CN108117495B - 螺芴环化合物、其用途及采用其的有机电致发光器件 - Google Patents
螺芴环化合物、其用途及采用其的有机电致发光器件 Download PDFInfo
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- CN108117495B CN108117495B CN201611079049.6A CN201611079049A CN108117495B CN 108117495 B CN108117495 B CN 108117495B CN 201611079049 A CN201611079049 A CN 201611079049A CN 108117495 B CN108117495 B CN 108117495B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 188
- 230000003111 delayed effect Effects 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 125000006575 electron-withdrawing group Chemical group 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 54
- -1 N-phenylcarbazolyl Chemical group 0.000 claims description 46
- 239000012044 organic layer Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000007725 thermal activation Methods 0.000 claims description 4
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 3
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 claims description 3
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- OSZBRXNBKKWJOM-UHFFFAOYSA-N 1-phenylphenazine Chemical compound C1=CC=CC=C1C1=CC=CC2=NC3=CC=CC=C3N=C12 OSZBRXNBKKWJOM-UHFFFAOYSA-N 0.000 claims description 2
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- 125000005509 dibenzothiophenyl group Chemical group 0.000 claims description 2
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 claims description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 2
- JGGSOWGJMBNDHS-UHFFFAOYSA-N 10-phenyl-5h-phenazine Chemical compound C12=CC=CC=C2NC2=CC=CC=C2N1C1=CC=CC=C1 JGGSOWGJMBNDHS-UHFFFAOYSA-N 0.000 claims 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims 1
- 125000001072 heteroaryl group Chemical group 0.000 abstract description 14
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 3
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 141
- 238000003786 synthesis reaction Methods 0.000 description 141
- 239000000047 product Substances 0.000 description 48
- 238000000921 elemental analysis Methods 0.000 description 47
- 239000003153 chemical reaction reagent Substances 0.000 description 46
- 239000004327 boric acid Substances 0.000 description 41
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 24
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 239000010410 layer Substances 0.000 description 21
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- JBLHBMFGQCZARA-UHFFFAOYSA-N 4-bromo-9-chlorophenanthrene Chemical compound BrC1=CC=CC=2C=C(C3=CC=CC=C3C1=2)Cl JBLHBMFGQCZARA-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- GRYSGIUOABBVCT-UHFFFAOYSA-N 3-bromofluoren-1-one Chemical compound C1=CC=C2C3=CC(Br)=CC(=O)C3=CC2=C1 GRYSGIUOABBVCT-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- QFUPJXCUNNWZJQ-UHFFFAOYSA-N 2-bromofluoren-1-one Chemical compound C1=CC=C2C3=CC=C(Br)C(=O)C3=CC2=C1 QFUPJXCUNNWZJQ-UHFFFAOYSA-N 0.000 description 11
- UILJRKFLYXOSIR-UHFFFAOYSA-N BrC=1C=CC(C2=CC3=CC=CC=C3C12)=O Chemical compound BrC=1C=CC(C2=CC3=CC=CC=C3C12)=O UILJRKFLYXOSIR-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- WJNPZGZNMIDHRN-UHFFFAOYSA-N 4-bromo-9,10-dichlorophenanthrene Chemical compound BrC1=CC=CC=2C(=C(C3=CC=CC=C3C1=2)Cl)Cl WJNPZGZNMIDHRN-UHFFFAOYSA-N 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- BBVQDWDBTWSGHQ-UHFFFAOYSA-N 2-chloro-1,3-benzoxazole Chemical compound C1=CC=C2OC(Cl)=NC2=C1 BBVQDWDBTWSGHQ-UHFFFAOYSA-N 0.000 description 7
- KQCFUSPSVXUTNB-UHFFFAOYSA-N 3,6-dibromofluoren-1-one Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC(=O)C3=CC2=C1 KQCFUSPSVXUTNB-UHFFFAOYSA-N 0.000 description 7
- MVDNLNISEATVFT-UHFFFAOYSA-N 4-bromo-1,8-dichlorophenanthrene Chemical compound BrC1=CC=C(C=2C=CC3=C(C=CC=C3C1=2)Cl)Cl MVDNLNISEATVFT-UHFFFAOYSA-N 0.000 description 7
- YICFKFZKOCHGPY-UHFFFAOYSA-N 4-bromo-2,7-dichlorophenanthrene Chemical compound BrC1=CC(=CC=2C=CC3=CC(=CC=C3C1=2)Cl)Cl YICFKFZKOCHGPY-UHFFFAOYSA-N 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- FYEFHYMUEWRCRF-UHFFFAOYSA-N 2,7-dibromofluoren-1-one Chemical compound BrC1=CC=C2C3=CC=C(Br)C(=O)C3=CC2=C1 FYEFHYMUEWRCRF-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 6
- RFTRFDMRINNTSI-UHFFFAOYSA-N 9,9-dimethyl-n-phenylfluoren-2-amine Chemical compound C1=C2C(C)(C)C3=CC=CC=C3C2=CC=C1NC1=CC=CC=C1 RFTRFDMRINNTSI-UHFFFAOYSA-N 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- UGFOTZLGPPWNPY-UHFFFAOYSA-N 7h-benzo[c]carbazole Chemical compound C1=CC=CC2=C3C4=CC=CC=C4NC3=CC=C21 UGFOTZLGPPWNPY-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- SAQLZRWIDDGGPF-UHFFFAOYSA-N 1-bromo-2-[2-(2-bromophenyl)propan-2-yl]benzene Chemical compound BrC1=C(C=CC=C1)C(C)(C)C1=C(C=CC=C1)Br SAQLZRWIDDGGPF-UHFFFAOYSA-N 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 3
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 3
- BSQLQMLFTHJVKS-UHFFFAOYSA-N 2-chloro-1,3-benzothiazole Chemical compound C1=CC=C2SC(Cl)=NC2=C1 BSQLQMLFTHJVKS-UHFFFAOYSA-N 0.000 description 3
- IMLDYQBWZHPGJA-UHFFFAOYSA-N 2-phenyl-9h-carbazole Chemical compound C1=CC=CC=C1C1=CC=C2C3=CC=CC=C3NC2=C1 IMLDYQBWZHPGJA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000003775 Density Functional Theory Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
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- 238000007738 vacuum evaporation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QNGVEVOZKYHNGL-UHFFFAOYSA-N 2-chloro-4,6-diphenylpyrimidine Chemical compound N=1C(Cl)=NC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 QNGVEVOZKYHNGL-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 2
- XUUWTDSXAKOQLB-UHFFFAOYSA-N bromo-bis(2,4,6-trimethylphenyl)borane Chemical compound CC1=CC(C)=CC(C)=C1B(Br)C1=C(C)C=C(C)C=C1C XUUWTDSXAKOQLB-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
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- 150000003384 small molecules Chemical class 0.000 description 2
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- 238000007740 vapor deposition Methods 0.000 description 2
- VASOMTXTRMYSKD-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boronic acid Chemical compound OB(O)C1=C(F)C(F)=C(F)C(F)=C1F VASOMTXTRMYSKD-UHFFFAOYSA-N 0.000 description 1
- AWSHWMCCOXZOKC-UHFFFAOYSA-N (4-pyridin-4-ylphenoxy)boronic acid Chemical compound C1=CC(OB(O)O)=CC=C1C1=CC=NC=C1 AWSHWMCCOXZOKC-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- OFCFYWOKHPOXKF-UHFFFAOYSA-N 1-(benzenesulfonyl)-4-chlorobenzene Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=CC=C1 OFCFYWOKHPOXKF-UHFFFAOYSA-N 0.000 description 1
- DDGPPAMADXTGTN-UHFFFAOYSA-N 2-chloro-4,6-diphenyl-1,3,5-triazine Chemical compound N=1C(Cl)=NC(C=2C=CC=CC=2)=NC=1C1=CC=CC=C1 DDGPPAMADXTGTN-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- OXPDQFOKSZYEMJ-UHFFFAOYSA-N 2-phenylpyrimidine Chemical compound C1=CC=CC=C1C1=NC=CC=N1 OXPDQFOKSZYEMJ-UHFFFAOYSA-N 0.000 description 1
- HUJGMBWRRXOKRH-UHFFFAOYSA-N 4-bromo-1-chlorophenanthrene Chemical compound BrC1=CC=C(C=2C=CC3=CC=CC=C3C1=2)Cl HUJGMBWRRXOKRH-UHFFFAOYSA-N 0.000 description 1
- AGSFPLMLEMCOFX-UHFFFAOYSA-N 7-chloro-1,3-benzoxazole Chemical compound ClC1=CC=CC2=C1OC=N2 AGSFPLMLEMCOFX-UHFFFAOYSA-N 0.000 description 1
- STJXCDGCXVZHDU-UHFFFAOYSA-N 7H-Dibenzo[c,g]carbazole Chemical compound N1C2=CC=C3C=CC=CC3=C2C2=C1C=CC1=CC=CC=C12 STJXCDGCXVZHDU-UHFFFAOYSA-N 0.000 description 1
- JSEQNGYLWKBMJI-UHFFFAOYSA-N 9,9-dimethyl-10h-acridine Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3NC2=C1 JSEQNGYLWKBMJI-UHFFFAOYSA-N 0.000 description 1
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- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 101710111444 Nitric oxide synthase, brain Proteins 0.000 description 1
- VWBYXJRDIQCSLW-UHFFFAOYSA-N O=[P](c1ccccc1)c1ccccc1 Chemical compound O=[P](c1ccccc1)c1ccccc1 VWBYXJRDIQCSLW-UHFFFAOYSA-N 0.000 description 1
- PCKPVGOLPKLUHR-UHFFFAOYSA-N OH-Indolxyl Natural products C1=CC=C2C(O)=CNC2=C1 PCKPVGOLPKLUHR-UHFFFAOYSA-N 0.000 description 1
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- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
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- YUFRAQHYKKPYLH-UHFFFAOYSA-N benzo[f]quinoxaline Chemical group C1=CN=C2C3=CC=CC=C3C=CC2=N1 YUFRAQHYKKPYLH-UHFFFAOYSA-N 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
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- 150000001768 cations Chemical class 0.000 description 1
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- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 description 1
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000008376 fluorenones Chemical class 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- JYGFTBXVXVMTGB-UHFFFAOYSA-N indolin-2-one Chemical compound C1=CC=C2NC(=O)CC2=C1 JYGFTBXVXVMTGB-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
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- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 150000002987 phenanthrenes Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 125000000335 thiazolyl group Chemical group 0.000 description 1
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- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种螺芴环化合物、其用途及采用其的有机电致发光器件。该螺芴环化合物结构如式(I)所示,其中,D1~D6独立地为氢或供电子基团,且不能同时为氢;供电子基团独立地选自取代或未取代的C2~C30的第一杂芳基;A1~A6独立地为氢或吸电子基团,且不能同时为氢;吸电子基团独立地选自氟原子、氰基、取代或未取代的C2~C30的第二杂芳基。本发明的螺芴环化合物具有较小ΔE(S1‑T1),易于实现热激发延迟荧光。
Description
技术领域
本发明涉及有机电致发光技术领域,更具体地,涉及一种螺芴环化合物、其在制备有机电致发光器件中的用途及采用其的热激活延迟荧光材料和有机电致发光器件。
背景技术
OLED中最早利用的染料是纯有机小分子发光材料。基于此类材料的器件,寿命长并且效率滚降小。但是,材料只能利用25%的S1发光,而占75%的T1因为自旋禁阻的原因只能通过非辐射跃迁的途径损失掉。1998 年,美国普林斯顿大学的Forrest等首次报道了基于T1发光的PHOLEDs。利用重金属Pt原子造成的旋轨耦合效应使得T1在室温下即可有效的发光,从而能够理论上实现100%的内量子效率。目前,大部分的磷光染料是基于Ir的配合物。Ir配合物的六面体构型有利于材料高的发光效率,同时减小材料堆叠造成的淬灭。高效的红绿蓝光Ir配合物均有报道,并且外量子效率都已超过30%,是应用最为成功的OLED染料。
但是,磷光材料也并不是完美的。首先,磷光材料T1的寿命一般在 1μs以上,远远高于荧光材料几十纳秒的寿命,因此,PHOLEDs在高电流密度下效率滚降严重。其次,磷光材料需要重金属原子来促进T1发光,但是,同样也是因为重金属的存在,使得磷光染料的价格昂贵,特别是稀有金属Ir配合物。再次,蓝色磷光材料宽的带隙导致蓝光PHOLEDs的寿命很短,这也是一直制约PHOLED进一步产业化的原因之一。
为了解决上述问题,除了对器件结构进行改进以外,对热激发延迟荧光(TADF)材料进行开发是提升器件中纯有机小分子材料激子利用率的重要途径。一方面,这类材料种类丰富,价格便宜;另一方面,这类材料能通过较小的ΔEST实现能量的隙间穿越,提高T1的利用率;再一方面,这类材料是目前解决蓝光材料瓶颈的有效途径,目前基于TADF材料制备的蓝光器件EQE已经超过20%,因此,对这类材料的开发具有重要意义。
截止目前,基于TADF材料的器件性能与传统磷光材料相比仍有较大的差距,尤其蓝光器件,存在较大的效率滚降问题。为了解决此问题,我们设计开发了具有TADF性质的发光主体材料,能将三线态激子迅速传递给发光客体染料,更有效的利用三线态激子,从而避免三线态激子的堆积,避免效率滚降严重的问题,使得器件在高亮度下仍维持较好的器件性能,更有利于推进商业化应用。
发明内容
本发明的主要目的在于提供一种螺芴环化合物,或者该化合物在制备有机电致发光器件中的用途,或者采用其的热激活延迟荧光材料和有机电致发光器件,以解决上述技术问题中的至少之一。
为了实现上述目的,作为本发明的一个方面,本发明提供了一种螺芴环化合物,该化合物结构如式(Ⅰ)所示:
其中,D1~D6独立地为氢或供电子基团,且不能同时为氢;所述供电子基团独立地选自取代或未取代的C2~C30的第一杂芳基;
A1~A6独立地为氢或吸电子基团,且不能同时为氢;所述吸电子基团独立地选自氟原子、氰基、取代或未取代的C2~C30的第二杂芳基。
作为本发明的另一个方面,本发明还提供了一种如上所述的螺芴环化合物在制备有机电致发光器件中的用途。
作为本发明的再一个方面,本发明还提供了一种热激活延迟荧光材料,所述热激活延迟荧光材料的主要成分为如上所述的螺芴环化合物。
作为本发明的还一个方面,本发明还提供了一种有机电致发光器件,该器件包括第一电极、第二电极和插入在所述第一电极和第二电极之间的若干有机层,其中所述若干有机层中至少有一层中含有如上所述的螺芴环化合物。
通过上述技术方案可知,本发明的螺芴环化合物具有较小ΔEST,从而易于实现热激发延迟荧光(TADF),是具有TADF性质的发光主体材料,相对于目前的TADF发光材料,本发明的化合物采用主体敏化客体的机理,能将主体的三线态激子通过TADF过程迅速传递给发光客体染料,更有效的利用三线态激子,从而避免三线态激子的堆积,避免效率滚降严重的问题,能够有效提高有机电致发光器件的荧光效率,且提高有机电致发光器件的发光效率;扩展了用于有机发光器件,特别是绿光器件的材料选项。
附图说明
图1是本发明的式(1)的螺芴环化合物的HOMO轨道分布图;
图2是本发明的式(1)的螺芴环化合物的LUMO轨道分布图;
图3是本发明的式(38)的螺芴环化合物的HOMO轨道分布图;
图4是本发明的式(38)的螺芴环化合物的LUMO轨道分布图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,以下结合具体实施例,并参照附图,对本发明作进一步的详细说明。
本发明公开了一种螺芴环化合物,该化合物结构如式(Ⅰ)所示:
其中,D1~D6独立地为氢或供电子基团,且不能同时为氢;所述供电子基团独立地选自取代或未取代的C2~C30的第一杂芳基;
A1~A6独立地为氢或吸电子基团,且不能同时为氢;所述吸电子基团独立地选自氟原子、氰基、取代或未取代的C2~C30的第二杂芳基。
作为优选,取代或未取代的C2~C30的第一杂芳基中,骨架上碳原子的个数为2~20;其中取代的C2~C30的第一杂芳基中,取代基团为C1~C4的烷基、F、Cl、Br;进一步优选地,第一杂芳基为芳氨基、呋喃基、噻吩基、吡咯基、苯并呋喃基、苯并噻吩基、异苯并呋喃基、吲哚基、二苯并呋喃基、二苯并噻吩基、咔唑基、吩噁嗪基、吩噻嗪基、吖啶基及其衍生物;再进一步优选地,第一杂芳基为二苯胺基、吩噁嗪基、吩噻嗪基、1- 苯基吩噻嗪基、1-苯基-9,9-二甲基吖啶基、N-苯基咔唑基、二苯并呋喃基、二苯并噻吩基、N,N-二苯基苯胺基、N-(9,9-二甲基-9H-芴-2-基)-N-苯基氨基、3-苯基咔唑基、苯并噻吩基、苯并咔唑基、二苯并咔唑基、9-苯基咔唑、9,9-二甲基吖啶基、9-苯基吩噁嗪基、N-苯基吩噁嗪基、N-苯基吩噻嗪基、N-苯基-9,9-二甲基吖啶基或咔唑基。
作为优选,取代或未取代的C2~C30的第二杂芳基中,骨架上碳原子的个数为6~20;其中,取代的C2~C30的第二杂芳基中,取代基团为C1~C4的烷基、F、Cl、Br;进一步优选地,第二杂芳基为吡啶基、噁唑基、噻唑基、喹啉基、嘧啶基、咪唑、苯基嘧啶、三嗪基、噁硼杂环基、砜基及其衍生物;再进一步优选地,第二杂芳基为苯并喹喔啉、喹唑啉基、喹喔啉基、喹啉基、1-苯基-苯并咪唑基、苯并噁唑基、苯并噻唑基、二苯磷酰基、4-吡啶苯基、2-苯基吡啶基、吡啶基、苯甲酰基、苯磺酰苯基、二苯并噁硼烷基、4,6-二苯基嘧啶基、4,6-二苯基三嗪基、二苯并噻砜基、 2,3,4,5,6-五氟苯基或10,10-二甲基二苯并硼烷基。
最优选地,该螺芴环化合物为具有下述式(1)~式(47)的结构式的化合物之一:
下面将以多个合成实施例为例来详述本发明的上述新化合物的具体制备方法,但本发明的制备方法并不限于这多个合成实施例,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。
本发明中所用的各种化学药品如石油醚、乙酸乙酯、正己烷、甲苯、四氢呋喃、二氯甲烷、乙酸、磷酸钾、叔丁醇钠、丁基锂等基础化工原料均可在国内化工产品市场买到,卤代菲(R=Br、Cl等)购自北京环灵科技有限公司,卤代芴酮(R=Br)购自武汉晟承宇科技有限公司。
合成实施例1
式(1)化合物的合成:
中间体1的合成:在三口烧瓶中,将4-溴-9,10-二氯菲溶于四氢呋喃 THF中,降温至-80℃,缓慢滴加丁基锂(1eq),温度不超过-75℃,滴加完升至室温反应1h,将溶有3,6-二溴芴酮的THF溶液加入反应瓶中,将混合液回流反应3h,TCL检测反应完毕后,降至室温。用二氯甲烷萃取后,合并有机相,旋除有机溶剂,用硅胶柱层(洗脱剂:石油醚:乙酸乙酯=10:1)分离得中间体1,收率为62.4%。
中间体2的合成:将中间体1、二苯胺、四三苯基膦钯(Pd(PPh3)4)、叔丁醇钠加入到甲苯中,氮气保护下升温至80℃反应3h,加水淬灭后,用二氯甲烷萃取分液得有机相,旋除有机溶剂,用硅胶柱层(洗脱剂:石油醚:乙酸乙酯=10:1)分离得中间体2,收率为78.6%。
式(1)化合物的合成:氮气保护下,Pd2(dba)4和1,1'-双(二苯基膦) 二茂铁加入干燥的DMF溶剂中,室温搅拌15min,加入中间体2并升温至80℃,将Zn(CN)2分批加入,反应液在80℃反应24h。待反应结束后,停止反应降至室温,用二氯甲烷萃取,有机层用无水硫酸镁干燥后,过滤,旋除溶剂,过柱分离(石油醚:乙酸乙酯=10:1)得目标式(1)化合物,收率为68.9%。
产物MS(m/e):724.3,元素分析(C53H32N4):理论值C,87.82%;H, 4.45%;N,7.73%;实测值C:87.78%,H:4.44%,N:7.52%。1H NMR(400 MHz,CDCl3)δ8.04(t,4H),7.78(d,2H),7.62(t,2H),7.43(d,2H),7.28(s, 2H),7.19-7.24(m,6H),6.95-7.11(m,14H)。
合成实施例2
式(2)化合物的合成:合成步骤同式(1)化合物,只是将4-溴-9,10- 二氯菲改变为4-溴-1,8-二氯菲,将二苯胺改为吩噻嗪,其它试剂不变,得到式(2)化合物。
产物MS(m/e):784.3,元素分析(C53H28N4S2):理论值C,81.10%, H,3.60%;N,7.14%;S,8.17%;实测值C,81.20%,H,3.51%;N,7.55%;S, 8.01%。1H NMR(400MHz,CDCl3)δ8.19(t,4H),7.78(d,2H),8.05(d,2H), 7.98(d,2H),7.82(d,2H),7.70(s,2H),7.15-7.23(m,12H),6.94-7.00(m,4H)。
合成实施例3
式(3)化合物的合成:合成步骤同式(1)化合物,只是将4-溴-9,10- 二氯菲改为4-溴-2,7-二氯菲,3,6-二溴芴酮改为2,7-二溴芴酮,其它试剂不变,得到式(3)化合物。
产物MS(m/e):724.3,元素分析(C53H32N4):理论值C,87.82%;H, 4.45%;N,7.73%;实测值C,87.52%;H,4.85%;N,7.72%。
合成实施例4
式(4)化合物的合成:合成步骤同式(1)化合物,只是将4-溴-9,10- 二氯菲改为4-溴-1,2,6,7-四氯菲,二苯胺改为咔唑,其它试剂不变,得到式(4)化合物。
产物MS(m/e):770.1,元素分析(C55H26N6):理论值C,85.70%;H, 3.40%;N,10.90%;实测值C,85.11%;H,3.43%;N,10.56%。
合成实施例5
式(5)化合物的合成:
中间体4的合成:合成步骤同中间体2,只是将4-溴-9,10-二氯菲改变为4-溴-9-氯菲,3,6-二溴芴酮改为2-溴芴酮,二苯胺改为(9,9-二甲基-10- 苯基-9,10-二氢吖啶-2-基)硼酸其它试剂不变,得到中间体4。
式(5)化合物的合成:100毫升三口瓶中加入异喹啉-1-硼酸、中间体4与甲苯,然后氮气保护下,加入Pd(dba)2、叔丁醇钠、以及P(tBu)3,然后混合物在氮气保护下在油浴上加热回流反应10h,停止反应,加水 (50mL)淬灭,EA(50mL*4)萃取,100mL饱和NaCl溶液洗,旋干后油泵抽干,过柱分离(石油醚:乙酸乙酯=10:1)得目标式(5)化合物,收率为62.3%。
产物MS(m/e):752.1,元素分析(C57H40N2):理论值C,90.92%;H, 5.35%;N,3.72%;实测值C,90.91%;H,5.11%;N,3.96%。1H NMR(400 MHz,CDCl3)δ8.48(d,1H),8.01-8.09(m,3H),7.89-7.92(m,3H),7.76-7.81 (m,4H),7.50-7.66(m,9H),7.48(s,1H),7.24-7.35(m,8H),7.06(t,1H),6.55(q, 1H),5.97(q,1H),3.34(q,1H),1.35(s,6H)。
合成实施例6
式(6)化合物的合成:合成步骤同式(5)化合物,只是将4-溴-9- 氯菲改变为4-溴-1,8-二氯菲,异喹啉-1-硼酸改为喹啉-2-硼酸,其它试剂不变,得到式(6)化合物。
产物MS(m/e):879.2,元素分析(C66H45N3):理论值C,90.07%;H, 5.15%;N,4.77%;实测值C,89.50%;H,5.55%;N,4.71%。1H NMR(400 MHz,CDCl3)δ8.53(d,2H),8.39(d,2H),8.22(d,1H),8.03-8.10(m,4H), 7.89(m,4H),7.78(q,2H),7.70(s,3H),7.24-7.55(m,13H),7.06(t,1H),6.55 (q,1H),5.97(m,4H),4.91(q,1H),3.47(q,1H),1.35(s,6H)。
合成实施例7
式(7)化合物的合成:合成步骤同式(5)化合物,只是将(9,9-二甲基-10-苯基-9,10-二氢吖啶-2-基)硼酸改变为(10-苯基-10H-吩噁嗪-3-)硼酸,异喹啉-1-硼酸改为[4-(1-苯基-1H-苯并咪唑-2-)苯基]硼酸,其它试剂不变,得到式(7)化合物。
产物MS(m/e):791.4,元素分析(C58H37N3O):理论值C,87.96%; H,4.71%;N,5.31%;O,2.02%;实测值C,88.96;H,4.81;N,5.35。
合成实施例8
式(8)化合物的合成:合成步骤同式(7)化合物,只是将4-溴-9- 氯菲改变为4-溴-1,8-二氯菲,其它试剂不变,得到式(8)化合物。
产物MS(m/e):983.4,元素分析(C71H45N5O):理论值C,86.65%; H,4.61%;N,7.12%;O,1.63%;实测值C,86.25%;H,4.62%;N,7.42%。
合成实施例9
式(9)化合物的合成:合成步骤同式(7)化合物,只是将4-溴-9- 氯菲改变为4-溴-1,8-二氯菲,将2-溴芴酮改为4-溴芴酮,将(9,9-二甲基-10- 苯基-9,10-二氢吖啶-2-基)硼酸改为(10-苯基-10,10-二氢-吩噻嗪-8-)硼酸,将异喹啉-1-硼酸改为喹唑啉-2-硼酸,其它试剂不变,得到式(9)化合物。
产物MS(m/e):743.2,元素分析(C53H33N3S):理论值C,85.57%; H,4.47%;N,5.65%;S,4.31%;实测值C,85.27%;H,4.41%;N,5.15%。
合成实施例10
式(10)化合物的合成:合成步骤同式(9)化合物,只是将喹唑啉 -2-硼酸改为喹喔啉-2-硼酸,其它试剂不变,得到式(10)化合物。
产物MS(m/e):743.1,元素分析(C53H33N3S):理论值C,85.57%; H,4.47%;N,5.65%;S,4.31%;实测值C,85.27%;H,4.48%;N,5.68%。
合成实施例11
式(11)化合物的合成:
中间体6的合成:步骤同中间体4,只是将4-溴-9-氯菲改为4-溴-2,7- 二氯菲,2-溴芴酮改为4-溴芴酮,(9,9-二甲基-10-苯基-9,10-二氢吖啶-2- 基)硼酸改为二苯并呋喃-3-硼酸,其它试剂不变,得到中间体6。
中间体7的合成:100毫升三口瓶中加入中间体6、双联硼酸酯、 Pd(dppf)Cl2,二氧六环和乙酸钾,然后氮气保护下,在油浴上加热升温90℃反应6h,停止反应,降至室温,加水(50mL)淬灭,EA(50mL*4)萃取,100mL饱和NaCl溶液洗,收集有机相加入无水MgSO4干燥,旋除有机相后,过柱分离(石油醚:乙酸乙酯=10:1)得中间体7,收率为61.9%。
式(11)化合物的合成:100毫升三口瓶中加入中间体7、2-氯苯并噁唑,然后氮气保护下加入Pd2(dba)3、三环己基膦、磷酸钾、二氧六环和水,在油浴上加热升温回流反应24h,停止反应,降至室温。加水(50mL)淬灭,EA(50mL*4)萃取,100mL饱和NaCl溶液洗,收集有机相加入无水MgSO4干燥,旋除有机相后,过柱分离(石油醚:乙酸乙酯=10:1) 得化合物式(11),收率为71.2%。
产物MS(m/e):740.1,元素分析(C53H28N2O3):理论值C,85.93%; H,3.81%;N,3.78%;O,6.48%;实测值C,86.93%;H,3.88%;N,3.68%。1H NMR(400MHz,CDCl3)δ8.52(s,2H),8.38(s,2H),8.03-7.98(t,2H), 7.81-7.92(m,5H),7.74-7.78(m,5H),7.67(d,2H),7.54(d,1H),7.43-7.31(m, 8H),7.24(t,1H)。
合成实施例12
式(12)化合物的合成:合成步骤同式(11)化合物,只是将二苯并呋喃-3-硼酸改为二苯并噻吩-3-硼酸,将2-氯苯并噁唑改为2-氯苯并噻唑,其它试剂不变,得到式(12)化合物。
产物MS(m/e):788.2,元素分析(C53H28N2S3):理论值C,80.68%; H,3.58%;N,3.55%;S,12.19%;实测值C,80.78%;H,3.52%;N,3.51%。
合成实施例13
式(13)化合物的合成:合成步骤同式(11)化合物,只是将4-溴芴酮改为3-溴芴酮,4-溴-2,7-二氯菲改为4-溴-1,8-二氯菲,二苯并呋喃-3-硼酸改为二苯并呋喃-2-硼酸,其它试剂不变,得到式(13)化合物。
产物MS(m/e):740.1,元素分析(C53H28N2O3):理论值C,85.93%; H,3.81%;N,3.78%;O,6.48%;实测值C,85.92%;H,3.82%;N,3.88%。
合成实施例14
式(14)化合物的合成:合成步骤同式(11)化合物,只是将4-溴芴酮改为3-溴芴酮,4-溴-2,7-二氯菲改为4-溴-9,10-二氯菲,其它试剂不变,得到式(14)化合物。
产物MS(m/e):740.1,元素分析(C53H28N2O3):理论值C,85.93%; H,3.81%;N,3.78%;O,6.48%;实测值C,85.88%;H,3.89%;N,3.81%。
合成实施例15
化合物式(15)的合成:合成步骤同式(11)化合物,只是将4-溴芴酮改为3-溴芴酮,4-溴-2,7-二氯菲改为4-溴-1,8-二氯菲,二苯并呋喃-3-硼酸改为二苯并噻吩-2-硼酸,将2-氯苯并噁唑改为2-氯苯并噻唑,其它试剂不变,得到式(15)化合物。
产物MS(m/e):788.1,元素分析(C53H28N2S3):理论值C,80.68%; H,3.58%;N,3.55%;S,12.19%;实测值C,80.48%;H,3.68%;N,3.57%。
合成实施例16
式(16)化合物的合成:合成步骤同式(11)化合物,只是将4-溴芴酮改为2-溴芴酮,4-溴-2,7-二氯菲改为4-溴-1,8-二氯菲,二苯并呋喃-3-硼酸改为二苯并噻吩-4-硼酸,将2-氯苯并噁唑改为2-氯苯并噻唑,其它试剂不变,得到式(16)化合物。
产物MS(m/e):788.1,元素分析(C53H28N2S3):理论值C,80.68%; H,3.58%;N,3.55%;S,12.19%;实测值C,80.48%;H,3.48%;N,3.51%。
合成实施例17
式(17)化合物的合成:合成步骤同式(5)化合物,只是将4-溴-9- 氯菲改为4-溴-1,8-二氯菲,(9,9-二甲基-10-苯基-9,10-二氢吖啶-2-基)硼酸改为异10H-吩噁嗪,异喹啉-1-硼酸改为5H-5-氧-苯并磷氧吲哚,其它试剂不变,得到式(17)化合物。
产物MS(m/e):917.3,元素分析(C63H37NO3P2):理论值C,82.43%; H,4.06%;N,1.53%;O,5.23%;P,6.75%;实测值C,82.73%;H,4.03%;N, 1.63%。
合成实施例18
式(18)化合物的合成:合成步骤同式(17)化合物,只是将5H-5- 氧-苯并磷氧吲哚改为二苯基氧磷,其它试剂不变,得到式(18)化合物。
产物MS(m/e):919.1,元素分析(C63H39NO3P2):理论值C,82.25%; H,4.27%;N,1.52%;O,5.22%;P,6.73%;实测值C,83.45%;H,4.17%;N, 1.57%。
合成实施例19
式(19)化合物的合成:合成步骤同式(5)化合物,只是将4-溴-9- 氯菲改为4-溴-1-氯菲,2-溴芴酮改为3-溴芴酮,(9,9-二甲基-10-苯基-9,10- 二氢吖啶-2-基)硼酸改为异10H-吩噻嗪,异喹啉-1-硼酸改为5-硼酸-1,10- 菲罗啉,其它试剂不变,得到式(19)化合物。
产物MS(m/e):715.1,元素分析(C51H29N3S):理论值C,85.57%; H,4.08%;N,5.87%;S,4.48%;实测值C,85.77%;H,4.09%;N,5.81%。
合成实施例20
式(20)化合物的合成:合成步骤同式(5)化合物,只是将4-溴-9- 氯菲改变为4-溴-1,8-二氯菲,2-溴芴酮改为3-溴芴酮,(9,9-二甲基-10-苯基-9,10-二氢吖啶-2-基)硼酸改为异10H-吩噻嗪,异喹啉-1-硼酸改为[4-(吡啶-4-基)苯基]硼酸,其它试剂不变,得到式(20)化合物。
产物MS(m/e):843.6,元素分析(C61H37N3S):理论值C,86.80%; H,4.42%;N,4.98%;S,3.80%;实测值C,86.60%;H,4.78%;N,4.93%。
合成实施例21
式(21)化合物的合成:合成步骤同式(5)化合物,只是将2-溴芴酮改为3-溴芴酮,(9,9-二甲基-10-苯基-9,10-二氢吖啶-2-基)硼酸改为9,9- 二甲基-N-苯基-9H-芴-2-胺,异喹啉-1-硼酸改为5-苯基-2-硼酸吡啶,其它试剂不变,得到式(21)化合物。
产物MS(m/e):776.1,元素分析(C59H40N2):理论值C,91.21%;H, 5.19%;N,3.6%;实测值C,91.61%;H,5.12%;N,3.91%。1H NMR(400MHz, CDCl3)δ8.94(d,1H),8.33(d,2H),8.22(d,1H),8.07(d,1H),7.80-8.01(m, 10H),7.62(s,3H),7.49-7.56(m,8H),7.34(d,3H),7.23(t,3H),7.08(q,2H),7.00 (d,1H),1.89(s,6H)。
合成实施例22
式(22)化合物的合成:合成步骤同式(5)化合物,只是将4-溴-9- 氯菲改变为4-溴-9,10-二氯菲,2-溴芴酮改为3-溴芴酮,(9,9-二甲基-10-苯基-9,10-二氢吖啶-2-基)硼酸改为10H-吩噻嗪,异喹啉-1-硼酸改为吡啶-4- 硼酸,其它试剂不变,得到式(22)化合物。
产物MS(m/e):691.3,元素分析(C49H29N3S):理论值C,85.07%; H,4.23%;N,6.07%;S,4.63%;实测值C,85.67%;H,4.23%;N,6.08%。1H NMR(400MHz,CDCl3)δ8.71(d,3H),8.01-8.07(m,5H),7.83-7.90(m,5H), 7.62-7.68(m,5H),7.53(t,1H),7.34(d,1H),7.16-7.24(m,7H),6.93-7.03(m,2H)。
合成实施例23
式(23)化合物的合成:合成步骤同式(11)化合物,只是将4-溴芴酮改为3-溴芴酮,4-溴-2,7-二氯菲改为4-溴-9-氯菲,二苯并呋喃-3-硼酸改为5-苯基-5,11-二氢吲哚并咔唑,2-氯苯并噁唑改为苯酰氯,其它试剂不变,得到式(23)化合物。
产物MS(m/e):774.2,元素分析(C58H34N2O):理论值C,89.90%; H,4.42%;N,3.62%;O,2.06%;实测值C,89.80%;H,4.46%;N,3.42%。
合成实施例24
式(24)化合物的合成:合成步骤同式(11)化合物,只是将4-溴芴酮改为3,6-二溴芴酮,4-溴-2,7-二氯菲改为4-溴-9-氯菲,二苯并呋喃-3-硼酸改为10H-吩噁嗪,2-氯苯并噁唑改为苯酰氯,其它试剂不变,得到式(24) 化合物。
产物MS(m/e):806.4,元素分析(C58H34N2O3):理论值C,86.33%; H,4.25%;N,3.47%;O,5.95%;实测值C,86.23%;H,4.23%;N,3.44%。
合成实施例25
式(25)化合物的合成:合成步骤同式(11)化合物,只是将4-溴芴酮改为3-溴芴酮,4-溴-2,7-二氯菲改为4-溴-9-氯菲,二苯并呋喃-3-硼酸改为2-苯基-9H-咔唑,2-氯苯并噁唑改为2-氯苯并噻吩-5,5-二氧基,其它试剂不变,得到式(25)化合物。
产物MS(m/e):795.2,元素分析(C57H33NO2S):理论值C,86.01%; H,4.18%;N,1.76%;O,4.02%;S,4.03%;实测值C,86.31%;H,4.28%;N, 1.77%。
合成实施例26
式(26)化合物的合成:合成步骤同式(25)化合物,只是将2-苯基 -9H-咔唑改为7H-二苯并[c,g]咔唑,其它试剂不变,得到式(26)化合物。
产物MS(m/e):819.3,元素分析(C59H33NO2S):理论值C,86.42%; H,4.06%;N,1.71%;O,3.90%;S,3.91%;实测值C,86.41%;H,4.16%;N, 1.73%。
合成实施例27
式(27)化合物的合成:合成步骤同式(25)化合物,只是将2-苯基 -9H-咔唑改为7H-苯并[c]咔唑,2-氯苯并噻吩-5,5-二氧基改为1-氯-4-(苯磺酰基)苯,其它试剂不变,得到式(27)化合物。
产物MS(m/e):771.1,元素分析(C55H33NO2S):理论值C,85.58%; H,4.31%;N,1.81%;O,4.15%;S,4.15%;实测值C,85.55%;H,4.32%;N, 1.81%。
合成实施例28
式(28)化合物的合成:合成步骤同式(27)化合物,只是将7H-苯并[c]咔唑改为5-苯基-5,11-二氢吲哚并咔唑,其它试剂不变,得到式(28) 化合物。
产物MS(m/e):886.2,元素分析(C63H38N2O2S):理论值C,85.30%; H,4.32%;N,3.16%;O,3.61%;S,3.61%;实测值C,85.32%;H,4.34%;N, 3.16%。
合成实施例29
式(29)化合物的合成:
中间体10的合成:合成步骤同中间体7,只是将4-溴-2,7-二氯菲改为 4-溴-9-氯菲,4-溴芴酮改为2-溴芴酮,二苯并呋喃-3-硼酸改为9,9-二甲基 -N-苯基-9H-芴-2-胺,其它试剂不变,得到中间体10。
式(29)化合物的合成:氮气保护下,将锌粉和THF混合,加入2 滴1,2-二溴乙烷,引发后,开始滴加溶有2,2'-(丙烷-2,2-二基)双(溴苯) 的THF的溶液,油浴加热维持回流状态,滴加完后回流反应2小时,用冰浴降温至0度。将上面得到的中间体10溶于100mlTHF,滴加到此溶液中,反应3小时后,抽滤,滤饼用THF淋洗,滤液旋干,柱层析(洗脱液:二氯甲烷:石油醚=6:1),得到式(29)化合物。
产物MS(m/e):827.4,元素分析(C63H46BN):理论值C,91.40%; H,5.60%;B,1.31%;N,1.69%;实测值C,91.44%;H,5.62%;N,1.69%。1H NMR(400MHz,CDCl3)δ8.03(q,4H),7.90(d,2H),7.86(d,2H),7.80(d, 1H),7.74(d,2H),7.38-7.31(m,3H),7.28-7.22(m,11H),7.08(d,2H).7.00(t,1H), 1.69(s,12H)。
合成实施例30
式(30)化合物的合成:合成步骤同式(29)化合物,只是将9,9-二甲基-N-苯基-9H-芴-2-胺改为[4-(10H-吩噁嗪-10-)苯基]硼酸,其它试剂不变,得到式(30)化合物。
产物MS(m/e):801.6,元素分析(C60H40BNO):理论值C,89.88%; H,5.03%;B,1.35%;N,1.75%;O,2.00%;实测值C,89.48%;H,5.02%N, 1.71%。
合成实施例31
式(31)化合物的合成:合成步骤同式(29)化合物,只是将4-溴芴酮改为3-溴芴酮,9,9-二甲基-N-苯基-9H-芴-2-胺改为[4-(10H-吩噻嗪-10-) 苯基]硼酸,2,2'-(丙烷-2,2-二基)双(溴苯)改为2,2'-氧二溴苯,其它试剂不变,得到式(31)化合物。
产物MS(m/e):791.2,元素分析(C57H34BNOS):理论值C,86.47%; H,4.33%;B,1.37%;N,1.77%;O,2.02%;S,4.05%;实测值C,86.53%;H, 4.31%;N,1.78%。1H NMR(400MHz,CDCl3)δ8.38(d,1H),8.09(d,1H), 8.01(d,1H),7.89(t,3H),7.80(d,1H),7.55-7.71(m,9H),7.16-7.37(m, 12H),6.92-7.09(m,6H)。
合成实施例32
式(32)化合物的合成:合成步骤同化合物式(31),只是将[4-(10H- 吩噻嗪-10-)苯基]硼酸改为[4-(9,9-二甲基吖啶-10-)苯基]硼酸,其它试剂不变,得到式(32)化合物。
产物MS(m/e):801.4,元素分析(C60H40BNO):理论值C,89.88%; H,5.13%;B,1.36%;N,1.73%;O,2.01%;实测值C,89.84%;H,5.13%;N, 1.71%。
合成实施例33
式(33)化合物的合成:合成步骤同式(30)化合物,只是将2-溴芴酮改为2,7-二溴芴酮,9,9-二甲基-N-苯基-9H-芴-2-胺改为二苯胺,其它试剂不变,得到式(33)化合物。
产物MS(m/e):878.2,元素分析(C66H47BN2):理论值C,90.19%; H,5.39%;B,1.23%;N,3.19%;实测值C,90.69%;H,5.31%;N,3.21%。
合成实施例34
式(34)化合物的合成:合成步骤同式(33)化合物,只是将二苯胺改为咔唑,其它试剂不变,得到式(34)化合物。
产物MS(m/e):874.1,元素分析(C66H43BN2):理论值C,90.61%; H,4.95%;B,1.24%;N,3.20%;实测值C,90.41%;H,4.92%;N,3.22%。
合成实施例35
式(35)化合物的合成:合成步骤同式(33)化合物,只是将2,7-二溴芴酮改为3,6-二溴芴酮,2,2'-(丙烷-2,2-二基)双(溴苯)改为二(2,4,6- 三甲基苯基)溴化硼,其它试剂不变,得到式(35)化合物。
产物MS(m/e):922.2,元素分析(C69H55BN2):理论值C,89.79%; H,6.01%;B,1.17%;N,3.04%;实测值C,89.71%;H,6.11%;N,3.03%。
合成实施例36
式(36)化合物的合成:合成步骤同式(35)化合物,只是将二苯胺换为咔唑,二(2,4,6-三甲基苯基)溴化硼改为2,2'-氧二溴苯,其它试剂不变,得到式(36)化合物。
产物MS(m/e):848.2,元素分析(C63H37BN2O):理论值C,89.15%; H,4.39%;B,1.27%;N,3.30%;O,1.88%;实测值C,89.35%;H,4.31%;N, 3.20%。
合成实施例37
式(37)化合物的合成:合成步骤同式(23)化合物,只是将苯酰氯改为2-氯-4,6-二苯基嘧啶,其它试剂不变,得到式(37)化合物。
产物MS(m/e):900.2,元素分析(C67H40N4):理论值C,89.31%;H, 4.47%;N,6.22%;实测值C,89.33%;H,4.41%;N,6.25%。1H NMR(400 MHz,CDCl3)δ8.57(m,3H),8.48(d,1H),8.19-8.23(m,2H),8.07-7.90(m, 8H),7.80(t,1H),7.70-7.11(m,24H),6.33(d,1H)。
合成实施例38
式(38)化合物的合成:合成步骤同式(37)化合物,只是将2-氯-4,6- 二苯基嘧啶改为2-氯-4,6-二苯基-1,3,5-三嗪,5-苯基-5,11-二氢吲哚并咔唑改为9,9-二甲基-9,10-二氢吖啶,其它试剂不变,得到式(38)化合物。
产物MS(m/e):778.2,元素分析(C57H38N4):理论值C,87.89%;H, 4.92%;N,7.19%;实测值C,87.29%;H,4.92%;N,7.11%。1H NMR(400 MHz,CDCl3)δ8.36(m,4H),8.07(d,1H),7.97(d,1H),7.90(d,1H),7.71-7.80 (m,6H),7.62(m,3H),7.50-7.47(m,6H),7.34-7.17(m,8H).6.90-6.98(m,2H)。
合成实施例39
式(39)化合物的合成:合成步骤同式(37)化合物,只是将3-溴芴酮改为3,6-二溴芴酮,5-苯基-5,11-二氢吲哚并咔唑改为二苯胺,其它试剂不变,得到式(39)化合物。
产物MS(m/e):904.2,元素分析(C67H44N4):理论值C,88.91%;H, 4.90%;N,6.19%;实测值C,88.21%;H,4.91%;N,6.29%。
合成实施例40
式(40)化合物的合成:合成步骤同式(39)化合物,只是将二苯胺改为10H-吩噁嗪,其它试剂不变,得到式(40)化合物。
产物MS(m/e):932.4,元素分析(C67H40N4O2):理论值C,86.24%; H,4.32%;N,6.00%;O,3.43%;实测值C,86.64%;H,4.36%;N,6.03%。
合成实施例41
式(41)化合物的合成:合成步骤同式(39)化合物,只是将3-溴芴酮改为2,7-二溴芴酮,5-苯基-5,11-二氢吲哚并咔唑改为二苯并呋喃-2-硼酸,其它试剂不变,得到式(41)化合物。
产物MS(m/e):903.2,元素分析(C66H37N3O2):理论值C,87.69%; H,4.13%;N,4.65%;O,3.54%;实测值C,87.29%;H,4.15%;N,4.62%。
合成实施例42
式(42)化合物的合成:合成步骤同式(41)化合物,只是将二苯并呋喃-2-硼酸改为二苯并噻吩-2-硼酸,其它试剂不变,得到式(42)化合物。
产物MS(m/e):935.2,元素分析(C66H37N3S2):理论值C,84.68%; H,3.98%;N,4.49%;S,6.85%;实测值C,84.28%;H,3.91%;N,4.43%。
合成实施例43
式(43)化合物的合成:合成步骤同式(5)化合物,只是将2-溴芴酮改为2,7-二溴芴酮,异喹啉-1-硼酸改为[4-(4,6-二苯基嘧啶-2-)苯基]硼酸, (9,9-二甲基-10-苯基-9,10-二氢吖啶-2-基)硼酸改为二苯胺,其它试剂不变,得到式(43)化合物。
产物MS(m/e):980.1,元素分析(C73H48N4):理论值C,89.36%;H, 4.93%;N,5.71%;实测值C,89.16%;H,4.94%;N,5.71%。
合成实施例44
式(44)化合物的合成:合成步骤同式(43)化合物,只是将二苯胺改为咔唑,其它试剂不变,得到式(44)化合物。
产物MS(m/e):976.5,元素分析(C73H44N4):理论值C,89.73%;H, 4.54%;N,5.73%;实测值C,89.23%;H,4.57%;N,5.73%。
合成实施例45
式(45)化合物的合成:合成步骤同式(44)化合物,只是将4-溴-9- 氯菲改为4-溴-2,7-二氯菲,2,7-二溴芴酮改为3,6-二溴芴酮,(4-(4,6-二苯基嘧啶-2-)苯基)硼酸改为五氟苯硼酸,其它试剂不变,得到式(45)化合物。
产物MS(m/e):1002.2,元素分析(C63H28F10N2):理论值C,75.45%; H,2.81%;N,2.79%;实测值C,75.42%;H,2.85%;N,2.71%。
合成实施例46
式(46)化合物的合成:合成步骤同式(45)化合物,只是将4-溴-2,7- 二氯菲改为4-溴-1,8-二氯菲,咔唑改为二苯胺,其它试剂不变,得到式(46) 化合物。
产物MS(m/e):1006.2,元素分析(C63H32F10N2):理论值C,75.15%; H,3.20%;F,18.87%;N,2.78%;实测值C,75.45%;H,3.21%;N,2.76%。
合成实施例47
式(47)化合物的合成:合成步骤同式(45)化合物,只是将4-溴-2,7- 二氯菲改为4-溴-9,10二氯菲,咔唑改为10H-吩噁嗪,其它试剂不变,得到式(47)化合物。
产物MS(m/e):1034.1,元素分析(C63H28F10N2O2):理论值C, 73.12%;H,2.73%;F,18.36%;N,2.71%;O,3.09%;实测值C,73.15%;H, 2.71%;N,2.76%。
合成的化合物的量化计算
本发明上述制备方法得到的螺芴环化合物式(1)~式(47)的能量结构可通过量子化学计算得到,采用高斯09软件为平台,以密度泛函理论方法(DFT)作为计算方法,以6-31g(d)为基组,对设计化合物进行了量化理论计算。通过对设计化合物几何构型的优化计算,得到化合物的空间构型,相应的分子轨道能级(HOMO能级、LUMO能级和Eg能级)分布及数据;进而以TD-DFT对化合物的激发态能级的计算,得到化合物的激发态能级(T1,S1);并从中筛选出具有较小ΔE(S1-T1)的延迟荧光材料。量化计算结果见表2。
表2部分化合物的量化计算结果
同时,作为示意性的实施例,图1-4将本发明的式(1)和式(38)的螺芴环化合物的HOMO轨道分布图和LUMO轨道分布图分别示出。
本发明还公开了一种如上所述螺芴环化合物在制备有机电致发光器件中的用途。
本发明还公开了一种热激活延迟荧光材料,该热激活延迟荧光材料的主要成分为如上所述的螺芴环化合物。
本发明还公开了一种有机电致发光器件,该器件包括第一电极、第二电极和插入在所述第一电极和第二电极之间的若干有机层,其中,该若干有机层中的至少一层中含有如上所述的螺芴环化合物。
下面通过将该化合物具体应用到有机电致发光器件中测试实际使用性能来展示和验证本发明的技术效果和优点。
为了方便比较这些发光材料的器件应用性能,本发明设计了一简单电发光器件,使用5CzBN(合成方法参考文献Mater.Horiz.,2016,3,145-151) 作为发光材料,本发明采用式(1)~式(47)作为主体材料,使用CBP (目前商业常用的主体材料)以及mCBP(文献报道与5CzBN搭配的主体材料)作为比较材料。下文 示出了OLED器件中各功能层所使用材料的结构式:
基片可以使用传统有机发光器件中的基板,例如玻璃或塑料。在本发明的有机电致发光器件制作中选用玻璃基板,ITO作阳极材料。
空穴传输层可以采用各种三芳胺类材料。在本发明的有机电致发光器件制作中所选用的空穴传输材料是NPB。
电子传输层可以采用各种电子传输材料。在本发明的有机电致发光器件制作中所选用的电子传输材料是Bphen。
阴极可以采用金属及其混合物结构,如Mg:Ag、Ca:Ag等,也可以是电子注入层/金属层结构,如LiF/Al、Li2O/Al等常见阴极结构。在本发明的有机电致发光器件制作中所选用的阴极材料是LiF/Al。
本发明中的化合物作为有机电致发光器件发光层中的主体材料, 5CzBN作为发光材料,共制备了多个有机电致发光器件,OLEDs真空蒸镀而成,其结构如下:ITO(50nm)/2-TNATA(60nm)NPB(20nm) /GH:5CzBN(5wt%)(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)。其中,GH(Green Host)为绿光主体材料。
上述有机电致发光器件各层中未注明来源的材料均是通过市售或本领域公知的制备方法自行制备得到的。
器件对比实施例1
本实施例中有机电致发光器件制备过程如下:
将涂布了ITO(50nm)透明导电层的玻璃板在商用清洗剂中超声处理,在去离子水中冲洗,在丙酮∶乙醇混合溶剂(体积比1∶1)中超声除油,在洁净环境下烘烤至完全除去水份,用紫外光和臭氧清洗,并用低能阳离子束轰击表面。
把上述带有阳极的玻璃基片置于真空腔内,抽真空至1×10-5~9× 10-3Pa,在上述阳极层膜上真空蒸镀2-TNATA(4,4',4"-三[N,N-(2-萘基)-苯基氨基]三苯胺),形成厚度为60nm的空穴注入层;在空穴注入层之上真空蒸镀化合物NPB,形成厚度为20nm的空穴传输层,蒸镀速率为0.1nm/s。
在上述空穴传输层上形成电致发光层,具体操作为:将作为发光层主体的化合物CBP放置在真空气相沉积设备的小室中,将作为掺杂剂的化合物5CzBN放置在真空气相沉积设备的另一室中,以不同的速率同时蒸发两种材料,化合物5CzBN的浓度为5wt%,蒸镀总膜厚为30nm。
在发光层之上真空蒸镀Bphen形成厚膜为20nm的电子传输层,其蒸镀速率为0.1nm/s。
在电子传输层上真空蒸镀0.5nm的LiF作为电子注入层和厚度为 150nm的Al层作为器件的阴极。
器件对比实施例2及器件实施例1~22
器件对比实施例2及器件实施例1~22采用和器件对比实施例1相同的制作方法,区别仅在于,将主体材料CBP分别置换为等当量的mCBP、式(1)、式(2)、式(6)、式(7)、式(9)、式(11)、式(14)、式(15)、式(17)、式(19)、式(20)、式(23)、式(26)、式(28)、式(29)、式(33)、式(35)、式(38)、式(39)、式(41)、式(44)或式(47)。
在相同亮度1000cd/m2下,测定有机电致发光器件的器件对比实施例 1、2及器件实施例1~22中制备得到的有机电致发光器件的驱动电压和电流效率,结果见表3。
表3有机电致发光器件性能
以上结果表明,本发明的新型有机材料用于有机电致发光器件,可以有效的降低器件工作电压,提高电流效率,是性能良好的有机发光材料。 TADF材料作荧光主体时,主体T1可以上转换回到其S1,进而通过能量传递( energy transfer,FET)给客体发光,提高荧光器件激子利用率。制备的荧光器件在要求亮度下(1000cd/m2),电流效率最大可达到12.6cd/A,电压可到4.7V,相比商业材料和文献报道所采用材料下降了1.7~2.2V,比较不同主体的器件发现,高的器件性能需要T1高效的上转换效率。
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (4)
1.一种热激活延迟荧光材料,其特征在于,主要成分为结构如式(Ⅰ)所示的化合物:
其中,D1~D6独立地为氢或供电子基团,且不能同时为氢;所述供电子基团独立地选自二苯胺基、吩噁嗪基、吩噻嗪基、1-苯基吩噻嗪基、1-苯基-9,9-二甲基吖啶基、N-苯基咔唑基、二苯并呋喃基、二苯并噻吩基、N,N-二苯基苯胺基、N-(9,9-二甲基-9H-芴-2-基)-N-苯基氨基、3-苯基咔唑基、苯并噻吩基、苯并咔唑基、二苯并咔唑基、9-苯基咔唑、9,9-二甲基吖啶基、9-苯基吩噁嗪基、N-苯基吩噁嗪基、N-苯基吩噻嗪基、N-苯基-9,9-二甲基吖啶基或咔唑基;
A1~A6独立地为氢或吸电子基团,且不能同时为氢;所述吸电子基团独立地选自氰基、苯并喹喔啉基、喹唑啉基、喹喔啉基、喹啉基、1-苯基-苯并咪唑基、苯并噁唑基、苯并噻唑基、二苯磷酰基、4-吡啶苯基、2-苯基吡啶基、吡啶基、苯甲酰基、苯磺酰苯基、二苯并噁硼烷基、4,6-二苯基嘧啶基、4,6-二苯基三嗪基、二苯并噻砜基、2,3,4,5,6-五氟苯基或10,10-二甲基二苯并硼烷基。
3.如权利要求1或2所述的热激活延迟荧光材料在制备有机电致发光器件中的用途。
4.一种有机电致发光器件,该器件包括第一电极、第二电极和插入在所述第一电极和第二电极之间的若干有机层,其特征在于,所述若干有机层中含有如权利要求1或2所述的热激活延迟荧光材料。
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