CN114524837A - Condensed ring compound containing boron nitrogen and dendritic structure, preparation method and application thereof, and organic electroluminescent device - Google Patents
Condensed ring compound containing boron nitrogen and dendritic structure, preparation method and application thereof, and organic electroluminescent device Download PDFInfo
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- CN114524837A CN114524837A CN202210192229.4A CN202210192229A CN114524837A CN 114524837 A CN114524837 A CN 114524837A CN 202210192229 A CN202210192229 A CN 202210192229A CN 114524837 A CN114524837 A CN 114524837A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 317
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 145
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 38
- 125000003118 aryl group Chemical group 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 239000010409 thin film Substances 0.000 claims description 20
- 229910052796 boron Inorganic materials 0.000 claims description 19
- 125000001072 heteroaryl group Chemical group 0.000 claims description 18
- 239000000412 dendrimer Substances 0.000 claims description 16
- 229920000736 dendritic polymer Polymers 0.000 claims description 12
- 230000009471 action Effects 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 229910052701 rubidium Inorganic materials 0.000 claims description 7
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 5
- -1 hydroxy, mercapto, amino Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 125000005842 heteroatom 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
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 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
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- 125000001424 substituent group Chemical group 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
- 125000001294 (C1-C30) cycloalkyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 230000000977 initiatory effect Effects 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
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- 150000001923 cyclic compounds Chemical class 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 50
- 230000000694 effects Effects 0.000 abstract description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 10
- 238000001228 spectrum Methods 0.000 abstract description 10
- 230000005281 excited state Effects 0.000 abstract description 8
- 230000002093 peripheral effect Effects 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 117
- 239000010410 layer Substances 0.000 description 96
- 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
- 238000012360 testing method Methods 0.000 description 75
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 70
- 238000000921 elemental analysis Methods 0.000 description 70
- 239000012300 argon atmosphere Substances 0.000 description 65
- 239000000463 material Substances 0.000 description 64
- 239000000243 solution Substances 0.000 description 64
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 59
- 239000002904 solvent Substances 0.000 description 59
- 239000012043 crude product Substances 0.000 description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 239000008367 deionised water Substances 0.000 description 48
- 229910021641 deionized water Inorganic materials 0.000 description 48
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Substances BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 45
- 238000001914 filtration Methods 0.000 description 42
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 42
- 238000003756 stirring Methods 0.000 description 39
- 238000002156 mixing Methods 0.000 description 37
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 35
- 229910052786 argon Inorganic materials 0.000 description 35
- 239000000047 product Substances 0.000 description 34
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 31
- 239000000203 mixture Substances 0.000 description 30
- 239000003960 organic solvent Substances 0.000 description 30
- 230000008569 process Effects 0.000 description 30
- 238000000605 extraction Methods 0.000 description 29
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 25
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 20
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- 239000007787 solid Substances 0.000 description 17
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 10
- 230000003111 delayed effect Effects 0.000 description 10
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- 239000011541 reaction mixture Substances 0.000 description 10
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- 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
- 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 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- 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 8
- 230000000052 comparative effect Effects 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
- 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
- 239000002585 base Substances 0.000 description 7
- 125000000623 heterocyclic group Chemical group 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
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- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
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- 229910015845 BBr3 Inorganic materials 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 238000001816 cooling Methods 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
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- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 5
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- 239000003153 chemical reaction reagent Substances 0.000 description 4
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- 238000000576 coating method Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 238000007645 offset printing Methods 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
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- 238000010438 heat treatment Methods 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 238000006138 lithiation reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- 238000005303 weighing 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
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 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
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- 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
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- 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
- OVJXIBKYESUKHO-UHFFFAOYSA-N 2-(3-bromophenyl)benzenethiol Chemical compound SC1=CC=CC=C1C1=CC=CC(Br)=C1 OVJXIBKYESUKHO-UHFFFAOYSA-N 0.000 description 1
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- 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 239000007818 Grignard reagent Substances 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
- 229910002666 PdCl2 Inorganic materials 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
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 229960001701 chloroform Drugs 0.000 description 1
- 239000003086 colorant Substances 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
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 238000006386 neutralization reaction Methods 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
- 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
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 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
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003786 synthesis reaction 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
- 238000005406 washing 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
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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
- 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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- C09K2211/10—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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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 center1、X2(independently selected from N, O, S, Se or Te), the compound with the structure can realize the separation of front line orbitals by using the resonance effect between boron atoms and nitrogen atoms, thereby realizing smaller Delta ESTAnd the TADF effect can reduce the relaxation degree of an excited state by utilizing the rigid skeleton structure of a specific fused ring unit, and realize higher luminous efficiency and narrower luminous spectrum.
Description
Technical Field
The invention relates to the technical field of organic light-emitting materials, in particular to a condensed ring 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) generally consist 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 an Exciton (exiton) is formed by combining a Hole (Hole) injected from a positive electrode and a negative electrode on an organic thin film with an Electron (Electron), and emits light by releasing energy in the form of light when the Exciton returns to a stable ground state from an excited state. OLEDs have features of rich colors, thin thickness, wide viewing angle, fast response, and capability of fabricating flexible devices, etc., and are considered to be the next generation of flat panel display and solid illumination technologies with the greatest development prospects.
Regarding the OLED material, most of the currently commercialized OLED display screens adopt an organic small-molecule light-emitting material based on a vacuum evaporation process, and the device efficiency of the material is high, but the material has the disadvantages of low utilization rate, high cost and the like. In contrast, solution processable (e.g., inkjet printing and roll-to-roll printing) organic electroluminescent materials have the advantages of reduced production cost and energy consumption, easy preparation of large-sized display screens, and the like, but have the disadvantage of low device efficiency. At present, the OLED luminescent materials used in the solution processing technology mainly include two types, i.e., a polymer luminescent material and a dendritic luminescent material. Among them, the polymer light emitting material has excellent solution processability, but has disadvantages of difficulty in purification, poor batch stability, and the like. Compared with a high-molecular luminescent material, the dendritic luminescent material is a luminescent material with a determined chemical structure, and the molecular size and the topological structure of the dendritic luminescent material can be accurately controlled in synthesis; meanwhile, the dendritic luminescent material also has good film-forming property and solution processing property, and luminescent materials with different luminescent wavelengths can be obtained by selecting different central cores, different dendritic construction 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, a Thermally Activated Delayed Fluorescence (TADF) material is a new generation of organic light emitting material following the traditional fluorescent and phosphorescent materials, and generally has a smaller singlet-triplet energy level difference (Δ E)ST) The triplet excited state is transferred to the singlet excited state to emit fluorescence by utilizing a thermally activated reverse system crossing (RISC) process, so that the singlet and triplet excitons are fully utilized, 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% can be overcome.
At present, non-condensed ring units such as triphenyl triazine, diphenyl sulfone and benzophenone are mostly adopted as central cores of the dendritic thermal activation delayed fluorescent material, and the relaxation of an excited state structure of the dendritic thermal activation delayed fluorescent material is strong, so that the problems of wide light emission spectrum (the half-peak width is generally 70-100nm, and the problems of 2018,2,1097, 2016,4,2442, 2016, Pigm 2016,133 and 380386) and low color purity are caused.
Therefore, how to develop a dendrimer compound having TADF effect, high luminous efficiency and narrow emission spectrum through reasonable chemical structure design to solve the above-mentioned drawbacks of the materials has become one of the problems to be solved by a great deal of prospective researchers in the field.
Disclosure of Invention
In view of the above, the present invention aims to provide a fused ring compound containing boron nitrogen and a dendritic structure, a preparation method and an application thereof, and an organic electroluminescent device. The compound provided by the invention comprises a condensed ring center and peripheral branches of boron atoms and nitrogen atoms, and can realize separation of front tracks by utilizing resonance effect between the boron atoms and the nitrogen atoms, thereby realizing smaller delta ESTAnd the TADF effect can reduce the relaxation degree of an excited state by utilizing the rigid framework structure of a specific fused ring unit, thereby realizing higher luminous efficiency and narrower luminous spectrum.
The invention provides a condensed ring compound containing boron nitrogen and a dendritic structure, which has a structure shown in a formula (1):
wherein:
1 2[ about X, X, q]：
In the present invention, X1And X2Independently selected from: n (R)0) O, S, Se or Te; q is 0 or 1. Wherein R is0Selected from: substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C3-C30 cycloalkyl, an aromatic group with 6-60 carbon atoms and a heteroaromatic group with 5-60 carbon atoms; wherein the heteroatoms in the heteroaromatic group are independently selected from Si, Ge, N, P, O, S or Se.
In some embodiments of the invention, q is 0 and X1N, O, S, Se or Te; in other embodiments of the present invention, q is 1 and X1Is N, X2Is 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 fused ring unit; the aromatic condensed ring unit contains one or more of five-membered heteroaromatic ring, six-membered heteroaromatic ring and six-membered heteroaromatic ring.
When the value of q is 0, the ratio,
by its own aromatic ring/aromaticThe carbon atoms at both ends of two carbon-carbon bonds in the heterocycle are respectively bonded with B and N, and B and X1Connecting;
through the two terminal carbon atoms of 1 carbon-carbon bond on the self aromatic ring/aromatic heterocyclic ring and B and N/X respectively1Connecting; the carbon-carbon bond is a carbon-carbon single bond or a carbon-carbon double bond. When the value of q is 1, the ratio,
the two carbon atoms at the two ends of the carbon-carbon bond on the self 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 a carbon-carbon double bond.
More specifically:
when q is 0:
When q is 1:
In the present invention, more preferably, the above
And
each independently selected from the group consisting of groups represented by formulas 1-16:
the groups represented by the above formulas 1 to 16 are bonded to the formula (I) through a carbon-carbon bond on the aromatic ring/aromatic heterocycle. As described in detail above.
1[ about L]：
In the present invention, said L1Selected from: substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 cycloalkyl, an aromatic group with 6-60 carbon atoms and a heteroaromatic group with 5-60 carbon atoms; wherein the heteroatoms in the heteroaromatic group are independently selected from Si, Ge, N, P, O, S or Se. L is1And
may also be through a single bond, -C (R)1R2)-、-(C＝O)-、-Si(R1R2)-、-N(R1)-、-PO(R1)-、-B(R1)-、-O-、-S-、-Se-、-(S＝O)-、-(SO2) -any of the above connections. Wherein, R is1、R2Each independently selected from: H. d, substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 haloalkane alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group and substituted or unsubstituted C5-C60 heteroaromatic group.
More preferably, said L1Selected from the following structures:
a b c[ about R, R and R, m, n and p]：
In the present invention, m, n and p are each Ra、RbAnd RcThe number of (b) is independently an integer selected from 0 to 5, and specifically may be 0 (i.e., there is no corresponding R)a、RbOr Rc) 1, 2, 3,4, 5; and at least 1 of m, n and p is not 0.
In the present invention, Ra、RbAnd RcEach independently of the other, a dendritic structure of formula (II). In some embodiments of the invention, two of m, n, and p are 0 and 1 is not 0 (i.e., R)a、RbAnd RcOnly 1 is present); preferably, where n and p are 0 and m is not 0 (i.e., R)bAnd RcAbsence, presence of only dendritic structures Ra) (ii) a More preferably, n and p are 0 and m is 1 or 2 (i.e., R)aThe number of (2) is 1 or 2). In other embodiments of the present invention, 1 of m, n and p is 0 and 2 are not 0 (i.e., Ra、RbAnd RcThere are 2); preferably, where m and p are other than 0 and n is 0 (i.e., R)bAbsence, presence of only dendritic structures RaAnd Rc) (ii) a More preferably, m and p are 1 (R)aAnd RcThe number of the (b) is 1), and m is 0. In other embodiments of the present invention, none of m, n, and p are 0 (i.e., Ra、RbAnd RcBoth present); preferably, m, n and p are all 1 (i.e., R)a、RbAnd RcThe number of the (B) is 1).
In the invention, the dendritic structure shown in the formula (II) is as follows:
wherein:
The above-mentioned
Each independently selected from the structures represented by formulas D-1 to D-30:
wherein the content of the first and second substances,
not including connecting lines of broken line segments in the above construction, i.e.
Only contains 1 connecting line segment and intermediate iteration unit
And (4) connecting. In the present invention, the asterisk in the structure indicates the junction.
In the formula (II), RxAs the last iteration unit
The substituents above are specifically selected from the following groups: H. d (i.e., deuterium), -CN,
Substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 alkyl halide, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group and substituted or unsubstituted C5-C60 heteroaromatic group.
Wherein, R is1、R2And R3Each independently selected from: H. d, substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 haloalkane alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group and substituted or unsubstituted C5-C60 heteroaromatic group. The R is1、R2And R3May be linked to each other via a single bond, -O-, -S-, or,
Is connected.
More preferably, RxSelected from the following structures:
in the formula (II), nxIs RxThe number of (b) is an integer of 1 to 6, and specifically 1, 2, 3,4, 5, 6.
In the formula (II), the compound is shown in the specification,
selected from: a carbon-carbon single bond, a C1-C30 straight-chain alkyl group, a substituted or unsubstituted C1-C30 branched-chain alkyl group, a substituted or unsubstituted C1-C30 alkyl halide alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, and a substituted or unsubstituted C1-C30 alkyl groupOxy, substituted or unsubstituted alkylthio of C1 to C30, or a substituent selected from the following structures:
more preferably, it is a mixture of more preferably,
selected from the following structures:
in the present invention, more preferably, Ra、RbAnd RcEach independently selected from the formula 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 formula I-1 to formula I-78:
the invention provides a condensed ring compound containing boron nitrogen and a dendritic structure as shown in a formula (1), which takes boron as the center of a main ring and N atoms and other atoms X1、X2(independently selected from N, O, S, Se or Te) and 3 aromatic ring/aromatic heterocycle Ar (i.e. R
) Is an element or group on the main ring, and has 3 atoms (N, X)1、X2) And 3 aromatic rings/aromatic heterocycles Ar are distributed at intervals (namely every two inorganic elements are connected through 1 aromatic ring/heterocycle Ar), and at least 1 of the 3 aromatic rings/heterocycles Ar is connected with a dendritic structure (namely R)a、Rb、RcAnd the dendritic structure is specifically represented by the formula (II)), thereby obtaining boron-centered inorganic element N, X1、X2And 3 aromatic ring/heterocyclic Ar interval distribution around the central boron atom the main body ring, and connect with certain condensed ring compound of dendritic structure on the main body ring; in general, the compounds are composed of a condensed ring center containing boron atoms and nitrogen atoms and peripheral branches, and can utilize boronThe resonance effect between atoms and nitrogen atoms effects a separation of the front line orbitals, thus achieving a smaller Δ ESTAnd the TADF effect can reduce the relaxation degree of an excited state by utilizing the rigid skeleton structure of the specific fused ring unit, and realize higher luminous efficiency and narrower luminous spectrum.
The test result shows that the condensed-ring compound shown as the formula (1) provided by the invention has smaller delta EST(<0.2eV), the thermal activation delayed fluorescence effect is shown, and the delayed fluorescence life is 46-103 mu s, so that the triplet exciton can be utilized, and the efficiency of the device can be improved. The result of the embodiment of the device shows that the solution processing type 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 maximum external quantum efficiency is remarkably higher than that of a comparison compound without a dendritic structure (0.7-8.8%), and the solution processing type organic electroluminescent device has a narrow electroluminescent spectrum, and the half-peak width of the electroluminescent spectrum is less than 40 nm.
The invention also provides a preparation method of the fused ring compound containing boron nitrogen and a dendritic structure, which is characterized by comprising the following steps:
reacting the fused 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 a compound Lu4-Ra、Lu5-RbAnd Lu6-RcOne or more of the above;
wherein, Lu1～Lu6Each independently selected from: hydrogen, halogen, hydroxy, mercapto, amino,
[ condensed Ring intermediate represented by the formula (III)]：
Wherein, X1、X2，
And m, n, and p are the same as those in the foregoing technical solutions, and are not described in detail herein.
Wherein L is1The types of the above-mentioned components are also consistent with those described in the foregoing technical solutions, and are not described herein again.
When q is 0:
in the present invention, the fused ring intermediate represented by the formula (iii) is preferably prepared by the following preparation method:
s1, Compound Ar1Reacting with compound Ar' to form compound C;
s2, Compound C and BBr3Reacting to form a condensed ring intermediate shown in a formula (III);
the compound Ar' is a compound Ar2' and/or Compound Ar3＇；
When q is 1:
s3, Compound Ar4Reaction with compound Ar "to form compound D;
s4, Compound D and BBr3Reacting to form compound E;
s5, Compound E and BBr3Reacting to form a compound F;
s6, Compound F and Tf2O (i.e. trifluoromethanesulfonic 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 as a formula (III);
the compound Ar' is a compound Ar5' and/or Compound Ar6＇；
Wherein:
formula Ar1＇～Ar6Of formulae C to G
X1、X2Are the same as those in the foregoing technical solutions, and are not described in detail here.
Regarding step S1:
in the present invention, the reaction is preferably carried out under the action of a catalyst. The catalyst is preferably Na2CO3、K2CO3、Cs2CO3One or more of NaH, NaOH and KOH. The catalyst and a compound Ar1The molar ratio of "" is preferably (0.5 to 8):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) and 1, 4-dioxane and tetrahydrofuran. The organic solvent and a compound Ar1The amount of the surfactant is preferably (50 to 500) mL to (0.1 to 10) mol.
In the present invention, the reaction is preferably carried out under a protective atmosphere. The protective gas type for providing the protective atmosphere is not specially limited, and the protective gas is conventional in the field, such as nitrogen, helium, argon and the like.
In the invention, the reaction temperature is preferably 25-180 ℃; the reaction time is preferably 4-48 h. After the above reaction, compound C is produced in the system.
Regarding step S2:
in the present invention, the reaction is preferably carried out under the action of a lithiating reagent. The lithiation reagent is preferably n-BuLi (i.e., n-butyllithium). The molar ratio of the lithiation reagent to the compound C is preferably (1-5) 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, cumene and tert-butyl benzene. 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 BBr3The molar ratio of the boron tribromide to the compound C is preferably (1-10) to 1.
The reaction is preferably carried out in the presence of an organic amine base (i.e., a basic organic amine) to neutralize the acid during the reaction. The organic amine base is preferably N, N-diisopropylethylamine and/or triethylamine. The mol ratio of the organic amine base to the compound C is preferably (1-10) to 1.
In the invention, the reaction temperature is preferably 90-200 ℃; the reaction time is preferably 8-48 h. After the reaction, a condensed ring intermediate shown in a formula (III) is generated in the system.
Specifically, in the above process, the mixing sequence of the materials is preferably as follows: firstly, mixing the compound C with an organic solvent, then dropwise adding a catalyst at a first temperature, and after dropwise adding, dropwise adding BBr at a second temperature3After the dropwise addition is finished, stirring and mixing at a third temperature; thereafter, an organic amine base is added dropwise at a fourth temperature. After the dropwise addition is finished, heating to the reaction temperature for reaction to generate a condensed ring intermediate shown in the formula (III). Wherein the first temperature is a low temperature of 0 ℃ or lower, and may be-5 to-78 ℃. The second temperature is also lower than 0 ℃, and can be specifically-5 to-78 ℃; preferably the same as the first temperature. The third temperature is preferably room temperature, and specifically can be 20-40 ℃. The stirring and mixing time is preferably 0.5-6 h. The fourth temperature is lower than the third temperature, namely, after stirring and mixing, the temperature is reduced, and then the organic amine alkali is dripped; specifically, the fourth temperature is-78-0 ℃. After all the materials are added, heating to the reaction temperature for reaction. After the reaction, a condensed ring intermediate represented by the formula (III) is generated in the system.
Regarding step S3:
the reaction is preferably carried out under the action of a base.The alkali is preferably Na2CO3、K2CO3、Cs2CO3One or more of NaH, NaOH and KOH. The base and a compound Ar4The molar ratio of "" is preferably (0.5 to 8):1.
The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of N-methylpyrrolidone (NMP), N-Dimethylethylenediamine (DMF), dimethyl sulfoxide (DMSO), 1, 4-dioxane and tetrahydrofuran. The organic solvent and a compound Ar4The amount of the surfactant is preferably (50 to 500) mL to (0.1 to 10) mol.
The reaction is preferably carried out under a protective atmosphere. The protective gas type for providing the protective atmosphere is not specially limited, and the protective gas is conventional in the field, such as nitrogen, helium, argon and the like.
The reaction temperature is preferably 25-180 ℃; the reaction time is preferably 4-48 h. 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 butyl lithium 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, cumene and tert-butyl benzene. 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.
The BBr3The molar ratio of the boron tribromide to the compound D is preferably (1-10): 1.
The mol ratio of the N, N-diisopropylethylamine to the compound D is preferably (1-10) to 1.
The reaction temperature is preferably 90-200 ℃; the reaction time is preferably 8-48 h. After the above reaction, compound E is produced in the system.
In particular toIn the process, the mixing sequence of the materials is preferably as follows: firstly, mixing the compound D with an organic solvent, dropwise adding a lithiation reagent at a first temperature, and after dropwise adding, dropwise adding BBr at a second temperature3After the dropwise addition is finished, stirring and mixing at a third temperature; thereafter, an organic amine base is added dropwise at a fourth temperature. After the dropwise addition, the temperature is raised to the reaction temperature for reaction to generate a compound E. Wherein the first temperature is a low temperature of 0 ℃ or lower, and may be-5 to-78 ℃. The second temperature is also lower than 0 ℃, and can be specifically-5 to-78 ℃; preferably the same as the first temperature. The third temperature is preferably room temperature, and specifically can be 20-40 ℃. The stirring and mixing time is preferably 0.5-6 h. The fourth temperature is lower than the third temperature, namely, after stirring and mixing, the temperature is reduced, and then the organic amine alkali is dripped; specifically, the fourth temperature is-78-0 ℃. After all the materials are added, heating 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 type for providing the protective atmosphere is not specially limited, and the protective gas is conventional in the field, such as nitrogen, helium, argon and the like.
The reaction temperature is preferably 25-60 ℃; the reaction time is preferably 4-48 h. After the above reaction, compound F is 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, trichloromethane, 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 type for providing the protective atmosphere is not specially limited, and the protective gas is conventional in the field, such as nitrogen, helium, argon and the like.
The reaction temperature is preferably 25-60 ℃; the reaction time is preferably 4-48 h. After the above reaction, compound G is 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-methylpyrrolidone (NMP), N-Dimethylethylenediamine (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 reaction temperature is preferably 25-60 ℃; the reaction time is preferably 4-48 h. After the reaction, a condensed ring intermediate shown in a formula (III) is generated in the system.
[ regarding the dendrimer Lu-R]：
Wherein:
Ra、Rband RcConsistent with the foregoing, further description is omitted here.
Lu4～Lu6Each independently selected from: hydrogen, halogen, hydroxy, mercapto, or a salt thereof,Amino group,
The source of the dendrimer Lu-R is not particularly limited in the present invention, and the dendrimer Lu-R may be generally commercially available or prepared according to a known preparation method in the art.
[ reaction of condensed Ring intermediate represented by the 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) More preferably Pd2(dba)3And/or Pd (PPh)3)4. The molar ratio of the catalyst to the fused ring intermediate of the formula (III) is preferably (0.001-0.1): 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, cumene and mesitylene. The dosage ratio of the organic solvent to the condensed ring intermediate in 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 type for providing the protective atmosphere is not specially limited, and the protective gas is conventional in the field, such as nitrogen, helium, argon and the like.
In the invention, the reaction temperature is preferably 60-180 ℃; the reaction time is preferably 8-48 h. After the reaction, a fused 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 a dendritic structure shown in the formula (I) in the technical scheme in an organic electroluminescent device.
The present invention also provides an organic electroluminescent device comprising: an anode, a cathode, and a thin film layer between the anode and the cathode;
the film layer contains the condensed ring compound which is shown in the formula (I) in the technical scheme and contains boron nitrogen and a dendritic structure.
The structure of the organic electroluminescent device is not particularly limited in the present invention, and may be a conventional organic electroluminescent device well known to those skilled in the art, and those skilled in the art may select and adjust the structure according to the application, quality requirements and product requirements. The structure of the organic electroluminescent device of the present invention preferably includes: a substrate; an anode disposed on the substrate; a thin film layer disposed on the anode; and the cathode is arranged on the thin film layer.
Wherein:
the thickness of the substrate is preferably 0.3-0.7 mm, and more preferably 0.4-0.6 mm. The substrate is not particularly limited in the present invention, and may be a substrate of a conventional organic electroluminescent device well known to those skilled in the art, which may be selected and adjusted according to the application, quality requirements, and product requirements, and in the present invention, the substrate is preferably glass or plastic.
The anode is preferably a material susceptible to 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 thin film layer can be one layer or multiple layers, and at least one layer is a light-emitting layer; the light-emitting layer contains a dendritic fused ring compound containing a boron atom and an oxygen atom represented by the formula (I) described in the above technical means.
In order to improve the performance and efficiency of the device, the thin film layer preferably further includes one or more layers 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 thin film layers comprise, in sequential contact: 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 the preparation process is preferably carried out by a process of vacuum evaporation, solution spin coating, solution blade 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 the organic electroluminescent layer is preferably prepared by a process of solution spin coating, solution blade coating, inkjet printing, offset printing or stereolithography.
In some embodiments of the present invention, the structure of the organic electroluminescent device is device structure a or device structure B. Wherein the device structure A is: PSS/the dendritic fused ring compound of the invention/TSPO 1/TmPyPB/LiF/Al; more specifically, the device structure a is: PSS (40 nm)/dendritic fused ring compound (30nm)/TSPO1(8nm)/TmPyPB (30nm)/LiF (0.8nm)/Al (100 nm). Wherein the device structure B is: PSS/the blend of the dendritic fused ring compound and the host material SiMCP 2/TSPO 1/TmPyPB/LiF/Al; more specifically, device structure B is: PSS (40 nm)/blend (mass ratio of 1:9) (30nm)/TSPO1(8nm)/TmPyPB (42nm)/LiF (1nm)/Al (100nm) of the dendritic fused ring compound and the host material SiMCP 2.
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 including a light emitting layer on the anode; a cathode is formed on the thin film layer.
The structure and material of the organic electroluminescent device in the preparation method, and the corresponding preferred principle, and the corresponding material and structure in the organic electroluminescent device, and the corresponding preferred principle may be corresponding, and are not described in detail herein.
The present invention first forms an anode on a substrate, and the present invention does not specifically limit the manner of forming the anode, and may be performed according to a method 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 present invention is not particularly limited in the manner of forming the thin film layer below and above the light-emitting layer, and may be formed by vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, or stereolithography. The formation method of the light emitting layer is not particularly limited in the present invention, and the light emitting layer may be formed by solution spin coating, solution blade coating, inkjet printing, offset printing, or stereoprinting. After the thin film layer is formed, the cathode is prepared on the surface thereof, and the cathode forming mode is not particularly limited in the present invention, and is preferably a method well known to those skilled in the art, including but not limited to vacuum deposition. The organic electroluminescent device is obtained through the processes.
The invention provides a condensed ring compound containing boron nitrogen and a dendritic structure as shown in a formula (1), which takes boron as the center of a main ring and N atoms and other atoms X1、X2(independently selected from N, O, S, Se or Te) and 3 aromatic ring/aromatic heterocycle Ar (i.e. R
) Is an element or group on the main ring, and has 3 atoms (N, X)1、X2) And 3 aromatic rings/aromatic heterocycles Ar are distributed at intervals (namely every two inorganic elements are connected through 1 aromatic ring/heterocycle Ar), and at least 1 of the 3 aromatic rings/heterocycles Ar is connected with a dendritic structure (namely R)a、Rb、RcAnd the dendritic structure is specifically represented by the formula (II)), thereby obtaining boron-centered inorganic element N, X1、X2And 3 aromatic ring/heterocyclic Ar interval distribution around the central boron atom the main body ring, and connect with certain condensed ring compound of dendritic structure on the main body ring; in summary, the compound is composed of a condensed ring center containing boron atoms and nitrogen atoms and peripheral branches, and can realize separation of front tracks by utilizing resonance effect between the boron atoms and the nitrogen atoms, thereby realizing small Delta ESTAnd the TADF effect, and the relaxation degree of an excited state can be reduced by utilizing the rigid skeleton structure of the specific condensed ring unit, so that higher luminous efficiency and narrower luminous spectrum are realized.
The test result shows that the condensed ring compound shown as the formula (1) provided by the invention has smaller delta EST(<0.2eV), the thermal activation delayed fluorescence effect is shown, and the delayed fluorescence life is 46-103 mu s, so that the triplet exciton can be utilized, and the efficiency of the device can be improved. The result of the embodiment of the device shows that the solution processing type 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 maximum external quantum efficiency is remarkably higher than that of a comparison compound without a dendritic structure (0.7-8.8%), and the solution processing type organic electroluminescent device has a narrow electroluminescent spectrum, and the half-peak width of the electroluminescent spectrum is less than 40 nm.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1: preparation of Compounds of formula I-1
The synthetic route and the process are as follows:
the compound of formula 1-1 (13) was weighed in a 500mL three-necked flask under an argon atmosphere.6g, 0.05mol), diphenylamine (20.3g,0.12mol) and CS2CO3(65.2g, 0.20mol), 80mL of N, N-Dimethylformamide (DMF) is added into a bottle, the temperature is raised to 150 ℃, the reaction solution is stirred for 10 hours under the protection of argon, then the reaction solution is cooled to room temperature, the reaction solution is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 1-2(18.4g, yield: 64.8%). Elemental analysis: theoretical value C, 63.18; h, 3.89; n, 4.91; test value C, 63.15; h, 3.91; and N, 4.87. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 568.0; experimental value 568.0 (M)+)。
In a 250mL two-necked flask, a compound of formula 1-2 (5.7g,10mmol) and dry o-xylene (80mL) were weighed out under argon atmosphere, a butyllithium solution (4.0mL,2.5M,10mmol) was added dropwise at-30 deg.C, and after completion of the addition, stirring was carried out at-30 deg.C for 2 hours, and then boron tribromide (2.8g,11.0mmol) was added dropwise to the system, and after completion of the addition, stirring was carried out at room temperature for 1 hour after 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.6g,20.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 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 obtain 1 to 3(2.3g, yield: 45.2%). Elemental analysis: theoretical value C, 72.18; h, 4.04; n, 5.61; test value C, 72.15; h, 4.02; and N, 5.64. ESI-MS: theoretical value 498.1; experimental value 498.1 (M)+)。
The compounds of formulae 1-4 are prepared according to the synthetic route described in adv.Funct.Mater.2014,24, 3413-3421.
A50 mL Schlenk flask was charged with a compound of formula 1-4 (1.77g, 1.1mmol), a compound of formula 1-3 (0.50g, 1mmol), Pd under an argon atmosphere2(dba)3(46mg，0.05mmol)、t-Bu3PHBF4(58mg, 0.20mmol), t-BuONa (0.19g, 2mmol), followed by 20mL of toluene, and reaction at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give the dendritic fused ring compound I-1(1.24g, yield: 56.2%). Elemental analysis: theoretical value C, 86.57; h, performing a chemical reaction on the mixture of the hydrogen peroxide and the nitrogen peroxide,6.67; n, 6.22; test value C, 86.52; h, 6.71; and N, 6.18. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 2024.1; experimental value 2024.0 (M)+)。
The photophysical properties of the fused ring compound prepared in example 1 of the present invention were measured, 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:
the compound of formula 2-1 (9.60g, 0.05mol), 3, 6-tert-butylcarbazole (33.50g,0.12mol) and CS were weighed in a 500mL three-necked flask under an argon atmosphere2CO3(65.2g, 0.20mol), 80mL of N, N-Dimethylformamide (DMF) is added into a bottle, the temperature is raised to 150 ℃, the reaction solution is stirred for 10 hours under the protection of argon, then the reaction solution is cooled to room temperature, the reaction solution is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 2-2(20.10g, yield: 56.6%). Elemental analysis: theoretical value C, 77.62; h, 7.22; n, 3.94; test value C, 77.59; h, 7.25; and N, 3.90. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 710.3; experimental value 710.4 (M)+)。
In a 250mL two-necked flask, a compound of formula 2-2 (7.10g,10mmol) and dry o-xylene (80mL) were weighed under argon atmosphere, a butyllithium solution (4.0mL,2.5M,10mmol) was added dropwise at-30 ℃, stirring was performed at-30 ℃ for 2 hours after the addition was completed, boron tribromide (2.8g,11.0mmol) was added dropwise to the system, and stirring was performed at room temperature for 1 hour after 20 minutes of the addition was completed. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.6g,20.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated from the filtered system and washed with methanol, and the crude product was separated by column to obtain 2-3(3.41g, 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: a theoretical value of 640.4; experimental value 640.3 (M)+)。
The compound of formula 2-3 (3.20g, 5mmol) was weighed in a 250mL two-necked flask, then 80mL of N, N-Dimethylformamide (DMF) was added to the flask, after stirring and dissolution, 20mL of DMF solution of NBS (0.89g, 5mmol) was slowly added dropwise in an ice-water bath, after completion of addition, the temperature was naturally raised, after completion of addition, the reaction solution was stirred at room temperature for 20 hours, the reaction solution was diluted with dichloromethane and poured into water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated by column to give 2-4(1.55g, yield: 43.2%). Elemental analysis: theoretical value C, 76.78; h, 6.72; n, 3.89; test value C, 76.81; h, 6.68; and N, 3.91. ESI-MS: theoretical value 718.3; experimental value 718.3 (M)+)。
A50 mL Schlenk flask was charged with a compound of formula 1-4 (1.77g, 1.1mmol), a compound of formula 2-4 (0.72g, 1mmol), Pd under an argon atmosphere2(dba)3(46mg，0.05mmol)、t-Bu3PHBF4(58mg, 0.20mmol), t-BuONa (0.19g, 2mmol), followed by 20mL of toluene, and reaction at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give dendritic fused ring compound I-19(0.98g, yield: 43.5%). Elemental analysis: theoretical value C, 86.64; h, 7.72; n, 5.61; test value C, 86.62; h, 7.75; and N, 5.57. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m/z)): a theoretical value of 2244.3; experimental value 2244.3 (M)+)。
The photophysical properties of the fused ring compound prepared in example 2 of the present invention were measured 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:
the compound of formula 2-3 (3.20g, 5mmol) was weighed in a 250mL two-necked flask, and 80mL of N, N-Dimethylformamide (DMF) was added to the flask,after the mixture was dissolved by stirring, a 20mL DMF solution of NBS (2.14g, 12mmol) was slowly dropped into an ice-water bath, and after the dropping, the temperature was naturally raised, the mixture was stirred at room temperature for 20 hours, the reaction mixture was diluted with methylene chloride and poured into water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain the product 3-1(2.09g, yield: 52.6%). Elemental analysis: theoretical value C, 69.19; h, 5.93; n, 3.51; test value C, 69.21; h, 5.95; and N, 3.47. ESI-MS: theoretical value 796.2; experimental value 796.2 (M)+)。
A50 mL Schlenk flask was charged with a compound of formula 1-4 (1.77g, 1.1mmol), a compound of formula 3-1 (0.40g, 0.5mmol), Pd under an argon atmosphere2(dba)3(46mg，0.05mmol)、t-Bu3PHBF4(58mg, 0.20mmol), t-BuONa (0.19g, 2mmol), followed by 20mL of toluene, and reaction at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give dendrimer fused ring compound I-20(0.66g, 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 value 3848.3 (M)+)。
The photophysical properties of the fused ring compound prepared in example 3 of the present invention were measured, 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:
the compound of formula 4-1 (13.49g, 0.05mol), 3, 6-tert-butylcarbazole (33.50g,0.12mol) and CS were weighed in a 500mL three-necked flask under an argon atmosphere2CO3(65.2g, 0.20mol), 80mL of N, N-Dimethylformamide (DMF) is added into a bottle, the temperature is raised to 150 ℃, the mixture is stirred and reacted for 10 hours under the protection of argon, then the mixture is cooled to room temperature, and the reaction solution is diluted by tolueneThen, the mixture was poured into water, and the organic phase was separated, dried over anhydrous sodium sulfate, filtered to remove the solvent, and the crude product was subjected to column separation to obtain 4-2(23.13g, yield: 58.7%). Elemental analysis: theoretical value C, 69.87; h, 6.37; n, 3.54; test value C, 69.82; h, 6.41; and N, 3.50. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 788.2; experimental value 788.3 (M)+)。
In a 250mL two-necked flask, a compound of formula 4-2 (7.88g,10mmol) and dry o-xylene (80mL) were weighed under argon atmosphere, a butyllithium solution (4.0mL,2.5M,10mmol) was added dropwise at-30 ℃, stirring was performed at-30 ℃ for 2 hours after the addition was completed, boron tribromide (2.8g,11.0mmol) was added dropwise to the system, and stirring was performed at room temperature for 1 hour after 20 minutes of the addition was completed. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.6g,20.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated from the filtered system and washed with methanol, and the crude product was separated by column to obtain 4-3(4.40g, yield: 61.3%). Elemental analysis: theoretical value C, 76.78; h, 6.72; n, 3.89; test value C, 76.81; h, 6.75; and N, 3.82. ESI-MS: theoretical 718.3; experimental value 718.3 (M)+)。
In a 100mL two-necked flask, under an argon atmosphere, a compound of formula 4-3 (2.15g, 3mmol), a boronic acid ester (1.5g,6mmol), PdCl2(dppf) (0.11g, 0.15mmol), potassium acetate (0.6g, 6mmol), 40mL of DMF was taken and added to a flask, and the reaction was stirred at 85 ℃ for 10 hours. Then, the reaction solution was cooled to room temperature, washed with deionized water, and extracted with methylene chloride solution to obtain an organic phase, which was concentrated and dried, and the crude product was separated by column to obtain 4-4(1.66g, yield: 72.3%). Elemental analysis: theoretical value C, 81.46; h, 7.89; n, 3.65; test value C, 81.40; h, 7.82; and N, 3.69. ESI-MS: theoretical value 766.5; experimental value 767.4([ M + H)]+)。
The compounds of the formulae 4-5 are prepared according to the synthetic route described in the Journal of Materials Chemistry C,2017,5, 9753-9760.
Magnesium turnings (0.13g, 5.5mmol) were weighed in a 250mL two-necked flask under an argon atmosphere, and the compound of formula 4-5 (4.4g, 5mmol) was dissolved in 50mL of a dry THF solutionAfter neutralization, the reaction mixture was added dropwise to a two-necked flask containing magnesium chips, the obtained Grignard reagent was filtered, and slowly added dropwise to a solution of cyanuric chloride (0.4g,2.2mmol) in THF at-20 ℃ and cooled to room temperature after the reaction was completed, and the reaction mixture was poured into water and extracted with dichloromethane to separate an organic phase. Dried by adding anhydrous sodium sulfate, the organic phase obtained by filtration was freed of the solvent, and the crude product was column-separated to obtain the products 4 to 6(1.5g, yield: 40%). Elemental analysis: theoretical value C, 83.70; h, 6.85; n, 7.38; test value C, 83.72; h, 6.81; and N, 7.43. MALDI-TOF (m/z): theoretical value 1705.9; experimental value 1705.9 (M)+)。
Under argon atmosphere, a 50mL Schlenk bottle was charged with the compound of formula 4-6 (0.85g, 0.5mmol), the compound of formula 4-4 (0.38g, 0.5mmol), and Pd as a catalyst2(dba)3(46mg, 0.05mmol) and ligand S-phos (82mg, 0.2mmol), 20mL of toluene was added to the flask, potassium carbonate (0.27g,2mmol) was dissolved in 1mL of water, the aqueous potassium carbonate solution was introduced into the flask, the temperature was raised to 110 deg.C, the reaction was stirred under argon for 24 hours, then cooled to room temperature, the reaction was poured into water and the organic phase was separated by extraction with dichloromethane. The organic phase was separated, and subjected to column separation and solvent removal to give dendrimer fused ring compound I-27(0.37g, yield: 32.2%). Elemental analysis: theoretical value C, 85.72; h, 7.15; n, 6.66; test value C, 85.75; h, 7.11; and N, 6.52. MALDI-TOF (m/z): theoretical value 2310.3; experimental value 2310.4 (M)+)。
The photophysical properties of the fused ring compound prepared in example 4 of the present invention were measured, 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 compound of formula 5-1 was prepared according to the synthetic route disclosed in Adv.Funct.Mater.2014,24, 3413-3421.
A50 mL Schlenk flask was charged with the compound of formula 5-1 (3.5g, 2mmol), 4' -diiododiphenyl ether (1.7g, 4) under argon atmospheremmol), cuprous iodide (0.1g, 0.5mmol) and anhydrous potassium carbonate (0.6g, 4mmol), 20mL of DMI was added to the flask, and the temperature was raised to 170 ℃ for 20 hours. The reaction mixture was cooled to room temperature, poured into water and extracted with dichloromethane to separate the organic phase. Dried by adding anhydrous sodium sulfate, the organic phase obtained by filtration was freed of the solvent, and the crude product was column-separated to obtain the product 5-2(1.6g, yield: 40%). Elemental analysis: theoretical value C, 75.76; h, 6.06; n, 4.83; test value C, 75.64; h, 6.12; and N, 4.86. MALDI-TOF (m/z): theoretical value 2027.8; experimental value 2027.8 (M)+)。
A50 mL three-necked flask was charged with a compound of formula 5-2 (1.0g, 0.5mmol), a compound of formula 4-4 (0.42g,0.55mmol), and Pd as a catalyst under an argon atmosphere2(dba)3(46mg, 0.05mmol) and ligand S-phos (82mg, 0.2mmol), 20mL of toluene was added to the flask, potassium carbonate (0.28g,4mmol) was dissolved in 2mL of water, the aqueous potassium carbonate solution was introduced into the flask, the temperature was raised to 110 deg.C, the reaction was stirred under argon for 16 hours, then cooled to room temperature, the reaction was poured into water and the organic phase was separated by extraction with dichloromethane. Dried by adding anhydrous sodium sulfate, the organic phase obtained by filtration was freed of the solvent, and the crude product was column-separated to give the product I-30(0.42g, yield: 32.8%). Elemental analysis: theoretical value C, 82.21; h, 6.74; n, 4.96; test value C, 82.25; h, 6.67; and N, 4.98. MALDI-TOF (m/z): theoretical value 2540.3; experimental value 2540.4 (M)+)。
The photophysical properties of the fused ring compound prepared in example 5 of the present invention were measured, 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:
a100 mL three-necked flask was charged with the compound of formula 1-4 (3.2g, 2mmol), dibromobutane (0.87g, 4mmol) and anhydrous potassium carbonate (0.6g, 4mmol) under an argon atmosphere, 20mL of DMF was taken and the flask was charged, and the temperature was raised to 120 ℃ to react for 20 hours. Cooling to room temperature, pouring the reaction mixture into water and adding dichloromethaneThe organic phase is separated off by extraction. Dried by adding anhydrous sodium sulfate, the organic phase obtained by filtration was freed of the solvent, and the crude product was column-separated to obtain the product 6-1(2.4g, yield: 70%). Elemental analysis: theoretical value C, 82.73; h, 7.06; n, 5.63; test value C, 82.63; h, 7.11; and N, 5.69. MALDI-TOF (m/z): theoretical value 1739.8; experimental value 1739.9 (M)+)。
In a 50mL two-necked flask under argon atmosphere, the compound of formula 4-3 (3.59g,5mmol) and sodium tert-butoxide (0.54g,10mmol) were weighed, 20mL of DMF was taken and added to the flask, and the temperature was raised to 120 ℃ for reaction for 20 hours. The reaction mixture was cooled to room temperature, poured into water and extracted with dichloromethane to separate the organic phase. Dried by adding anhydrous sodium sulfate, the organic phase obtained by filtration was freed of the solvent, and the crude product was separated by column to give the product 6-2(1.76g, yield: 52.4%). Elemental analysis: theoretical value C, 84.16; h, 7.66; n, 4.18; test value C, 84.13; h, 7.60; and 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 (1.34g,2mmol) and dried dichloromethane (30mL) were weighed under an argon atmosphere, and boron tribromide (1.5g,6mmol) was added dropwise at 0 ℃ to react at room temperature for 5 hours. Poured into water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the filtered organic phase, and the crude product was separated by column to give 6-3(1.08g, yield: 82.3%). Elemental analysis: theoretical value C, 84.13; h, 7.52; n, 4.27; test value C, 84.10; h, 7.53; and N, 4.26. ESI-MS: theoretical value 656.4; experimental value 657.2([ M + H)]+)。
A50 mL two-necked flask was charged with the compound of formula 6-1 (1.70g, 1mmol), the compound of formula 6-3 (0.66g, 1mmol) and anhydrous potassium carbonate (0.28g, 2mmol) under argon, and 10mL of DMF was taken and charged into the flask, and the temperature was raised to 120 ℃ to react for 20 hours. After cooling to room temperature, the reaction mixture was poured into water and the organic phase was separated by extraction with dichloromethane. After drying over anhydrous sodium sulfate, the organic phase obtained by filtration was freed of the solvent and the crude product was isolated on a column to give the product I-31(1.00g, yield: 43.2%). Elemental analysis: theoretical value C, 86.01; h, 7.39; n, 5.44; test value C, 86.03; h, 7.35; and N, 5.48. MALDI-TOF (m/z): theoretical value 2316.4; experimental value 2316.4 (M)+)。
The photophysical properties of the fused ring compound prepared in example 6 of the present invention were measured, 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 Tetrahedron Letters,2003,44, 957-959.
A50 mL Schlenk flask was charged with a compound of formula 7-1 (1.2g, 1.1mmol), a compound of formula 3-1 (0.40g, 0.5mmol), and Pd as a catalyst under an argon atmosphere2(dba)3(92mg, 0.1mmol) and ligand S-phos (164mg, 0.4mmol), 20mL of toluene was added to the flask, potassium carbonate (0.54g,4mmol) was dissolved in 2mL of water, an aqueous solution of potassium carbonate was introduced into the flask, and the temperature was raised to 110 ℃ for reaction for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and desolvation to give dendritic fused ring compound I-22(0.29g, yield: 23.2%). Elemental analysis: theoretical value C, 88.05; h, 7.11; n, 4.42; test value C, 88.01; h, 7.06; and N, 4.46. MALDI-TOF (m/z): theoretical value 2535.4; experimental value 2535.4 (M)+)。
The photophysical properties of the fused ring compound prepared in example 7 of the present invention were measured, 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 are prepared according to the synthetic route disclosed in the literature Polym. chem.,2015,6, 1180-1191.
A50 mL three-necked flask was charged with the compound of formula 8-1 (1.2g, 0.5mmol) and the compound of formula 4-4 under an argon atmosphereSubstance (0.42g,0.55mmol), catalyst Pd2(dba)3(46mg, 0.05mmol) and ligand S-phos (82mg, 0.2mmol), 20mL of toluene was added to the flask, potassium carbonate (0.28g,4mmol) was dissolved in 2mL of water, the aqueous potassium carbonate solution was introduced into the flask, the temperature was raised to 110 deg.C, the reaction was stirred under argon for 16 hours, then cooled to room temperature, the reaction was poured into water and the organic phase was separated by extraction with dichloromethane. Dried by adding anhydrous sodium sulfate, the organic phase obtained by filtration was freed of the solvent, and the crude product was column-separated to give the product I-32(0.63g, yield: 42.3%). Elemental analysis: theoretical value C, 85.25; h, 6.88; n, 4.26; test value C, 85.21; h, 6.81; and N, 4.24. MALDI-TOF (m/z): a theoretical value of 2956.6; experimental value 2956.6 (M)+)。
The photophysical properties of the fused ring compound prepared in example 8 of the present invention were measured, and the results are shown in table 1.
Example 9: preparation of the Compounds of formula I-33
The synthetic route and the process are as follows:
the compounds of formula 9-1 are prepared according to the synthetic route disclosed in the literature Polym. chem.,2015,6, 1180-1191.
A50 mL two-necked flask was charged with the compound of formula 9-1 (0.93g, 0.5mmol), the compound of formula 4-3 (0.39g, 0.55mmol) and anhydrous potassium carbonate (0.28g, 2mmol) under argon, 10mL of DMF was taken and charged into the flask, and the temperature was raised to 120 ℃ to react for 20 hours. The reaction mixture was cooled to room temperature, poured into water and extracted with dichloromethane to separate the organic phase. Dried by adding anhydrous sodium sulfate, the organic phase obtained by filtration was freed of the solvent, and the crude product was column-separated to give the product I-33(0.73g, yield: 58.2%). Elemental analysis: theoretical value C, 84.31; h, 7.40; n, 3.37; test value C, 84.27; h, 7.45; and N, 3.32. MALDI-TOF (m/z): theoretical value 2491.4; experimental value 2491.4 (M)+)。
The photophysical properties of the fused ring compound prepared in example 9 of the present invention were measured 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 are prepared according to the synthetic routes disclosed in the document J.Am.chem.Soc.1996,118, 4354-4360.
A50 mL two-necked flask was charged with the compound of formula 10-1 (0.1g, 0.5mmol), the compound of formula 4-3 (0.39g, 0.55mmol) and anhydrous potassium carbonate (0.28g, 2mmol) under argon, 10mL of DMF was taken and charged into the flask, and the temperature was raised to 120 ℃ to react for 20 hours. The reaction mixture was cooled to room temperature, poured into water and extracted with dichloromethane to separate the organic phase. Dried by adding anhydrous sodium sulfate, the organic phase obtained by filtration was freed of the solvent, and the crude product was column-separated to give the product I-34(0.59g, yield: 43.5%). Elemental analysis: theoretical value C, 73.93; h, 6.35; s, 1.03; test value C, 73.91; h, 6.31; and S, 1.09. MALDI-TOF (m/z): theoretical value 2711.2; experimental value 2711.1 (M)+)。
The photophysical properties of the fused ring compound prepared in example 10 of the present invention were measured 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:
in a 500mL three-necked flask, a compound of formula 1-1 (13.6g, 0.05mol), 9-dimethylacridine (23.5g,0.12mol) and CS were weighed under an argon atmosphere2CO3(65.2g, 0.20mol), 80mL of N, N-Dimethylformamide (DMF) is added into a bottle, the temperature is raised to 150 ℃, the reaction solution is stirred for 10 hours under the protection of argon, then the reaction solution is cooled to room temperature, the reaction solution is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 11-2(20.19g, yield: 62.3%). Elemental analysis: theory of thingsTheoretical 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)+)。
In a 250mL two-necked flask, a compound of formula 11-2 (6.48g,10mmol) and dry o-xylene (80mL) were weighed under argon atmosphere, a butyllithium solution (4.0mL,2.5M,10mmol) was added dropwise at-30 ℃, stirring was performed at-30 ℃ for 2 hours after the addition was completed, boron tribromide (2.8g,11.0mmol) was added dropwise to the system, and stirring was performed at room temperature for 1 hour after 20 minutes of the addition was completed. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.6g,20.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated from the filtered system and washed with methanol, and the crude product was separated by column to obtain 11-3(2.51g, 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 value 578.2 (M)+)。
The compound of formula 11-1 is prepared according to the synthetic route disclosed in org.Lett.2018,20, 7864-7868.
A50 mL Schlenk flask was charged with a compound of formula 11-1 (1.3g, 1.1mmol), a compound of formula 11-3 (0.58g, 1mmol), Pd under an argon atmosphere2(dba)3(46mg，0.05mmol)、t-Bu3PHBF4(58mg, 0.20mmol), t-BuONa (0.19g, 2mmol), followed by 20mL of toluene, and reaction at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give dendritic fused ring compound I-36(0.59g, yield: 35.2%). Elemental analysis: theoretical value C, 86.26; h, 5.55; n, 7.54; test value C, 86.21; h, 5.51; and N, 7.58. MALDI-TOF (m/z): theoretical value 1669.7; experimental value 1669.7 (M)+)。
The photophysical properties of the fused ring compounds prepared in example 11 of the present invention were measured 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:
in a 500mL three-necked flask, the compound of formula 1-1 (13.6g, 0.05mol), spirosilacridine (41.6g,0.12mol) and CS were weighed under an argon atmosphere2CO3(65.2g, 0.20mol), 80mL of N, N-Dimethylformamide (DMF) is added into a bottle, the temperature is raised to 150 ℃, the reaction is stirred for 10 hours under the protection of argon, then the solution is cooled to room temperature, the reaction solution is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent is removed from the organic phase obtained by filtration, and the crude product is subjected to column separation to obtain the product 12-2(24.16g, yield: 52.3%). Elemental analysis: theoretical value C, 69.98; h, 3.70; n, 3.02; test value C, 69.92; h, 3.61; and N, 3.76. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 924.1; experimental value 924.2 (M)+)。
In a 250mL two-necked flask, a compound of formula 12-2 (9.24g,10mmol) and dry o-xylene (80mL) were weighed under argon atmosphere, a butyllithium solution (4.0mL,2.5M,10mmol) was added dropwise at-30 ℃, stirring was performed at-30 ℃ for 2 hours after the addition was completed, boron tribromide (2.8g,11.0mmol) was added dropwise to the system, and stirring was performed at room temperature for 1 hour after 20 minutes of the addition was completed. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.6g,20.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated from the filtration system and washed with methanol, and the crude product was separated by column to obtain 12-3(3.09g, yield: 36.2%). Elemental analysis: theoretical value C, 75.79; h, 3.77; n, 3.27; test value C, 75.71; h, 3.82; and N, 3.31. ESI-MS: theoretical value 854.1; experimental value 854.1 (M)+)。
Under argon atmosphere, a 250mL Schlenk flask was charged with the compound of formula 12-1 (7.6g, 20mmol) and sodium hydride (5.6g, 22mmol), and 80mL of DMF was added to the flask and stirred at room temperature for 1 hour. TBS-Cl (3.6g, 24mmol) was then added dropwise thereto and the reaction mixture was stirred for another 4 hours, then poured into water, and the crude product obtained by filtration was subjected to column separation to obtain 12-4(8.0g, yield: 80%). Elemental analysis: theoretical value C, 48.29; h, 5.47; n, 2.82; test value C,4823; h, 5.41; and N, 2.85. ESI-MS: theoretical value 495.0; experimental value 495.0 (M)+)。
A100 mL Schlenk flask was charged with a compound of formula 12-4 (5.0g, 10mmol), silacridine (5.0g, 22mmol), Pd under an argon atmosphere2(dba)3(0.46g，0.5mmol)、t-Bu3PHBF4(0.58g, 2.0mmol), t-BuONa (3.8g, 40mmol), then 40mL of toluene was injected and reacted at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. Dried by adding anhydrous sodium sulfate, and the organic phase obtained by filtration was freed from the solvent. The resulting crude product and tetrabutylammonium fluoride (5.3g, 20mmol) were added to 30mL THF and stirred for 4 hours. The product 12-5(6.0g, yield: 60%) was obtained by column separation and solvent removal. Elemental analysis: theoretical value C, 75.06; h, 6.15; n, 6.25; test value C, 75.12; h, 6.13; and N, 6.27. ESI-MS: theoretical value 671.2; experimental value 671.2 (M)+)。
A100 mL Schlenk flask was charged with a compound of formula 12-4 (1.0g, 2mmol), a compound of formula 12-5 (2.7g, 4mmol), Pd under an argon atmosphere2(dba)3(0.09g，0.1mmol)、t-Bu3PHBF4(0.12g, 0.4mmol), t-BuONa (0.4g, 4mmol), then 40mL of toluene was injected and reacted at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. Dried by adding anhydrous sodium sulfate, and the organic phase obtained by filtration was freed from the solvent. The resulting crude product and tetrabutylammonium fluoride (5.3g, 20mmol) were added to 30mL THF and stirred for 4 hours. The product 12-6(1.2g, yield: 40%) was obtained by column separation and solvent removal. Elemental analysis: theoretical value C, 75.24; h, 5.93; n, 6.27; test value C, 75.22; h, 5.91; and N, 6.29. MALDI-TOF (m/z): theoretical value 1562.5; experimental value 1562.5.
A50 mL Schlenk flask was charged with a compound of formula 12-6 (0.8g, 0.55mmol), a compound of formula 12-3 (0.43g, 0.5mmol), Pd under an argon atmosphere2(dba)3(46mg，0.05mmol)、t-Bu3PHBF4(58mg, 0.20mmol), t-BuONa (0.19g, 2mmol), followed by 20mL of toluene, and reaction at 110 ℃ for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane 100mL for extraction, and removingWashing with water for several times. The organic phase was separated, and subjected to column separation and solvent removal to give dendritic fused ring compound I-37(0.26g, 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 value 2337.8 (M)+)。
The photophysical properties of the fused ring compound prepared in example 12 of the present invention were measured, 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:
the compound of formula 1-1 (13.6g, 0.05mol), spiroacridine (39.7g,0.12mol) and CS were weighed in a 500mL three-necked flask under an argon atmosphere2CO3(65.2g, 0.20mol), 80mL of N, N-Dimethylformamide (DMF) is added into a bottle, the temperature is raised to 150 ℃, the reaction solution is stirred for 10 hours under the protection of argon, then the reaction solution is cooled to room temperature, the reaction solution is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 13-1(23.91g, yield: 53.6%). Elemental analysis: theoretical value C, 75.18; h, 3.83; n, 3.13; test value C, 75.12; h, 3.81; and N, 3.16. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 892.1; experimental value 892.2 (M)+)。
A compound of formula 13-1 (8.92g,10mmol) and dry o-xylene (80mL) are weighed out in a 250mL two-necked flask under argon atmosphere, butyllithium solution (4.0mL,2.5M,10mmol) is added dropwise at-30 ℃, stirring is performed for 2 hours at-30 ℃ after the addition is completed, boron tribromide (2.8g,11.0mmol) is added dropwise to the system, and stirring is performed for 1 hour at room temperature after 20 minutes of addition is completed. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.6g,20.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. Cooling the reaction to room temperature, separating out solid in a filtering system, washing with methanol, and separating the crude product by a column to obtain a product 13-2 (2.8)2g, yield: 34.3%). Elemental analysis: theoretical value C, 81.67; h, 3.92; n, 3.40; test value C, 81.62; h, 3.85; and N, 3.31. ESI-MS: theoretical value 822.2; experimental value 822.3 (M)+)。
The compounds of formula 13-3 were prepared according to the synthetic route disclosed in chem.sci.,2019,10, 2915-2923.
A50 mL Schlenk flask was charged with a compound of formula 13-3 (1.6g, 1.1mmol), a compound of formula 13-2 (0.82g, 1mmol), Pd under an argon atmosphere2(dba)3(46mg，0.05mmol)、t-Bu3PHBF4(58mg, 0.20mmol), t-BuONa (0.19g, 2mmol), followed by 20mL of toluene, and reaction at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give dendritic fused ring compound I-38(0.75g, 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 value 2194.0 (M)+)。
The photophysical properties of the fused ring compound prepared in example 13 of the present invention were measured, 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 (6.8g, 20mmol) and sodium hydride (5.6g, 22mmol) under argon, and 80mL of DMF was taken and added to the flask and stirred at room temperature for 1 hour. TBS-Cl (3.6g, 24mmol) was then added dropwise and the reaction stirred for 4 hours, after which the reaction was poured into water and the crude product from the filtration was isolated as a column to give 14-2(7.3g, yield: 80%). Elemental analysis: theoretical value C, 47.49; h, 4.65; n, 3.08; test value C, 47.42; h, 4.62; and N, 3.09. ESI-MS: theoretical value 452.9; experimental value 453.0 (M)+)。
Under an argon atmosphere, a 100mL Schlenk flask was charged with a compound of formula 14-2Substance (4.5g, 10mmol), phenoxazine (4.0g, 22mmol), Pd2(dba)3(0.46g，0.5mmol)、t-Bu3PHBF4(0.58g, 2.0mmol), t-BuONa (3.8g, 40mmol), then 40mL of toluene was injected and reacted at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. Dried by adding anhydrous sodium sulfate, and the organic phase obtained by filtration was freed from the solvent. The resulting crude product and tetrabutylammonium fluoride (5.3g, 20mmol) were added to 30mL THF and stirred for 4 hours. The product 14-3(3.4g, yield: 62%) was obtained by column separation and solvent removal. Elemental analysis: theoretical value 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 value 545.1 (M)+)。
A100 mL Schlenk flask was charged with a compound of formula 14-2 (0.9g, 2mmol), a compound of formula 14-3 (2.2g, 4mmol), Pd under an argon atmosphere2(dba)3(0.09g，0.1mmol)、t-Bu3PHBF4(0.12g, 0.4mmol), t-BuONa (0.4g, 4mmol), then 40mL of toluene was injected and reacted at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. Dried by adding anhydrous sodium sulfate, and the organic phase obtained by filtration was freed from the solvent. The resulting crude product and tetrabutylammonium fluoride (5.3g, 20mmol) were added to 30mL THF and stirred for 4 hours. The product 14-4(1.1g, yield: 43%) was obtained by column separation and solvent removal. Elemental analysis: theoretical value C, 79.48; h, 3.97; n, 7.72; test value C, 79.42; h, 3.91; and N, 7.75. MALDI-TOF (m/z): theoretical value 1562.5; experimental value 1562.5 (M)+)。
The compound of formula 1-1 (13.6g, 0.05mol), phenoxazine (21.9g,0.12mol) and CS were weighed in a 500mL three-necked flask under an argon atmosphere2CO3(65.2g, 0.20mol), 80mL of N, N-Dimethylformamide (DMF) is added into a bottle, the temperature is raised to 150 ℃, the reaction solution is stirred for 10 hours under the protection of argon, then the reaction solution is cooled to room temperature, the reaction solution is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 14-5(12.99g, yield: 43.6%). Elemental analysis: theoretical value C, 60.23; h,3.03; n, 4.68; test value C, 60.20; h, 3.01; and N, 4.66. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 595.9; experimental value 595.9 (M)+)。
In a 250mL two-necked flask under argon atmosphere, the compound of formula 14-5 (5.95g,10mmol) and dry o-xylene (80mL) were weighed out, a butyllithium solution (4.0mL,2.5M,10mmol) was added dropwise at-30 deg.C, stirring was performed at-30 deg.C for 2 hours after the addition was completed, boron tribromide (2.8g,11.0mmol) was added dropwise to the system, and stirring was performed at room temperature for 1 hour after 20 minutes of completion of the addition. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.6g,20.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated from the filtered system and washed with methanol, and the crude product was separated by column to give 14-6(1.75g, yield: 33.2%). Elemental analysis: theoretical value C, 68.35; h, 3.06; n, 5.31; test value C, 68.31; h, 3.05; and N, 5.35. ESI-MS: theoretical value 526.1; experimental value 526.2 (M)+)。
A50 mL Schlenk flask was charged with a compound of formula 14-4 (0.7g, 0.55mmol), a compound of formula 14-6 (0.26g, 0.5mmol), Pd under an argon atmosphere2(dba)3(46mg，0.05mmol)、t-Bu3PHBF4(58mg, 0.20mmol), t-BuONa (0.19g, 2mmol), followed by 20mL of toluene, and reaction at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give dendritic fused ring compound I-41(0.19g, yield: 22.3%). Elemental analysis: theoretical value C, 79.76; h, 3.88; n, 7.34; test value C, 79.71; h, 3.85; and N, 7.39. MALDI-TOF (m/z): theoretical value 1715.5; experimental value 1715.6 (M)+)。
The photophysical properties of the fused ring compound prepared in example 14 of the present invention were measured, 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:
in a 500mL three-necked flask, a compound of formula 1-1 (13.6g, 0.05mol), N-phenyl-1-benzofuran-3-amine (25.1g,0.12mol) and CS were weighed under an argon atmosphere2CO3(65.2g, 0.20mol), 80mL of N, N-Dimethylformamide (DMF) is added into a bottle, the temperature is raised to 150 ℃, the reaction solution is stirred for 10 hours under the protection of argon, then the reaction solution is cooled to room temperature, the reaction solution is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 15-2(14.6g, yield: 45.1%). Elemental analysis: theoretical value C, 62.79; h, 3.41; n, 4.31; test value C, 62.82; h, 3.43; and N, 4.25. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 648.0; experimental value 648.1 (M)+)。
In a 250mL two-necked flask, under argon atmosphere, a compound of formula 15-2 (6.5g,10mmol) and dry o-xylene (80mL) were weighed, a butyllithium solution (4.0mL,2.5M,10mmol) was added dropwise at-30 ℃, stirring was performed at-30 ℃ for 2 hours after the addition was completed, boron tribromide (2.8g,11.0mmol) was added dropwise to the system, and stirring was performed at room temperature for 1 hour after 20 minutes of addition was completed. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.6g,20.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated from the filtration system and washed with methanol, and the crude product was separated by column to obtain 15-3(2.1g, yield: 36.3%). Elemental analysis: theoretical value C, 70.50; h, 3.48; n, 4.84; test value C, 70.42; h, 3.42; and N, 4.86. ESI-MS: theoretical value 579.3; experimental value 579.1 (M)+)。
A50 mL Schlenk flask was charged with a compound of formula 1-4 (1.77g, 1.1mmol), a compound of formula 15-3 (0.58g, 1mmol), Pd under an argon atmosphere2(dba)3(46mg，0.05mmol)、t-Bu3PHBF4(58mg, 0.20mmol), t-BuONa (0.19g, 2mmol), followed by 20mL of toluene, and reaction at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give the dendritic fused ring compound I-6(0.84g, yield: 39.9%). Elemental analysis: theoretical value C,85.56; h, 6.41; n, 5.99; test value C, 85.51; h, 6.38; and N, 5.91. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 2105.6; experimental value 2105.6 (M)+)。
The photophysical properties of the fused ring compound prepared in example 15 of the present invention were measured, 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:
the compound of formula 1-1 (6.8g, 0.025mol), N, 9-diphenyl-9-carbazol-4-amine (20.1g,0.06mol) and CS were weighed in a 500mL three-necked flask under an argon atmosphere2CO3(32.6g, 0.10mol), 60mL of N, N-Dimethylformamide (DMF) is added into a bottle, the temperature is raised to 150 ℃, the mixture is stirred and reacted for 10 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 16-2(10.2g, yield: 45.3%). Elemental analysis: theoretical value C, 72.01; h, 4.03; n, 6.22; test value C, 71.98; h, 4.06; and N, 6.17. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 900.7; experimental value 900.2 (M)+)。
A compound of formula 16-2 (4.5g,5mmol) and dry o-xylene (80mL) were weighed out in a 250mL two-necked flask under argon atmosphere, a butyllithium solution (2.0mL,2.5M,5mmol) was added dropwise at-30 deg.C, stirring was performed at-30 deg.C for 2 hours after the addition was completed, boron tribromide (1.4g,5.5mmol) was added dropwise to the system, and stirring was performed at room temperature for 1 hour after 20 minutes of completion of the addition. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.3g,10.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated from the filtration system and washed with methanol, and the crude product was separated by column to give 16-3(1.0g, yield: 23.2%). Elemental analysis: theoretical value C, 78.18; h, 4.13; n, 6.75; test value C, 78.12;h, 4.12; and N, 6.72. ESI-MS: theoretical value 829.6; experimental value 829.4 (M)+)。
A50 mL Schlenk flask was charged with a compound of formula 1-4 (1.77g, 1.1mmol), a compound of formula 16-3 (0.83g, 1mmol), Pd under an argon atmosphere2(dba)3(46mg，0.05mmol)、t-Bu3PHBF4(58mg, 0.20mmol), t-BuONa (0.19g, 2mmol), followed by 20mL of toluene, and reaction at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give the dendritic fused ring compound I-8(1.09g, yield: 46.2%). Elemental analysis: theoretical value C, 86.67; h, 6.33; n, 6.54; test value C, 86.61; h, 6.29; and N, 6.60. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 2355.9; experimental value 2355.8 (M)+)。
The photophysical properties of the fused ring compound prepared in example 16 of the present invention were measured, 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:
the compound of formula 1-1 (13.6g, 0.05mol), 7H-dibenzocarbazole (32.1g,0.12mol) and CS were weighed in a 500mL three-necked flask under an argon atmosphere2CO3(65.2g, 0.20mol), 100mL of N, N-Dimethylformamide (DMF) is added into a bottle, the temperature is raised to 150 ℃, the mixture is stirred and reacted for 10 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 17-2(20.5g, yield: 53.4%). Elemental analysis: theoretical value C, 72.08; h, 3.42; n, 3.65; test value C, 72.01; h, 3.46; and N, 3.61. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 766.5; experimental value 766.1 (M)+)。
Under argon atmosphere, at 250mL double portA compound of formula 17-2 (7.7g,10mmol) and dried o-xylene (80mL) were weighed in a flask, butyl lithium solution (4.0mL,2.5M,10mmol) was added dropwise at-30 deg.C, stirring was carried out for 2 hours at-30 deg.C after addition was completed, boron tribromide (2.8g,11.0mmol) was added dropwise to the system, and stirring was carried out for 1 hour at room temperature after completion of addition for 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.6g,20.0mmol) is dropwise added into the reaction system, and after the dropwise addition is finished, the temperature is raised to 125 ℃ for reaction for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated from the filtration system and washed with methanol, and the crude product was separated by column to obtain 17-3(2.4g, yield: 35.2%). Elemental analysis: theoretical value C, 79.45; h, 3.48; n, 4.03; test value C, 79.41; h, 3.47; and N, 4.08. ESI-MS: a theoretical value of 695.4; experimental value 695.1 (M)+)。
A50 mL Schlenk flask was charged with a compound of formula 1-4 (1.77g, 1.1mmol), a compound of formula 17-3 (0.70g, 1mmol), Pd under an argon atmosphere2(dba)3(46mg，0.05mmol)、t-Bu3PHBF4(58mg, 0.20mmol), t-BuONa (0.19g, 2mmol), then 20mL of toluene was injected and reacted at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give the dendrimer fused ring compound I-3(1.17g, yield: 52.6%). Elemental analysis: theoretical value C, 87.58; h, 6.26; n, 5.67; test value C, 87.52; h, 6.21; and 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)+)。
The photophysical properties of the fused ring compound prepared in example 17 of the present invention were measured, 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:
the compound of formula 1-1 (13.6g, 0.05mol), 3, 6-diazacarbazole (20.3g,0.12mol) were weighed in a 500mL three-necked flask under an argon atmosphereAnd CS2CO3(65.2g, 0.20mol), 80mL of N, N-Dimethylformamide (DMF) is added into a bottle, the temperature is raised to 150 ℃, the reaction solution is stirred for 10 hours under the protection of argon, then the reaction solution is cooled to room temperature, the reaction solution is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 18-2(12.8g, yield: 45.2%). Electrospray ionization mass spectrometry (ESI-MS): theoretical value 570.3; experimental value 570.3 (M)+)。
In a 250mL two-necked flask, a compound of formula 18-2 (5.7g,10mmol) and dry o-xylene (80mL) were weighed under argon atmosphere, a butyllithium solution (4.0mL,2.5M,10mmol) was added dropwise at-30 ℃, stirring was performed at-30 ℃ for 2 hours after the addition was completed, boron tribromide (2.8g,11.0mmol) was added dropwise to the system, and stirring was performed at room temperature for 1 hour after 20 minutes of the addition was completed. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.6g,20.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated from the filtered system and washed with methanol, and the crude product was separated by column to give 18-3(2.2g, yield: 43.5%). ESI-MS: theoretical value 499.1; experimental value 499.1 (M)+)。
Under argon atmosphere, a 50mL Schlenk flask was charged with a compound of formula 1-4 (1.77g, 1.1mmol), a compound of formula 18-3 (0.50g, 1mmol), Pd2(dba)3(46mg，0.05mmol)、t-Bu3PHBF4(58mg, 0.20mmol), t-BuONa (0.19g, 2mmol), followed by 20mL of toluene, and reaction at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give the dendritic fused ring compound I-1(1.06g, yield: 52.5%). Elemental analysis: theoretical value 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 value 2025.5 (M)+)。
The photophysical properties of the fused ring compound prepared in example 18 of the present invention were measured, 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 (10.2g, 110mmol), a compound of formula 19-1 (15.2g, 50mmol), Pd were added under an argon atmosphere in a 500mL Schlenk flask2(dba)3(0.9g, 1mmol), BINAP (2.5mg, 4mmol), t-BuONa (21.1g, 220mmol), followed by injection of 200mL of toluene and reaction at 100 ℃ for 24 hours. The temperature is reduced to room temperature, deionized water and 300mL of dichloromethane are added for extraction, and the mixture is washed by the deionized water for multiple times. The organic phase was separated, and subjected to column separation and solvent removal to give dendritic fused ring compound 19-2(12.3g, yield: 74.8%). Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 329.2; experimental value 329.3 (M)+)。
Under an argon atmosphere, 3-chloro 5-bromoiodobenzene (25.4g, 80mmol), a compound of formula 19-2 (9.9g, 30mmol), Pd were added to a 250mL Schlenk flask2(dba)3(0.5g，0.6mmol)、P(t-Bu)3(0.5g, 2.4mmol) and t-BuONa (15.4g, 160mmol), and then 150mL of toluene was injected and reacted at ordinary temperature for 24 hours. Deionized water and 300mL of methylene chloride were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give the dendritic fused ring compound 19-3(16.0g, yield: 86.4%). Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 619.2; experimental value 619.2 (M)+)。
Aniline (1.9g, 20mmol), a compound of formula 19-3 (12.4g, 20mmol), Pd were added under an argon atmosphere in a 250mL Schlenk flask2(dba)3(0.4g, 0.4mmol), S-Phos (0.7g, 1.6mmol), t-BuONa (3.8g, 40mmol), 100mL of toluene was injected, and the reaction was refluxed for 24 hours. Deionized water and dichloromethane 200mL were added for extraction and washed several times with deionized water. The organic phase was separated, and subjected to column separation and solvent removal to give the dendritic fused ring compound 19-4(7.3g, yield: 56.2%). Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF: (MALDI-TOF))m/z)): theoretical value 639.4; experimental value 639.5 (M)+)。
Under argon atmosphere, weighing the compound of formula 19-4 (0.6g,10mmol) and dry tert-butyl benzene (80mL) in a 250mL two-neck flask, dropwise adding a butyl lithium solution (4.0mL,2.5M,10mmol) at-30 ℃, stirring for 2 hours at 50 ℃ after dropwise adding, then cooling to 0 ℃, dropwise adding boron tribromide (5.1g,20.0mmol) into the system, and stirring for 1 hour at room temperature after 20 minutes after dropwise adding. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.6g,20.0mmol) is dropwise added into the reaction system, and the temperature is raised to 165 ℃ after the dropwise addition is finished to react for 14 hours. After the reaction was cooled to room temperature, a solid was precipitated from the filtered system and washed with methanol, and the crude product was separated by column to give 19-5(3.5g, yield: 57.2%). Elemental analysis: theoretical value C, 70.57; h, 3.45; n, 6.86; test value C, 70.52; h, 3.48; and N, 6.84. ESI-MS: theoretical value 612.8; experimental value 612.6 (M)+)。
A50 mL Schlenk flask was charged with a compound of formula 1-4 (5.3g, 3.3mmol), a compound of formula 19-5 (0.61g, 1mmol), Pd under an argon atmosphere2(dba)3(138mg，0.15mmol)、t-Bu3PHBF4(174mg, 0.60mmol), t-BuONa (0.57g, 6mmol), 30mL of toluene was injected and the reaction was carried out at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give dendritic fused ring compound I-18(2.24g, yield: 42.1%). Elemental analysis: theoretical value C, 86.61; h, 6.87; n, 6.31; test value C, 86.67; h, 6.81; and N, 6.28. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 5325.1; experimental value 5325.2 (M)+)。
The photophysical properties of the fused ring compound prepared in example 19 of the present invention were measured, 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:
in a 500mL three-necked flask, the compound of formula 1-1 (13.6g, 0.05mol), 3-benzofuranol (13.4g,0.10mol), and K are weighed under an argon atmosphere2CO3(13.8g, 0.10mol), 80mL of N-methylpyrrolidone (NMP) is added into a bottle, the temperature is raised to 150 ℃, the mixture is stirred and reacted for 10 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 20-1(8.9g, yield: 46%). Elemental analysis: theoretical value C, 43.56; h, 1.83; test value C, 43.52; h, 1.89. ESI-MS: theoretical value 386.0; experimental value 386.1 (M)+)。
In a 250mL three-necked flask, under an argon atmosphere, the compound of formula 20-1 (7.7g, 0.02mol), diphenylamine (6.7g,0.04mol) and CS were weighed2CO3(13.0g, 0.04mol), 60mL of N, N-Dimethylformamide (DMF) is added into a bottle, the temperature is raised to 150 ℃, the mixture is stirred and reacted for 10 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 20-2(7.2g, yield: 67.2%). Elemental analysis: theoretical value C, 58.35; h, 3.20; n, 2.62; test value C, 58.37; h, 3.11; and N, 2.68. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 535.2; experimental value 535.1 (M)+)。
In a 250mL two-necked flask, a compound of formula 20-2 (0.5g,10mmol) and dry o-xylene (80mL) were weighed under argon atmosphere, a butyllithium solution (4.0mL,2.5M,10mmol) was added dropwise at-30 ℃, stirring was performed at-30 ℃ for 2 hours after the addition was completed, boron tribromide (2.8g,11.0mmol) was added dropwise to the system, and stirring was performed at room temperature for 1 hour after 20 minutes of the addition was completed. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.6g,20.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated from the filtered system and washed with methanol, and the crude product was separated by column to obtain 20-3(2.2g, yield: 48.4%). Elemental analysis: theoretical value C, 67.28; h, 3.26; n, 3.02; test value C, 67.21; h, 3.29; and N, 3.08. ESI-MS: theoretical value 464.1; experimental value 464.2(M +).
A50 mL Schlenk flask was charged with a compound of formula 1-4 (1.77g, 1.1mmol), a compound of formula 20-3 (0.46g, 1mmol), Pd under an argon atmosphere2(dba)3(46mg，0.05mmol)、t-Bu3PHBF4(58mg, 0.20mmol), t-BuONa (0.19g, 2mmol), followed by 20mL of toluene, and reaction at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give the dendritic fused ring compound I-62(0.95g, yield: 48.1%). Elemental analysis: theoretical value C, 85.73; h, 6.43; n, 5.67; test value C, 85.76; h, 6.41; and 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 +).
The photophysical properties of the fused ring compound prepared in example 20 of the present invention were measured 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:
the compound of formula 1-1 (13.6g, 0.05mol), 3-bromophenylthiophenol (9.5g,0.05mol) and K were weighed in a 500mL three-necked flask under an argon atmosphere2CO3(13.8g, 0.10mol), 80mL of N-methylpyrrolidone (NMP) is added into a bottle, the temperature is raised to 150 ℃, the mixture is stirred and reacted for 10 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 21-1(12.3g, yield: 56.1%). Elemental analysis: theoretical value C, 32.69; h, 1.37; s, 7.27; test value C, 32.61; h, 1.34; and S, 7.29. ESI-MS: theoretical value 440.9; experimental value 440.8 (M)+)。
The compound of formula 21-1 (8.8g, 0.02mol), diphenylamine (I) and (II) were weighed in a 250mL three-necked flask under an argon atmosphere6.7g,0.04mol) and CS2CO3(13.0g, 0.04mol), 60mL of N, N-Dimethylformamide (DMF) is added into a bottle, the temperature is raised to 150 ℃, the mixture is stirred and reacted for 10 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 21-2(6.4g, 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; and S, 5.48. Electrospray ionization mass spectrometry (ESI-MS): a theoretical value of 590.2; experimental value 590.1 (M)+)。
In a 250mL two-necked flask under argon atmosphere, weighing the compound of formula 21-2 (0.6g,10mmol) and dry o-xylene (80mL), dropwise adding a butyllithium solution (4.0mL,2.5M,10mmol) at-30 ℃, stirring at-30 ℃ for 2 hours after dropwise adding, dropwise adding boron tribromide (2.8g,11.0mmol) into the system, and stirring at room temperature for 1 hour after 20 minutes after dropwise adding. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.6g,20.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated from the filtered system and washed with methanol, and the crude product was separated by column to obtain 21-3(2.2g, 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; and S, 6.10. ESI-MS: theoretical value 519.1; experimental value 519.2 (M)+)。
A50 mL Schlenk flask was charged with a compound of formula 1-4 (3.54g, 2.2mmol), a compound of formula 21-3 (0.52g, 1mmol), Pd under an argon atmosphere2(dba)3(92mg，0.1mmol)、t-Bu3PHBF4(232mg, 0.40mmol), t-BuONa (0.38g, 4mmol), 30mL of toluene was injected and the reaction was carried out at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give dendrimer fused ring compound I-66(1.31g, 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 interstitial substanceSpectrum (MALDI-TOF (m/z)): theoretical value 3587.8; experimental value 3587.7(M +).
The photophysical properties of the fused ring compound prepared in example 21 of the present invention were measured, 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:
the compound of formula 1-1 (13.6g, 0.05mol), phenylselenol (7.8g,0.05mol) and K were weighed in a 500mL three-necked flask under an argon atmosphere2CO3(13.8g, 0.10mol), 80mL of N-methylpyrrolidone (NMP) is added into a bottle, the temperature is raised to 150 ℃, the mixture is stirred and reacted for 10 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 22-1(9.8g, 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 value 408.8 (M)+)。
A compound of formula 22-1 (8.2g, 0.02mol), t-butylcarbazole (11.2g,0.04mol), and CS were weighed in a 250mL three-necked flask under an argon atmosphere2CO3(13.0g, 0.04mol), 60mL of N, N-Dimethylformamide (DMF) is added into a bottle, the temperature is raised to 150 ℃, the mixture is stirred and reacted for 10 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 22-2(11.0g, yield: 82.3%). Elemental analysis: theoretical value C, 57.51; h, 4.68; n, 2.10; test value C, 57.46; h, 4.61; and N, 2.05. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 668.4; experimental value 668.3 (M)+)。
A compound of formula 22-2 (0.7g,10mmol) and dry o-xylene (80mL) were weighed in a 250mL two-necked flask under argon atmosphere and added dropwise at-30 deg.CButyl lithium solution (4.0mL,2.5M,10mmol) was stirred at-30 ℃ for 2 hours after the addition, boron tribromide (2.8g,11.0mmol) was added dropwise to the system, and stirring was carried out at room temperature for 1 hour after 20 minutes from the addition. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.6g,20.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated from the filtration system and washed with methanol, and the crude product was separated by column to give 22-3(2.1g, 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: a theoretical value of 597.3; experimental value 597.4 (M)+)。
A50 mL Schlenk flask was charged with a compound of formula 1-4 (1.77g, 1.1mmol), a compound of formula 22-3 (0.60g, 1mmol), Pd under an argon atmosphere2(dba)3(46mg，0.05mmol)、t-Bu3PHBF4(58mg, 0.20mmol), t-BuONa (0.19g, 2mmol), followed by 20mL of toluene, and reaction at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give dendritic fused ring compound I-73(1.19g, yield: 56.2%). Elemental analysis: theoretical value C, 83.67; h, 6.83; n, 5.27; test value C, 83.61; h, 6.88; and 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 +).
The photophysical properties of the fused ring compound prepared in example 22 of the present invention were measured, 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:
in a 500mL three-necked flask, a compound of formula 1-1 (13.6g, 0.05mol), phenyl-tellurol (10.3g,0.05mol), and K were weighed under an argon atmosphere2CO3(13.8g, 0.10mol), 80mL of N-methylpyrrolidone (NMP) is added into a bottle, the temperature is raised to 150 ℃,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 by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain 23-1(10.3g, 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)+)。
The compound of formula 23-1 (9.2g, 0.02mol), tert-butylcarbazole (11.2g,0.04mol) and CS were weighed in a 250mL three-necked flask under an argon atmosphere2CO3(13.0g, 0.04mol), 60mL of N, N-Dimethylformamide (DMF) is added into a bottle, the temperature is raised to 150 ℃, the mixture is stirred and reacted for 10 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is diluted by toluene and poured into water, an organic phase is separated, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain the product 23-2(11.3g, 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 value 717.1 (M)+)。
In a 250mL two-necked flask under argon atmosphere, weighing the compound of formula 23-2 (0.7g,10mmol) and dry o-xylene (80mL), dropwise adding a butyllithium solution (4.0mL,2.5M,10mmol) at-30 ℃, stirring for 2 hours at-30 ℃ after dropwise adding, dropwise adding boron tribromide (2.8g,11.0mmol) into the system, and stirring for 1 hour at room temperature after 20 minutes of dropwise adding. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.6g,20.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated from the filtered system and washed with methanol, and the crude product was separated by column to give 23-3(1.8g, 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 value 645.9 (M)+)。
A50 mL Schlenk flask was charged with a compound of formula 1-4 (1.77g, 1.1mmol), a compound of formula 23-3 (0.65g, 1mmol), Pd under an argon atmosphere2(dba)3(46mg，0.05mmol)、t-Bu3PHBF4(58mg, 0.20mmol), t-BuONa (0.19g, 2mmol), then 20mL of toluene was injected and reacted at 110 ℃ for 24 hours. Cooled to room temperature, added with deionized water and dichloromethane 100mL for extraction, and washed with deionized water several times. The organic phase was separated, and subjected to column separation and solvent removal to give dendritic fused ring compound I-77(0.99g, 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 +).
The photophysical properties of the fused ring compound prepared in example 23 of the present invention were measured, and the results are shown in table 1.
TABLE 1 photophysical properties of the fused ring compounds obtained in examples 1 to 23
Note: in Table 1,. DELTA.ESTIs the difference between the singlet level and the triplet level, obtained by reacting the compound with 10-4The test sample was prepared by dissolving the concentration of mol/L in a toluene solution, and the difference between the initial (onset) value of the fluorescence spectrum and the phosphorescence spectrum was measured using a HORIBA FluoroMax spectrophotometer (Japan). The delayed fluorescence lifetime was measured by doping a sample of polystyrene with a compound at a concentration of 1 wt% and measuring the sample by a time-resolved fluorescence spectrometer, the measuring instrument being an Edinburgh fluorescence spectrometer (FLS-980, UK).
As can be seen from the test results in Table 1, the fused ring compounds provided by the present invention have smaller Δ EST(<0.2eV), the thermal activation delayed fluorescence effect is shown, and the delayed fluorescence life is 46-103 mus, so that the triplet exciton can be utilized, and the efficiency of the device can be improved.
Device embodiment: examples 24 to 50
As device embodiments, the present invention provides two types of device structures (device structure a and device structure B) for preparing an organic electroluminescent device:
the device structure a is: PSS (40 nm)/dendritic fused ring compound (30nm)/TSPO1(8nm)/TmPyPB (30nm)/LiF (0.8nm)/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 fused ring compound at 1500rpm for 1 minute and annealed at 80 ℃ for 30 minutes, and then at 4X 10-4Sequentially depositing TSPO1, TmPyPB and a LiF/Al cathode under Pa vacuum degree to obtain the organic electroluminescent device, wherein TSPO1 and TmPyPB are respectively used as a hole blocking layer and an electron transport layer, and the structural formulas of the layers are as follows:
the device structure B is: PSS (40 nm)/blend (mass ratio of 1:9) (30nm)/TSPO1(8nm)/TmPyPB (42nm)/LiF (1nm)/Al (100nm) of the dendritic fused ring compound and the host material SiMCP 2.
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 on indium tin oxide supported on a glass substrate, annealed at 120 ℃ for 30 minutes, and then spin-coated with the invented dendrimer fused ring compound and SiMCP2 at a rotation speed of 1500rpm in a mass ratio of 1:9 the mixed toluene solution was annealed at 80 ℃ for 30 minutes for 1 minute, and then at 4X 10-4Sequentially depositing TSPO1, TmPyPB and a LiF/Al cathode under the vacuum degree of Pa to obtain the organic electroluminescent device, wherein the structural formula of a main material SiMCP2 is shown as follows:
example 24
The compound of formula I-1 obtained in example 1 was used as an object, and the compound of formula I-1 was directly used as an organic light-emitting layer, and an organic electroluminescent device was prepared using the structure described in "device Structure A".
Example 25
The compound of formula I-19 obtained in example 2 was used as the target, and the compound of formula I-19 was directly used as the organic light-emitting layer, and the structure described in "device structure a" was used to prepare an organic electroluminescent device.
Example 26
To compound the formula I-1 obtained in example 1, a compound of the formula I-1 was mixed with SiMCP2 at a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 27
Taking the compound of formula I-19 obtained in example 2 as an object, the compound of formula I-19 and SiMCP2 are mixed according to the mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 28
Taking the compound of formula I-20 obtained in example 3 as an object, the compound of formula I-20 and SiMCP2 are mixed according to the mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 29
To compound of formula I-27 obtained in example 4, a compound of formula I-27 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 30
Taking the compound of formula I-30 obtained in example 5 as a subject, the compound of formula I-30 and SiMCP2 are mixed according to the mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 31
To compound formula I-31 obtained in example 6, a compound of formula I-31 was mixed with sipep 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 32
To compound of formula I-22 obtained in example 7, a compound of formula I-22 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 33
To compound of formula I-32 obtained in example 8, a compound of formula I-32 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 34
To compound of formula I-33 obtained in example 9, a compound of formula I-33 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 35
To compound of formula I-34 obtained in example 10, a compound of formula I-34 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 36
To compound of formula I-36 obtained in example 11, a compound of formula I-36 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 37
To compound of formula I-37 obtained in example 12, a compound of formula I-37 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 38
To compound of formula I-38 obtained in example 13, a compound of formula I-38 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 39
To compound of formula I-41 obtained in example 14, a compound of formula I-41 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 40
To compound of formula I-6 obtained in example 15, a compound of formula I-6 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
EXAMPLE 41
To compound of formula I-8 obtained in example 16, a compound of formula I-8 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 42
To compound of formula I-3 obtained in example 17, a compound of formula I-3 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 43
To compound of formula I-2 obtained in example 18, a compound of formula I-2 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 44
To compound of formula I-18 obtained in example 19, a compound of formula I-18 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 45
To compound of formula I-62 obtained in example 20, a compound of formula I-62 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 46
To proceed with the compound of formula I-66 obtained in example 21, a compound of formula I-66 was mixed with sipep 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 47
To compound of formula I-73 obtained in example 22, a compound of formula I-73 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 48
To compound of formula I-77 obtained in example 23, a compound of formula I-77 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Comparative example 1
The method takes a compound BNN without a dendritic structure as an implementation object, directly takes the BNN as an organic light-emitting layer, and prepares the organic electroluminescent device by utilizing the structure of the device structure A.
Comparative example 2
A compound BNO without a dendritic structure is taken as an implementation object, BNO is directly taken as an organic light-emitting layer, and the structure of 'device structure A' is utilized to prepare an organic electroluminescent device.
Comparative example 3
Taking a compound BNN without a dendritic molecular structure as an implementation object, and mixing the BNN with SiMCP2 according to the mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Comparative example 4
Taking a compound BNO without a dendritic molecular structure as an implementation object, and mixing the BNO with SiMCP2 according to a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
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 tests, and the results are shown in table 2.
TABLE 2 Properties of organic electroluminescent devices obtained in examples 24 to 48 and comparative examples 1 to 4
Note: in Table 2, the on-state voltage is 1cd m in luminance-2The driving voltage of the time device; the maximum external quantum efficiency is obtained according to a current-voltage curve and an electroluminescence spectrum of the device by a calculation method described in the literature (Jpn.J.appl.Phys.2001,40, L783); the half-peak width is the peak width at half of the spectral peak height of the electroluminescence spectrum at room temperature, i.e. a straight line parallel to the peak bottom is drawn through the midpoint of the peak height, and the straight line is the distance between two intersecting points on both sides of the peak.
The test results in table 2 show that the solution-processed organic electroluminescent device prepared from the dendritic fused ring compound provided by the invention has very high luminous efficiency, the maximum external quantum efficiency is 16.0-26.9%, the maximum external quantum efficiency is significantly higher than that of a comparative compound without a dendritic structure (1.2-8.6%), and the solution-processed organic electroluminescent device has a narrow electroluminescent spectrum, and the half-peak width of the electroluminescent spectrum is less than 40 nm.
The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, 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, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention 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 approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A fused ring compound containing boron nitrogen and a dendritic structure, having a structure of formula (1):
in formula (I):
X1and X2Independently selected from: n (R)0) O, S, Se or Te; q is 0 or 1;
R0selected from: a substituted or unsubstituted C1-C30 straight chain alkyl group, a substituted or unsubstituted C1-C30 branched chain alkyl group, a substituted or unsubstituted C3-C30 naphthenic group, an aromatic group with 6-60 carbon atoms and a heteroaromatic group with 5-60 carbon atoms; wherein the heteroatoms in the heteroaromatic group are independently selected from Si, Ge, N, P, O, S or Se;
m, n and p are respectively and independently selected from integers of 0-5, and at least 1 of m, n and p is not 0;
Ra、Rband RcEach independently selected from the group consisting of dendrimers of the formula (II)The structure is as follows:
in formula (II):
wherein the content of the first and second substances,
the dotted line segment connecting line in the above structure is not included;
Rxas the last iteration unit
And (c) a substituent selected from: H. d, -CN,
Substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 alkyl halide, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group, and substituted or unsubstituted C5-C60 heteroaromatic group;
wherein, R is1、R2And R3Each independently selected from: H. d, substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 haloalkane, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group and substituted or unsubstituted C5-C60 heteroaromatic group; the R is1、R2And R3May be linked to each other by a single bond, -O-, -S-, or,
And
one or more of the above;
nxis RxNumber of (2)Selected from integers of 1 to 6;
L1selected from: substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 cycloalkyl, an aromatic group with 6-60 carbon atoms and a heteroaromatic group with 5-60 carbon atoms; wherein the heteroatoms in the heteroaromatic group are independently selected from Si, Ge, N, P, O, S or Se; l is1And
or
May also be through a single bond, -C (R)1R2)-、-(C＝O)-、-Si(R1R2)-、-N(R1)-、-PO(R1)-、-B(R1)-、-O-、-S-、-Se-、-(S＝O)-、-(SO2) -any of the connections is made;
2. the compound of claim 1, wherein said compound is selected from the group consisting of
And
each independently selected from the group consisting of formula 1-16:
q＝0：
or
q＝1：
3. A compound of claim 1, wherein R isa、RbAnd RcEach independently selected from the formula R-1 to R-58:
4. the compound of claim 1, wherein the compound is selected from the group consisting of formula I-1 to formula I-78:
5. a method for producing a fused ring compound containing boron nitrogen and a dendritic structure according to any one of claims 1 to 4, characterized by comprising the steps of:
reacting the fused 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 a compound Lu4-Ra、Lu5-RbAnd Lu6-RcOne or more of the above;
wherein, Lu1～Lu6Each independently selected from: hydrogen, halogen, hydroxy, mercapto, amino,
6. The method according to claim 5, wherein the reaction temperature is-78 to 180 ℃.
7. The method according to claim 5, 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.
8. Use of the condensed cyclic compound containing boron nitrogen and a dendritic structure according to any one of claims 1 to 4 in an organic electroluminescent device.
9. An organic electroluminescent device comprising: an anode, a cathode, and a thin film layer located between the anode and the cathode;
the thin film layer contains the condensed ring compound containing boron nitrogen and a dendritic structure according to any one of claims 1 to 4.
10. The organic electroluminescent device according to claim 9, 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 ring compound containing boron nitrogen and a dendritic structure according to any one of claims 1 to 4.
Priority Applications (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 |
| CN113788852A (en) * | 2021-09-03 | 2021-12-14 | 清华大学 | Luminescent material, application thereof and organic electroluminescent device comprising luminescent material |
| 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 |
| 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 |
| 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 |
| 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 |
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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 |
| 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 |
| 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 |
| 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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