CN117143030A - Naphthyl substituted electricity-absorbing fragment compound, electron transport material and application - Google Patents
Naphthyl substituted electricity-absorbing fragment compound, electron transport material and application Download PDFInfo
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- CN117143030A CN117143030A CN202210549294.8A CN202210549294A CN117143030A CN 117143030 A CN117143030 A CN 117143030A CN 202210549294 A CN202210549294 A CN 202210549294A CN 117143030 A CN117143030 A CN 117143030A
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- 239000000463 material Substances 0.000 title claims abstract description 86
- 150000001875 compounds Chemical class 0.000 title claims abstract description 53
- 125000001624 naphthyl group Chemical group 0.000 title claims description 13
- 239000012634 fragment Substances 0.000 title description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 18
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 17
- 229910052805 deuterium Inorganic materials 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000001072 heteroaryl group Chemical group 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- -1 pyridopyrazinyl Chemical group 0.000 claims description 14
- 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 9
- 239000004305 biphenyl Substances 0.000 claims description 9
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 6
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 6
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- 125000002541 furyl group Chemical group 0.000 claims description 6
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 6
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 claims description 6
- 125000005561 phenanthryl group Chemical group 0.000 claims description 6
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 6
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 6
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 6
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 claims description 6
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 6
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000004306 triazinyl group Chemical group 0.000 claims description 6
- 125000005580 triphenylene group Chemical group 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 abstract description 79
- 238000002347 injection Methods 0.000 abstract description 35
- 239000007924 injection Substances 0.000 abstract description 35
- 230000002349 favourable effect Effects 0.000 abstract description 6
- 238000009825 accumulation Methods 0.000 abstract description 5
- 238000013508 migration Methods 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 194
- 238000006243 chemical reaction Methods 0.000 description 188
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 177
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 129
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 97
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 82
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 82
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 82
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 68
- 239000000243 solution Substances 0.000 description 48
- 239000000843 powder Substances 0.000 description 44
- 238000001953 recrystallisation Methods 0.000 description 44
- 239000007795 chemical reaction product Substances 0.000 description 43
- 229910000027 potassium carbonate Inorganic materials 0.000 description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 235000019270 ammonium chloride Nutrition 0.000 description 34
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 31
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 24
- 238000001704 evaporation Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- 239000000706 filtrate Substances 0.000 description 17
- 230000005525 hole transport Effects 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 239000012074 organic phase Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 239000002019 doping agent Substances 0.000 description 14
- 230000008020 evaporation Effects 0.000 description 14
- 238000010907 mechanical stirring Methods 0.000 description 14
- ZMCWFMOZBTXGKI-UHFFFAOYSA-N tritert-butyl borate Chemical compound CC(C)(C)OB(OC(C)(C)C)OC(C)(C)C ZMCWFMOZBTXGKI-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000000758 substrate Substances 0.000 description 10
- 239000004327 boric acid Substances 0.000 description 9
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- IBGUDZMIAZLJNY-UHFFFAOYSA-N 1,4-dibromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=C(Br)C2=C1 IBGUDZMIAZLJNY-UHFFFAOYSA-N 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- KPTRDYONBVUWPD-UHFFFAOYSA-N naphthalen-2-ylboronic acid Chemical compound C1=CC=CC2=CC(B(O)O)=CC=C21 KPTRDYONBVUWPD-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- AMEVJOWOWQPPJQ-UHFFFAOYSA-N 2,4-dichloro-6-phenyl-1,3,5-triazine Chemical compound ClC1=NC(Cl)=NC(C=2C=CC=CC=2)=N1 AMEVJOWOWQPPJQ-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- RCKMXYKAMYSKPY-UHFFFAOYSA-N 4,6-dichloro-2-phenyl-1h-triazine Chemical compound N1C(Cl)=CC(Cl)=NN1C1=CC=CC=C1 RCKMXYKAMYSKPY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- ABMYEXAYWZJVOV-UHFFFAOYSA-N pyridin-3-ylboronic acid Chemical compound OB(O)C1=CC=CN=C1 ABMYEXAYWZJVOV-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 3
- QBLFZIBJXUQVRF-UHFFFAOYSA-N (4-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Br)C=C1 QBLFZIBJXUQVRF-UHFFFAOYSA-N 0.000 description 2
- DMDPAJOXRYGXCB-UHFFFAOYSA-N (9,9-dimethylfluoren-2-yl)boronic acid Chemical compound C1=C(B(O)O)C=C2C(C)(C)C3=CC=CC=C3C2=C1 DMDPAJOXRYGXCB-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- CXHXFDQEFKFYQJ-UHFFFAOYSA-N 2-bromo-4-chloro-1-iodobenzene Chemical compound ClC1=CC=C(I)C(Br)=C1 CXHXFDQEFKFYQJ-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010549 co-Evaporation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- NHVNWPIMHDTDPP-UHFFFAOYSA-N dibenzothiophen-3-ylboronic acid Chemical compound C1=CC=C2C3=CC=C(B(O)O)C=C3SC2=C1 NHVNWPIMHDTDPP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CJRHLSZJEFJDLA-UHFFFAOYSA-N methyl 5-bromo-2-iodobenzoate Chemical compound COC(=O)C1=CC(Br)=CC=C1I CJRHLSZJEFJDLA-UHFFFAOYSA-N 0.000 description 2
- HUMMCEUVDBVXTQ-UHFFFAOYSA-N naphthalen-1-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=CC2=C1 HUMMCEUVDBVXTQ-UHFFFAOYSA-N 0.000 description 2
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- CAYQIZIAYYNFCS-UHFFFAOYSA-N (4-chlorophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Cl)C=C1 CAYQIZIAYYNFCS-UHFFFAOYSA-N 0.000 description 1
- HIHYAKDOWUFGBK-UHFFFAOYSA-N 1,3-dibromo-5-phenylbenzene Chemical group BrC1=CC(Br)=CC(C=2C=CC=CC=2)=C1 HIHYAKDOWUFGBK-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-GSNKEKJESA-N 1-bromo-2,3,4,5,6,7,8-heptadeuterionaphthalene Chemical compound BrC1=C([2H])C([2H])=C([2H])C2=C([2H])C([2H])=C([2H])C([2H])=C21 DLKQHBOKULLWDQ-GSNKEKJESA-N 0.000 description 1
- CTPUUDQIXKUAMO-UHFFFAOYSA-N 1-bromo-3-iodobenzene Chemical compound BrC1=CC=CC(I)=C1 CTPUUDQIXKUAMO-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-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
- UOXJNGFFPMOZDM-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]ethylsulfanyl-methylphosphinic acid Chemical compound CC(C)N(C(C)C)CCSP(C)(O)=O UOXJNGFFPMOZDM-UHFFFAOYSA-N 0.000 description 1
- QKJAZPHKNWSXDF-UHFFFAOYSA-N 2-bromoquinoline Chemical compound C1=CC=CC2=NC(Br)=CC=C21 QKJAZPHKNWSXDF-UHFFFAOYSA-N 0.000 description 1
- KTTRHLOWOKRRKS-UHFFFAOYSA-N 2-chloro-4-naphthalen-2-yl-6-phenyl-1,3,5-triazine Chemical compound C1(=NC(C2=CC=CC=C2)=NC(=N1)C1=CC=C2C(C=CC=C2)=C1)Cl KTTRHLOWOKRRKS-UHFFFAOYSA-N 0.000 description 1
- KJZQIXWSZPPOHO-UHFFFAOYSA-N 5-phenyltriazine Chemical compound C1=CC=CC=C1C1=CN=NN=C1 KJZQIXWSZPPOHO-UHFFFAOYSA-N 0.000 description 1
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 1
- WDDLHUWVLROJLA-UHFFFAOYSA-N 9,9'-spirobi[fluorene]-2-ylboronic acid Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=C(B(O)O)C=C12 WDDLHUWVLROJLA-UHFFFAOYSA-N 0.000 description 1
- 239000005758 Cyprodinil Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- HAORKNGNJCEJBX-UHFFFAOYSA-N cyprodinil Chemical compound N=1C(C)=CC(C2CC2)=NC=1NC1=CC=CC=C1 HAORKNGNJCEJBX-UHFFFAOYSA-N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005509 dibenzothiophenyl group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process 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
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000005730 thiophenylene group Chemical group 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- 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
- C07D401/02—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 two hetero rings
- C07D401/04—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 two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
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Abstract
The application provides a compound of formula (I), which has high bond energy among atoms, good thermal stability, favorable solid state accumulation among molecules, proper energy level between adjacent layers and favorable injection and migration of excitons. When the organic electroluminescent material is used as an electron transport material, the driving voltage of the organic electroluminescent device can be effectively reduced, the luminous efficiency of the organic electroluminescent device can be improved, and the service life of the organic electroluminescent device can be prolonged. The application also provides an organic electroluminescent device and a display device comprising the compound of formula (I).
Description
Technical Field
The application relates to the technical field of organic light-emitting display, in particular to a naphthyl substituted electricity-absorbing fragment compound, an electron transmission material and application.
Background
Electroluminescence (EL) refers to a phenomenon in which a light emitting material emits light when excited by current and voltage under the action of an electric field, and is a light emitting process in which electric energy is directly converted into light energy. The organic electroluminescent display (OLED) has the advantages of self-luminescence, low voltage DC drive, full solidification, wide viewing angle, light weight, simple composition and process, etc., compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, has large viewing angle and low power, the response speed can reach 1000 times of the liquid crystal display, and the manufacturing cost is lower than that of the liquid crystal display with the same resolution. Therefore, the organic electroluminescent device has very wide application prospect.
With the continuous advancement of OLED technology in the two fields of illumination and display, people pay more attention to the research on efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is usually the result of the optimized collocation of device structures and various organic materials, which provides great opportunities and challenges for chemists to design and develop functional materials with various structures.
Organic electroluminescent materials have many advantages over inorganic luminescent materials, such as: the film can be formed on any substrate by vapor deposition or spin coating, flexible display and large-area display can be realized, and the optical performance, the electrical performance, the stability and the like of the material can be adjusted by changing the molecular structure, so that the material has a large space. In the most common OLED device structures, the following classes of organic materials are typically included: a hole injecting material, a hole transporting material, an electron transporting material, a light emitting material (containing a host material and a guest material), and the like. Currently, an electron transport material is an important functional material, which has a direct effect on the mobility of electrons and ultimately affects the luminous efficiency of an OLED. The problem of low mobility of the current commercial electron transport materials is an important limiting factor in the development of device performance, and the method is worthy of more exploration for developing materials with higher mobility.
Disclosure of Invention
The application aims to provide a compound which can improve the working efficiency and prolong the service life of an organic electroluminescent device when being used as an electron transport material.
In a first aspect the present application provides a compound of formula (I):
wherein,
Ar 1 and Ar is a group 2 Each independently selected from C which is unsubstituted or substituted with Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl groupA base; ar (Ar) 1 And Ar is a group 2 At least one of which has not less than 10C atoms and at least one selected from C which is unsubstituted or substituted with Rc 6 -C 30 An aryl group;
X 1 -X 3 each independently selected from C or N, and at least one selected from N;
R 1 -R 5 each independently selected from hydrogen, deuterium, C unsubstituted or substituted with Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, R 1 -R 5 At least one of the substituents is selected from the group consisting of:
Y 1 -Y 8 each independently selected from CR or N, R is selected from hydrogen, deuterium, C unsubstituted or substituted with Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl;
the heteroatoms on the heteroaryl groups are each independently selected from O, S or N;
the substituents Rc of each group are each independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
The second aspect of the present application provides an electron transport material comprising at least one of the compounds provided in the first aspect of the present application.
The third aspect of the present application provides an organic electroluminescent device comprising at least one of the electron transport materials provided in the second aspect of the present application.
A fourth aspect of the application provides a display device comprising the organic electroluminescent device provided in the third aspect of the application.
The compound provided by the application has a parent structure of a naphthyl substituted electricity-absorbing segment, has high bond energy among atoms, good thermal stability, and is favorable for solid accumulation among molecules, when the compound is used as an electron transport material, the compound has a proper energy level with adjacent layers, is favorable for injection and migration of excitons, can effectively reduce driving voltage, has higher electron migration rate, and can realize good luminous efficiency and service life in an organic electroluminescent device. The compound provided by the application has a larger conjugate plane, is favorable for molecular accumulation, shows good thermodynamic stability, and shows long service life in a device. The organic electroluminescent device provided by the application comprises the compound as an electron transport material, so that the driving voltage can be effectively reduced, the luminous efficiency can be improved, and the service life of the organic electroluminescent device can be prolonged. The display device provided by the application has excellent display effect.
Of course, it is not necessary for any one product or method of practicing the application to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the application or the technical solutions of the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it being obvious that the drawings in the description below are only some embodiments of the application, and that other embodiments may be obtained according to these drawings by a person skilled in the art.
Fig. 1 is a schematic structural view of a typical organic electroluminescent device.
Detailed Description
The following description of the embodiments of the present application will be made more apparent and fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the application are shown. Based on the embodiments of the present application, all other embodiments obtained by the person skilled in the art based on the present application are included in the scope of protection of the present application.
In a first aspect the present application provides a compound of formula (I):
wherein,
Ar 1 and Ar is a group 2 Selected from C unsubstituted or substituted by Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl; ar (Ar) 1 And Ar is a group 2 At least one of which has not less than 10C atoms and Ar 1 And Ar is a group 2 At least one of which is selected from C which is unsubstituted or substituted by Rc 6 -C 30 An aryl group;
X 1 -X 3 each independently selected from C or N, and at least one selected from N;
R 1 -R 5 each independently selected from hydrogen, deuterium, C unsubstituted or substituted with Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, R 1 -R 5 At least one of the substituents is selected from the group consisting of:
Y 1 -Y 8 each independently selected from CR or N, R is selected from hydrogen, deuterium, C unsubstituted or substituted with Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl;
the heteroatoms on the heteroaryl groups are each independently selected from O, S or N;
the substituents Rc of each group are each independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
Preferably, R 1 -R 5 Each independently selected from hydrogen, deuterium, C unsubstituted or substituted with Rc 6 -C 18 Aryl, C unsubstituted or substituted by Rc 3 -C 18 Heteroaryl groups.
Preferably, R is selected from hydrogen, deuterium, C, unsubstituted or substituted by Rc 6 -C 18 Aryl, C unsubstituted or substituted by Rc 3 -C 18 Heteroaryl groups.
More preferably, the R 1 -R 5 Each independently selected from the following groups unsubstituted or substituted with Rc: hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl.
More preferably, the Ar 1 And Ar is a group 2 Each independently selected from the following groups unsubstituted or substituted with Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thiophenylene, benzothiophenyl, dibenzothiophenyl, aza-dibenzothiophenyl, 9-dimethylfluorenyl, spirofluorenyl.
More preferably, R is selected from the following groups, unsubstituted or substituted with Rc: hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl.
For example, the compound of formula (I) may be selected from the compounds shown in A1 to a32 below:
The compound of the formula (I) provided by the application has high bond energy among atoms, good thermal stability and is beneficial to solid accumulation among molecules. In addition, the preparation process of the compound shown in the formula (I) is simple and feasible, raw materials are easy to obtain, and the preparation process is suitable for industrial production.
The second aspect of the present application provides an electron transport material comprising at least one of the compounds provided in the first aspect of the present application.
When the compound provided by the application is applied to an electron transport layer as an electron transport material, the compound has a matched energy level with adjacent layers, is beneficial to electron injection and migration, and can effectively reduce driving voltage. Meanwhile, the organic electroluminescent device has higher electron migration rate, and can realize good luminous efficiency and service life in the organic electroluminescent device. The compound provided by the application also has a larger conjugate plane, is favorable for molecular accumulation, shows good thermodynamic stability, and can prolong the service life of the compound when used in an organic electroluminescent device.
The third aspect of the present application provides an organic electroluminescent device comprising at least one of the electron transport materials provided in the second aspect of the present application. Therefore, the organic electroluminescent device provided by the application has low driving voltage, high luminous efficiency and long service life.
In the present application, the kind and structure of the organic electroluminescent device are not particularly limited, and may be organic electroluminescent devices of different types and structures known in the art, as long as the electron transport material provided by the present application can be used.
The organic electroluminescent device of the present application may be a light emitting device having a top emission structure, and examples thereof include an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a transparent or semitransparent cathode in this order on a substrate.
The organic electroluminescent device of the present application may be a light emitting device having a bottom light emitting structure, and may include a transparent or semitransparent anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode structure in this order on a substrate.
The organic electroluminescent device of the present application may be a light emitting device having a double-sided light emitting structure, and may include a transparent or semitransparent anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a transparent or semitransparent cathode structure in this order on a substrate.
In the organic electroluminescent device of the present application, an electron blocking layer may be provided between the hole transport layer and the light emitting layer, a hole blocking layer may be provided between the light emitting layer and the electron transport layer, and a light extraction layer may be provided on the transparent electrode on the light emitting side. However, the structure of the organic electroluminescent device of the present application is not limited to the above-described specific structure, and each of the above-described layers may be omitted or added if necessary. The thickness of each layer is not particularly limited as long as the object of the present application can be achieved. For example, the organic electroluminescent device may include an anode made of metal, a hole injection layer (5 nm to 20 nm), a hole transport layer (80 nm to 140 nm), an electron blocking layer (5 nm to 20 nm), a light emitting layer (150 nm to 400 nm), a hole blocking layer (5 nm to 20 nm), an electron transport layer (300 nm to 800 nm), an electron injection layer (5 nm to 20 nm), a transparent or semitransparent cathode, and a light extraction layer (50 nm to 90 nm) in this order on a substrate.
Fig. 1 shows a schematic view of a typical organic electroluminescent device, in which a substrate 1, a reflective anode electrode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode electrode 8 are disposed in this order from bottom to top.
It will be appreciated that fig. 1 schematically illustrates only one typical organic electroluminescent device structure, and the present application is not limited to this structure, and the electron transport material of the present application may be used in any type of organic electroluminescent device.
In the organic electroluminescent device of the present application, various materials used for the layer in the prior art may be used for the other layers, except that the electron transport layer contains the electron transport material provided by the present application.
For convenience, the organic electroluminescent device of the present application will be described below with reference to fig. 1, but this is not meant to limit the scope of the present application in any way. It is understood that all organic electroluminescent devices capable of using the electron transport material of the present application are within the scope of the present application.
In the present application, the substrate 1 is not particularly limited, and conventional substrates used in the organic electroluminescent device in the related art, for example, glass, polymer materials, glass with Thin Film Transistor (TFT) elements, polymer materials, and the like can be used.
In the present application, the reflective anode material 2 is not particularly limited, and may be selected from Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO) 2 ) The transparent conductive material such as zinc oxide (ZnO) may be selected from metallic materials such as silver and its alloy, aluminum and its alloy, organic conductive materials such as poly 3, 4-ethylenedioxythiophene (PEDOT), and the like, or a multilayer structure of the above materials.
In the present application, the material of the hole injection layer 3 is not particularly limited, and a hole injection layer material known in the art may be used. For example, at least one of known Hole Transport Materials (HTM) is selected as the hole injection material.
In the present application, the hole injection layer 3 may further include a p-type dopant, the kind of which is not particularly limited, and various p-type dopants known in the art may be employed. For example, the p-type dopant may be selected from, but is not limited to, at least one of the following p-1 to p-3 compounds:
in the present application, the amount of the p-type dopant is not particularly limited, and may be an amount well known to those skilled in the art.
In the present application, the material of the hole transport layer 4 is not particularly limited, and may be made of a Hole Transport Material (HTM) well known in the art. The number of layers of the hole transport layer 4 is not particularly limited and may be adjusted according to actual needs as long as the object of the present application is satisfied, for example, 1 layer, 2 layers, 3 layers, 4 layers or more.
For example, the HTM for the hole injection layer material and the HTM for the hole transport layer material may be selected from, but are not limited to, at least one of the following HT-1 to HT-31 compounds:
in the present application, the light emitting layer 5 may include a blue light emitting layer, a green light emitting layer, or a red light emitting layer, and a light emitting material in the light emitting layer 5 is not particularly limited, and various light emitting materials known to those skilled in the art may be used, for example, a material of the light emitting layer 5 may include a host material and a guest material.
In the present application, the host material may be selected from, but is not limited to, at least one of the following BH-1 to BH-10 compounds:
in the present application, the guest material is not particularly limited, and at least one of the light emitting layer guest materials known in the art may be used. For example, the light emitting layer guest material may be selected from, but is not limited to, at least one of the following BD-1 to BD-9 compounds:
in the present application, the amount of the guest material for the light emitting layer is not particularly limited, and may be an amount known to those skilled in the art.
In the present application, the electron transport layer 6 contains at least one of the electron transport materials of the present application, and the electron transport layer 6 may also contain a combination of at least one of the electron transport materials of the present application and at least one of the known electron transport materials. The number of layers of the electron transport layer 6 is not particularly limited and may be adjusted according to actual needs as long as the object of the present application is satisfied, for example, 1 layer, 2 layers, 3 layers, 4 layers or more.
For example, known electron transport materials may be selected from, but are not limited to, at least one of the following ET-1 to ET-57 compounds:
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in the present application, the electron transport layer 6 may further include n-type dopants, the kind of which is not particularly limited, and various n-type dopants known in the art may be employed, for example, the following n-type dopants may be employed:
in the present application, the amount of the n-type dopant is not particularly limited, and may be an amount well known to those skilled in the art.
In the present application, the material of the electron injection layer 7 is not particularly limited, and electron injection materials known in the art may be used, for example, may include, but not limited to, liQ, liF, naCl, csF, li in the prior art 2 O、Cs 2 CO 3 At least one of materials such as BaO, na, li, ca.
In the present application, the material of the cathode electrode 8 is not particularly limited, and may be selected from, but not limited to, metals such as magnesium silver mixture, liF/Al, ITO, al, metal mixtures, oxides, and the like.
A fourth aspect of the application provides a display device comprising the organic electroluminescent device provided in the third aspect of the application. Including but not limited to displays, televisions, tablet computers, mobile communication terminals, etc.
The method of preparing the organic electroluminescent device of the present application is not particularly limited, and any method known in the art may be employed, for example, the present application may be prepared by the following preparation method:
(1) Cleaning a reflective anode electrode 2 on an OLED device substrate 1 for top light emission, respectively performing steps of medicine washing, water washing, hairbrushes, high-pressure water washing, air knives and the like in a cleaning machine, and then performing heating treatment;
(2) Vacuum evaporating a hole injection material on the reflective anode electrode 2 as a hole injection layer 3;
(3) Vacuum evaporating a hole transport material on the hole injection layer 3 as a hole transport layer 4;
(4) Vacuum evaporating a light-emitting layer 5 on the hole transport layer 4, wherein the light-emitting layer 5 comprises a host material and a guest material;
(5) Vacuum evaporating an electron transport material on the light-emitting layer 5 as an electron transport layer 6;
(6) Vacuum evaporating an electron injection material on the electron transport layer 6 as an electron injection layer 7;
(7) A cathode material is vacuum-evaporated on the electron injection layer 7 as a cathode electrode 8.
Only the structure of a typical organic electroluminescent device and a method for manufacturing the same are described above, and it should be understood that the present application is not limited to such a structure. The electron transport material of the present application may be used for an organic electroluminescent device of any structure, and the organic electroluminescent device may be prepared using any preparation method known in the art.
The method for synthesizing the compound of the present application is not particularly limited, and may be synthesized by any method known to those skilled in the art. The synthesis of the compounds of the present application is illustrated below.
Synthesis of compound A1:
into a reaction flask were charged 100mmol of 1-naphthalene boric acid, 100mmol of p-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst to be added was 1mol% of 1-naphthalene boric acid.
N 2 Under protection, M1 (100 mmol,1 eq.) is added to a 3L three-necked flask equipped with a mechanical stirring and low-temperature thermometer, tetrahydrofuran 1L, liquid nitrogen is cooled to-90 ℃ to-80 ℃, n-butyllithium (250 mmol,2.5 eq.) is added dropwise, the temperature is kept (-90 ℃ to-80 ℃) for 30min after the dropwise addition, tri-tert-butyl borate (120 mmol,1.2 eq.) is added, the temperature is naturally raised to zero ℃ after the addition, and stirring is continued for 8 hours. After the reaction was completed, 1000mL of 10wt% aqueous ammonium chloride solution was added, the solution was separated, the organic phase was washed with 300mL of 10wt% aqueous ammonium chloride solution each time, and the filtrate was concentrated to obtain a black solid, which was crystallized with toluene to obtain pale yellow sandy solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of 2, 4-dichloro-6-phenyl-1, 3, 5-triazine, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water,and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of M3, 100mmol of 9,9' -spirobifluorene-2-boric acid, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
1 H NMR(400MHz,Chloroform)8.95(s,1H),8.36-8.19(m,3H),7.96(s,1H),7.89(d,J＝8.0Hz,4H),7.78(d,J＝8.0Hz,2H),7.68(s,1H),7.63(d,J＝8.0Hz,4H),7.50-7.40(m,4H),7.34(d,J＝8.4Hz,5H),7.30–7.19(m,6H).
Synthesis of compound A2:
into a reaction flask were charged 100mmol of 2-naphthaleneboric acid, 100mmol of p-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst to be added was 1mol% of 2-naphthaleneboric acid.
N 2 Under protection, M1 (100 mmol,1 eq.) and tetrahydrofuran 1L are added into a 3L three-mouth bottle with a mechanical stirring and low-temperature thermometer, and the liquid nitrogen is cooled to-90 ℃ to-80 DEG CN-butyllithium (120 mmol,1.2 eq.) was added dropwise, the temperature was kept (-90 ℃ C. To-80 ℃ C.) for 30min after the addition was completed, tri-tert-butyl borate (120 mmol,1.2 eq.) was added, the temperature was naturally raised to zero degree after the addition was completed, and stirring was continued for 8 hours. After the reaction was completed, 1000mL of 10wt% aqueous ammonium chloride solution was added, the solution was separated, the organic phase was washed with 300mL of 10wt% aqueous ammonium chloride solution each time, and the filtrate was concentrated to obtain a black solid, which was crystallized with toluene to obtain pale yellow sandy solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of 2, 4-dichloro-6-phenyl-1, 3, 5-triazine, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of M3, 100mmol of 9,9' -spirobifluorene-2-boric acid, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A2. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
1 H NMR(400MHz,Chloroform)8.36(s,1H),8.08(t,J＝7.6Hz,3H),7.97(d,J＝12.0Hz,4H),7.89(d,J＝8.0Hz,4H),7.68(s,1H),7.66–7.53(m,6H),7.44(d,J＝8.4Hz,4H),7.36(d,J＝8.8Hz,5H),7.24(t,J＝7.2Hz,3H).
Synthesis of compound A3:
into a reaction flask were charged 100mmol of 1, 4-dibromonaphthalene, 100mmol of pyridine-3-boronic acid, 414g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 1, 4-dibromonaphthalene.
Into a reaction flask were charged 100mmol of M1, 100mmol of p-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M2. Wherein Pd (PPh) 3 ) 4 The amount of (C) added was 1mol% based on M1.
Into a reaction flask were charged 100mmol of M2, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol), 800mL of dioxane, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 80℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of 9, 9-dimethylfluorene-2-boronic acid, 100mmol of 2-phenyl-4, 6-dichloro-triazine, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 9, 9-dimethylfluorene-2-boronic acid.
Into a reaction flask were charged 100mmol of M3 and 100mmol of MM4, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
1 H NMR(400MHz,Chloroform)9.24(s,1H),8.95(s,1H),8.70(s,1H),8.34(d,J＝10.0Hz,2H),8.25(s,1H),8.03(d,J＝8.0Hz,3H),7.84(d,J＝10.0Hz,2H),7.61–7.42(m,6H),7.40(s,1H),7.34(d,J＝8.4Hz,4H),7.25(d,J＝7.6Hz,4H),1.69(s,6H).
Synthesis of compound A4:
into a reaction flask were charged 100mmol of 3-pyridineboronic acid, 100mmol of 1, 4-dibromonaphthalene, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst to be added was 1mol% of 3-pyridineboronic acid.
N 2 Under protection, M1 (100 mmol,1 eq.) is added to a 3L three-necked flask equipped with a mechanical stirring and low-temperature thermometer, tetrahydrofuran 1L, liquid nitrogen is cooled to-90 ℃ to-80 ℃, n-butyllithium (120 mmol,1.2 eq.) is added dropwise, the temperature is kept (-90 ℃ to-80 ℃) for 30min after the dropwise addition, tri-tert-butyl borate (120 mmol,1.2 eq.) is added, the temperature is naturally raised to zero ℃ after the addition, and stirring is continued for 8 hours. After the reaction, 1000mL of 10wt% ammonium chloride aqueous solution is added, the solution is separated, the organic phase is washed with 300mL of 10wt% ammonium chloride aqueous solution each time, the filtrate is concentrated to obtain black solid, and toluene is used for crystallization to obtain pale yellow sandy solid M 2。
Into a reaction flask were charged 100mmol of M2, 100mmol of p-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
N 2 Under protection, M3 ((100 mmol,1 eq.) and tetrahydrofuran (1L) are added into a 3L three-port bottle with a mechanical stirring and low-temperature thermometer, liquid nitrogen is cooled to-90 ℃ to-80 ℃, n-butyllithium (120 mmol,1.2 eq.) is added dropwise, the temperature is kept (-90 ℃ to-80 ℃) for 30min after the dropwise addition, tri-tert-butyl borate (120 mmol,1.2 eq.) is added, the temperature is naturally raised to zero ℃ after the addition, stirring is continued for 8 hours.
Into a reaction flask were charged 100mmol of M4, 100mmol of 2- (4-biphenyl) -4-chloro-6-phenyl-1, 3, 5-triazine, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M4.
1 H NMR(400MHz,Chloroform)9.24(s,1H),8.95-8.70(m,3H),8.34(d,J＝10.0Hz,3H),7.96(s,1H),7.77(d,J＝12.0Hz,4H),7.64–7.11(m,6H),7.40(d,J＝8.0Hz,4H),7.35–7.21(m,6H).
Synthesis of compound A5:
into a reaction flask were charged 100mmol of phenylboronic acid, 100mmol of 2, 7-dibromonaphthalene, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The addition amount of (2) was 1mol% of phenylboronic acid.
N 2 Under protection, M1 (100 mmol,1 eq.) is added to a 3L three-necked flask equipped with a mechanical stirrer, tetrahydrofuran 1L is cooled to-90 ℃ to-80 ℃ by liquid nitrogen, n-butyllithium (120 mmol,1.2 eq.) is added dropwise, the temperature is kept (-90 ℃ to-80 ℃) for 30min after the dropwise addition, tri-tert-butyl borate (120 mmol,1.2 eq.) is added, the temperature is naturally raised to zero ℃ after the addition is completed, and stirring is continued for 8 hours. After the reaction was completed, 1000mL of 10wt% aqueous ammonium chloride solution was added, the solution was separated, the organic phase was washed with 300mL of 10wt% aqueous ammonium chloride solution each time, and the filtrate was concentrated to obtain a black solid, which was crystallized with toluene to obtain pale yellow sandy solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of p-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
N 2 Under protection, M3 (100 mmol,1 eq.) and tetrahydrofuran (1L) are added into a 3L three-port bottle with a mechanical stirring and low-temperature thermometer, liquid nitrogen is cooled to-90 ℃ to-80 ℃, n-butyllithium (120 mmol,1.2 eq.) is added dropwise, the temperature is kept at (-90 ℃ to-80 ℃) for 30min after the dropwise addition, tri-tert-butyl borate (120 mmol,1.2 eq.) is added, the temperature is naturally raised to zero ℃ after the addition, and stirring is continued for 8 hours. After the reaction was completed, 1000mL of 10wt% aqueous ammonium chloride solution was added, the solution was separated, the organic phase was washed with 300mL of 10wt% aqueous ammonium chloride solution each time, and the filtrate was concentrated to obtain a black solid, which was crystallized with toluene to obtain pale yellow sandy solid M4.
Into a reaction flask were charged 100mmol of M4, 100mmol of 2-chloro-4- (2-naphthyl) -6-phenyl-1, 3, 5-triazine, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A5. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M4.
1 H NMR(400MHz,Chloroform)9.09(s,1H),8.42(d,J＝8.0Hz,2H),8.34–8.27(m,3H),8.16(s,1H),8.10–7.89(m,3H),7.75(s,1H),7.68(d,J＝10.0Hz,4H),7.57(s,1H),7.52–7.40(m,6H),7.40-7.25(m,6H).
Synthesis of compound A7:
into a reaction flask were charged 100mmol of p-bromophenylboric acid, 100mmol of 2-bromoquinoline, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The addition amount of (2) is 1mol% of the p-bromophenylboric acid.
N 2 Under protection, M1 (100 mmol,1 eq.) and tetrahydrofuran 1L are added into a 3L three-necked flask equipped with a mechanical stirring and low-temperature thermometer, liquid nitrogen is cooled to-90 ℃ to-80 ℃, n-butyllithium (120 mmol,1.2 eq.) is added dropwise, the temperature is kept (-90 ℃ to-80 ℃) for 30min after the dropwise addition, and the boric acid is addedTert-butyl ester (120 mmol,1.2 eq.) was added and after completion of the addition, the temperature was raised naturally to zero degrees and stirring was continued for 8 hours. After the reaction was completed, 1000mL of 10wt% aqueous ammonium chloride solution was added, the solution was separated, the organic phase was washed with 300mL of 10wt% aqueous ammonium chloride solution each time, and the filtrate was concentrated to obtain a black solid, which was crystallized with toluene to obtain pale yellow sandy solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of 2, 4-dichloro-6-1, 3, 5-phenyltriazine, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
N 2 Under protection, M3 (100 mmol,1 eq.) is added to a 3L three-necked flask equipped with a mechanical stirrer, tetrahydrofuran 1L is cooled to-10 ℃ to 0 ℃ by liquid nitrogen, phenylmagnesium bromide (100 mmol,1.0 eq.) is added dropwise, and after the dropwise addition, the flask is kept warm (0 ℃) for 30min and stirring is continued for 8 hours. After the reaction was completed, 1000mL of 10wt% aqueous ammonium chloride solution was added, the solution was separated, and the organic phase was washed with 300mL of 10wt% aqueous ammonium chloride solution each time, and the filtrate was concentrated to obtain solid M4.
100mmol of M4, 300mmol of benzene and 200mL of trifluoromethanesulfonic acid were charged in a reaction flask and reacted at 100℃for 12 hours. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M5.
N 2 Under protection, M5 (100 mmol,1 eq.) and tetrahydrofuran (1L) are added into a 3L three-necked flask equipped with a mechanical stirring and low-temperature thermometer, liquid nitrogen is cooled to-90 ℃ to-80 ℃, n-butyllithium (120 mmol,1.2 eq.) is added dropwise, the temperature is kept at (-90 ℃ to-80 ℃) for 30min after the dropwise addition, tri-tert-butyl borate (120 mmol,1.2 eq.) is added, the temperature is naturally raised to zero ℃ after the addition, and stirring is continued for 8 hours. After the reaction, 1000mL of 10wt% ammonium chloride aqueous solution was added, the solution was separated, and the organic phase was separated every timeThe mixture was washed with 300mL of a 10wt% aqueous ammonium chloride solution, and the filtrate was concentrated to give a black solid, which was crystallized from toluene to give a pale yellow sandy solid M6.
Into a reaction flask were charged 100mmol of M3, 100mmol of M6, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A7. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
1 H NMR(400MHz,Chloroform)8.69(s,2H),8.44(s,1H),8.38(d,J＝12.0Hz,3H),8.15–8.02(m,3H),7.92(t,J＝10.0Hz,2H),7.78(s,1H)-7.56(m,8H),7.34(d,J＝8.4Hz,4H),7.25(d,J＝8.8Hz,4H),7.18-7.10(m,4H).
Synthesis of compound a 16:
into a reaction flask were charged 100mmol of 1-naphthalene boric acid, 100mmol of 3, 5-dibromobiphenyl, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst to be added was 1mol% of 1-naphthalene boric acid.
N 2 Under protection, M1 (100 mmol,1 eq.) is added to a 3L three-necked flask equipped with a mechanical stirrer, tetrahydrofuran 1L is cooled to-90 ℃ to-80 ℃ by liquid nitrogen, n-butyllithium (120 mmol,1.2 eq.) is added dropwise, the temperature is kept (-90 ℃ to-80 ℃) for 30min after the dropwise addition, tri-tert-butyl borate (120 mmol,1.2 eq.) is added, the temperature is naturally raised to zero ℃ after the addition is completed, and stirring is continued for 8 hours. After the reaction was completed, 10wt% was added% of an aqueous ammonium chloride solution 1000mL, separating, washing the organic phase with 300mL of an aqueous ammonium chloride solution of 10wt% each time, concentrating the filtrate to obtain a black solid, and crystallizing with toluene to obtain a pale yellow sandy solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of 2-phenyl-4, 6-dichloro-triazine, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of M3, 100mmol of 9,9' -spirobifluorene-2-boric acid, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a16. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
1 H NMR(400MHz,Chloroform)8.95(s,1H),8.45(t,J＝8.4Hz,1H),8.38(d,J＝11.2Hz,4H),8.20(d,J＝8.4Hz,2H),8.08(s,1H),7.89(d,J＝8.0Hz,4H),7.80–7.69(m,6H),7.62(d,J＝8.0Hz,3H),7.49(d,J＝8.0Hz,4H),7.40(d,J＝8.4Hz,2H),7.34(d,J＝8.4Hz,3H),7.24(d,J＝8.0Hz,4H).
Synthesis of compound a 18:
into a reaction flask were charged 100mmol of 2-bromo-4-chloro-1-iodobenzene, 100mmol of 1-naphthaleneboronic acid, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) Reacting at 60 DEG CAnd 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst to be added was 1mol% of 2-bromo-4-chloro-1-iodobenzene.
Into a reaction flask were charged 100mmol of M1, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M2. Wherein Pd (PPh) 3 ) 4 The amount of (C) added was 1mol% based on M1.
Into a reaction flask were charged 100mmol of M2, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol), 800mL of dioxane, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 80℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of dibenzothiophene-3-boronic acid, 100mmol of 2-phenyl-4, 6-dichloro-triazine, 41.4g of potassium carbonate (300 mmol), 8.00 mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The addition amount of (2) was 1mol% of dibenzothiophene-3-boronic acid.
Into a reaction flask were charged 100mmol of M3, 100mmol of M4, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) At 60 DEG CThe reaction was carried out for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a18. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
1 H NMR(400MHz,Chloroform)8.60(s,1H),8.52–8.43(m,3H),8.15(s,1H),7.97(s,1H),7.88(d,J＝10.0Hz,2H),7.78(t,J＝8.4Hz,4H),7.67(s,1H),7.56-7.46(m,4H),7.40(d,J＝8.0Hz,6H),7.33(d,J＝7.6Hz,4H).
Synthesis of compound a 22:
N 2 under protection, 1-bromonaphthalene (200 mmol,1 eq.) is added to a 3L three-necked flask equipped with a mechanical stirring and a low-temperature thermometer, tetrahydrofuran 1L, liquid nitrogen is cooled to-90 ℃ to-80 ℃, n-butyllithium (240 mmol,1.2 eq.) is added dropwise, the temperature is kept (-90 ℃ to-80 ℃) for 30min after the dropwise addition, the temperature is naturally raised to zero ℃ after the addition is finished, cyanuric chloride (100 mmol,1.0 eq.) is added, and stirring is continued for 8 hours. After the reaction was completed, 1000mL of 10wt% aqueous ammonium chloride solution was added, the solution was separated, the organic phase was washed with 300mL of 10wt% aqueous ammonium chloride solution each time, and the filtrate was concentrated to obtain a black solid, which was crystallized with toluene to obtain pale yellow sandy solid M1.
Into a reaction flask were charged 100mmol of 2-naphthaleneboric acid, 100mmol of m-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M2. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst to be added was 1mol% of 2-naphthaleneboric acid.
N 2 Under protection, M2 (100 mmol,1 eq.) and tetrahydrofuran (1L) are added into a 3L three-mouth bottle with a mechanical stirring and low-temperature thermometer, and the liquid nitrogen is cooled to-90 ℃ to-80 DEG CN-butyllithium (120 mmol,1.2 eq.) was added dropwise, the temperature was kept (-90 ℃ C. To-80 ℃ C.) for 30min after the addition was completed, tri-tert-butyl borate (120 mmol,1.2 eq.) was added, the temperature was naturally raised to zero degree after the addition was completed, and stirring was continued for 8 hours. After the reaction was completed, 1000mL of 10wt% aqueous ammonium chloride solution was added, the solution was separated, the organic phase was washed with 300mL of 10wt% aqueous ammonium chloride solution each time, and the filtrate was concentrated to obtain a black solid, which was crystallized with toluene to obtain pale yellow sandy solid M3.
Into a reaction flask were charged 100mmol of M3, 100mmol of M1, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a22. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
1 H NMR(400MHz,Chloroform)9.09(s,1H),8.49(s,1H),8.39(d,J＝12.0Hz,4H),8.16(s,1H),8.11–8.04(m,6H),7.99(d,J＝8.0Hz,4H),7.70(s,1H),7.65–7.53(m,7H).
Synthesis of compound a 30:
into a reaction flask were charged 100mmol of p-bromoiodobenzene, 100mmol of 2-naphthaleneboric acid, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The addition amount of (2) was 1mol% of p-bromoiodobenzene.
N 2 Under protection, M1 (100 mmol,1 eq.) is added to a 3L three-necked flask equipped with a mechanical stirrer and a low-temperature thermometer, tetrahydrofuran 1L and liquid nitrogen are cooled to-N-butyllithium (120 mmol,1.2 eq.) is added dropwise at 90 ℃ to-80 ℃, after the dropwise addition, the temperature is kept (-90 ℃ to-80 ℃) for 30min, tri-tert-butyl borate (120 mmol,1.2 eq.) is added, after the addition, the temperature is naturally raised to zero ℃ and stirring is continued for 8 hours. After the reaction was completed, 1000mL of 10wt% aqueous ammonium chloride solution was added, the solution was separated, the organic phase was washed with 300mL of 10wt% aqueous ammonium chloride solution each time, and the filtrate was concentrated to obtain a black solid, which was crystallized with toluene to obtain pale yellow sandy solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of cyprodinil, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of methyl 2-iodo-5-bromo-benzoate, 100mmol of 1-naphthalene boronic acid, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst added was 1mol% of 2-iodo-5-bromo-benzoic acid methyl ester.
100mmol of M4 and 300mL of trifluoromethanesulfonic acid were added to the reaction flask, and the mixture was reacted at 100℃for 12 hours. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M5.
N 2 Under protection, M5 (100 mmol,1 eq.) is added to a 3L three-necked flask equipped with a mechanical stirrer and a low-temperature thermometer, tetrahydrofuran is added in 1L, liquid nitrogen is cooled to-10 ℃ to 0 ℃, phenylmagnesium bromide (100 mmol,1.0 eq.) is added dropwise, and after the dropwise addition, the temperature is kept (0 ℃) for 30min, and stirring is continued for 8 hours. ReactionAfter completion, 1000mL of 10wt% aqueous ammonium chloride solution was added, the solution was separated, and the organic phase was washed with 300mL of 10wt% aqueous ammonium chloride solution each time, and the filtrate was concentrated to give solid M6.
100mmol of M6, 300mmol of benzene and 200mL of trifluoromethanesulfonic acid were charged in a reaction flask and reacted at 100℃for 12 hours. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M7.
N 2 Under protection, M6 (100 mmol,1 eq.) is added to a 3L three-necked flask equipped with a mechanical stirring and low-temperature thermometer, tetrahydrofuran 1L, liquid nitrogen is cooled to-90 ℃ to-80 ℃, n-butyllithium (120 mmol,1.2 eq.) is added dropwise, the temperature is kept (-90 ℃ to-80 ℃) for 30min after the dropwise addition, tri-tert-butyl borate (120 mmol,1.2 eq.) is added, the temperature is naturally raised to zero ℃ after the addition, and stirring is continued for 8 hours. After the reaction was completed, 1000mL of 10wt% aqueous ammonium chloride solution was added, the solution was separated, the organic phase was washed with 300mL of 10wt% aqueous ammonium chloride solution each time, and the filtrate was concentrated to obtain a black solid, which was crystallized with toluene to obtain pale yellow sandy solid M7.
Into a reaction flask were charged 100mmol of M3, 100mmol of M7, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a30. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
1 H NMR(400MHz,Chloroform)8.90(s,1H),8.44(d,J＝6.0Hz,2H),8.35(s,2H),8.30(s,2H),8.23(s,1H),8.08(d,J＝12.0Hz,2H),7.98(d,J＝10.0Hz,2H),7.85(s,2H),7.78(s,1H),7.59(d,J＝10.0Hz,4H),7.50(s,3H),7.38(s,1H),7.33–7.23(m,6H),7.18(s,1H),7.09(d,J＝8.0Hz,6H).
Synthesis of compound a 31:
N 2 under protection, 1-bromonaphthalene-D7 (100 mmol,1 eq.) is added into a 3L three-necked flask equipped with a mechanical stirring and low-temperature thermometer, tetrahydrofuran 1L is cooled to-90 ℃ to-80 ℃, n-butyllithium (250 mmol,2.5 eq.) is added dropwise, the temperature is kept at (-90 ℃ to-80 ℃) for 30min after the dropwise addition, tributyl borate (120 mmol,1.2 eq.) is added, the temperature is naturally raised to zero ℃ after the addition is finished, and stirring is continued for 8 hours. After the reaction was completed, 1000mL of 10wt% aqueous ammonium chloride solution was added, the solution was separated, the organic phase was washed with 300mL of 10wt% aqueous ammonium chloride solution each time, and the filtrate was concentrated to obtain a black solid, which was crystallized with toluene to obtain pale yellow sandy solid M2. Into a reaction flask were charged 100mmol of M1, 100mmol of p-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M2. Wherein Pd (PPh) 3 ) 4 The amount of (C) added was 1mol% based on M1.
N 2 Under protection, M2 (100 mmol,1 eq.) is added to a 3L three-necked flask equipped with a mechanical stirring and low-temperature thermometer, tetrahydrofuran 1L, liquid nitrogen is cooled to-90 ℃ to-80 ℃, n-butyllithium (250 mmol,2.5 eq.) is added dropwise, the temperature is kept (-90 ℃ to-80 ℃) for 30min after the dropwise addition, tri-tert-butyl borate (120 mmol,1.2 eq.) is added, the temperature is naturally raised to zero ℃ after the addition, and stirring is continued for 8 hours. After the reaction was completed, 1000mL of 10wt% aqueous ammonium chloride solution was added, the solution was separated, the organic phase was washed with 300mL of 10wt% aqueous ammonium chloride solution each time, and the filtrate was concentrated to obtain a black solid, which was crystallized with toluene to obtain pale yellow sandy solid M3.
Into a reaction flask were charged 100mmol of M3, 100mmol of 2, 4-dichloro-6-phenyl-1, 3, 5-triazine, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. Stopping the reaction after the reaction is completed, and reversing The reaction mixture was cooled to room temperature, water was added, filtration and washing were carried out, and the obtained solid was purified by recrystallization from toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
Into a reaction flask were charged 100mmol of M4, 100mmol of 9,9' -spirobifluorene-2-boric acid, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a31. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M4.
1 H NMR(400MHz,Chloroform)8.36(s,1H),8.19(s,1H),8.08(d,J＝8.4Hz,2H),8.03–7.87(m,5H),7.68(s,1H),7.63(d,J＝8.0Hz,6H),7.30–7.19(m,8H).
Synthesis of compound a 32:
into a reaction flask were charged 100mmol of 1, 4-dibromonaphthalene, 100mmol of deuterated phenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 1, 4-dibromonaphthalene.
N 2 Under the protection, adding M1 (100 mmol,1 eq.) and tetrahydrofuran 1L into a 3L three-mouth bottle with a mechanical stirring and low-temperature thermometer, cooling liquid nitrogen to-90 ℃ to-80 ℃, dropwise adding n-butyllithium (120 mmol,1.2 eq.) and preserving heat (-90 ℃ to-80 ℃) for 30min after the dropwise adding, adding tri-tert-butyl borate (120 mmol,1.2 eq.) and naturally heating to zero ℃ after the adding, and continuously stirring8 hours. After the reaction was completed, 1000mL of 10wt% aqueous ammonium chloride solution was added, the solution was separated, the organic phase was washed with 300mL of 10wt% aqueous ammonium chloride solution each time, and the filtrate was concentrated to obtain a black solid, which was crystallized with toluene to obtain pale yellow sandy solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of p-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
N 2 Under protection, M3 ((100 mmol,1 eq.) and tetrahydrofuran (1L) are added into a 3L three-port bottle with a mechanical stirring and low-temperature thermometer, liquid nitrogen is cooled to-90 ℃ to-80 ℃, n-butyllithium (120 mmol,1.2 eq.) is added dropwise, the temperature is kept (-90 ℃ to-80 ℃) for 30min after the dropwise addition, tri-tert-butyl borate (120 mmol,1.2 eq.) is added, the temperature is naturally raised to zero ℃ after the addition, stirring is continued for 8 hours.
Into a reaction flask were charged 100mmol of 2, 4-dichloro-6-phenyl-1, 3, 5-triazine, 100mmol of 9,9' -spirobifluorene-2-boronic acid, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M5. Wherein Pd (PPh) 3 ) 4 The amount of (2), 4-dichloro-6-phenyl-1, 3, 5-triazine added was 1mol%.
Into a reaction flask were charged 100mmol of M4, 100mmol of M5, 41.4g of potassium carbonate (300 mmol), 800mL of Tetrahydrofuran (THF) and 200mL of waterAnd 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a32. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M4.
1 H NMR(400MHz,Chloroform)9.00(s,1H),8.36(s,1H),8.19(d,J＝8.4Hz,2H),8.08(s,1H),8.03–7.87(m,5H),7.77–7.52(m,4H),7.58–7.52(m,4H),7.38(d,J＝6.4Hz,4H),7.32–7.20(m,8H).
Other compounds of the present application can be synthesized by selecting appropriate raw materials according to the above-described ideas for synthesizing the compounds A1, A2, A3, A4, A5, A7, a16, a18, a22, a30, a31 or a32, or by selecting any other appropriate methods and raw materials.
Example 1
Ultrasonic treating the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, flushing in deionized water, ultrasonic degreasing in an acetone-ethanol mixed solvent, baking in a clean environment until water is completely removed, cleaning with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam;
then placing the above-mentioned glass substrate with anode in vacuum cavity, vacuumizing to less than 10 -5 In the method, a hole injection layer is vacuum-evaporated on the anode layer film, wherein the material of the hole injection layer comprises a hole injection layer material HT-11 and a p-type dopant p-1, evaporation is performed by utilizing a multi-source co-evaporation method, the evaporation rate of the hole injection layer material HT-11 is regulated to be 0.1nm/s, the evaporation rate of the p-type dopant p-1 is 3% of the evaporation rate of the hole injection layer material HT-11, and the evaporation film thickness is 10nm; the hole injection layer material HT-11 and p-type dopant p-1 are as follows:
then, a hole transport material HT-5 was vacuum-deposited as a hole transport layer on top of the hole injection layer, wherein the deposition rate was 0.1nm/s, the deposition film thickness was 80nm, and the hole transport material HT-5 was as follows:
then, vacuum evaporation plating is carried out on the hole transmission layer, the light-emitting layer comprises a main body material BH-2 and a fluorescent doping agent BD-1, evaporation plating is carried out by utilizing a multi-source co-evaporation method, wherein the evaporation plating rate of the main body material BH-2 is regulated to be 0.1nm/s, the evaporation plating rate of the fluorescent doping agent BD-1 is 3% of the evaporation plating rate of the main body material BH-2, and the thickness of the evaporation plating film is 30nm; the host material BH-2 and the fluorescent dopant BD-1 are as follows:
Then, an electron transport layer is vacuum-evaporated on the light-emitting layer, wherein the electron transport material is a compound A1, the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 30nm; the electron transport material A1 is as follows:
then, liF with the thickness of 0.5nm is vacuum evaporated on the electron transport layer to be used as an electron injection layer, wherein the evaporation rate is 0.1nm/s;
finally, an Al layer with the thickness of 150nm is vacuum evaporated on the electron injection layer to be used as a cathode electrode of the organic electroluminescent device, wherein the evaporation rate is 0.1nm/s.
Examples 2 to 12
The same as in example 1 was conducted except that the electron transport material was replaced with A2, A3, A4, A5, A7, a16, a18, a22, a30, a31 or a32, respectively, in place of A1. See in particular table 1.
Comparative example 1
The procedure of example 1 was repeated except that ET-6 was used as the electron transport material; ET-6 is as follows:
the organic electroluminescent device prepared by the above procedure was subjected to the following performance measurement:
the driving voltage, current efficiency and life of the organic electroluminescent devices prepared in examples 1 to 8 and comparative example 1 were measured using a digital source meter and a luminance meter under the same luminance, specifically, the voltage was increased at a rate of 0.1V per second, and the luminance of the organic electroluminescent device was measured to reach 1000cd/m 2 The voltage at the time is the driving voltage, and the current density at the time is measured; the ratio of brightness to current density is the current efficiency; the lifetime test of LT95 is as follows: at 1000cd/m using a luminance meter 2 Under the condition of brightness, constant current is kept, and the brightness of the organic electroluminescent device is measured to be reduced to 950cd/m 2 Time in hours. The results are shown in Table 1.
TABLE 1 organic electroluminescent device Performance results
As can be seen from Table 1, the compounds A1, A2, A3, A4, A5, A7, A16, A18, A22, A30, A31 and A32 prepared by the application are used as electron transport materials for organic electroluminescent devices, can effectively reduce driving voltage, improve current efficiency, prolong the service life of the devices, and are electron transport materials with good performance.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application are included in the protection scope of the present application.
Claims (10)
1. A compound of formula (I):
wherein,
Ar 1 and Ar is a group 2 Each independently selected from C which is unsubstituted or substituted with Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl; ar (Ar) 1 And Ar is a group 2 At least one of which has not less than 10C atoms and at least one selected from C which is unsubstituted or substituted with Rc 6 -C 30 An aryl group;
X 1 -X 3 each independently selected from C or N, and at least one selected from N;
R 1 -R 5 each independently selected from hydrogen, deuterium, C unsubstituted or substituted with Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, R 1 -R 5 At least one of the substituents is selected from the group consisting of:
Y 1 -Y 8 each independently selected from CR or N, R is selected from hydrogen, deuterium, C unsubstituted or substituted with Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl;
the heteroatoms on the heteroaryl groups are each independently selected from O, S or N;
the substituents Rc of each group are each independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
2. The compound of claim 1, wherein R 1 -R 5 Each independently selected from hydrogen, deuterium, C unsubstituted or substituted with Rc 6 -C 18 Aryl, C unsubstituted or substituted by Rc 3 -C 18 Heteroaryl groups.
3. The compound of claim 1, wherein R is selected from hydrogen, deuterium, C unsubstituted or substituted with Rc 6 -C 18 Aryl, C unsubstituted or substituted by Rc 3 -C 18 Heteroaryl groups.
4. The compound of claim 1, wherein Ar 1 And Ar is a group 2 Each independently selected from the following groups unsubstituted or substituted with Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl.
5. The compound of claim 1, wherein said R 1 -R 5 Each independently selected from the following groups unsubstituted or substituted with Rc: hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl.
6. The compound of claim 1, wherein R is selected from the following groups that are unsubstituted or substituted with Rc: hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl.
7. The compound of claim 1, wherein the compound is selected from the group consisting of the compounds shown in A1 to a32 below:
8. an electron transport material comprising at least one of the compounds of any of claims 1-7.
9. An organic electroluminescent device comprising at least one of the electron transport materials of claim 8.
10. A display device comprising the organic electroluminescent device of claim 9.
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