hole transport layer 104 and a second hole transport layer 105, respectively. Next, on the surface of the second hole transport layer 105, compound 3-3A, compound 3-3B and compound 3-4 were co-evaporated at a mass ratio of 45:45:10 to form an organic light-emitting layer 106 (thickness 40 nm). Subsequently, compound 5 is sequentially evaporated on the surface of the organic light-emitting layer to form a hole blocking layer 107 (thickness 10 nm), and compound 6 and LiQ with a mixing ratio of 4:6 (mass ratio) are formed into an electron transport layer 108 (thickness 30 nm). Finally, magnesium (Mg) and silver (Ag) are mixed and deposited on the surface of the electron transport layer 108 at an evaporation rate of 1:9 to form a second electrode 109 with a thickness of 10 nm as a cathode, completing the manufacture of the organic light-emitting device.
在上述器件制备过程中，真空度全程保持在2×10-7Torr至5×10-6Torr之间；有机物的蒸镀速率在
化合物1,2,5,6,7和LiQ的化学结构如前所述，化合物3-3A,3-3B,3-4的化学结构如表7所示。The chemical structures of compounds 1, 2, 5, 6, 7 and LiQ are as described above, and the chemical structures of compounds 3-3A, 3-3B, and 3-4 are shown in Table 7.
表7Table 7
绿光器件实施例2～10Green light device embodiments 2 to 10
除了在形成发光时，分别以下表8中化合物(H17、H53、H102、H138、H192、H212、H255、H281、H311、H341)替代化合物H16外，采用与绿光器件实施例1相同的方法制作有机电致发光器件。An organic electroluminescent device was prepared by the same method as in Example 1 of the green light device, except that compound H16 was replaced by the compounds in Table 8 (H17, H53, H102, H138, H192, H212, H255, H281, H311, and H341) respectively when forming light emission.
对比例8～10Comparative Examples 8 to 10
除了在形成发光层时，以化合物HTH,HTI和HTJ替代化合物H17外，采用与绿光器件实施例1相同的方法制作有机电致发光器件。化合物HTH,HTI和HTJ的化学结构如下所示。The organic electroluminescent device was prepared in the same manner as in Example 1 of the green light device, except that the compound HTH, HTI and HTJ were used instead of the compound H17 when forming the light-emitting layer. The chemical structures of the compounds HTH, HTI and HTJ are shown below.
对如上制得的有机电致发光器件，其工作电压和效率通过计算机控制的Keithley2400测试系统计算得到。黑暗条件下的器件寿命使用配备电源和光电二极管作为检测单元的Polaronix(McScience Co.)寿命测量系统得到，LT95表示器件亮度衰减至初始亮度的95％时所需的时间。测试结果如表8所示。For the organic electroluminescent device prepared as above, its operating voltage and efficiency were calculated by a computer-controlled Keithley 2400 test system. The device life under dark conditions was obtained using a Polaronix (McScience Co.) life measurement system equipped with a power supply and a photodiode as a detection unit, and LT95 represents the time required for the device brightness to decay to 95% of the initial brightness. The test results are shown in Table 8.
表8Table 8
从表4、表6和表8可以看出，将本发明的化合物用于蓝光、红光和绿光有机电致发光器件的空穴传输层，均能够有效地降低驱动电压、提升器件效率以及延长使用寿命。具体地，在对比例1～4中，胺基和联苯基位于芴的不同位置，所表现出的器件性能在驱动电压、器件效率和使用寿命方面各有优劣；在对比例8～10以及对比例5～7中，随着芴上连接的芳基从无到有，从苯变为联苯，器件的驱动电压降低且效率和寿命均有提高，这可能是由于共轭的延长导致分子间有效的共轭接触增加，更有利于载流子在分子间跃迁(hopping)。而在蓝光器件实施例中，和对比例1～4相比，器件的驱动电压至少降低了4.0％、器件效率至少提升了3.8％，LT95寿命至少提升了16.7％；在红光器件实施例中，和对比例5～7相比，器件的驱动电压至少降低了5.7％、器件效率至少提升了11.1％，LT95寿命至少提升了15.5％；在绿光器件实施例中，和对比例8～10相比，器件的驱动电压至少降低了5.7％、器件效率至少提升了11.1％，LT95寿命至少提升了15.5％。究其原因，可能是非平面结构的芳基并环烷基的引入，促使分子形成各向同性的无定形态堆积，从而器件工作时薄膜形貌更加趋于稳定；与此同时，基于芴的共轭骨架能确保分子具有良好的空穴传输特性。因此，将本发明的化合物用作有机电致发光器件的空穴传输层，在驱动电压、器件效率和稳定性方面均显示出优异的特性。As can be seen from Table 4, Table 6 and Table 8, the use of the compounds of the present invention in the hole transport layer of blue, red and green organic electroluminescent devices can effectively reduce the driving voltage, improve the device efficiency and extend the service life. Specifically, in Comparative Examples 1 to 4, the amino group and the biphenyl group are located at different positions of the fluorene, and the device performance exhibited has advantages and disadvantages in terms of driving voltage, device efficiency and service life; in Comparative Examples 8 to 10 and Comparative Examples 5 to 7, as the aromatic group connected to the fluorene is changed from nothing to something, from benzene to biphenyl, the driving voltage of the device is reduced and the efficiency and life are improved. This may be due to the extension of conjugation, which leads to an increase in effective conjugated contact between molecules, which is more conducive to carrier hopping between molecules. In the blue light device embodiment, compared with comparative examples 1 to 4, the driving voltage of the device is at least reduced by 4.0%, the device efficiency is at least increased by 3.8%, and the LT95 life is at least increased by 16.7%; in the red light device embodiment, compared with comparative examples 5 to 7, the driving voltage of the device is at least reduced by 5.7%, the device efficiency is at least increased by 11.1%, and the LT95 life is at least increased by 15.5%; in the green light device embodiment, compared with comparative examples 8 to 10, the driving voltage of the device is at least reduced by 5.7%, the device efficiency is at least increased by 11.1%, and the LT95 life is at least increased by 15.5%. The reason may be that the introduction of the non-planar structure of the aromatic and cycloalkyl group prompts the molecule to form an isotropic amorphous stacking, so that the film morphology is more stable when the device is working; at the same time, the conjugated skeleton based on fluorene can ensure that the molecule has good hole transport properties. Therefore, the compound of the present invention is used as a hole transport layer of an organic electroluminescent device, showing excellent characteristics in terms of driving voltage, device efficiency and stability.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.
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