CN114524837B - Condensed-cyclic compound containing boron nitrogen and dendritic structure, preparation method and application thereof, and organic electroluminescent device - Google Patents
Condensed-cyclic compound containing boron nitrogen and dendritic structure, preparation method and application thereof, and organic electroluminescent device Download PDFInfo
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- CN114524837B CN114524837B CN202210192229.4A CN202210192229A CN114524837B CN 114524837 B CN114524837 B CN 114524837B CN 202210192229 A CN202210192229 A CN 202210192229A CN 114524837 B CN114524837 B CN 114524837B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 296
- 238000006243 chemical reaction Methods 0.000 claims description 145
- 238000000034 method Methods 0.000 claims description 43
- 230000008569 process Effects 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000010409 thin film Substances 0.000 claims description 21
- 230000009471 action Effects 0.000 claims description 9
- 239000000412 dendrimer Substances 0.000 claims description 9
- -1 hydroxy, mercapto, amino Chemical group 0.000 claims description 4
- 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 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 150000001923 cyclic compounds Chemical class 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 33
- 229910052796 boron Inorganic materials 0.000 abstract description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 10
- 230000005281 excited state Effects 0.000 abstract description 8
- 238000001228 spectrum Methods 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 230000002093 peripheral effect Effects 0.000 abstract description 5
- 229910052714 tellurium Inorganic materials 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 147
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 120
- 239000010410 layer Substances 0.000 description 95
- 239000012074 organic phase Substances 0.000 description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 87
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 84
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 80
- 238000012360 testing method Methods 0.000 description 76
- 238000000921 elemental analysis Methods 0.000 description 70
- 239000012300 argon atmosphere Substances 0.000 description 59
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 59
- 239000000243 solution Substances 0.000 description 58
- 239000002904 solvent Substances 0.000 description 56
- 239000012043 crude product Substances 0.000 description 54
- 238000001914 filtration Methods 0.000 description 53
- 239000008367 deionised water Substances 0.000 description 49
- 229910021641 deionized water Inorganic materials 0.000 description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 45
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 42
- 229910052786 argon Inorganic materials 0.000 description 40
- 238000001816 cooling Methods 0.000 description 39
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 38
- 239000000047 product Substances 0.000 description 38
- 239000000463 material Substances 0.000 description 37
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 36
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 35
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 35
- 238000000605 extraction Methods 0.000 description 33
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 30
- 239000003960 organic solvent Substances 0.000 description 30
- FCDNEESKPPIAJZ-UHFFFAOYSA-N bis[3,5-di(carbazol-9-yl)phenyl]-diphenylsilane Chemical compound C1=CC=CC=C1[Si](C=1C=C(C=C(C=1)N1C2=CC=CC=C2C2=CC=CC=C21)N1C2=CC=CC=C2C2=CC=CC=C21)(C=1C=C(C=C(C=1)N1C2=CC=CC=C2C2=CC=CC=C21)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 FCDNEESKPPIAJZ-UHFFFAOYSA-N 0.000 description 29
- 238000002156 mixing Methods 0.000 description 29
- 230000001681 protective effect Effects 0.000 description 25
- 125000003118 aryl group Chemical group 0.000 description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 238000005406 washing Methods 0.000 description 22
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- 229940078552 o-xylene Drugs 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 150000002430 hydrocarbons Chemical group 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 11
- 238000002347 injection Methods 0.000 description 11
- 239000007924 injection Substances 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- TXBFHHYSJNVGBX-UHFFFAOYSA-N (4-diphenylphosphorylphenyl)-triphenylsilane Chemical compound C=1C=CC=CC=1P(C=1C=CC(=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 TXBFHHYSJNVGBX-UHFFFAOYSA-N 0.000 description 9
- 230000003111 delayed effect Effects 0.000 description 9
- 125000001072 heteroaryl group Chemical group 0.000 description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 8
- 125000000623 heterocyclic group Chemical group 0.000 description 8
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 8
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 230000005525 hole transport Effects 0.000 description 5
- 238000007641 inkjet printing Methods 0.000 description 5
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 5
- 238000010129 solution processing Methods 0.000 description 5
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000010146 3D printing Methods 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 229920000144 PEDOT:PSS Polymers 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229920000736 dendritic polymer Polymers 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007645 offset printing Methods 0.000 description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 238000001748 luminescence spectrum Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- BKPDQETYXNGMRE-UHFFFAOYSA-N 1-tert-butyl-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(C(C)(C)C)=CC=C2 BKPDQETYXNGMRE-UHFFFAOYSA-N 0.000 description 2
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 2
- TYXSZNGDCCGIBO-UHFFFAOYSA-N 3-tert-butyl-9h-carbazole Chemical compound C1=CC=C2C3=CC(C(C)(C)C)=CC=C3NC2=C1 TYXSZNGDCCGIBO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical group [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- YWBHROUQJYHSOR-UHFFFAOYSA-N $l^{1}-selanylbenzene Chemical compound [Se]C1=CC=CC=C1 YWBHROUQJYHSOR-UHFFFAOYSA-N 0.000 description 1
- 125000001294 (C1-C30) cycloalkyl group Chemical group 0.000 description 1
- DQXKOHDUMJLXKH-PHEQNACWSA-N (e)-n-[2-[2-[[(e)-oct-2-enoyl]amino]ethyldisulfanyl]ethyl]oct-2-enamide Chemical compound CCCCC\C=C\C(=O)NCCSSCCNC(=O)\C=C\CCCCC DQXKOHDUMJLXKH-PHEQNACWSA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- RRZMBTOLAQISOU-UHFFFAOYSA-N 1-benzofuran-3-ol Chemical compound C1=CC=C2C(O)=COC2=C1 RRZMBTOLAQISOU-UHFFFAOYSA-N 0.000 description 1
- RSGRRCWDCXLEHS-UHFFFAOYSA-N 1-bromo-3-chloro-5-iodobenzene Chemical compound ClC1=CC(Br)=CC(I)=C1 RSGRRCWDCXLEHS-UHFFFAOYSA-N 0.000 description 1
- BXXWFOGWXLJPPA-UHFFFAOYSA-N 2,3-dibromobutane Chemical compound CC(Br)C(C)Br BXXWFOGWXLJPPA-UHFFFAOYSA-N 0.000 description 1
- HNGQQUDFJDROPY-UHFFFAOYSA-N 3-bromobenzenethiol Chemical compound SC1=CC=CC(Br)=C1 HNGQQUDFJDROPY-UHFFFAOYSA-N 0.000 description 1
- GGUFVZFOCZNPEG-UHFFFAOYSA-N 4,5,6-triphenyltriazine Chemical compound C1=CC=CC=C1C1=NN=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 GGUFVZFOCZNPEG-UHFFFAOYSA-N 0.000 description 1
- PHHUQAFGPIDWPU-UHFFFAOYSA-N 5h-pyrrolo[3,2-c:4,5-c']dipyridine Chemical compound N1C2=CC=NC=C2C2=C1C=CN=C2 PHHUQAFGPIDWPU-UHFFFAOYSA-N 0.000 description 1
- DSJHYRQILJITBY-UHFFFAOYSA-N 7h-dibenzocarbazole Chemical compound C12=CC=CC=C2N=C2C1=C1C=CC=CC1=C1C=CCC=C12 DSJHYRQILJITBY-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 101150050192 PIGM gene Proteins 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 150000008282 halocarbons Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- RGRGVHJGSLNISC-UHFFFAOYSA-N n-phenyl-1-benzofuran-3-amine Chemical compound C=1OC2=CC=CC=C2C=1NC1=CC=CC=C1 RGRGVHJGSLNISC-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001296 phosphorescence spectrum Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other heteroatoms
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
- C09K2211/1085—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms with other heteroatoms
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Abstract
The invention provides a condensed ring compound containing boron nitrogen and a dendritic structure, a preparation method and application thereof, and an organic electroluminescent device. The compound provided by the invention comprises a condensed ring center containing boron atoms and nitrogen atoms and peripheral branches, and other inorganic elements X are distributed on the condensed ring center 1 、X 2 (independently selected from N, O, S, se or Te) the compound of the above structure can realize separation of front-line orbitals by utilizing resonance effect between boron atom and nitrogen atom, thereby realizing smaller delta E ST And TADF effect, and can utilize the rigid skeleton structure of specific condensed ring unit to reduce the relaxation degree of excited state, so as to implement higher luminous efficiency and narrower luminous spectrum.
Description
Technical Field
The invention relates to the technical field of organic luminescent materials, in particular to a condensed-cyclic compound containing boron nitrogen and a dendritic structure, a preparation method and application thereof, and an organic electroluminescent device.
Background
Organic Light Emitting Devices (OLEDs) are generally composed of an ITO anode, a Hole injection layer (TIL), a Hole Transport Layer (HTL), a light Emitting Layer (EL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and a cathode, and 1-2 organic layers may be omitted as needed, and excitons (exiton) are formed by combining holes (Hole) injected from the anode and the cathode on an organic thin film with electrons (Electron) and releasing energy in the form of light emission when the excitons return to a stable ground state from an excited state to emit light. OLEDs are characterized by rich color, thin thickness, wide viewing angle, rapid response, and capability of producing flexible devices, and are considered to be the next generation flat panel display and solid lighting technologies with the most promising development.
For OLED materials, the current commercial OLED display screens mostly adopt organic small molecule luminescent materials based on a vacuum evaporation process, and the devices of the materials have the defects of higher efficiency, low utilization rate, higher cost and the like. In contrast, organic electroluminescent materials that are solution processable (e.g., inkjet printing and roll-to-roll printing processes) have the advantages of reduced production costs and energy consumption, easy manufacture of large-sized displays, etc., but suffer from lower device efficiency. Currently, the OLED luminescent materials used in the solution processing technology mainly include two kinds of polymer luminescent materials and dendritic luminescent materials. Among them, the polymer luminescent material has excellent solution processability, but has the disadvantages of difficult purification, poor batch stability, and the like. Compared with a high molecular luminescent material, the dendritic luminescent material is a luminescent material with a definite chemical structure, and the molecular size and the topological structure of the dendritic luminescent material can be precisely controlled in synthesis; meanwhile, the dendritic luminescent material also has good film forming performance and solution processing performance, and luminescent materials with different luminescent wavelengths can be obtained by selecting different central cores, different branch building units and different peripheral modification groups, so that the dendritic luminescent material is one of OLED material systems with development prospects.
On the other hand, thermally activated delayed fluorescence (thermally activated delayed fluorescence, TADF) materials are new generation organic luminescent materials following traditional fluorescent and phosphorescent materials, which generally have a small singlet-triplet energy level difference (Δe) ST ) The triplet state excited state is transferred to the singlet state excited state to emit fluorescence by utilizing a thermal activated reverse intersystem crossing (RISC) process, so that the full utilization of singlet state and triplet state excitons is realized, and the internal quantum efficiency of 100% is realized, and the defect that the traditional fluorescent material can only realize the internal quantum efficiency of 25% is overcome.
At present, most dendritic thermal activation delay fluorescent materials adopt non-condensed ring units such as triphenyltriazine, diphenyl sulfone, benzophenone and the like as a central core, and the excited state structure relaxation is strong, so that the luminescence spectrum is wide (the half-peak width is generally 70-100nm, mater. Chem. Front.,2018,2,1097; J. Mater. Chem. C,2016,4,2442; dye. Pigm.2016,133, 380386) and the color purity is not high.
Therefore, how to develop dendritic compounds with both TADF effect and high luminous efficiency and narrow luminous spectrum through reasonable chemical structural design, and solve the defects faced by the above materials has become one of the problems to be solved in the field of many prospective researchers.
Disclosure of Invention
In view of the above, the present invention aims to provide a condensed-cyclic compound containing boron nitrogen and a dendritic structure, a preparation method and application thereof, and an organic electroluminescent device. The compound provided by the invention comprises condensed ring centers and peripheral branches of boron atoms and nitrogen atoms, and can realize separation of front line orbitals by utilizing resonance effect between the boron atoms and the nitrogen atoms, thereby realizing smaller delta E ST And TADF effect, and can utilize the rigid skeleton structure of specific condensed ring unit to reduce the relaxation degree of excited state, so as to implement higher luminous efficiency and narrower luminous spectrum.
The invention provides a condensed-cyclic compound containing boron nitrogen and a dendritic structure, which has the structure shown in a formula (1):
wherein:
1 2 [ about X, X, q ]]：
In the present invention, X 1 And X 2 Independently selected from: n (R) 0 ) O, S, se or Te; q is 0 or 1. Wherein R is 0 Selected from: a substituted or unsubstituted C1-C30 linear hydrocarbon group, a substituted or unsubstituted C1-C30 branched hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, an aromatic group having 6 to 60 carbon atoms, a heteroaromatic group having 5 to 60 carbon atoms; wherein the heteroatoms in the heteroaromatic group Independently selected from Si, ge, N, P, O, S or Se.
In some embodiments of the invention, q is 0, X 1 N, O, S, se or Te; in other embodiments of the invention, q is 1, X 1 Is N, X 2 Is N.
[ about And->]：
In the present invention,each independently selected from: a substituted or unsubstituted six-membered aromatic ring unit, a substituted or unsubstituted six-membered heteroaromatic ring unit, a substituted or unsubstituted five-membered heteroaromatic ring unit, a substituted or unsubstituted aromatic condensed ring unit; the aromatic condensed ring unit contains one or more of five-membered heteroaromatic rings, six-membered heteroaromatic rings and six-membered heteroaromatic rings.
When q is set to be 0, the catalyst,through two carbon-carbon bonds on its own aromatic ring/aromatic heterocyclic ring, with B and N, and B and X, respectively 1 Connecting; />Through 1 carbon-carbon bond on its own aromatic ring/aromatic heterocyclic ring, and B and N/X respectively 1 Connecting; the carbon-carbon bond is a carbon-carbon single bond or a carbon-carbon double bond. When q is 1, < >>The carbon atoms at both ends of two carbon-carbon bonds on the aromatic ring/aromatic heterocyclic ring are respectively connected with B and X/Y, and B and Z; the two carbon-carbon bonds are preferably adjacent carbon-carbon bonds; the two carbon-carbon bonds are each independently a carbon-carbon single bond or carbonA carbon double bond.
More specifically:
q=0:
two carbon atoms through their own 1 carbon-carbon bond are respectively connected with B and N in formula (I), and two carbon atoms through their own other 1 carbon-carbon bond are respectively connected with B and X in formula (I) 1 Is connected, and the two carbon-carbon bonds are +.>Adjacent two carbon-carbon bonds on the same aromatic ring/aromatic heterocyclic ring;
two carbon atoms through any 1 carbon-carbon bond of their own are respectively linked to B and N in formula (I);
two carbon atoms through any 1 carbon-carbon bond of their own are respectively linked to B and N in formula (I).
q=1:
two carbon atoms through their own 1 carbon-carbon bond are respectively connected with B and N in formula (I), and two carbon atoms through their own other 1 carbon-carbon bond are respectively connected with B and X in formula (I) 1 Is connected, and the two carbon-carbon bonds are +.>Adjacent two carbon-carbon bonds on the same aromatic ring/aromatic heterocyclic ring;
two carbon atoms through their own 1 carbon-carbon bond are respectively connected with B and N in formula (I), and two carbon atoms through their own other 1 carbon-carbon bond are respectively connected with B and X in formula (I) 2 Is connected, and the two carbon-carbon bonds are +.>Adjacent two carbon-carbon bonds on the same aromatic ring/aromatic heterocyclic ring;
Two carbon atoms bound by their own 1 carbon-carbon bond to B and X in formula (I), respectively 1 Two carbon atoms linked to and through another 1 carbon-carbon bond of their own, respectively to B and X in formula (I) 2 Is connected, and the two carbon-carbon bonds are +.>Adjacent two carbon-carbon bonds on the same aromatic ring/aromatic heterocyclic ring.
In the present invention, more preferably, theAnd->Each independently selected from the group represented by formulas 1 to 16:
the groups represented by the above formulas 1 to 16 are linked to the formula (I) through carbon-carbon bonds on their own aromatic ring/aromatic heterocyclic ring. In particular as described hereinbefore.
1 [ concerning L]：
In the invention, the L 1 Selected from: substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, substituted or unsubstituted C1-C30 cycloalkyl groupA radical, an aromatic radical having 6 to 60 carbon atoms, a heteroaromatic radical having 5 to 60 carbon atoms; wherein the heteroatoms in the heteroaromatic group are independently selected from Si, ge, N, P, O, S or Se. L (L) 1 And (3) withBetween them can also pass through single bond, -C (R) 1 R 2 )-、-(C＝O)-、-Si(R 1 R 2 )-、-N(R 1 )-、-PO(R 1 )-、-B(R 1 )-、-O-、-S-、-Se-、-(S＝O)-、-(SO 2 ) -any one of the connections is made. Wherein the R is 1 、R 2 Each independently selected from: H. d, a substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, and a substituted or unsubstituted C5-C60 heteroaromatic group.
More preferably, the L 1 Selected from the following structures:
a b c [ concerning R, R and R, m, n and p ]]：
In the present invention, m, n and p are each R a 、R b And R is c Independently of each other, an integer selected from 0 to 5, in particular 0 (i.e. no corresponding R a 、R b Or R is c ) 1, 2, 3, 4, 5; and at least 1 of m, n and p is other than 0.
In the present invention, R a 、R b And R is c Independent dendritic structures of formula (II). In some embodiments of the invention, two of m, n and p are 0,1 are other than 0 (i.e., R a 、R b And R is c Only 1 is present); preferably, where n and p are 0 and m is other than 0 (i.e. R b And R is c Is absent, only dendritic structure R a ) The method comprises the steps of carrying out a first treatment on the surface of the More preferably, n and p are 0, m is 1 or 2 (i.e. R a Is 1 or 2). In other embodiments of the invention, 1 of m, n and p is 0,2 is other than 0 (i.e., R a 、R b And R is c There are 2); preferably, where m and p are other than 0 and n is 0 (i.e. R b Is absent, only dendritic structure R a And R is c ) The method comprises the steps of carrying out a first treatment on the surface of the More preferably, m and p are 1 (R a And R is c The number of (2) is 1), and m is 0. In other embodiments of the invention, m, n and p are each other than 0 (i.e., R a 、R b And R is c All present); preferably, m, n and p are all 1 (i.e. R a 、R b And R is c The number of (2) is 1).
In the invention, the dendritic structure shown in the formula (II) is as follows:
Wherein:
representing a first generation of initial priming core units;
representing an intermediate iteration unit;
representing the last iteration unit; wherein x represents algebra of the dendritic structural iteration unit of formula (II), <>Corresponding to the x-th generation branch; x is an integer from 2 to 3, preferably 3 (i.e. the dendritic structure is 3 generation of iteration elements in total).
The saidEach independently selected from structures represented by formulae D-1 to D-30:
wherein,the connection line of the broken line section in the above structure is not included, i.e. +.>Contains only 1 connecting line segment and is associated with the intermediate iteration unit +.>And (5) connection. In the present invention, asterisks in the structure indicate the junction.
In the formula (II), R x Is the last iteration unitThe substituents on the above are specifically selected from the following groups: H. d (i.e. deuterium), -CN,> a linear hydrocarbon group of substituted or unsubstituted C1 to C30, a branched hydrocarbon group of substituted or unsubstituted C1 to C30, a halogenated hydrocarbon group of substituted or unsubstituted C1 to C30, a cycloalkyl group of substituted or unsubstituted C3 to C30, an aromatic group of substituted or unsubstituted C6 to C60, a heteroaromatic group of substituted or unsubstituted C5 to C60.
Wherein the R is 1 、R 2 And R is 3 Each independently selected from: H. d, a substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, Substituted or unsubstituted C6 to C60 aromatic groups, substituted or unsubstituted C5 to C60 heteroaromatic groups. The R is 1 、R 2 And R is 3 Can also pass through single bond-O-, -S-, one or more of the connections in (a).
More preferably, R x Selected from the following structures:
in the formula (II), n x Is R x The number of (3) is an integer selected from 1 to 6, and may be specifically 1, 2, 3, 4, 5, or 6.
In the formula (II),selected from: a carbon-carbon single bond, a C1-C30 straight chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 alkylthio group, or a structure selected from the group consisting of:
more preferably, the method further comprises the steps of,selected from the following structures:
in the invention, it is more preferable thatPreferably, R a 、R b And R is c Each independently selected from the formulas R-1 to R-58:
/>
in the present invention, most preferably, the compound represented by the formula (I) is selected from the group consisting of the formulas I-1 to I-78:
/>
/>
/>
/>
/>
the invention provides a condensed-ring compound containing boron nitrogen and dendritic structure, which is shown as a formula (1), takes boron as the center of a main ring and takes N atoms and other atoms X 1 、X 2 (independently selected from N, O, S, se or Te) and 3 aromatic rings/aromatic heterocycles Ar (i.e ) Is an element and a group on the main ring, and 3 atoms (N, X 1 、X 2 ) And 3 aromatic rings/heterocyclic rings Ar (i.e., 1 aromatic ring/heterocyclic ring Ar is bonded between every two inorganic elements), at least 1 of the 3 aromatic rings/heterocyclic rings Ar is bonded with a dendritic structure (i.e., R a 、R b 、R c And the dendritic structure is specifically of the formula (II)), thereby obtaining an inorganic element N, X centered on boron 1 、X 2 And 3 main body rings which surround the central boron atom are distributed at intervals in the aromatic ring/the heterocyclic ring Ar, and the main body rings are connected with condensed ring compounds with certain dendritic structures; in summary, the compound is composed of condensed ring centers containing boron atoms and nitrogen atoms and peripheral branches, and can realize separation of front orbitals by utilizing resonance effect between the boron atoms and the nitrogen atoms, thereby realizing smaller delta E ST And TADF effect, can utilize the above-mentioned rigid skeleton structure of the specific condensed ring unit to reduce the relaxation degree of excited state, realize higher luminous efficiency and narrower luminescence spectrum.
The test result shows that the condensed-cyclic compound shown in the formula (1) provided by the invention has smaller delta E ST (<0.2 eV), exhibits a thermally activated delayed fluorescence effect with a delayed fluorescence lifetime of 46-103 mus, thereby facilitating the utilization of triplet excitons and improving device efficiency. The device example results show that the solution processing type organic electroluminescent device prepared from the dendritic fused ring compound shown in the formula (1) provided by the invention not only has very high luminescence The efficiency is higher than 16.0%, the maximum external quantum efficiency is obviously higher than the device efficiency (0.7-8.8%) of the comparative compound without the dendritic structure, and the electroluminescent light spectrum has a narrower electroluminescent spectrum, and the half-peak width is smaller than 40nm.
The invention also provides a preparation method of the condensed ring compound containing boron nitrogen and dendritic structures, which is characterized by comprising the following steps:
reacting the condensed ring intermediate shown in the formula (III) with a dendritic compound Lu-R to generate a compound shown in the formula (I);
the dendritic compound Lu-R is selected from the compounds Lu 4 -R a 、Lu 5 -R b And Lu 6 -R c One or more of the following;
wherein Lu 1 ～Lu 6 Each independently selected from: hydrogen, halogen, hydroxy, mercapto, amino,
[ concerning the condensed ring intermediate represented by formula (III)]：
Wherein X is 1 、X 2 ，And m, n and p are the same as those described in the foregoing technical solutions, and are not described in detail herein.
Wherein L is 1 The types of (a) are also the same as those described in the previous technical schemes, and are not repeated here.
When q=0:
in the present invention, the condensed ring intermediate represented by the formula (iii) is preferably produced by the following production method:
s1, compound Ar 1 'reacting with a compound Ar' to form a compound C;
s2, compound C and BBr 3 Reacting to form a condensed ring intermediate shown in a formula (III);
the compound Ar' is a compound Ar 2 ' and/or Compound Ar 3 ＇；
When q=1:
s3, compound Ar 4 'reacting with a compound Ar' to form a compound D;
s4, compound D and BBr 3 Reacting to form a compound E;
s5, compound E and BBr 3 Reacting to form a compound F;
s6 Compounds F and Tf 2 O (i.e., triflic anhydride) to form compound G;
s7, reacting a compound G in the presence of DBU (namely 1, 8-diazabicyclo [5.4.0] undec-7-ene) to form a condensed ring intermediate shown in a formula (III);
the compound Ar' is a compound Ar 5 ' and/or Compound Ar 6 ＇；
Wherein:
ar (Ar) 1 ＇～Ar 6 ' in formulae C to GX 1 、X 2 Are identical to those described in the previous technical solutions, and are not described in detail herein.
Regarding step S1:
in the present invention, the reaction is preferably carried out under the action of a catalyst. The catalyst is preferably Na 2 CO 3 、K 2 CO 3 、Cs 2 CO 3 One or more of NaH, naOH and KOH. The catalyst and the compound Ar 1 The molar ratio of' is preferably (0.5-8) to 1.
In the present invention, the reaction is preferably carried out in an organic solvent medium. Wherein the organic solvent is preferably one or more of N, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), 1, 4-dioxane and tetrahydrofuran. The organic solvent and the compound Ar 1 The ratio of the amount of the 'to the' is preferably (50-500) mL to (0.1-10) mol.
In the present invention, the reaction is preferably carried out under a protective atmosphere. The protective gas for providing the protective atmosphere is not particularly limited, and the protective gas is conventional protective gas in the field, such as nitrogen, helium or argon.
In the invention, the temperature of the reaction is preferably 25-180 ℃; the reaction time is preferably 4 to 48 hours. After the above reaction, compound C was produced in the system.
Regarding step S2:
in the present invention, the reaction is preferably carried out under the action of a lithiating agent. The lithiating agent is preferably n-BuLi (i.e., n-butyllithium). The molar ratio of the lithiation reagent to the compound C is preferably (1 to 5) to 1.
In the present invention, the reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of o-xylene, m-xylene, p-xylene, isopropyl benzene and tert-butylbenzene. The dosage ratio of the organic solvent to the compound C is preferably (50-500) mL to (0.1-10) mol. The organic solvent is preferably a dry organic solvent.
In the present invention, the BBr 3 The molar ratio of (i.e., boron tribromide) to compound C is preferably (1 to 10) to 1.
The reaction is preferably carried out in the presence of an organic amine base (i.e., a basic organic amine) for neutralizing the acid during the reaction. The organic amine base is preferably N, N-diisopropylethylamine and/or triethylamine. The molar ratio of the organic amine base to the compound C is preferably (1-10) to 1.
In the invention, the temperature of the reaction is preferably 90-200 ℃; the reaction time is preferably 8 to 48 hours. After the above reaction, a condensed ring intermediate represented by formula (III) is formed in the system.
Specifically, in the above process, the mixing sequence of each material is preferably: firstly, mixing a compound C with an organic solvent, then dropwise adding a catalyst at a first temperature, and then dropwise adding BBr at a second temperature after the dropwise adding is finished 3 After the dripping is finished, stirring and mixing at a third temperature; then, at a fourth temperature, an organic amine base is added dropwise. After the dripping is finished, the temperature is raised to the reaction temperature to react, and a condensed ring intermediate shown in a formula (III) is generated. Wherein the first temperature is a low temperature of below 0 ℃, specifically-5 to-78 ℃. The second temperature is also a low temperature below 0 ℃, and can be specifically between-5 ℃ and-78 ℃; preferably the same as the first temperature. The third temperature is preferably room temperature, and may specifically be 20 to 40 ℃. The stirring and mixing time is preferably 0.5 to 6 hours. The fourth temperature is less than the third temperature, namely, after stirring and mixing, the temperature is reduced, and then organic amine alkali is added dropwise; specifically, the fourth temperature is-78-0 ℃. After all materials are added, the temperature is raised to the reaction temperature for reaction. After the reaction, a condensed ring intermediate represented by formula (III) is formed in the system.
Regarding step S3:
the reaction is preferably carried out under the action of a base. The base is preferably Na 2 CO 3 、K 2 CO 3 、Cs 2 CO 3 One or more of NaH, naOH and KOH. The base is combined with a compound Ar 4 The molar ratio of' is preferably (0.5-8) to 1.
The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of N-methyl pyrrolidone (NMP), N-dimethyl ethylenediamine (DMF), dimethyl sulfoxide (DMSO), 1, 4-dioxane and tetrahydrofuran. The organic solvent and the compound Ar 4 The ratio of the amount of the 'to the' is preferably (50-500) mL to (0.1-10) mol.
The reaction is preferably carried out under a protective atmosphere. The protective gas for providing the protective atmosphere is not particularly limited, and the protective gas is conventional protective gas in the field, such as nitrogen, helium or argon.
The temperature of the reaction is preferably 25-180 ℃; the reaction time is preferably 4 to 48 hours. After the above reaction, compound D is produced in the system.
Regarding step S4:
the reaction is preferably carried out under the action of butyllithium. The butyllithium is preferably n-BuLi (i.e., n-butyllithium) and tert-BuLi (i.e., tert-butyllithium). The molar ratio of the butyllithium to the compound D is preferably (1-5) to 1.
The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of o-xylene, m-xylene, p-xylene, isopropyl benzene and tert-butylbenzene. The dosage ratio of the organic solvent to the compound D is preferably (50-500) mL to (0.1-10) mol. The organic solvent is preferably a dry organic solvent.
Said BBr 3 The molar ratio of (i.e., boron tribromide) to compound D is preferably (1 to 10) to 1.
The molar ratio of the N, N-diisopropylethylamine to the compound D is preferably (1-10) to 1.
The temperature of the reaction is preferably 90-200 ℃; the reaction time is preferably 8 to 48 hours. After the above reaction, compound E was produced in the system.
Specifically, in the above process, the mixing sequence of each material is preferably: firstly, mixing the compound D with an organic solvent, then dropwise adding a lithiation reagent at a first temperature, and then dropwise adding BBr at a second temperature after the dropwise adding is finished 3 After the dripping is finished, stirring and mixing at a third temperature; then, at a fourth temperature, an organic amine base is added dropwise. After the dripping is finished, the temperature is raised to the reaction temperature to react, and the compound E is generated. Wherein the first temperature is a low temperature of below 0 ℃, specifically-5 to-78 ℃. The second temperature is also a low temperature below 0 ℃, and can be specifically between-5 ℃ and-78 ℃; preferably the same as the first temperature. The third temperature is preferably room temperature, and may specifically be 20 to 40 ℃. The stirring and mixing time is preferably 0.5 to 6 hours. The fourth temperature < the third temperature, i.e. during the stirring After mixing, cooling, and then dropwise adding organic amine alkali; specifically, the fourth temperature is-78-0 ℃. After all materials are added, the temperature is raised to the reaction temperature for reaction. After the reaction, compound E was produced in the system.
Regarding step S5:
the reaction is preferably carried out under the action of a catalyst. The catalyst is preferably one of boron tribromide, naOH and KOH. The molar ratio of the catalyst to the compound E is preferably (2-8) to 1.
The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of dichloromethane, benzene and tetrahydrofuran. The dosage ratio of the organic solvent to the compound E is preferably (50-500) mL to (0.1-10) mol.
The reaction is preferably carried out under a protective atmosphere. The protective gas for providing the protective atmosphere is not particularly limited, and the protective gas is conventional protective gas in the field, such as nitrogen, helium or argon.
The temperature of the reaction is preferably 25-60 ℃; the reaction time is preferably 4 to 48 hours. After the above reaction, compound F was produced in the system.
Regarding step S6:
the reaction is preferably carried out under the action of a catalyst. The catalyst is preferably one of trifluoromethanesulfonic anhydride, trifluoromethanesulfonic acid and trifluoroacetic anhydride. The molar ratio of the catalyst to the compound F is preferably (2-8) to 1.
The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of dichloromethane, chloroform, pyridine, benzene and tetrahydrofuran. The dosage ratio of the organic solvent to the compound F is preferably (50-500) mL to (0.1-10) mol.
The reaction is preferably carried out under a protective atmosphere. The protective gas for providing the protective atmosphere is not particularly limited, and the protective gas is conventional protective gas in the field, such as nitrogen, helium or argon.
The temperature of the reaction is preferably 25-60 ℃; the reaction time is preferably 4 to 48 hours. After the above reaction, compound G was produced in the system.
Regarding step S7:
the reaction is preferably carried out in a microwave reactor.
The reaction is preferably carried out under the action of a catalyst. The catalyst is preferably 1, 8-diazabicyclo [5.4.0] undec-7-ene (DPU). The molar ratio of the catalyst to the compound G is preferably (2-8) to 1.
The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of N-methyl pyrrolidone (NMP), N-dimethyl ethylenediamine (DMF), dimethyl sulfoxide (DMSO), 1, 4-dioxane and tetrahydrofuran. The dosage ratio of the organic solvent to the compound E is preferably (50-500) mL to (0.1-10) mol.
The temperature of the reaction is preferably 25-60 ℃; the reaction time is preferably 4 to 48 hours. After the above reaction, a condensed ring intermediate represented by formula (III) is formed in the system.
[ concerning dendrimer Lu-R ]]：
Wherein:
R a 、R b and R is c In accordance with the foregoing, a detailed description is omitted herein.
Lu 4 ～Lu 6 Each independently selected from: hydrogen, halogen, hydroxy, mercapto, amino,
The source of the dendrimer Lu-R is not particularly limited in the present invention, and is generally commercially available or may be prepared according to a preparation method known in the art.
[ reaction of condensed Ring intermediate of formula (III) with dendrimer Lu-R ]]：
In the present invention, the reaction is preferably carried out under the action of a catalyst. The catalyst is preferably palladium chloride, palladium acetate,Tris (dibenzylideneacetone) dipalladium (i.e., pd 2 (dba) 3 ) And tetrakis (triphenylphosphine) palladium (i.e. Pd (PPh) 3 ) 4 ) One or more of them, more preferably Pd 2 (dba) 3 And/or Pd (PPh) 3 ) 4 . The molar ratio of the catalyst to the condensed ring intermediate of formula (III) is preferably (0.001-0.1) to 1.
In the present invention, the reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of toluene, o-xylene, m-xylene, p-xylene, isopropyl benzene and mesitylene. The dosage ratio of the organic solvent to the condensed ring intermediate of the formula (III) is preferably (50-500) mL to (0.1-10) mol.
In the present invention, the reaction is preferably carried out under a protective atmosphere. The protective gas for providing the protective atmosphere is not particularly limited, and the protective gas is conventional protective gas in the field, such as nitrogen, helium or argon.
In the invention, the temperature of the reaction is preferably 60-180 ℃; the reaction time is preferably 8 to 48 hours. After the reaction, a condensed ring compound containing boron nitrogen and a dendritic structure shown in the formula (I) is generated in the system.
The invention also provides application of the condensed-ring compound containing boron nitrogen and dendritic structures shown in the formula (I) in the technical scheme in an organic electroluminescent device.
The invention also provides an organic electroluminescent device, comprising: an anode, a cathode, and a thin film layer between the anode and the cathode;
the thin film layer contains the condensed ring compound containing boron nitrogen and dendritic structure shown in the formula (I) in the technical scheme.
The structure of the organic electroluminescent device is not particularly limited, and the organic electroluminescent device can be a conventional organic electroluminescent device well known to those skilled in the art, and those skilled in the art can select and adjust the organic electroluminescent device according to application conditions, quality requirements and product requirements. The structure of the organic electroluminescent device according to the present invention preferably includes: a substrate; an anode disposed on the substrate; a thin film layer disposed on the anode; and a cathode disposed on the thin film layer.
Wherein:
the thickness of the substrate is preferably 0.3 to 0.7mm, more preferably 0.4 to 0.6mm. The kind of the substrate is not particularly limited, and the substrate of the conventional organic electroluminescent device known to those skilled in the art may be selected and adjusted according to the application, quality requirements and product requirements, and is preferably glass or plastic in the present invention.
The anode is preferably a material that facilitates hole injection, more preferably a conductive metal or conductive metal oxide, and most preferably indium tin oxide.
The cathode is preferably a metal including, but not limited to, calcium, magnesium, barium, aluminum, and silver, preferably aluminum.
The film layer can be one layer or a plurality of layers, and at least one layer is a light-emitting layer; the light-emitting layer contains the dendritic fused ring compound containing boron atoms and oxygen atoms and shown in the formula (I) in the technical scheme.
To improve the performance and efficiency of the device, the thin film layer preferably further includes one or more of a hole injection layer, a hole transport layer, and an electron blocking layer. The thin film layer between the light emitting layer and the cathode preferably further includes one or more of a hole blocking layer, an electron injection layer, and an electron transport layer. Most preferably, the film layer comprises, in order: a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron injection layer, and an electron transport layer. The materials and thicknesses of the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer and the electron transport layer are not particularly limited in the present invention, and may be selected and adjusted according to materials and thicknesses well known to those skilled in the art. The preparation process of the electrode, the hole injection layer, the hole transport layer, the electron blocking layer, the hole blocking layer, the electron injection layer and the electron transport layer is not particularly limited, and is preferably prepared by adopting the processes of vacuum evaporation, solution spin coating, solution knife coating, ink-jet printing, offset printing or three-dimensional printing. The thin film layer is preferably an organic thin film layer. The process for preparing the organic electroluminescent layer is not particularly limited, and is preferably prepared by using a process of solution spin coating, solution blade coating, inkjet printing, offset printing or three-dimensional printing.
In some embodiments of the present invention, the organic electroluminescent device is configured as device structure a or device structure B. Wherein, the device structure A is: ITO/PEDOT PSS/dendritic fused ring compound/TSPO 1/TmPyPB/LiF/Al; more specifically, the device structure a is: ITO/PEDOT PSS (40 nm)/the dendritic fused ring compound (30 nm)/TSPO 1 (8 nm)/TmPyPB (30 nm)/LiF (0.8 nm)/Al (100 nm). Wherein, the device structure B is: ITO/PEDOT PSS/blend of dendritic fused ring compound and host material SiMCP2 of the invention/TSPO 1/TmPyPB/LiF/Al; more specifically, the device structure B is: ITO/PEDOT: PSS (40 nm)/blend of the dendritic fused ring compound and SiMCP2 as a main material (mass ratio: 1:9) (30 nm)/TSPO 1 (8 nm)/TmPyPB (42 nm)/LiF (1 nm)/Al (100 nm).
The preparation method of the organic electroluminescent device is not particularly limited, and can be carried out according to the following method: forming an anode on the substrate; forming one or more thin film layers on the anode, wherein the thin film layers comprise a light-emitting layer; a cathode is formed on the thin film layer.
The structure and the materials of the organic electroluminescent device and the corresponding preferred principles of the preparation method of the invention can correspond to the corresponding materials and structures of the organic electroluminescent device and the corresponding preferred principles, and are not described in detail herein.
The present invention is not particularly limited in the manner of forming the anode on the substrate at first, and may be carried out according to methods well known to those skilled in the art. And then a thin film layer is arranged on the anode, and specifically comprises a thin film layer below the light-emitting layer, the light-emitting layer and a thin film layer above the light-emitting layer. The method of forming the thin film layer below and above the light-emitting layer is not particularly limited, and the thin film layer may be formed by vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, or three-dimensional printing. The formation mode of the light emitting layer is not particularly limited, and may be formed by solution spin coating, solution blade coating, inkjet printing, offset printing, or three-dimensional printing. The present invention is not particularly limited in the manner of forming the cathode after the formation of the above-mentioned thin film layer and preparing the cathode on the surface thereof, and is preferably a method well known to those skilled in the art, including but not limited to vacuum deposition. Through the above process, the organic electroluminescent device is obtained.
The invention provides a condensed-ring compound containing boron nitrogen and dendritic structure, which is shown as a formula (1), takes boron as the center of a main ring and takes N atoms and other atoms X 1 、X 2 (independently selected from N, O, S, se or Te) and 3 aromatic rings/aromatic heterocycles Ar (i.e ) Is an element and a group on the main ring, and 3 atoms (N, X 1 、X 2 ) And 3 aromatic rings/heterocyclic rings Ar (i.e., 1 aromatic ring/heterocyclic ring Ar is bonded between every two inorganic elements), at least 1 of the 3 aromatic rings/heterocyclic rings Ar is bonded with a dendritic structure (i.e., R a 、R b 、R c And the dendritic structure is specifically of the formula (II)), thereby obtaining an inorganic element N, X centered on boron 1 、X 2 And 3 main body rings which surround the central boron atom are distributed at intervals in the aromatic ring/the heterocyclic ring Ar, and the main body rings are connected with condensed ring compounds with certain dendritic structures; in summary, the compound is composed of condensed ring centers containing boron atoms and nitrogen atoms and peripheral branches, and can realize separation of front orbitals by utilizing resonance effect between the boron atoms and the nitrogen atoms, thereby realizing smaller delta E ST And TADF effect, can utilize the above-mentioned rigid skeleton structure of the specific condensed ring unit to reduce the relaxation degree of excited state, realize higher luminous efficiency and narrower luminescence spectrum.
The test result shows that the invention provides a thick compound represented by the formula (1)The fused ring compound has smaller delta E ST (<0.2 eV), exhibits a thermally activated delayed fluorescence effect with a delayed fluorescence lifetime of 46-103 mus, thereby facilitating the utilization of triplet excitons and improving device efficiency. The device example results show that the solution processing organic electroluminescent device prepared from the dendritic fused ring compound shown in the formula (1) provided by the invention has high luminous efficiency, the maximum external quantum efficiency is more than 16.0%, the device efficiency is obviously higher than that of a comparative compound without a dendritic structure (0.7-8.8%), the device has a narrower electroluminescent spectrum, and the half-peak width is less than 40nm.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
Example 1: preparation of Compounds of formula I-1
The synthetic route and the process are as follows:
compounds of formula 1-1 (13.6 g,0.05 mol), diphenylamine (20.3 g,0.12 mol) and CS were weighed out in a 500mL three-necked flask under an argon atmosphere 2 CO 3 (65.2 g,0.20 mol) 80mL of N, N-Dimethylformamide (DMF) was taken and added to a bottle, the temperature was raised to 150℃and the reaction was stirred under argon for 10 hours, then cooled to room temperature, the reaction mixture was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to give the product 1-2 (18.4 g, yield: 64.8%). Elemental analysis: theoretical value C,63.18; h,3.89; n,4.91; test value C,63.15; h,3.91; n,4.87. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 568.0; experimental values 568.0 (M + )。
The compound of formula 1-2 (5.7 g,10 mmol) and dried ortho-xylene were weighed under argon in a 250mL two-necked flask (80 mL) of a butyllithium solution (4.0 mL,2.5M,10 mmol) was added dropwise at-30℃and stirred for 2 hours at-30℃after the addition, and boron tribromide (2.8 g,11.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after the addition was completed for 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.6 g,20.0 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c for reaction for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give product 1-3 (2.3 g, yield: 45.2%). Elemental analysis: theoretical value C,72.18; h,4.04; n,5.61; test value C,72.15; h,4.02; n,5.64.ESI-MS: theoretical value 498.1; experimental values 498.1 (M + )。
The compounds of formulae 1 to 4 were prepared according to the synthetic route described in the literature adv.funct.mater.2014,24, 3413-3421.
Compounds of formulas 1-4 (1.77 g,1.1 mmol), compounds of formulas 1-3 (0.50 g,1 mmol), pd were placed in 50mL Schlenk bottles under argon atmosphere 2 (dba) 3 (46mg，0.05mmol)、t-Bu 3 PHBF 4 (58 mg,0.20 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-1 (1.24 g, yield: 56.2%). Elemental analysis: theoretical value C,86.57; h,6.67; n,6.22; test value C,86.52; h,6.71; n,6.18. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 2024.1; experimental values 2024.0 (M + )。
Photophysical properties of the fused ring compound prepared in example 1 of the present invention were examined, and the results are shown in Table 1.
Example 2: preparation of Compounds of formula I-19
The synthetic route and the process are as follows:
weighing the compound of formula 2-1 in a 500mL three-necked flask under argon atmosphereSubstance (9.60 g,0.05 mol), 3, 6-tert-butylcarbazole (33.50 g,0.12 mol) and CS 2 CO 3 (65.2 g,0.20 mol) 80mL of N, N-Dimethylformamide (DMF) was taken and added to a bottle, the temperature was raised to 150℃and the reaction was stirred under argon for 10 hours, then cooled to room temperature, the reaction mixture was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to give the product 2-2 (20.10 g, yield: 56.6%). Elemental analysis: theoretical C,77.62; h,7.22; n,3.94; test value C,77.59; h,7.25; n,3.90. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 710.3; experimental values 710.4 (M + )。
A compound of formula 2-2 (7.10 g,10 mmol) and dried o-xylene (80 mL) were weighed into a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃after the dropwise addition, and then boron tribromide (2.8 g,11.0 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after the dropwise addition was completed for 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.6 g,20.0 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c for reaction for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give product 2-3 (3.41 g, yield: 53.2%). Elemental analysis: theoretical value C,86.23; h,7.71; n,4.37; test value C,86.27; h,7.65; n,4.35.ESI-MS: theoretical value 640.4; experimental values 640.3 (M + )。
In a 250mL two-necked flask, a compound (3.20 g,5 mmol) of the formula 2-3 was weighed, 80mL of N, N-Dimethylformamide (DMF) was added to the flask, after stirring and dissolution, 20mL of DMF solution of NBS (0.89 g,5 mmol) was slowly added dropwise to an ice-water bath, after the dropwise addition was completed, the temperature was naturally raised, stirring was carried out at room temperature for 20 hours, the reaction solution was diluted with methylene chloride and poured into water, an organic phase was separated, anhydrous sodium sulfate was added and dried, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated in a column to obtain a product 2-4 (1.55 g, yield: 43.2%). Elemental analysis: theoretical C,76.78; h,6.72; n,3.89; test value C,76.81; h,6.68; n,3.91.ESI-MS: theoretical 718.3; experimental value 718.3 (M + )。
Compounds of formulae 1-4 (1.77 g,1.1 mmol), 2-4 (0.72 g,1 mmol), pd were placed in 50mL Schlenk flask under argon 2 (dba) 3 (46mg，0.05mmol)、t-Bu 3 PHBF 4 (58 mg,0.20 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-19 (0.98 g, yield: 43.5%). Elemental analysis: theoretical value C,86.64; h,7.72; n,5.61; test value C,86.62; h,7.75; n,5.57. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 2244.3; experimental values 2244.3 (M + )。
Photophysical properties of the fused ring compound prepared in example 2 of the present invention were examined, and the results are shown in Table 1.
Example 3: preparation of Compounds of formula I-20
The synthetic route and the process are as follows:
in a 250mL two-necked flask, a compound (3.20 g,5 mmol) of formula 2-3 was weighed, 80mL of N, N-Dimethylformamide (DMF) was added to the flask, after stirring and dissolution, 20mL of DMF solution of NBS (2.14 g,12 mmol) was slowly added dropwise to an ice-water bath, after the dropwise addition was completed, the temperature was naturally raised, stirring was carried out at room temperature for 20 hours, the reaction solution was diluted with methylene chloride and poured into water, an organic phase was separated, anhydrous sodium sulfate was added and dried, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated in a column to obtain the product 3-1 (2.09 g, yield: 52.6%). Elemental analysis: theoretical C,69.19; h,5.93; n,3.51; test value C,69.21; h,5.95; n,3.47.ESI-MS: theoretical 796.2; experimental value 796.2 (M + )。
In a 50mL Schlenk flask under argon atmosphere, the compound of formula 1-4 (1.77 g,1.1 mmol), the compound of formula 3-1 (0.40 g,0.5 mmol), pd were added 2 (dba) 3 (46mg，0.05mmol)、t-Bu 3 PHBF 4 (58mg，020 mmol), t-BuONa (0.19 g,2 mmol) and then 20mL toluene was injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-20 (0.66 g, yield: 34.2%). Elemental analysis: theoretical value C,86.70; h,7.20; n,5.82; test value C,86.65; h,7.22; n,5.77. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 3848.2; experimental values 3848.3 (M + )。
Photophysical properties of the fused ring compound prepared in example 3 of the present invention were examined, and the results are shown in Table 1.
Example 4: preparation of Compounds of formula I-27
The synthetic route and the process are as follows:
a compound of formula 4-1 (13.49 g,0.05 mol), 3, 6-t-butylcarbazole (33.50 g,0.12 mol) and CS were weighed out under an argon atmosphere in a 500mL three-necked flask 2 CO 3 (65.2 g,0.20 mol) 80mL of N, N-Dimethylformamide (DMF) was taken and added to a bottle, the temperature was raised to 150℃and the reaction was stirred under argon for 10 hours, then cooled to room temperature, the reaction mixture was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to give 4-2 (23.13 g, yield: 58.7%). Elemental analysis: theoretical value C,69.87; h,6.37; n,3.54; test value C,69.82; h,6.41; n,3.50. Electrospray ionization mass spectrometry (ESI-MS): theoretical 788.2; experimental values 788.3 (M + )。
A compound of formula 4-2 (7.88 g,10 mmol) and dried o-xylene (80 mL) were weighed into a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃after the dropwise addition, and then boron tribromide (2.8 g,11.0 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after the dropwise addition was completed for 20 minutes. Cooling to 0deg.C again, and adding N, N-diisopropylethylamine (2.6) g,20.0 mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ for reaction for 20 hours after the completion of dropwise addition. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give 4-3 (4.40 g, yield: 61.3%). Elemental analysis: theoretical C,76.78; h,6.72; n,3.89; test value C,76.81; h,6.75; n,3.82.ESI-MS: theoretical 718.3; experimental value 718.3 (M + )。
In a 100mL two-necked flask, the compound of formula 4-3 (2.15 g,3 mmol) and the borate (1.5 g,6 mmol), pdCl were weighed under an argon atmosphere 2 (dppf) (0.11 g,0.15 mmol) and potassium acetate (0.6 g,6 mmol) were added to a flask with 40mL of DMF, and the temperature was raised to 85℃and the reaction was stirred for 10 hours. Then cooled to room temperature, the reaction solution was washed with deionized water, extracted with methylene chloride solution to give an organic phase which was concentrated and dried, and the crude product was separated by column to give product 4-4 (1.66 g, yield: 72.3%). Elemental analysis: theoretical value C,81.46; h,7.89; n,3.65; test value C,81.40; h,7.82; n,3.69.ESI-MS: theoretical value 766.5; experimental value 767.4 ([ M+H)] + )。
The compounds of formulae 4 to 5 were prepared according to the synthetic route described in document Journal of Materials Chemistry C,2017,5,9753-9760.
Magnesium turnings (0.13 g,5.5 mmol) were weighed into a 250mL two-neck flask under argon atmosphere, the compound of formula 4-5 (4.4 g,5 mmol) was dissolved in 50mL dry THF solution, then added dropwise to the two-neck flask containing magnesium turnings, the resulting grits were filtered and slowly added dropwise to a solution of cyanuric chloride (0.4 g,2.2 mmol) in THF at-20 ℃, after the reaction was completed, cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with dichloromethane. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated as a column to give the product 4-6 (1.5 g, yield: 40%). Elemental analysis: theoretical value C,83.70; h,6.85; n,7.38; test value C,83.72; h,6.81; n,7.43.MALDI-TOF (m/z): theoretical value 1705.9; experimental values 1705.9 (M + )。
In a 50mL Schlenk flask under argon atmosphere are added the compound of formula 4-6 (0.85 g,0.5 mmol), the compound of formula 4-4 (0.38 g,0.5 mmol), and the catalyst Pd 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 110℃and the reaction was stirred under argon for 24 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-27 (0.37 g, yield: 32.2%). Elemental analysis: theoretical value C,85.72; h,7.15; n,6.66; test value C,85.75; h,7.11; n,6.52.MALDI-TOF (m/z): theoretical 2310.3; experimental values 2310.4 (M + )。
Photophysical properties of the fused ring compound prepared in example 4 of the present invention were examined, and the results are shown in Table 1.
Example 5: preparation of Compounds of formula I-30
The synthetic route and the process are as follows:
the compounds of formula 5-1 were prepared according to the synthetic route disclosed in the literature adv.funct.mater.2014,24, 3413-3421.
In a 50mL Schlenk flask, under argon atmosphere, a compound of formula 5-1 (3.5 g,2 mmol), 4' -diiododiphenyl ether (1.7 g,4 mmol), cuprous iodide (0.1 g,0.5 mmol) and anhydrous potassium carbonate (0.6 g,4 mmol) were added, 20mL of DMI was taken and added to the flask, and the temperature was raised to 170℃for 20 hours. The temperature was lowered to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated as 5-2 (1.6 g, yield: 40%). Elemental analysis: theoretical C,75.76; h,6.06; n,4.83; test value C,75.64; h,6.12; n,4.86.MALDI-TOF (m/z): theoretical value 2027.8; experimental values 2027.8 (M + )。
A50 mL three-necked flask was charged with the compound of formula 5-2 (1.0 g,0.5 mmol), the compound of formula 4-4 (0.42 g,0.55 mmol), and catalyst Pd under an argon atmosphere 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (8)2mg,0.2 mmol) of toluene was added to a bottle, potassium carbonate (0.28 g,4 mmol) was dissolved in 2mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 110℃and the reaction was stirred under argon for 16 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated as a column to give the product I-30 (0.42 g, yield: 32.8%). Elemental analysis: theoretical value C,82.21; h,6.74; n,4.96; test value C,82.25; h,6.67; n,4.98.MALDI-TOF (m/z): theoretical value 2540.3; experimental values 2540.4 (M + )。
Photophysical properties of the fused ring compound prepared in example 5 of the present invention were examined, and the results are shown in Table 1.
Example 6: preparation of Compounds of formula I-31
The synthetic route and the process are as follows:
in a 100mL three-necked flask, a compound of formula 1-4 (3.2 g,2 mmol), dibromobutane (0.87 g,4 mmol) and anhydrous potassium carbonate (0.6 g,4 mmol) were added under argon atmosphere, 20mL DMF was taken and added to the flask, and the temperature was raised to 120℃for 20 hours. The temperature was lowered to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated as a column to give the product 6-1 (2.4 g, yield: 70%). Elemental analysis: theoretical value C,82.73; h,7.06; n,5.63; test value C,82.63; h,7.11; n,5.69.MALDI-TOF (m/z): theoretical value 1739.8; experimental values 1739.9 (M + )。
In a 50mL two-necked flask, the compound of formula 4-3 (3.59 g,5 mmol) and sodium tert-butoxide (0.54 g,10 mmol) were weighed under argon atmosphere, 20mL DMF was taken and added to the flask, and the temperature was raised to 120℃for 20 hours of reaction. The temperature was lowered to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was separated by column to give the product 6-2 (1.76 g, yield: 52.4%). Elemental analysis: theoretical C,84.16; h,7.66; n,4.18; test value C,84.13; h,7.60; n,4.12.ESI-MS: theoretical value 670.4; experimental value 671.2 ([ M+H)] + )。
In a 50mL two-necked flask, a compound of formula 6-2 (1.34 g,2 mmol) and dried methylene chloride (30 mL) were weighed under argon atmosphere, and boron tribromide (1.5 g,6 mmol) was added dropwise at 0℃and reacted at room temperature for 5 hours after the addition. Pouring into water, separating out the organic phase, adding anhydrous sodium sulfate for drying, removing the solvent from the organic phase obtained by filtration, and separating the crude product by a column to obtain a product 6-3 (1.08 g, yield: 82.3%). Elemental analysis: theoretical C,84.13; h,7.52; n,4.27; test value C,84.10; h,7.53; n,4.26.ESI-MS: theoretical value 656.4; experimental value 657.2 ([ M+H)] + )。
In a 50mL two-necked flask, a compound of formula 6-1 (1.70 g,1 mmol), a compound of formula 6-3 (0.66 g,1 mmol) and anhydrous potassium carbonate (0.28 g,2 mmol) were charged under argon atmosphere, 10mL of DMF was taken and added to the flask, and the temperature was raised to 120℃for 20 hours of reaction. The temperature was lowered to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated as column to give the product I-31 (1.00 g, yield: 43.2%). Elemental analysis: theoretical value C,86.01; h,7.39; n,5.44; test value C,86.03; h,7.35; n,5.48.MALDI-TOF (m/z): theoretical value 2316.4; experimental values 2316.4 (M + )。
Photophysical properties of the fused ring compound prepared in example 6 of the present invention were examined, and the results are shown in Table 1.
Example 7: preparation of Compounds of formula I-22
The synthetic route and the process are as follows:
the compounds of formula 7-1 were prepared according to the synthetic route described in documents Tetrahedron Letters,2003,44,957-959.
A50 mL Schlenk flask was charged with the compound of formula 7-1 (1.2 g,1.1 mmol), formula 3-1 under argon atmosphereCompound (0.40 g,0.5 mmol) and catalyst Pd 2 (dba) 3 (92 mg,0.1 mmol) and ligand S-phos (164 mg,0.4 mmol) were added to a flask, 20mL of toluene was taken, potassium carbonate (0.54 g,4 mmol) was dissolved in 2mL of water, and an aqueous potassium carbonate solution was introduced into the flask and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-22 (0.29 g, yield: 23.2%). Elemental analysis: theoretical C,88.05; h,7.11; n,4.42; test value C,88.01; h,7.06; n,4.46.MALDI-TOF (m/z): theoretical value 2535.4; experimental values 2535.4 (M + )。
Photophysical properties of the fused ring compound prepared in example 7 of the present invention were examined, and the results are shown in Table 1.
Example 8: preparation of Compounds of formula I-32
The synthetic route and the process are as follows:
the compounds of formula 8-1 were prepared according to the synthetic route disclosed in literature polym.chem.,2015,6,1180-1191.
A50 mL three-necked flask was charged with the compound of formula 8-1 (1.2 g,0.5 mmol), the compound of formula 4-4 (0.42 g,0.55 mmol), and catalyst Pd under an argon atmosphere 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.28 g,4 mmol) was dissolved in 2mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 110℃and the reaction was stirred under argon for 16 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated as a column to give the product I-32 (0.63 g, yield: 42.3%). Elemental analysis: theoretical value C,85.25; h,6.88; n,4.26; test value C,85.21; h,6.81; n,4.24.MALDI-TOF (m/z): theoretical value 2956.6; experimental values 2956.6 (M + )。
Photophysical properties of the fused ring compound prepared in example 8 of the present invention were examined, and the results are shown in Table 1.
Example 9: preparation of Compounds of formula I-33
The synthetic route and the process are as follows:
the compounds of formula 9-1 were prepared according to the synthetic route disclosed in literature polym.chem.,2015,6,1180-1191.
A50 mL two-necked flask was charged with the compound of formula 9-1 (0.93 g,0.5 mmol), the compound of formula 4-3 (0.39 g,0.55 mmol) and anhydrous potassium carbonate (0.28 g,2 mmol) under argon atmosphere, 10mL DMF was taken and added to the flask, and the temperature was raised to 120℃for 20 hours. The temperature was lowered to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated as column to give the product I-33 (0.73 g, yield: 58.2%). Elemental analysis: theoretical value C,84.31; h,7.40; n,3.37; test value C,84.27; h,7.45; n,3.32.MALDI-TOF (m/z): theoretical value 2491.4; experimental values 2491.4 (M + )。
Photophysical properties of the fused ring compound prepared in example 9 of the present invention were examined, and the results are shown in Table 1.
Example 10: preparation of Compounds of formula I-34
The synthetic route and the process are as follows:
the compounds of formula 10-1 were prepared according to the synthetic route disclosed in document J.Am.chem.Soc.1996,118, 4354-4360.
In a 50mL two-necked flask, a compound of formula 10-1 (0.1 g,0.5 mmol), a compound of formula 4-3 (0.39 g,0.55 mmol) and anhydrous potassium carbonate (0.28 g,2 mmol) were charged under argon atmosphere, 10mL DMF was taken and added to the flask, and the temperature was raised to 120℃for 20 hours. Cooling to room temperature, pouring the reaction solution into water and extracting and separating the solution by using dichloromethane The organic phase is taken off. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated as a column to give the product I-34 (0.59 g, yield: 43.5%). Elemental analysis: theoretical value C,73.93; h,6.35; s,1.03; test value C,73.91; h,6.31; s,1.09.MALDI-TOF (m/z): theoretical value 2711.2; experimental values 2711.1 (M + )。
Photophysical properties of the fused ring compound prepared in example 10 of the present invention were examined, and the results are shown in Table 1.
Example 11: preparation of Compounds of formula I-36
The synthetic route and the process are as follows:
compounds of formula 1-1 (13.6 g,0.05 mol), 9-dimethylacridine (23.5 g,0.12 mol) and CS were weighed out in a 500mL three-necked flask under an argon atmosphere 2 CO 3 (65.2 g,0.20 mol) 80mL of N, N-Dimethylformamide (DMF) was taken and added to a bottle, the temperature was raised to 150℃and the reaction was stirred under argon for 10 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated by column separation to give 11-2 (20.19 g, yield: 62.3%). Elemental analysis: theoretical value C,66.48; h,4.65; n,4.31; test value C,66.42; h,4.61; n,4.36. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 648.1; experimental value 648.2 (M + )。
A compound of formula 11-2 (6.48 g,10 mmol) and dried o-xylene (80 mL) were weighed into a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃after the dropwise addition, and further boron tribromide (2.8 g,11.0 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after the dropwise addition was completed for 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.6 g,20.0 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c for reaction for 20 hr. After the reaction is cooled to room temperature, solid is separated out from the filtering system and washed by methanol, and the crude product passes throughColumn separation gave product 11-3 (2.51 g, yield: 43.4%). Elemental analysis: theoretical value C,74.63; h,4.87; n,4.84; test value C,74.68; h,4.82; n,4.92.ESI-MS: theoretical value 578.2; experimental values 578.2 (M + )。
The compounds of formula 11-1 were prepared according to the synthetic route disclosed in the literature org. Lett.2018,20, 7864-7868.
In a 50mL Schlenk flask under argon atmosphere, the compound of formula 11-1 (1.3 g,1.1 mmol), the compound of formula 11-3 (0.58 g,1 mmol), pd were added 2 (dba) 3 (46mg，0.05mmol)、t-Bu 3 PHBF 4 (58 mg,0.20 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-36 (0.59 g, yield: 35.2%). Elemental analysis: theoretical C,86.26; h,5.55; n,7.54; test value C,86.21; h,5.51; n,7.58.MALDI-TOF (m/z): theoretical value 1669.7; experimental values 1669.7 (M + )。
Photophysical properties of the fused ring compound prepared in example 11 of the present invention were examined, and the results are shown in Table 1.
Example 12: preparation of Compounds of formula I-37
The synthetic route and the process are as follows:
compounds of formula 1-1 (13.6 g,0.05 mol), spiroacridine (41.6 g,0.12 mol) and CS were weighed out in a 500mL three-necked flask under an argon atmosphere 2 CO 3 (65.2 g,0.20 mol) 80mL of N, N-Dimethylformamide (DMF) was taken and put into a bottle, the temperature was raised to 150℃and the reaction was stirred under argon for 10 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to obtain the product 12-2 (24.16 g, yield: 52.3%). Elemental analysis: theoretical value C,69.98; h,3.70; n,3.02;test value C,69.92; h,3.61; n,3.76. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 924.1; experimental values 924.2 (M + )。
A compound of formula 12-2 (9.24 g,10 mmol) and dried o-xylene (80 mL) were weighed into a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃after the dropwise addition, and further boron tribromide (2.8 g,11.0 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after the dropwise addition was completed for 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.6 g,20.0 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c for reaction for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give 12-3 (3.09 g, yield: 36.2%). Elemental analysis: theoretical value C,75.79; h,3.77; n,3.27; test value C,75.71; h,3.82; n,3.31.ESI-MS: theoretical value 854.1; experimental values 854.1 (M + )。
A250 mL Schlenk flask was charged with the compound of formula 12-1 (7.6 g,20 mmol) and sodium hydride (5.6 g,22 mmol) under argon, 80mL DMF was taken and stirred at room temperature for 1 hour. TBS-Cl (3.6 g,24 mmol) was then added dropwise and the reaction was stirred for another 4 hours, then the reaction solution was poured into water, and the crude product obtained by filtration was separated into a column to obtain the product 12-4 (8.0 g, yield: 80%). Elemental analysis: theoretical value C,48.29; h,5.47; n,2.82; test value C,48.23; h,5.41; n,2.85.ESI-MS: theoretical value 495.0; experimental value 495.0 (M + )。
In a 100mL Schlenk flask under argon atmosphere was added the compound of formula 12-4 (5.0 g,10 mmol), silacridine (5.0 g,22 mmol), pd 2 (dba) 3 (0.46g，0.5mmol)、t-Bu 3 PHBF 4 (0.58 g,2.0 mmol), t-BuONa (3.8 g,40 mmol) and then 40mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. Anhydrous sodium sulfate was added to dry, and the organic phase obtained by filtration was freed from the solvent. The crude product obtained and tetrabutylammonium fluoride (5.3 g,20 mmol) were added to 30ml of THF and stirred for 4 hours. The product 12-5 (6.0 g, yield: 60%) was obtained by column separation and desolventizing. Elemental analysis: theoretical value C,75.06; h,6.15; n,6.25; test value C,75.12; h,6.13; n,6.27.ESI-MS: theoretical value 671.2; experimental values 671.2 (M + )。
In a 100mL Schlenk flask under argon atmosphere, the compound of formula 12-4 (1.0 g,2 mmol), the compound of formula 12-5 (2.7 g,4 mmol), pd were added 2 (dba) 3 (0.09g，0.1mmol)、t-Bu 3 PHBF 4 (0.12 g,0.4 mmol), t-Buona (0.4 g,4 mmol) and then 40mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. Anhydrous sodium sulfate was added to dry, and the organic phase obtained by filtration was freed from the solvent. The crude product obtained and tetrabutylammonium fluoride (5.3 g,20 mmol) were added to 30mL THF and stirred for 4 hours. Column separation and desolventizing gave product 12-6 (1.2 g, yield: 40%). Elemental analysis: theoretical C,75.24; h,5.93; n,6.27; test value C,75.22; h,5.91; n,6.29.MALDI-TOF (m/z): theoretical 1562.5; experimental 1562.5.
In a 50mL Schlenk flask under argon atmosphere, the compound of formula 12-6 (0.8 g,0.55 mmol), the compound of formula 12-3 (0.43 g,0.5 mmol), pd were added 2 (dba) 3 (46mg，0.05mmol)、t-Bu 3 PHBF 4 (58 mg,0.20 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-37 (0.26 g, yield: 22.3%). Elemental analysis: theoretical value C,78.01; h,5.34; n,5.39; test value C,78.06; h,5.28; n,5.37.MALDI-TOF (m/z): theoretical value 2337.8; experimental values 2337.8 (M + )。
Photophysical properties of the fused ring compound prepared in example 12 of the present invention were examined, and the results are shown in Table 1.
Example 13: preparation of Compounds of formula I-38
The synthetic route and the process are as follows:
compounds of formula 1-1 (13.6 g,0.05 mol), spiroacridine (39.7 g,0.12 mol) and CS were weighed out in a 500mL three-necked flask under an argon atmosphere 2 CO 3 (65.2 g,0.20 mol) 80mL of N, N-Dimethylformamide (DMF) was taken and added to a bottle, the temperature was raised to 150℃and the reaction was stirred under argon for 10 hours, then cooled to room temperature, the reaction mixture was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to give the product 13-1 (23.91 g, yield: 53.6%). Elemental analysis: theoretical value C,75.18; h,3.83; n,3.13; test value C,75.12; h,3.81; n,3.16. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 892.1; experimental values 892.2 (M + )。
A compound of formula 13-1 (8.92 g,10 mmol) and dried o-xylene (80 mL) were weighed into a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃after the dropwise addition, and then boron tribromide (2.8 g,11.0 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after the dropwise addition was completed for 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.6 g,20.0 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c for reaction for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give product 13-2 (2.82 g, yield: 34.3%). Elemental analysis: theoretical value C,81.67; h,3.92; n,3.40; test value C,81.62; h,3.85; n,3.31.ESI-MS: theoretical value 822.2; experimental values 822.3 (M + )。
The compounds of formula 13-3 were prepared according to the synthetic route disclosed in document chem.
In a 50mL Schlenk flask under argon atmosphere, the compound of formula 13-3 (1.6 g,1.1 mmol), the compound of formula 13-2 (0.82 g,1 mmol), pd were added 2 (dba) 3 (46mg，0.05mmol)、t-Bu 3 PHBF 4 (58 mg,0.20 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. Separating the organic phaseThe resulting mixture was subjected to column separation and solvent removal to give dendritic fused ring compound I-38 (0.75 g, yield: 34.1%). Elemental analysis: theoretical value C,88.07; h,5.69; n,5.74; test value C,88.02; h,5.72; n,5.71.MALDI-TOF (m/z): theoretical value 2194.0; experimental values 2194.0 (M + )。
Photophysical properties of the fused ring compound prepared in example 13 of the present invention were examined, and the results are shown in Table 1.
Example 14: preparation of Compounds of formula I-41
The synthetic route and the process are as follows:
a250 mL Schlenk flask was charged with the compound of formula 14-1 (6.8 g,20 mmol) and sodium hydride (5.6 g,22 mmol) under argon, 80mL DMF was taken and stirred at room temperature for 1 hour. TBS-Cl (3.6 g,24 mmol) was then added dropwise and the reaction was stirred for another 4 hours, then the reaction solution was poured into water, and the crude product obtained by filtration was separated into a column to give the product 14-2 (7.3 g, yield: 80%). Elemental analysis: theoretical C,47.49; h,4.65; n,3.08; test value C,47.42; h,4.62; n,3.09.ESI-MS: theoretical value 452.9; experimental values 453.0 (M + )。
In a 100mL Schlenk flask under argon atmosphere was added the compound of formula 14-2 (4.5 g,10 mmol), phenoxazine (4.0 g,22 mmol), pd 2 (dba) 3 (0.46g，0.5mmol)、t-Bu 3 PHBF 4 (0.58 g,2.0 mmol), t-BuONa (3.8 g,40 mmol) and then 40mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. Anhydrous sodium sulfate was added to dry, and the organic phase obtained by filtration was freed from the solvent. The crude product obtained and tetrabutylammonium fluoride (5.3 g,20 mmol) were added to 30ml of THF and stirred for 4 hours. Column separation and desolventization gave product 14-3 (3.4 g, yield: 62%). Elemental analysis: theoretical C,79.25; h,4.25; n,7.70; test value C,79.21; h,4.20; n,7.73.ESI-MS: theoretical value 545.1; experimental values 545.1 (M + )。
Under argon gasIn a 100mL Schlenk flask, the compound of formula 14-2 (0.9 g,2 mmol), the compound of formula 14-3 (2.2 g,4 mmol), pd were placed under an atmosphere 2 (dba) 3 (0.09g，0.1mmol)、t-Bu 3 PHBF 4 (0.12 g,0.4 mmol), t-Buona (0.4 g,4 mmol) and then 40mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. Anhydrous sodium sulfate was added to dry, and the organic phase obtained by filtration was freed from the solvent. The crude product obtained and tetrabutylammonium fluoride (5.3 g,20 mmol) were added to 30mL THF and stirred for 4 hours. Column separation and desolventization gave product 14-4 (1.1 g, yield: 43%). Elemental analysis: theoretical value C,79.48; h,3.97; n,7.72; test value C,79.42; h,3.91; n,7.75.MALDI-TOF (m/z): theoretical 1562.5; experimental value 1562.5 (M + )。
In a 500mL three-necked flask, a compound of formula 1-1 (13.6 g,0.05 mol), phenoxazine (21.9 g,0.12 mol) and CS were weighed under an argon atmosphere 2 CO 3 (65.2 g,0.20 mol) 80mL of N, N-Dimethylformamide (DMF) was taken and added to a bottle, the temperature was raised to 150℃and the reaction was stirred under argon for 10 hours, then cooled to room temperature, the reaction mixture was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to give 14-5 (12.99 g, yield: 43.6%). Elemental analysis: theoretical value C,60.23; h,3.03; n,4.68; test value C,60.20; h,3.01; n,4.66. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 595.9; experimental values 595.9 (M + )。
A compound of formula 14-5 (5.95 g,10 mmol) and dried o-xylene (80 mL) were weighed into a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃after the dropwise addition, and further boron tribromide (2.8 g,11.0 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after the dropwise addition was completed for 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.6 g,20.0 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c for reaction for 20 hr. After the reaction is cooled to room temperature, solid is separated out from the filtration system and washed by methanol, and the crude product is separated by a column to obtain a product 14- 6 (1.75 g, 33.2% yield). Elemental analysis: theoretical value C,68.35; h,3.06; n,5.31; test value C,68.31; h,3.05; n,5.35.ESI-MS: theoretical 526.1; experimental values 526.2 (M + )。
In a 50mL Schlenk flask under argon atmosphere, the compound of formula 14-4 (0.7 g,0.55 mmol), the compound of formula 14-6 (0.26 g,0.5 mmol), pd were added 2 (dba) 3 (46mg，0.05mmol)、t-Bu 3 PHBF 4 (58 mg,0.20 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-41 (0.19 g, yield: 22.3%). Elemental analysis: theoretical C,79.76; h,3.88; n,7.34; test value C,79.71; h,3.85; n,7.39.MALDI-TOF (m/z): theoretical value 1715.5; experimental values 1715.6 (M + )。
Photophysical properties of the fused ring compound prepared in example 14 of the present invention were examined, and the results are shown in Table 1.
Example 15: preparation of Compounds of formula I-6
The synthetic route and the process are as follows:
compounds of formula 1-1 (13.6 g,0.05 mol), N-phenyl-1-benzofuran-3-amine (25.1 g,0.12 mol) and CS were weighed in a 500mL three-necked flask under argon atmosphere 2 CO 3 (65.2 g,0.20 mol) 80mL of N, N-Dimethylformamide (DMF) was taken and put into a bottle, the temperature was raised to 150℃and the reaction was stirred under argon for 10 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated by column separation to give 15-2 (14.6 g, yield: 45.1%). Elemental analysis: theoretical value C,62.79; h,3.41; n,4.31; test value C,62.82; h,3.43; n,4.25. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 648.0; experimental values 648.1 (M + )。
A compound of formula 15-2 (6.5 g,10 mmol) and dried o-xylene (80 mL) were weighed into a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃after the dropwise addition, and then boron tribromide (2.8 g,11.0 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after the dropwise addition was completed for 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.6 g,20.0 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c for reaction for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give 15-3 (2.1 g, yield: 36.3%). Elemental analysis: theoretical value C,70.50; h,3.48; n,4.84; test value C,70.42; h,3.42; n,4.86.ESI-MS: theoretical 579.3; experimental values 579.1 (M + )。
In a 50mL Schlenk flask under argon atmosphere, the compound of formula 1-4 (1.77 g,1.1 mmol), the compound of formula 15-3 (0.58 g,1 mmol), pd were added 2 (dba) 3 (46mg，0.05mmol)、t-Bu 3 PHBF 4 (58 mg,0.20 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-6 (0.84 g, yield: 39.9%). Elemental analysis: theoretical value C,85.56; h,6.41; n,5.99; test value C,85.51; h,6.38; n,5.91. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 2105.6; experimental values 2105.6 (M + )。
Photophysical properties of the fused ring compound prepared in example 15 of the present invention were examined, and the results are shown in Table 1.
Example 16: preparation of Compounds of formula I-8
The synthetic route and the process are as follows:
weighing in a 500mL three-necked flask under argon atmosphere1-1 Compound (6.8 g,0.025 mol), N, 9-diphenyl-9-carbazol-4-amine (20.1 g,0.06 mol) and CS 2 CO 3 (32.6 g,0.10 mol) 60mL of N, N-Dimethylformamide (DMF) was taken and put into a bottle, the temperature was raised to 150℃and the reaction was stirred under argon for 10 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to give 16-2 (10.2 g, yield: 45.3%). Elemental analysis: theoretical value C,72.01; h,4.03; n,6.22; test value C,71.98; h,4.06; n,6.17. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 900.7; experimental value 900.2 (M + )。
A compound of formula 16-2 (4.5 g,5 mmol) and dried o-xylene (80 mL) were weighed into a 250mL two-necked flask under argon atmosphere, a butyllithium solution (2.0 mL,2.5M,5 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃and then boron tribromide (1.4 g,5.5 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (1.3 g,10.0 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give 16-3 (1.0 g, yield: 23.2%). Elemental analysis: theoretical value C,78.18; h,4.13; n,6.75; test value C,78.12; h,4.12; n,6.72.ESI-MS: theoretical value 829.6; experimental values 829.4 (M + )。
Compounds of formula 1-4 (1.77 g,1.1 mmol), compounds of formula 16-3 (0.83 g,1 mmol), pd were placed in 50mL Schlenk bottles under argon atmosphere 2 (dba) 3 (46mg，0.05mmol)、t-Bu 3 PHBF 4 (58 mg,0.20 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-8 (1.09 g, yield: 46.2%). Elemental analysis: theoretical value C,86.67; h,6.33; n,6.54; test value C,86.61; h,6.29; n,6.60. Matrix-assisted laser desorption ionization flightInter mass spectrometry (MALDI-TOF (m/z)): theoretical value 2355.9; experimental values 2355.8 (M + )。
Photophysical properties of the fused ring compound prepared in example 16 of the present invention were examined, and the results are shown in Table 1.
Example 17: preparation of Compounds of formula I-3
The synthetic route and the process are as follows:
in a 500mL three-necked flask, a compound of formula 1-1 (13.6 g,0.05 mol), 7H-dibenzocarbazole (32.1 g,0.12 mol) and CS were weighed under an argon atmosphere 2 CO 3 (65.2 g,0.20 mol) 100mL of N, N-Dimethylformamide (DMF) was taken in a flask, heated to 150℃and reacted under stirring under argon for 10 hours, then cooled to room temperature, the reaction mixture was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated by column separation to give the product 17-2 (20.5 g, yield: 53.4%). Elemental analysis: theoretical value C,72.08; h,3.42; n,3.65; test value C,72.01; h,3.46; n,3.61. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 766.5; experimental values 766.1 (M + )。
A compound of formula 17-2 (7.7 g,10 mmol) and dried o-xylene (80 mL) were weighed into a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃after the dropwise addition, and further boron tribromide (2.8 g,11.0 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after the dropwise addition was completed for 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.6 g,20.0 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c for reaction for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give 17-3 (2.4 g, yield: 35.2%). Elemental analysis: theoretical value C,79.45; h,3.48; n,4.03; test value C,79.41; h,3.47; n,4.08.ESI-MS: theoretical value 695.4; experimental values 695.1 (M + )。
In a 50mL Schlenk flask under argon atmosphere, the compound of formula 1-4 (1.77 g,1.1 mmol), the compound of formula 17-3 (0.70 g,1 mmol), pd were added 2 (dba) 3 (46mg，0.05mmol)、t-Bu 3 PHBF 4 (58 mg,0.20 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-3 (1.17 g, yield: 52.6%). Elemental analysis: theoretical value C,87.58; h,6.26; n,5.67; test value C,87.52; h,6.21; n,5.61. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 2221.8; experimental value 2221.4 (M + )。
Photophysical properties of the fused ring compound prepared in example 17 of the present invention were examined, and the results are shown in Table 1.
Example 18: preparation of Compounds of formula I-2
The synthetic route and the process are as follows:
a compound of formula 1-1 (13.6 g,0.05 mol), 3, 6-diazacarbazole (20.3 g,0.12 mol) and CS were weighed out under an argon atmosphere in a 500mL three-necked flask 2 CO 3 (65.2 g,0.20 mol) 80mL of N, N-Dimethylformamide (DMF) was taken and added to a bottle, the temperature was raised to 150℃and the reaction was stirred under argon for 10 hours, then cooled to room temperature, the reaction mixture was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to give 18-2 (12.8 g, yield: 45.2%). Electrospray ionization mass spectrometry (ESI-MS): theoretical value 570.3; experimental values 570.3 (M + )。
In a 250mL two-necked flask under argon atmosphere, the compound of formula 18-2 (5.7 g,10 mmol) and dried o-xylene (80 mL) were weighed, a butyllithium solution (4.0 mL,2.5M,10 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃after the dropwise addition, and then three were dropwise added to the systemBoron bromide (2.8 g,11.0 mmol) was added dropwise and stirred at room temperature for 1 hour after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.6 g,20.0 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c for reaction for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give product 18-3 (2.2 g, yield: 43.5%). ESI-MS: theoretical value 499.1; experimental values 499.1 (M + )。
Compounds of formula 1-4 (1.77 g,1.1 mmol), compounds of formula 18-3 (0.50 g,1 mmol), pd were placed in 50mL Schlenk bottles under argon atmosphere 2 (dba) 3 (46mg，0.05mmol)、t-Bu 3 PHBF 4 (58 mg,0.20 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-1 (1.06 g, yield: 52.5%). Elemental analysis: theoretical C,84.24; h,6.27; n,8.99; test value C,84.27; h,6.25; n,8.92. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 2025.5; experimental values 2025.5 (M + )。
Photophysical properties of the fused ring compound prepared in example 18 of the present invention were examined, and the results are shown in Table 1.
Example 19: preparation of Compounds of formula I-18
The synthetic route and the process are as follows:
aniline (10.2 g,110 mmol), the compound of formula 19-1 (15.2 g,50 mmol), pd were placed in a 500mL Schlenk flask under argon atmosphere 2 (dba) 3 (0.9 g,1 mmol), BINAP (2.5 mg,4 mmol), t-Buona (21.1 g,220 mmol), then 200mL toluene was injected and reacted at 100℃for 24 hours. Cooling to room temperature, adding deionized water and 300mL of dichloromethane for extraction, and washing with deionized water for multiple times. Separating organic phase, separating with column, and removing solvent to obtain branch Condensed-cyclic compound 19-2 (12.3 g, yield: 74.8%). Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 329.2; experimental values 329.3 (M + )。
3-chloro-5-bromoiodobenzene (25.4 g,80 mmol), the compound of formula 19-2 (9.9 g,30 mmol), pd were placed in a 250mL Schlenk flask under argon atmosphere 2 (dba) 3 (0.5g，0.6mmol)、P(t-Bu) 3 (0.5 g,2.4 mmol), t-Buona (15.4 g,160 mmol) and then 150mL toluene were injected and reacted at room temperature for 24 hours. Deionized water and 300mL of methylene chloride were added for extraction, and the mixture was washed with deionized water multiple times. The organic phase was separated, and the solvent was removed by column separation to give 19-3 (16.0 g, yield: 86.4%) as a dendritic fused ring compound. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical 619.2; experimental value 619.2 (M + )。
Aniline (1.9 g,20 mmol), the compound of formula 19-3 (12.4 g,20 mmol), pd were placed in a 250mL Schlenk flask under argon atmosphere 2 (dba) 3 (0.4 g,0.4 mmol), S-Phos (0.7 g,1.6 mmol), t-Buona (3.8 g,40 mmol) and then 100mL toluene were injected and reacted at reflux for 24 hours. Deionized water and 200mL of dichloromethane were added for extraction, and the mixture was washed with deionized water multiple times. The organic phase was separated, and the solvent was removed by column separation to give 19-4 (7.3 g, yield: 56.2%) as a dendritic fused ring compound. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 639.4; experimental values 639.5 (M + )。
In a 250mL two-necked flask under argon atmosphere, the compound of formula 19-4 (0.6 g,10 mmol) and dried tert-butylbenzene (80 mL) were weighed, a butyllithium solution (4.0 mL,2.5M,10 mmol) was dropwise added at-30℃and stirred for 2 hours at 50℃and then cooled to 0℃and boron tribromide (5.1 g,20.0 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after 20 minutes. The temperature was lowered to 0℃again, N-diisopropylethylamine (2.6 g,20.0 mmol) was added dropwise to the reaction system, and after the completion of the addition, the temperature was raised to 165℃to react for 14 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give product 19-5 (3.5 g, yield: 57.2%). Elemental analysis: theoretical value C,70.57; h,3.45; n,6.86; test value C,70.52; h,3.48; n,6.84.ESI-MS: theoretical value 612.8; experimental values 612.6 (M + )。
In a 50mL Schlenk flask under argon atmosphere, the compound of formula 1-4 (5.3 g,3.3 mmol), the compound of formula 19-5 (0.61 g,1 mmol), pd were added 2 (dba) 3 (138mg，0.15mmol)、t-Bu 3 PHBF 4 (174 mg,0.60 mmol), t-Buona (0.57 g,6 mmol) and then 30mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-18 (2.24 g, yield: 42.1%). Elemental analysis: theoretical value C,86.61; h,6.87; n,6.31; test value C,86.67; h,6.81; n,6.28. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 5325.1; experimental values 5325.2 (M + )。
Photophysical properties of the fused ring compound prepared in example 19 of the present invention were examined, and the results are shown in Table 1.
Example 20: preparation of Compounds of formula I-62
The synthetic route and the process are as follows:
compounds of formula 1-1 (13.6 g,0.05 mol), 3-benzofuranol (13.4 g,0.10 mol) and K were weighed out under argon in a 500mL three-necked flask 2 CO 3 (13.8 g,0.10 mol) 80mL of N-methylpyrrolidone (NMP) was added to a bottle, the temperature was raised to 150℃and the reaction was stirred under argon for 10 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a product 20-1 (8.9 g, yield: 46%). Elemental analysis: theoretical value C,43.56; h,1.83; test value C,43.52; h,1.89.ESI-MS: theoretical 386.0; experimental value 386.1 (M + )。
Under argon atmosphere, the mixture was weighed in a 250mL three-necked flaskTaking a compound of formula 20-1 (7.7 g,0.02 mol), diphenylamine (6.7 g,0.04 mol) and CS 2 CO 3 (13.0 g,0.04 mol) 60mL of N, N-Dimethylformamide (DMF) was taken in a bottle, heated to 150℃and reacted under stirring under argon for 10 hours, then cooled to room temperature, the reaction mixture was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to give 20-2 (7.2 g, yield: 67.2%). Elemental analysis: theoretical value C,58.35; h,3.20; n,2.62; test value C,58.37; h,3.11; n,2.68. Electrospray ionization mass spectrometry (ESI-MS): theoretical 535.2; experimental value 535.1 (M + )。
A compound of formula 20-2 (0.5 g,10 mmol) and dried o-xylene (80 mL) were weighed into a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃after the dropwise addition, and then boron tribromide (2.8 g,11.0 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after the dropwise addition was completed for 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.6 g,20.0 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c for reaction for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give 20-3 (2.2 g, yield: 48.4%). Elemental analysis: theoretical value C,67.28; h,3.26; n,3.02; test value C,67.21; h,3.29; n,3.08.ESI-MS: theoretical value 464.1; experimental value 464.2 (m+).
Compounds of formula 1-4 (1.77 g,1.1 mmol), 20-3 (0.46 g,1 mmol), pd were placed in 50mL Schlenk flask under argon 2 (dba) 3 (46mg，0.05mmol)、t-Bu 3 PHBF 4 (58 mg,0.20 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-62 (0.95 g, yield: 48.1%). Elemental analysis: theoretical value C,85.73; h,6.43; n,5.67; test value C,85.76; h,6.41; n,5.69. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m +. z)): theoretical value 1975.4; experimental value 1975.2 (m+).
Photophysical properties of the fused ring compound prepared in example 20 of the present invention were examined, and the results are shown in Table 1.
Example 21: preparation of Compounds of formula I-66
The synthetic route and the process are as follows:
compounds of formula 1-1 (13.6 g,0.05 mol), 3-bromothiophenol (9.5 g,0.05 mol) and K were weighed out under argon atmosphere in a 500mL three-necked flask 2 CO 3 (13.8 g,0.10 mol) 80mL of N-methylpyrrolidone (NMP) was added to a bottle, the temperature was raised to 150℃and the reaction was stirred under argon for 10 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column (12.3 g, yield: 56.1%). Elemental analysis: theoretical value C,32.69; h,1.37; s,7.27; test value C,32.61; h,1.34; s,7.29.ESI-MS: theoretical value 440.9; experimental values 440.8 (M + )。
Compounds of formula 21-1 (8.8 g,0.02 mol), diphenylamine (6.7 g,0.04 mol) and CS were weighed out in a 250mL three-necked flask under an argon atmosphere 2 CO 3 (13.0 g,0.04 mol) 60mL of N, N-Dimethylformamide (DMF) was taken and put into a bottle, the temperature was raised to 150℃and the reaction was stirred under argon for 10 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to give 21-2 (6.4 g, yield: 54.3%). Elemental analysis: theoretical value C,48.84; h,2.73; n,2.37; s,5.43; test value C,48.81; h,2.78; n,2.31; s,5.48. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 590.2; experimental values 590.1 (M + )。
A compound of formula 21-2 (0.6 g,10 mmol) and dried ortho-xylene (80 mL) were weighed in a 250mL two-necked flask under argon atmosphere, inButyl lithium solution (4.0 mL,2.5M,10 mmol) was added dropwise at-30℃and stirred for 2 hours at-30℃after the addition, and boron tribromide (2.8 g,11.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after the addition for 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.6 g,20.0 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c for reaction for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give 21-3 (2.2 g, yield: 43.1%). Elemental analysis: theoretical value C,55.54; h,2.72; n,2.70; s,6.18; test value C,55.59; h,2.71; n,2.78; s,6.10.ESI-MS: theoretical 519.1; experimental values 519.2 (M + )。
In a 50mL Schlenk flask under argon atmosphere, the compound of formula 1-4 (3.54 g,2.2 mmol), the compound of formula 21-3 (0.52 g,1 mmol), pd were added 2 (dba) 3 (92mg，0.1mmol)、t-Bu 3 PHBF 4 (232 mg,0.40 mmol), t-Buona (0.38 g,4 mmol) and then 30mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-66 (1.31 g, yield: 36.6%). Elemental analysis: theoretical value C,86.04; h,6.91; n,5.86; s,0.89; test value C,86.14; h,6.85; n,5.80; s,0.81. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 3587.8; experimental value 3587.7 (m+).
Photophysical properties of the fused ring compound prepared in example 21 of the present invention were examined, and the results are shown in Table 1.
Example 22: preparation of Compounds of formula I-73
The synthetic route and the process are as follows:
compounds of formula 1-1 (13.6 g,0.05 mol), phenylselenol (7.8 g,0.05 mol) and K were weighed in a 500mL three-necked flask under an argon atmosphere 2 CO 3 (13.8 g,0.10 mol) 80mL of N-methylThe reaction mixture was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, and the organic phase obtained by filtration was freed from the solvent, and the crude product was isolated by column separation to give the product 22-1 (9.8 g, yield: 48.2%). Elemental analysis: theoretical value C,35.24; h,1.73; test value C,35.24; h,1.73.ESI-MS: theoretical value 408.9; experimental values 408.8 (M + )。
A compound of formula 22-1 (8.2 g,0.02 mol), tert-butylcarbazole (11.2 g,0.04 mol) and CS were weighed out under argon in a 250mL three-necked flask 2 CO 3 (13.0 g,0.04 mol) 60mL of N, N-Dimethylformamide (DMF) was taken in a bottle, heated to 150℃and reacted under stirring under argon for 10 hours, then cooled to room temperature, the reaction mixture was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to give the product 22-2 (11.0 g, yield: 82.3%). Elemental analysis: theoretical value C,57.51; h,4.68; n,2.10; test value C,57.46; h,4.61; n,2.05. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 668.4; experimental values 668.3 (M + )。
A compound of formula 22-2 (0.7 g,10 mmol) and dried o-xylene (80 mL) were weighed into a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃after the dropwise addition, and then boron tribromide (2.8 g,11.0 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after the dropwise addition was completed for 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.6 g,20.0 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c for reaction for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give product 22-3 (2.1 g, yield: 35.1%). Elemental analysis: theoretical value C,64.35; h,4.89; n,2.35; test value C,64.31; h,4.92; n,2.31.ESI-MS: theoretical value 597.3; experimental values 597.4 (M + )。
Compounds of formula 1-4 (1.77 g,1.1 mmol), 22-3 were placed in 50mL Schlenk bottles under argon atmosphereSubstance (0.60 g,1 mmol), pd 2 (dba) 3 (46mg，0.05mmol)、t-Bu 3 PHBF 4 (58 mg,0.20 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-73 (1.19 g, yield: 56.2%). Elemental analysis: theoretical value C,83.67; h,6.83; n,5.27; test value C,83.61; h,6.88; n,5.21. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 2124.6; experimental value 2124.5 (m+).
Photophysical properties of the fused ring compound prepared in example 22 of the present invention were examined, and the results are shown in Table 1.
Example 23: preparation of Compounds of formula I-77
The synthetic route and the process are as follows:
compounds of formula 1-1 (13.6 g,0.05 mol), phenyltellurion (10.3 g,0.05 mol) and K were weighed in a 500mL three-necked flask under an argon atmosphere 2 CO 3 (13.8 g,0.10 mol) 80mL of N-methylpyrrolidone (NMP) was added to a bottle, the temperature was raised to 150℃and the reaction was stirred under argon for 10 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a product 23-1 (10.3 g, yield: 45.2%). Elemental analysis: theoretical value C,31.50; h,1.54; test value C,31.56; h,1.50.ESI-MS: theoretical value 457.6; experimental value 457.5 (M + )。
A compound of formula 23-1 (9.2 g,0.02 mol), tert-butylcarbazole (11.2 g,0.04 mol) and CS were weighed out under argon in a 250mL three-necked flask 2 CO 3 (13.0 g,0.04 mol) 60mL of N, N-Dimethylformamide (DMF) was taken and added to a bottle, the temperature was raised to 150℃and the reaction was stirred under argon for 10 hours, then cooled to room temperature, and the reaction was carried out The reaction mixture was diluted with toluene, poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the crude product was separated by column to give 23-2 (11.3 g, yield: 78.5%). Elemental analysis: theoretical value C,53.60; h,4.36; n,1.95; test value C,53.66; h,4.31; n,1.98. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 717.0; experimental values 717.1 (M + )。
A compound of formula 23-2 (0.7 g,10 mmol) and dried o-xylene (80 mL) were weighed into a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃after the dropwise addition, and then boron tribromide (2.8 g,11.0 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after the dropwise addition was completed for 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.6 g,20.0 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c for reaction for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give product 23-3 (1.8 g, yield: 28.3%). Elemental analysis: theoretical value C,59.51; h,4.53; n,2.17; test value C,59.57; h,4.51; n,2.11.ESI-MS: theoretical value 645.9; experimental values 645.9 (M + )。
Compounds of formula 1-4 (1.77 g,1.1 mmol), 23-3 (0.65 g,1 mmol), pd were placed in 50mL Schlenk flask under argon 2 (dba) 3 (46mg，0.05mmol)、t-Bu 3 PHBF 4 (58 mg,0.20 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give dendritic fused ring compound I-77 (0.99 g, yield: 45.6%). Elemental analysis: theoretical value C,81.78; h,6.77; n,5.12; test value C,81.71; h,6.72; n,5.21. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 2188.3; experimental value 2188.2 (m+).
Photophysical properties of the fused ring compound prepared in example 23 of the present invention were examined, and the results are shown in Table 1.
TABLE 1 photophysical Properties of the fused Ring Compounds obtained in examples 1 to 23
Note that: in Table 1, ΔE ST By bringing the compound to 10 as the difference between the singlet energy level and the triplet energy level -4 The concentration of mol/L was dissolved in toluene to prepare a sample to be measured, and the difference between the initial (onset) values of the fluorescence spectrum and the phosphorescence spectrum was measured, and the test instrument was HORIBA FluoroMax spectrofluorometer (Japanese). The delayed fluorescence lifetime was measured by doping a compound at a concentration of 1wt% in polystyrene to prepare a sample to be tested using a time resolved fluorescence spectrometer, test instrument Edinburgh fluorescence spectrometer (FLS-980, uk).
As can be seen from the test results in Table 1, the fused ring compounds provided by the invention have smaller delta E ST (<0.2 eV), exhibits a thermally activated delayed fluorescence effect with a delayed fluorescence lifetime of 46 to 103 mus, thus facilitating the utilization of triplet excitons and improving device efficiency.
Device example: examples 24 to 50
As device examples, the present invention provides two types of device structures (device structure a and device structure B) to prepare an organic electroluminescent device:
the device structure A is as follows: ITO/PEDOT PSS (40 nm)/the dendritic fused ring compound (30 nm)/TSPO 1 (8 nm)/TmPyPB (30 nm)/LiF (0.8 nm)/Al (100 nm).
The steps for preparing the device by adopting the device structure A are as follows: poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) was spin-coated on Indium Tin Oxide (ITO) supported on a glass substrate, annealed at 120℃for 30 minutes, followed by spin-coating a toluene solution of the inventive dendrimer compound at 1500rpm for 1 minute, and annealed at 80℃for 30 minutes, and then annealed at 4X 10 -4 Sequentially depositing TSPO1, tmPyPB and LiF/Al cathodes under the vacuum degree of Pa to obtain the organic electroluminescent device, wherein the TSPO1 and the TmPyPB serve as a hole blocking layer and an electron transport layer respectively, and the structural formula is shown as follows:
The device structure B is as follows: ITO/PEDOT: PSS (40 nm)/blend of the dendritic fused ring compound and SiMCP2 as a main material (mass ratio: 1:9) (30 nm)/TSPO 1 (8 nm)/TmPyPB (42 nm)/LiF (1 nm)/Al (100 nm).
The steps for preparing the device by adopting the device structure B are as follows: poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) was spin-coated onto indium tin oxide supported on a glass substrate, annealed at 120 ℃ for 30 minutes, followed by spin-coating the inventive dendritic fused ring compound with sipcp 2 at a spin speed of 1500rpm in a mass ratio of 1:9, and annealing at 80℃for 30 minutes, followed by 4X 10 -4 Sequentially depositing TSPO1, tmPyPB and LiF/Al cathodes under the vacuum degree of Pa to obtain the organic electroluminescent device, wherein the structural formula of the host material SiMCP2 is as follows:
example 24
The compound of the formula I-1 obtained in the example 1 is taken as an implementation object, and the compound of the formula I-1 is directly taken as an organic light-emitting layer, so that an organic electroluminescent device is prepared by utilizing the structure of a device structure A.
Example 25
The compound of the formula I-19 obtained in example 2 is taken as an implementation object, and the compound of the formula I-19 is directly taken as an organic light-emitting layer, so that an organic electroluminescent device is prepared by utilizing the structure of a device structure A.
Example 26
Taking the compound of the formula I-1 obtained in the example 1 as an implementation object, mixing the compound of the formula I-1 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 27
Taking the compound of the formula I-19 obtained in the example 2 as an implementation object, mixing the compound of the formula I-19 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 28
Taking the compound of the formula I-20 obtained in the example 3 as an implementation object, mixing the compound of the formula I-20 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 29
Taking the compound of the formula I-27 obtained in the example 4 as an implementation object, mixing the compound of the formula I-27 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 30
Taking the compound of the formula I-30 obtained in the example 5 as an implementation object, mixing the compound of the formula I-30 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 31
Taking the compound of the formula I-31 obtained in the example 6 as an implementation object, mixing the compound of the formula I-31 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 32
Taking the compound of the formula I-22 obtained in the example 7 as an implementation object, mixing the compound of the formula I-22 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 33
Taking the compound of the formula I-32 obtained in the example 8 as an implementation object, mixing the compound of the formula I-32 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 34
Taking the compound of the formula I-33 obtained in the example 9 as an implementation object, mixing the compound of the formula I-33 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 35
Taking the compound of the formula I-34 obtained in the example 10 as an implementation object, mixing the compound of the formula I-34 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 36
Taking the compound of the formula I-36 obtained in the example 11 as an implementation object, mixing the compound of the formula I-36 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 37
Taking the compound of the formula I-37 obtained in the example 12 as an implementation object, mixing the compound of the formula I-37 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 38
Taking the compound of the formula I-38 obtained in the example 13 as an implementation object, the compound of the formula I-38 and SiMCP2 are mixed according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 39
Taking the compound of the formula I-41 obtained in the example 14 as an implementation object, the compound of the formula I-41 and SiMCP2 are mixed according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 40
Taking the compound of the formula I-6 obtained in the example 15 as an implementation object, the compound of the formula I-6 and SiMCP2 are mixed according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 41
Taking the compound of the formula I-8 obtained in the example 16 as an implementation object, mixing the compound of the formula I-8 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 42
Taking the compound of the formula I-3 obtained in the example 17 as an implementation object, the compound of the formula I-3 and SiMCP2 are mixed according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 43
Taking the compound of the formula I-2 obtained in the example 18 as an implementation object, the compound of the formula I-2 and SiMCP2 are mixed according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 44
Taking the compound of the formula I-18 obtained in the example 19 as an implementation object, mixing the compound of the formula I-18 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 45
Taking the compound of the formula I-62 obtained in the example 20 as an implementation object, mixing the compound of the formula I-62 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 46
Taking the compound of the formula I-66 obtained in the example 21 as an implementation object, the compound of the formula I-66 and SiMCP2 are mixed according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 47
Taking the compound of the formula I-73 obtained in the example 22 as an implementation object, mixing the compound of the formula I-73 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Example 48
Taking the compound of the formula I-77 obtained in the example 23 as an implementation object, mixing the compound of the formula I-77 with SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Comparative example 1
The BNN is directly used as an organic light-emitting layer by taking a compound BNN which does not contain a dendritic structure as an implementation object, and the structure of a device structure A is utilized to prepare the organic electroluminescent device.
Comparative example 2
The BNO is directly used as an organic light-emitting layer by taking a compound BNO without a dendritic structure as an implementation object, and the structure of a device structure A is utilized to prepare the organic electroluminescent device.
Comparative example 3
Taking BNN which does not contain a branch molecular structure as an implementation object, and mixing BNN and SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
Comparative example 4
Taking BNO which does not contain a branch molecular structure as an implementation object, and mixing BNO and SiMCP2 according to a mass ratio of 1:9 are mixed to be used as an organic light-emitting layer, and the structure of the device structure B is utilized to prepare the organic electroluminescent device.
In the above comparative examples 1 to 4, the chemical structures of the compounds BNN and BNO are as follows:
the organic electroluminescent devices obtained in device examples 24 to 48 and comparative examples 1 to 4 were subjected to performance test, and the results are shown in Table 2.
Table 2 Properties of the organic electroluminescent devices obtained in examples 24 to 48 and comparative examples 1 to 4
Note that: in Table 2, the luminance is 1cdm -2 The driving voltage of the device; the maximum external quantum efficiency is obtained according to the current-voltage curve and the electroluminescence spectrum of the device and the calculation method described in the literature (Jpn.J.appl.Phys.2001, 40, L783); half width of peakThe peak width at half the peak height of the electroluminescent spectrum at room temperature, i.e. the distance between the two points where the line intersects the two sides of the peak, is a line parallel to the bottom of the peak through the midpoint of the peak height.
As can be seen from the test results in Table 2, the solution processing organic electroluminescent device prepared from the dendritic fused ring compound provided by the invention has high luminous efficiency, the maximum external quantum efficiency is 16.0-26.9%, the device efficiency is obviously higher than that of a comparative compound without a dendritic structure (1.2-8.6%), the device has narrower electroluminescent spectrum, and the half-peak width is less than 40nm.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to aid in understanding the method of the invention and its core concept, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (7)
1. A fused ring compound containing boron nitrogen and a dendritic structure, having the structure of formula (1):
The compound shown in the formula (I) is selected from the formula I-1 to the formula I-78:
2. a process for the preparation of a fused ring compound containing boron nitrogen and a dendritic structure as claimed in claim 1, comprising the steps of:
reacting the condensed ring intermediate shown in the formula (III) with a dendritic compound Lu-R to generate a compound shown in the formula (I);
the dendritic compound Lu-R is selected from the compounds Lu 4 -R a 、Lu 5 -R b And Lu 6 -R c One or more of the following;
wherein Lu 1 ～Lu 6 Each independently selected from: hydrogen, halogen, hydroxy, mercapto, amino,
3. The method according to claim 2, wherein the temperature of the reaction is-78 to 180 ℃.
4. The process according to claim 2, wherein the reaction is carried out under the action of a catalyst;
the catalyst is selected from one or more of palladium chloride, palladium acetate, tris (dibenzylideneacetone) dipalladium and tetrakis (triphenylphosphine) palladium.
5. Use of a condensed-cyclic compound containing boron nitrogen and a dendritic structure according to claim 1 in an organic electroluminescent device.
6. An organic electroluminescent device comprising: an anode, a cathode, and a thin film layer between the anode and the cathode;
the thin film layer contains the condensed cyclic compound containing boron nitrogen and dendritic structure as claimed in claim 1.
7. The organic electroluminescent device of claim 6, wherein the thin film layer is one or more layers and at least one layer is a light emitting layer;
the light-emitting layer contains the condensed cyclic compound containing boron nitrogen and a dendritic structure according to claim 1.
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| CN111718364A (en) * | 2019-03-19 | 2020-09-29 | 赛诺拉有限公司 | Organic molecules for optoelectronic devices |
| WO2021013993A1 (en) * | 2019-07-25 | 2021-01-28 | Cynora Gmbh | Organic molecules for optoelectronic devices |
| WO2022018176A1 (en) * | 2020-07-24 | 2022-01-27 | Cynora Gmbh | Organic molecules for optoelectronic devices |
| WO2022018181A1 (en) * | 2020-07-24 | 2022-01-27 | Cynora Gmbh | Organic molecules for optoelectronic devices |
| CN114621274A (en) * | 2020-12-10 | 2022-06-14 | 季华实验室 | Boron-nitrogen compound, organic electroluminescent composition and organic electroluminescent device comprising same |
| CN114621271A (en) * | 2020-12-10 | 2022-06-14 | 季华实验室 | Boron-nitrogen compound, organic electroluminescent composition and organic electroluminescent device comprising same |
| CN114621272A (en) * | 2020-12-10 | 2022-06-14 | 季华实验室 | Boron-nitrogen compound, organic electroluminescent composition and organic electroluminescent device comprising same |
| CN113788852A (en) * | 2021-09-03 | 2021-12-14 | 清华大学 | Luminescent material, application thereof and organic electroluminescent device comprising luminescent material |
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