CN114685351B - OLED main body material based on triptycene framework and preparation method and application thereof - Google Patents
OLED main body material based on triptycene framework and preparation method and application thereof Download PDFInfo
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- CN114685351B CN114685351B CN202210322954.9A CN202210322954A CN114685351B CN 114685351 B CN114685351 B CN 114685351B CN 202210322954 A CN202210322954 A CN 202210322954A CN 114685351 B CN114685351 B CN 114685351B
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 title abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 90
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 58
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 28
- 238000004440 column chromatography Methods 0.000 claims description 26
- -1 dibromo diphenyl sulfone Chemical compound 0.000 claims description 25
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 14
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 238000000859 sublimation Methods 0.000 claims description 6
- 230000008022 sublimation Effects 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- RDOWQLZANAYVLL-UHFFFAOYSA-N phenanthridine Chemical compound C1=CC=C2C3=CC=CC=C3C=NC2=C1 RDOWQLZANAYVLL-UHFFFAOYSA-N 0.000 claims description 4
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 claims description 3
- DLAKCVTXQRIHEY-UHFFFAOYSA-N 1-bromo-3-(4-bromophenyl)benzene Chemical compound C1=CC(Br)=CC=C1C1=CC=CC(Br)=C1 DLAKCVTXQRIHEY-UHFFFAOYSA-N 0.000 claims description 3
- CDBAGRHVFMGOON-UHFFFAOYSA-N 2,4-dibromoquinazoline Chemical compound C1=CC=CC2=NC(Br)=NC(Br)=C21 CDBAGRHVFMGOON-UHFFFAOYSA-N 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- IOAFFMBGDUUARX-UHFFFAOYSA-N 1,2-dibromo-3-(2-phenylphenyl)benzene Chemical group BrC1=CC=CC(C=2C(=CC=CC=2)C=2C=CC=CC=2)=C1Br IOAFFMBGDUUARX-UHFFFAOYSA-N 0.000 claims description 2
- QGZAUMUFTXCDBD-UHFFFAOYSA-N 1,2-dibromonaphthalene Chemical compound C1=CC=CC2=C(Br)C(Br)=CC=C21 QGZAUMUFTXCDBD-UHFFFAOYSA-N 0.000 claims description 2
- UGYDNPLIENMVEP-UHFFFAOYSA-N 1,2-dibromophenanthridine Chemical compound C1=CC=C2C3=C(Br)C(Br)=CC=C3N=CC2=C1 UGYDNPLIENMVEP-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- JXDSEHLVLUASEI-UHFFFAOYSA-N 1,3-dibromoisoquinoline Chemical compound C1=CC=C2C(Br)=NC(Br)=CC2=C1 JXDSEHLVLUASEI-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 claims description 2
- HQJQYILBCQPYBI-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 claims description 2
- QWHWUPMHZINGAU-UHFFFAOYSA-N 2,3-dichloro-1,8-naphthyridine Chemical compound ClC=1C(=NC2=NC=CC=C2C1)Cl QWHWUPMHZINGAU-UHFFFAOYSA-N 0.000 claims description 2
- OGVLEPMNNPZAPS-UHFFFAOYSA-N 2,3-difluoropyridine Chemical compound FC1=CC=CN=C1F OGVLEPMNNPZAPS-UHFFFAOYSA-N 0.000 claims description 2
- AOEHEEBFRCAFGC-UHFFFAOYSA-N 2,4-dibromopyrimidine Chemical compound BrC1=CC=NC(Br)=N1 AOEHEEBFRCAFGC-UHFFFAOYSA-N 0.000 claims description 2
- PODXMJZWPPXECD-UHFFFAOYSA-N 6,11-dibromophenanthro[9,10-b]pyrazine Chemical compound C1=CN=C2C3=CC(Br)=CC=C3C3=CC=C(Br)C=C3C2=N1 PODXMJZWPPXECD-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- KBBSSGXNXGXONI-UHFFFAOYSA-N phenanthro[9,10-b]pyrazine Chemical compound C1=CN=C2C3=CC=CC=C3C3=CC=CC=C3C2=N1 KBBSSGXNXGXONI-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 66
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 54
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 40
- 239000012043 crude product Substances 0.000 description 40
- 239000012074 organic phase Substances 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 20
- 239000003208 petroleum Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 19
- 238000001035 drying Methods 0.000 description 17
- 238000001914 filtration Methods 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 238000012790 confirmation Methods 0.000 description 16
- 238000000605 extraction Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 13
- 239000010408 film Substances 0.000 description 10
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- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- ZABORCXHTNWZRV-UHFFFAOYSA-N 10-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]phenoxazine Chemical compound O1C2=CC=CC=C2N(C2=CC=C(C=C2)C2=NC(=NC(=N2)C2=CC=CC=C2)C2=CC=CC=C2)C2=C1C=CC=C2 ZABORCXHTNWZRV-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- OQHQEAWJHGJETN-UHFFFAOYSA-N ac1mk4x0 Chemical compound C12=CC=CC=C2C2C3=CC=C(N)C=C3C1C1=CC=CC=C12 OQHQEAWJHGJETN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
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- KXAHDPKQOFASEB-UHFFFAOYSA-N 1,4-dibromoisoquinoline Chemical compound C1=CC=C2C(Br)=CN=C(Br)C2=C1 KXAHDPKQOFASEB-UHFFFAOYSA-N 0.000 description 1
- QBELEDRHMPMKHP-UHFFFAOYSA-N 1-bromo-2-chlorobenzene Chemical compound ClC1=CC=CC=C1Br QBELEDRHMPMKHP-UHFFFAOYSA-N 0.000 description 1
- QBNABJXQGRVIRA-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)sulfonylbenzene Chemical compound C1=CC(Br)=CC=C1S(=O)(=O)C1=CC=C(Br)C=C1 QBNABJXQGRVIRA-UHFFFAOYSA-N 0.000 description 1
- XAHITOJPIWZJHD-UHFFFAOYSA-N 2,5-dibromopyrimidine Chemical compound BrC1=CN=C(Br)N=C1 XAHITOJPIWZJHD-UHFFFAOYSA-N 0.000 description 1
- PJZDEYKZSZWFPX-UHFFFAOYSA-N 2,6-dibromonaphthalene Chemical compound C1=C(Br)C=CC2=CC(Br)=CC=C21 PJZDEYKZSZWFPX-UHFFFAOYSA-N 0.000 description 1
- KHTSXPVKNKHVDM-UHFFFAOYSA-N 2,6-dichloro-1,8-naphthyridine Chemical compound N1=C(Cl)C=CC2=CC(Cl)=CN=C21 KHTSXPVKNKHVDM-UHFFFAOYSA-N 0.000 description 1
- MBTGBRYMJKYYOE-UHFFFAOYSA-N 2,6-difluoropyridine Chemical compound FC1=CC=CC(F)=N1 MBTGBRYMJKYYOE-UHFFFAOYSA-N 0.000 description 1
- ODJZWBLNJKNOJK-UHFFFAOYSA-N 2,7-dibromonaphthalene Chemical compound C1=CC(Br)=CC2=CC(Br)=CC=C21 ODJZWBLNJKNOJK-UHFFFAOYSA-N 0.000 description 1
- LTZIIBSPYWTOQV-UHFFFAOYSA-N 2,7-dibromophenanthrene-9,10-dione Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3C(=O)C(=O)C2=C1 LTZIIBSPYWTOQV-UHFFFAOYSA-N 0.000 description 1
- BCTQOZWTYDPEPM-UHFFFAOYSA-N 2,7-dichloro-1,8-naphthyridine Chemical compound C1=CC(Cl)=NC2=NC(Cl)=CC=C21 BCTQOZWTYDPEPM-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- QUYMYFMHZFARQL-UHFFFAOYSA-N 3,8-dibromophenanthridine Chemical compound BrC=1C=CC2=C3C=CC(=CC3=CN=C2C=1)Br QUYMYFMHZFARQL-UHFFFAOYSA-N 0.000 description 1
- AOVCGMIQXVVCPS-UHFFFAOYSA-N BrC1(CC=C(C=C1)C=1C(=CC=CC=1)C1=CC=CC=C1)Br Chemical group BrC1(CC=C(C=C1)C=1C(=CC=CC=1)C1=CC=CC=C1)Br AOVCGMIQXVVCPS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
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Abstract
The invention discloses an OLED (organic light emitting diode) main body material based on a triptycene framework as well as a preparation method and application thereof, and belongs to the field of organic electroluminescent materials and devices. The structure of the compound of the invention is shown as formula 1
Description
Technical Field
The invention relates to the field of organic electroluminescent materials and devices, in particular to an OLED (organic light emitting diode) main body material based on a triptycene framework as well as a preparation method and application thereof.
Background
Organic Light Emitting Diodes (OLEDs), as a new generation display technology, have the advantages of low cost, low power consumption, flexibility, rich colors, wide viewing angles, etc., as compared to conventional displays, and are increasingly used in the fields of solid state lighting, flat panel display, etc. With the development of research, the light emitting materials have been also expanded to the third generation, the first generation OLED material is a conventional fluorescent molecule, the second generation is a phosphorescent OLED material, and the third generation Thermal Activated Delayed Fluorescence (TADF) material, wherein the phosphorescent OLED material and the thermal activated delayed fluorescence material can effectively utilize 75% of triplet excitons so as to obtain high External Quantum Efficiency (EQE), but the stability and lifetime of the device limit the practical application thereof. Fluorescence quenching is one of the important factors influencing the performance of the OLED device, and people can uniformly disperse guest molecules in a host material by selecting a proper host material and utilizing host-guest doping to enhance the performance of the OLED device, so that the host material can reduce the concentration fluorescence quenching on one hand, and can transfer the energy of the host material to the guest material through energy transfer on the other hand, thereby improving the performance of the OLED device.
Currently, a large number of new OLED light-emitting layer guest materials have been developed, in contrast to the relatively late research of host materials for OLED devices. The triptycene is a molecule with a non-planar structure, has a larger framework and a larger cavity, is beneficial to uniform dispersion of small molecular materials, and inhibits the aggregation quenching effect of the small molecular materials, thereby improving the efficiency of an OLED device.
Disclosure of Invention
The invention provides an OLED (organic light emitting diode) main body material based on a triptycene framework, and a preparation method and application thereof.
The present invention first provides a compound represented by formula 1:
wherein, in formula 1, ar represents one or more aromatic rings or aromatic condensed rings.
Specifically, ar is selected from any one of the following groups: benzene, biphenyl, terphenyl, naphthalene, pyridine, naphthyridine, phenanthridine, quinoline, isoquinoline, pyrimidine, diphenyl sulfone, dibenzo [ f, h ] quinoxaline and derivatives thereof;
the structure of Ar is as follows:
wherein the connection position of Ar and the formula 1 can be any position in the Ar cyclic structure.
The compound may specifically be any one of the following:
the invention also provides a preparation method of the compound shown in the formula 1, which comprises the following steps:
1) Will be formula A 1 A compound of the formula A 2 Reacting the compound under the catalysis of palladium to obtain a compound shown as a formula B;
2) Reacting the compound shown in the formula B under the catalysis of palladium to obtain a compound shown in a formula C;
3) And (3) reacting the compound shown in the formula C with an aromatic ring or aromatic condensed ring compound to obtain the compound shown in the formula 1.
In the above preparation method, step 1), the reaction is carried out in Pd (OAc) 2 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene (xanthphos) and sodium tert-butoxide;
pd (OAc) 2 And the formula A 1 The mol ratio of the compounds is 0.05-0.2; specifically, the ratio of 0.1;
the 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene and the compound of formula A 1 The mol ratio of the compounds is 0.1-0.4; specifically, the molar ratio can be 0.2;
the sodium tert-butoxide is of the formula A 1 The mol ratio of the compounds is 1-3; specifically, the ratio of 3;
the formula A 1 Compounds and said A 2 The mol ratio of the compounds is 1; specifically 1;
the reaction of step 1) is carried out in a solvent; specifically, the solvent is at least one of toluene, tetrahydrofuran, 1, 4-dioxane, dimethyl sulfoxide and dimethylformamide;
in the step 1), the reaction temperature is 70-120 ℃, and can be 120 ℃; the reaction time is 3-6 hours; specifically, the time can be 4 hours;
in the step 1), after the reaction, the system is cooled to room temperature and is extracted by water and dichloromethane, and an extracted organic phase is dried by anhydrous sodium sulfate, filtered and distilled to remove the organic phase to obtain a crude product.
The step 1) also comprises a step of purifying the crude product; specifically, the purification method adopts at least one of recrystallization, column chromatography and sublimation; more specifically, column chromatography (petroleum ether: dichloromethane volume ratio 4.
In the above preparation method, step 2), the reaction is carried out in Pd (OAc) 2 The tri-tert-butylphosphonium tetrafluoroborate and potassium carbonate;
pd (OAc) 2 The molar ratio of the compound to the compound shown in the formula B is 0.05-0.2; specifically, the ratio of 0.1;
the molar ratio of the tri-tert-butylphosphonium tetrafluoroborate to the compound shown in the formula B is 0.1-0.4; specifically, the ratio of 0.2;
the molar ratio of the potassium carbonate to the compound shown in the formula B is 1-3; specifically, the ratio of 3;
the reaction in step 2) is carried out in a solvent; specifically, the solvent is at least one of toluene, dimethylformamide and dimethylacetamide;
in the step 2), the reaction temperature is 100-140 ℃, and can be 120 ℃; the reaction time is 10 to 16 hours, and specifically can be 12 hours;
in step 2), after the reaction, the system is cooled to room temperature and extracted by water and ethyl acetate, and the extracted organic phase is dried by anhydrous sodium sulfate, filtered and distilled to remove the organic liquid phase to obtain a crude product.
The step 2) also comprises a step of purifying the crude product; specifically, the purification method adopts at least one of recrystallization, column chromatography and sublimation; more specifically, the purification can be performed by column chromatography (petroleum ether: dichloromethane volume ratio 3.
In the preparation method, in the step 3), the reaction temperature is 100-150 ℃, and specifically can be 120 ℃; the reaction time is 12 to 48 hours, specifically 24 hours;
the aromatic ring or aromatic condensed ring compound is dibromo biphenyl, m-dibromo benzene, dibromo terphenyl, 1-bromo-3- (4-bromophenyl) benzene, dibromo naphthalene, dibromo isoquinoline, 6, 11-dibromo dibenzo [ f, h ] quinoxaline, dibromo pyrimidine, dibromo phenanthridine, dibromo diphenyl sulfone, difluoropyridine, dibromo quinazoline or dichloro-1, 8-naphthyridine;
the molar ratio of the compound represented by the formula C to the aromatic ring or aromatic fused ring compound is 2.5-4; specifically, the ratio can be 3;
in the step 3), the reaction is carried out under any one of the following conditions a) to c):
a) In sodium tert-butoxide, pd (OAc) 2 And tri-tert-butylphosphonium tetrafluoroborate;
specifically, the molar ratio of the compound shown in the formula C to sodium tert-butoxide is 1-3; specifically, the ratio of 1;
the compound of formula C is reacted with Pd (OAc) 2 The molar ratio of (A) to (B) may be 1; specifically, 1;
the molar ratio of the compound shown in the formula C to the tri-tert-butylphosphonium tetrafluoroborate can be 1; specifically, 1;
b) In the presence of potassium carbonate, copper and 18-crown-6;
specifically, the molar ratio of the compound shown in the formula C to potassium carbonate is 1-3; specifically 1;
the molar ratio of the compound shown in the formula C to copper can be 1; specifically 1;
the molar ratio of the compound shown in the formula C to the 18-crown-6 can be 1.2-0.8; specifically, 1;
c) In the presence of sodium tert-butoxide;
specifically, the molar ratio of the compound represented by the formula C to sodium tert-butoxide can be 1;
the reaction in step 3) is also carried out in a solvent; specifically, the solvent is at least one of toluene, dimethylformamide and dimethylacetamide;
in the step 3), after the reaction, the system is cooled to room temperature and is extracted by water and ethyl acetate, and the extracted organic phase is dried by anhydrous sodium sulfate, filtered and distilled to remove the organic liquid phase to obtain a crude product.
The step 3) also comprises a step of purifying the crude product; specifically, the purification method adopts at least one of recrystallization, column chromatography and sublimation; specifically, the purification can be performed by column chromatography (petroleum ether: dichloromethane volume ratio 5.
In the above preparation method, the steps 1) to 3) are carried out in an inert atmosphere; specifically, the method is carried out under the protection of nitrogen.
The application of the compound shown in the formula 1 in the preparation of the organic light-emitting diode device also belongs to the protection scope of the invention.
Specifically, the host material of the light-emitting layer of the organic light-emitting diode device comprises the compound.
The invention finally provides an organic light-emitting diode device, wherein the main material of the light-emitting layer of the organic light-emitting diode device comprises the compound.
The organic light-emitting diode device sequentially comprises an anode, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode from bottom to top.
The room temperature in the present invention is well known to those skilled in the art and is generally 15 to 35 ℃.
The invention has the following advantages:
(1) The OLED main body material based on the triptycene framework is simple in synthesis method, high in product yield and capable of being prepared in large scale;
(2) The OLED main body material based on the triptycene framework has a wide application range, and can be suitable for most common yellow light and green light materials;
(3) The organic film formed by the OLED main body material based on the triptycene skeleton has high surface smoothness, oxidation and reduction resistance and high luminous efficiency, and can be used as a luminous layer of an organic light-emitting diode;
(4) The organic light-emitting diode with the organic thin film layer formed by the OLED main body material based on the triptycene skeleton as the light-emitting layer has the advantages of high efficiency, low driving voltage, long service life and low-efficiency roll-off.
Drawings
Fig. 1 is a schematic structural diagram of an organic light emitting diode prepared according to the present invention.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention.
The experimental procedures in the following examples are all conventional ones unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The title reported in 2018 by Timothy m. Swager, stephen l. Buchwald et al for 2-amino-triptycene in the following examples is: the literature synthesis of Molecular Design of Deep Blue Thermally Activated Delayed Fluorescence Materials applied to a biocompatible Triptycene Scaffold and digital Angle tuning, (chem. Mater.2018,30, 1462-1466), and suitable raw Materials for the synthesis steps can be obtained from commercial sources.
The synthetic route is as follows:
the following examples used 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene (xanthphos) and tri-tert-butylphosphonium tetrafluoroborate, respectively, and were purchased from Beijing Yinaoka technologies, inc.: a66803 And A90323.
Example 1 preparation of Compound of formula D
The method comprises the following specific steps:
(1) 5.00g (18.6 mmol) of 2-amino-triptycene, 10.66g (55.69 mmol) of o-bromochlorobenzene, 5.35g (55.69 mmol) of sodium tert-butoxide, 0.417g (1.86 mmol) of palladium acetate, 3.58g (3.72 mmol) of 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene (xanthphos) and 150mL of toluene were successively added to a 500mL two-necked round-bottomed flask under nitrogen protection, and the mixture was refluxed at 120 ℃ for 4 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of dichloromethane into the reaction system for extraction, drying and filtering an extracted organic phase by using anhydrous sodium sulfate, and then distilling to remove the organic phase to obtain a crude product B. The crude product was purified by column chromatography (petroleum ether: dichloromethane to volume ratio 4. The white powder was B, with a yield of 88%.
The structure confirmation data for B are as follows: 1 H NMR(300MHz,Chloroform-d)δ7.37(dt,J＝6.3,2.2Hz,4H),7.30(dd,J＝7.9,1.4Hz,2H),7.23(d,J＝2.2Hz,1H),7.11(ddd,J＝16.9,7.6,1.6Hz,2H),7.04–6.96(m,4H),6.80–6.70(m,2H),5.37(d,J＝11.0Hz,2H).
(2) To a 500mL two-necked round-bottomed flask, under nitrogen protection, were added compound B,5.00g (13.2 mmol), potassium carbonate 5.47g (39.6 mmol), palladium acetate 0.295g (1.32 mmol), tri-t-butylphosphine tetrafluoroborate 0.766g (2.64 mmol), and 150mL of toluene in that order, and the mixture was refluxed at 120 ℃ for 12 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate into the reaction system for extraction, drying and filtering an extracted organic phase by using anhydrous sodium sulfate, and then distilling to remove the organic phase to obtain a crude product C. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 3). The yellow powder was C in 78% yield.
The structure confirmation data for C are as follows: 1 H NMR(300MHz,Chloroform-d)δ8.03(s,1H),7.95(dt,J＝7.8,1.0Hz,1H),7.45–7.38(m,5H),7.33–7.30(m,2H),7.16(ddd,J＝8.1,6.0,2.2Hz,1H),7.03–6.94(m,4H),5.55(s,1H),5.49(s,1H).
(3) To a 500mL two-necked round-bottomed flask, under a nitrogen blanket, were added compound C,1.00g (2.91 mmol), 4-dibromobiphenyl, 0.302g (0.97 mmol), sodium tert-butoxide, 0.839g (8.73 mmol), palladium acetate, 0.065g (0.291 mmol), tri-tert-butylphosphonium tetrafluoroborate, 0.168g (0.582 mmol), and 50mL of toluene in this order, and the mixture was refluxed at 120 ℃ for 24 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate to extract, drying the extracted organic phase by using anhydrous sodium sulfate, filtering, and distilling to remove the organic liquid phase to obtain a crude product D. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 5. The white powder was D, yield 63%.
D the structure confirmation data is as follows, HRMS (MALDI TOF) m/z calcd for C 84 H 72 N 2 O 4 [M+H]+836.3191,found 836.3348.
Example 2 preparation of Compound of formula N
The method comprises the following specific steps:
(1) To a 250mL two-necked round-bottomed flask, under nitrogen protection, were added in this order compound C,0.800g (2.33 mmol), m-dibromobenzene 0.184g (0.776 mmol), potassium carbonate 0.784g (6.99 mmol), copper 0.296g (4.66 mmol), 18-crown-6.123g (0.466 mmol), and 50mL of toluene, and the mixture was refluxed at 120 ℃ for 24 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate into the reaction system for extraction, drying the extracted organic phase by using anhydrous sodium sulfate, filtering, and distilling to remove the organic liquid phase to obtain a crude product N. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 5. The white powder was N, the yield was 58%.
The structure confirmation data for N is as follows: HRMS (MALDI TOF) m/z calcd for C 58 H 36 N 2 [M] + 760.2878,found 760.3673.
Example 3 preparation of Compound of formula E
The method comprises the following specific steps:
(1) To a 500mL two-necked round-bottomed flask, under a nitrogen blanket, were added 1.00g (2.91 mmol), 0.376g (0.97 mmol) of 4, 4-dibromoterphenyl, 0.838g (8.73 mmol) of sodium tert-butoxide, 0.065g (0.291 mmol) of palladium acetate, 0.168g (0.582 mmol) of tri-tert-butylphosphonium tetrafluoroborate, and 50mL of toluene in this order, and the mixture was refluxed at 120 ℃ for 24 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate into the reaction system for extraction, drying the extracted organic phase by using anhydrous sodium sulfate, filtering, and distilling to remove the organic liquid phase to obtain a crude product E. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 5). The white powder was E, yield 61%.
The structure confirmation data for E is as follows: HRMS (APCI) m/z calcd for C 70 H 46 N 2 [M + H] + 914.3361,found 914.3348.
Example 4 preparation of Compound of formula F
The method comprises the following specific steps:
(1) To a 500mL two-necked round-bottomed flask, 1.00g (2.91 mmol), 0.302g (0.97 mmol) of 1-bromo-3- (4-bromophenyl) benzene, 0.838g (8.73 mmol) of sodium t-butoxide, 0.065g (0.291 mmol) of palladium acetate, 0.168g (0.582 mmol) of tri-t-butylphosphonium tetrafluoroborate, and 50mL of toluene were successively added under a nitrogen atmosphere, and the mixture was refluxed at 120 ℃ for 24 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate into the reaction system for extraction, drying and filtering an extracted organic phase by using anhydrous sodium sulfate, and then distilling to remove the organic phase to obtain a crude product F. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 5). The white powder was F, with a yield of 40%.
The structure confirmation data for F is as follows: RMS (APCI) m/z calcd for C 64 H 42 N 2 [M + H] + 838.3348,found 838.3673.
Example 5 preparation of Compound of formula G
The method comprises the following specific steps:
(1) To a 500mL two-necked round-bottomed flask, under nitrogen protection, were added 1.00g (2.91 mmol), 0.277g (0.97 mmol) of 2, 6-dibromonaphthalene, 0.838g (8.73 mmol) of sodium tert-butoxide, 0.065g (0.291 mmol) of palladium acetate, 0.168g (0.582 mmol) of tri-tert-butylphosphonium tetrafluoroborate, and 50mL of toluene in this order, and the mixture was refluxed at 120 ℃ for 24 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate into the reaction system for extraction, drying and filtering an extracted organic phase by using anhydrous sodium sulfate, and then distilling to remove the organic phase to obtain a crude product G. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 5. The white powder was G, in 63% yield.
The structure confirmation data for G is as follows: HRMS (APCI) m/z calcd for C 62 H 40 N 2 [M + H] + 812.3191,found 812.3278.
Example 6 preparation of Compound of formula H
The method comprises the following specific steps:
(1) Under nitrogen protection, to a 500mL two-necked round-bottomed flask, compound C,1.00g (2.91 mmol), 0.278g (0.97 mmol) of 1, 4-dibromoisoquinoline, 0.838g (8.73 mmol) of sodium tert-butoxide, 0.065g (0.291 mmol) of palladium acetate, 0.168g (0.582 mmol) of tri-tert-butylphosphine tetrafluoroborate, and 50mL of toluene were added in this order, and the mixture was refluxed at 120 ℃ for 24 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate into the reaction system for extraction, drying and filtering an extracted organic phase by using anhydrous sodium sulfate, and then distilling to remove the organic phase to obtain a crude product H. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 5. The white powder was H, yield 60%.
The structure confirmation data for H are as follows: HRMS (APCI) m/z calcd for C 61 H 39 N 3 [M + H] + 813.3144,found 813.3278.
Example 7 preparation of a Compound of formula I
The method comprises the following specific steps:
(1) To a 500mL two-necked round-bottomed flask, under nitrogen protection, were added 1.00g (2.91 mmol), 0.193g (0.97 mmol) of 2, 6-dichloro-1, 8-naphthyridine, 0.838g (8.73 mmol) of sodium tert-butoxide, 0.065g (0.291 mmol) of palladium acetate, 0.168g (0.582 mmol) of tri-tert-butylphosphonium tetrafluoroborate, and 50mL of toluene in this order, and the mixture was refluxed at 120 ℃ for 24 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate into the reaction system for extraction, drying and filtering an extracted organic phase by using anhydrous sodium sulfate, and then distilling to remove the organic phase to obtain a crude product I. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 5. The white powder was I, yield 63%.
The structure confirmation data for I are as follows: HRMS (APCI) m/z calcd for C 60 H 38 N 4 [M + H] + 814.3096,found 814.4277.
Example 8 preparation of Compound of formula J
The method comprises the following specific steps:
(1) To a 500mL two-necked round-bottomed flask, under a nitrogen blanket, were added compound C in the order of 1.00g (2.91 mmol), 0.229g (0.97 mmol) of 2, 5-dibromopyrimidine, 0.838g (8.73 mmol) of sodium tert-butoxide, 0.065g (0.291 mmol) of palladium acetate, 0.168g (0.582 mmol) of tri-tert-butylphosphonium tetrafluoroborate, and 50mL of toluene, and the mixture was refluxed at 120 ℃ for 24 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate into the reaction system for extraction, drying the extracted organic phase by using anhydrous sodium sulfate, filtering, and distilling to remove the organic liquid phase to obtain a crude product J. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 5. The white powder was J, yield 63%.
The structure confirmation data for J are as follows: HRMS (APCI) m/z calcd for C 56 H 34 N 4 [M + H] + 764.2940,found 764.3067.
Example 9 preparation of a Compound of formula K
The method comprises the following specific steps:
(1) To a 500mL two-necked round-bottomed flask, under a nitrogen blanket, were added 1.00g (2.91 mmol), 0.326g (0.97 mmol) of 3, 8-dibromophenanthridine, 0.838g (8.73 mmol) of sodium tert-butoxide, 0.065g (0.291 mmol) of palladium acetate, 0.168g (0.582 mmol) of tri-tert-butylphosphonium tetrafluoroborate, and 50mL of toluene in this order, and the mixture was refluxed at 120 ℃ for 24 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate into the reaction system for extraction, drying and filtering an extracted organic phase by using anhydrous sodium sulfate, and then distilling to remove the organic phase to obtain a crude product K. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 5. The white powder was K, yield 63%.
The structure confirmation data for K is as follows: HRMS (APCI) m/z calcd for C 65 H 39 N 3 [M + H] + 861.3144,found 861.3367.
Example 10 preparation of Compound of formula L
The method comprises the following specific steps:
(1) Under the air atmosphere, 0.800g (2.186 mmol) of 2, 7-dibromo-9, 10-phenanthrenequinone, 0.350g (5.733 mmol) of ethylenediamine and 50mL of acetic acid are sequentially added into a 500mL double-neck round-bottom flask, reflux is carried out at 120 ℃ for 10 hours, after a reaction system is cooled to room temperature, a reaction liquid is poured into 200mL of cold water, reduced pressure suction filtration is carried out, and a solid is sequentially washed by water and ethanol, so that 0.690g of white powder is obtained. The white powder was the precursor compound for preparation L in 94% yield.
(2) To a 500mL two-necked round-bottomed flask, 1.00g (2.91 mmol), 0.373g (0.97 mmol) of the precursor compound, 0.838g (8.73 mmol) of sodium tert-butoxide, 0.065g (0.291 mmol) of palladium acetate, 0.168g (0.582 mmol) of tri-tert-butylphosphonium tetrafluoroborate and 50mL of toluene were successively added under nitrogen atmosphere, and the mixture was refluxed at 120 ℃ for 24 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate into the reaction system for extraction, drying the extracted organic phase by using anhydrous sodium sulfate, filtering, and distilling to remove the organic liquid phase to obtain a crude product L. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 5. The white powder was L, yield 63%.
The structure validation data for L is as follows: HRMS (APCI) m/z calcd for C 68 H 42 N 4 [M + H] + 914.3409,found 914.3482.
Example 11 preparation of a Compound of formula M
The method comprises the following specific steps:
(1) To a 500mL two-necked round-bottomed flask, under nitrogen atmosphere, were added 1.00g (2.91 mmol) of Compound C, 0.364g (0.97 mmol) of 4,4' -dibromodiphenylsulfone, 0.838g (8.73 mmol) of sodium t-butoxide, 0.065g (0.291 mmol) of palladium acetate, 0.168g (0.582 mmol) of tri-t-butylphosphonium tetrafluoroborate, and 50mL of toluene in this order, and the mixture was refluxed at 120 ℃ for 24 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate into the reaction system for extraction, drying and filtering an extracted organic phase by using anhydrous sodium sulfate, and then distilling to remove the organic phase to obtain a crude product M. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 5. The white powder was M in 63% yield.
The structure confirmation data for M is as follows: HRMS (APCI) m/z calcd for C 64 H 42 N 2 O 2 S[M + H] + 902.2967,found 902.5376.
Example 12 preparation of Compound of formula O
The method comprises the following specific steps:
(1) To a 250mL two-necked round-bottomed flask, under a nitrogen blanket, were added in this order compound C,0.100g (0.291 mmol), 0.011g (0.0970 mmol) of 2, 6-difluoropyridine, 0.083g (0.873 mmol) of sodium tert-butoxide, and 10mL of toluene, and the mixture was refluxed at 120 ℃ for 24 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate into the reaction system for extraction, drying the extracted organic phase by using anhydrous sodium sulfate, filtering, and distilling to remove the organic liquid phase to obtain a crude product O. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 5. The white powder was O, yield 58%.
The structure confirmation data for O is as follows: HRMS (APCI) m/z calcd for C 57 H 35 N 3 [M + H] + 761.2831,found 761.5486.
Example 13 preparation of a Compound of formula P
The method comprises the following specific steps:
(1) To a 250mL two-necked round-bottomed flask, under nitrogen atmosphere, were added in the order of 0.100g (0.291 mmol), 0.028g (0.0970 mmol) of 2, 4-dibromoquinazoline, 0.083g (0.873 mmol) of sodium t-butoxide, and 10mL of toluene, and the mixture was refluxed at 120 ℃ for 24 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate into the reaction system for extraction, drying the extracted organic phase by using anhydrous sodium sulfate, filtering, and distilling to remove the organic liquid phase to obtain a crude product P. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 5. The white powder was P, yield 58%.
The structure confirmation data for P are as follows: HRMS (APCI) m/z calcd for C 60 H 36 N 4 [M + H] + 812.2940,found 812.4606.
Example 14 preparation of Compound of formula Q
The method comprises the following specific steps:
(1) To a 250mL two-necked round-bottomed flask, 0.100g (0.291 mmol), 0.019g (0.0970 mmol) of 2, 7-dichloro-1, 8-naphthyridine, 0.083g (0.873 mmol) of sodium tert-butoxide, 10mL of toluene were added in this order under nitrogen and refluxed at 120 ℃ for 24 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate into the reaction system for extraction, drying and filtering an extracted organic phase by using anhydrous sodium sulfate, and then distilling to remove the organic phase to obtain a crude product Q. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 5. The white powder was Q, and the yield was 58%.
The structure confirmation data for Q is as follows: HRMS (APCI) m/z calcd for C 60 H 36 N 4 [M + H] + 812.2940,found 812.4606.
Example 15 preparation of a Compound of formula R
The method comprises the following specific steps:
(1) To a 500mL two-necked round-bottomed flask, under nitrogen protection, were added compound C,1.00g (2.91 mmol), 0.276g (0.97 mmol) of 2, 7-dibromonaphthalene, 0.083g (0.873 mmol) of sodium tert-butoxide, 0.033g (0.146 mmol) of palladium acetate, 0.168g (0.582 mmol) of tri-tert-butylphosphonium tetrafluoroborate, and 50mL of toluene in this order, and the mixture was refluxed at 120 ℃ for 24 hours. And after the reaction system is cooled to room temperature, adding 300mL of water and 300mL of ethyl acetate into the reaction system for extraction, drying the extracted organic phase by using anhydrous sodium sulfate, filtering, and distilling to remove the organic liquid phase to obtain a crude product R. The crude product was purified by column chromatography (petroleum ether: dichloromethane volume ratio 5. The white powder was R, yield 63%.
The structure confirmation data for R are as follows: HRMS (APCI) m/z calcd for C 62 H 40 N 2 [M + H] + 812.3191,found 812.3278.
Example 16
The organic light emitting diode device using the triptycene skeleton-based host material D prepared in embodiment 1 of the present invention as a light emitting layer was manufactured and performance evaluated. Fig. 1 is a schematic structural diagram of an organic light emitting diode.
The manufacturing method of the organic light-emitting diode device with the main fluorescent material D based on the triptycene framework as the light-emitting layer comprises the following steps:
1) Pretreatment of the glass substrate: selecting strips with a diameter of 3X 3mm 2 A glass substrate having an Indium Tin Oxide (ITO) film pattern as a transparent electrode; and cleaning the glass substrate with purified water, putting the glass substrate into ethanol for ultrasonic treatment, and treating the glass substrate with a plasma cleaning machine to obtain the pretreated glass substrate.
2) Vacuum evaporation: vacuum deposition of the subsequent layers was performed on the pretreated glass substrate by a vacuum deposition method. First, a glass substrate was placed in a vacuum deposition chamber, and the pressure was reduced to 6X 10 -4 Pa is atThe following steps of (1); then, from the light emitting layer, the organic compound heated by resistance is subjected to vacuum evaporation at a film forming rate of 1 to 1.5nm/s, and a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode are sequentially evaporated. Wherein, the glass substrate with the ITO transparent electrode is used as an anode; NPB with the film thickness of 40nm is used as a hole transport layer; the material with the film thickness of 15nm and based on the triptycene framework is used as a main material and is doped with PXZ-TRZ to be used as a light emitting layer, wherein the doping proportion of the PXZ-TRZ is 5wt%; TPBi with the film thickness of 60nm is used as an electron transport layer; lithium fluoride with the film thickness of 0.8nm is used as an electron injection layer; aluminum having a film thickness of 80nm was provided with a metal mask so as to be orthogonal to the ITO stripes to form cathodes, thereby obtaining organic light-emitting diodes. The film thickness was measured by a stylus-type film thickness measuring instrument.
Among them, each layer of hole transport layer material NPB (N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine), electron transport layer material TPBi (1, 3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene), light emitting layer material PXZ-TRZ (10- (4, 6-diphenyl l-1,3, 5-triazin-2-yl) phenyl) -10H-phenoxazine), electron injection layer material lithium fluoride and cathode material aluminum were purchased from sienbaolite optoelectronics limited.
3) Packaging the device: the prepared organic electroluminescent device was sealed in a nitrogen atmosphere glove box having a water oxygen concentration of 0.1ppm or less, and then the film-forming substrate was covered with a sealing cap made of glass with an epoxy type ultraviolet-curable resin and sealed by curing under self-tapping.
(II) evaluation of Performance of organic light-emitting diode device having triptycene skeleton-based host Material D as light-emitting layer
Applying a direct current to the fabricated organic light emitting diode, and evaluating the light emitting performance using a Spectrascan PR670 luminance meter; the current-voltage characteristics were measured using a computer controlled Keithley 2400 digital source meter. The light emitting properties of the organic light emitting diode were measured under the condition that the applied direct current voltage was varied.
The fabricated organic light emitting diode device had CIE color coordinate values of (0.35, 0.59), external Quantum Efficiency (EQE) of 18.9%, current efficiency of 58.52cd/A, and power efficiency of 52.51lm/W.
An organic light emitting diode device was fabricated by the above method except that the compound prepared in examples 2 to 15 was used instead of the material D. The results obtained are shown in Table 1 below.
Table 1 table of performance data for organic light emitting diode devices prepared from the compounds of examples 1 to 15
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. It will be apparent to those skilled in the art that various other modifications and variations can be made in the above-described embodiments, and it is not intended to be exhaustive or to limit the embodiments to the precise form disclosed. All obvious changes and modifications of the present invention shall fall within the scope of the present invention.
Claims (12)
1. A compound represented by formula 1:
wherein, in the formula 1, ar is selected from any one of the following groups: benzene, biphenyl, terphenyl, naphthalene, pyridine, naphthyridine, phenanthridine, quinoline, isoquinoline, pyrimidine, diphenyl sulfone, dibenzo [ f, h ] quinoxaline.
2. The compound of claim 1, wherein: the compound is any one of the following compounds:
3. a process for the preparation of a compound according to claim 1 or 2, comprising the steps of:
1) Will be formula A 1 A compound of formula A 2 Reacting the compound under the catalysis of palladium to obtain a compound shown as a formula B;
2) Reacting the compound shown in the formula B under the catalysis of palladium to obtain a compound shown in a formula C;
3) Reacting the compound shown in the formula C with an aromatic ring or aromatic condensed ring compound to obtain a compound shown in the formula 1;
the aromatic or aromatic fused ring compound is dibromobiphenyl, m-dibromobenzene, dibromoterphenyl, 1-bromo-3- (4-bromophenyl) benzene, dibromonaphthalene, dibromo isoquinoline, 6, 11-dibromo dibenzo [ f, h ] quinoxaline, dibromo pyrimidine, dibromo phenanthridine, dibromo diphenyl sulfone, difluoropyridine, dibromo quinazoline or dichloro-1, 8-naphthyridine.
4. The production method according to claim 3, characterized in that: in step 1), the reaction is carried out in Pd (OAc) 2 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene (xanthphos) and sodium tert-butoxide;
pd (OAc) 2 And the formula A 1 The mol ratio of the compounds is 0.05-0.2;
the 4, 5-bis (diphenylphosphine)) -9, 9-dimethylxanthene with said formula A 1 The mol ratio of the compounds is 0.1-0.4;
the sodium tert-butoxide is as described for formula A 1 The molar ratio of the compounds is 1-3;
the formula A 1 Compounds and said A 2 The mol ratio of the compounds is 1;
the reaction of step 1) is carried out in a solvent;
in the step 1), the reaction temperature is 70-120 ℃, and the reaction time is 3-6 hours;
the step 1) also comprises a purification step after the reaction.
5. The method of claim 4, wherein: the solvent in the step 1) is at least one of toluene, tetrahydrofuran, 1, 4-dioxane, dimethyl sulfoxide and dimethylformamide;
the purification method in step 1) employs at least one of recrystallization, column chromatography, and sublimation.
6. The production method according to any one of claims 3 to 5, characterized in that: in step 2), the reaction is carried out in Pd (OAc) 2 The tri-tert-butylphosphonium tetrafluoroborate and potassium carbonate;
pd (OAc) 2 The molar ratio of the compound to the compound shown in the formula B is 0.05-0.2;
the molar ratio of the tri-tert-butylphosphonium tetrafluoroborate to the compound shown in the formula B is 0.1-0.4;
the molar ratio of the potassium carbonate to the compound shown in the formula B is 1-3;
the reaction in step 2) is carried out in a solvent;
in the step 2), the reaction temperature is 100-140 ℃, and the reaction time is 10-16 hours;
the step 2) also comprises a purification step after the reaction.
7. The method of claim 6, wherein: the solvent in the step 2) is at least one of toluene, dimethylformamide and dimethylacetamide;
the purification method in the step 2) adopts at least one of recrystallization, column chromatography and sublimation.
8. The production method according to any one of claims 3 to 5, characterized in that: in the step 3), the reaction temperature is 100-150 ℃, and the reaction time is 12-48 hours;
the molar ratio of the compound shown in the formula C to the aromatic ring or aromatic condensed ring compound is 2.5-4;
in the step 3), the reaction is carried out under any one of the following conditions a) to c):
a) In sodium tert-butoxide, pd (OAc) 2 And tri-tert-butylphosphonium tetrafluoroborate;
b) In the presence of potassium carbonate, copper and 18-crown-6;
c) In the presence of sodium tert-butoxide;
the reaction in step 3) is also carried out in a solvent;
the step 3) also comprises a purification step after the reaction.
9. The method of claim 8, wherein: a) Wherein the molar ratio of the compound shown in the formula C to the sodium tert-butoxide is 1-3;
the compound of formula C with Pd (OAc) 2 The molar ratio of (A) to (B) is 1;
the molar ratio of the compound shown in the formula C to the tri-tert-butylphosphonium tetrafluoroborate is 1.1-0.4;
b) Wherein the molar ratio of the compound shown in the formula C to potassium carbonate is 1-3;
the molar ratio of the compound shown in the formula C to copper is 1;
the molar ratio of the compound shown in the formula C to 18-crown-6 is 1.2-0.8;
c) Wherein the molar ratio of the compound shown in the formula C to the sodium tert-butoxide is 1-3;
the solvent in the step 3) is at least one of toluene, dimethylformamide and dimethylacetamide;
the purification method in step 3) employs at least one of recrystallization, column chromatography and sublimation.
10. Use of a compound according to claim 1 or 2 for the preparation of an organic light emitting diode device.
11. Use according to claim 10, characterized in that: a host material of a light-emitting layer of the organic light-emitting diode includes the compound of claim 1 or 2.
12. An organic light emitting diode device, characterized in that: the host material of the light-emitting layer includes the compound of claim 1 or 2.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011207792A (en) * | 2010-03-29 | 2011-10-20 | Fujifilm Corp | Compound comprising triptycene structure |
| JP2012236786A (en) * | 2011-05-11 | 2012-12-06 | Konica Minolta Holdings Inc | Ptycene-based compound, organic electroluminescent element and illuminating system |
| CN103420897A (en) * | 2013-01-09 | 2013-12-04 | 烟台九目化学制品有限公司 | Triptycene derivative and application thereof |
| CN111995562A (en) * | 2020-09-14 | 2020-11-27 | 深圳大学 | Triptycene D-A type thermal activation delayed fluorescent material, electronic device and application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011207792A (en) * | 2010-03-29 | 2011-10-20 | Fujifilm Corp | Compound comprising triptycene structure |
| JP2012236786A (en) * | 2011-05-11 | 2012-12-06 | Konica Minolta Holdings Inc | Ptycene-based compound, organic electroluminescent element and illuminating system |
| CN103420897A (en) * | 2013-01-09 | 2013-12-04 | 烟台九目化学制品有限公司 | Triptycene derivative and application thereof |
| CN111995562A (en) * | 2020-09-14 | 2020-11-27 | 深圳大学 | Triptycene D-A type thermal activation delayed fluorescent material, electronic device and application |
Non-Patent Citations (1)
| Title |
|---|
| 曹菁 等.多蝶烯及其衍生物的合成与应用进展.《化学进展》.2011,第23卷(第11期),第2200-2214页. * |
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