CN112480156B - Fused ring compound containing boron atom and sulfur atom, and preparation method and application thereof - Google Patents
Fused ring compound containing boron atom and sulfur atom, and preparation method and application thereof Download PDFInfo
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- CN112480156B CN112480156B CN202011411782.XA CN202011411782A CN112480156B CN 112480156 B CN112480156 B CN 112480156B CN 202011411782 A CN202011411782 A CN 202011411782A CN 112480156 B CN112480156 B CN 112480156B
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- fused ring
- ring compound
- organic
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 70
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 title abstract description 18
- 229910052796 boron Inorganic materials 0.000 title abstract description 16
- 125000004434 sulfur atom Chemical group 0.000 title abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000000463 material Substances 0.000 claims description 25
- 238000000926 separation method Methods 0.000 abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 230000005281 excited state Effects 0.000 abstract description 7
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 4
- 125000001424 substituent group Chemical group 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 99
- 238000006243 chemical reaction Methods 0.000 description 65
- 239000012074 organic phase Substances 0.000 description 64
- 239000012300 argon atmosphere Substances 0.000 description 54
- 239000000243 solution Substances 0.000 description 52
- 238000012360 testing method Methods 0.000 description 46
- 239000012043 crude product Substances 0.000 description 43
- 238000000921 elemental analysis Methods 0.000 description 43
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 38
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 37
- 239000000047 product Substances 0.000 description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000002904 solvent Substances 0.000 description 30
- 239000008367 deionised water Substances 0.000 description 29
- 229910021641 deionized water Inorganic materials 0.000 description 29
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 29
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 28
- 238000001914 filtration Methods 0.000 description 27
- 238000003756 stirring Methods 0.000 description 27
- 230000008569 process Effects 0.000 description 25
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 22
- 238000007738 vacuum evaporation Methods 0.000 description 22
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 14
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 14
- 239000012044 organic layer Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 10
- 238000010129 solution processing Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- 229940078552 o-xylene Drugs 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 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 6
- 125000001072 heteroaryl group Chemical group 0.000 description 6
- RZWQDAUIUBVCDD-UHFFFAOYSA-M sodium;benzenethiolate Chemical compound [Na+].[S-]C1=CC=CC=C1 RZWQDAUIUBVCDD-UHFFFAOYSA-M 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 5
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 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 3
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 3
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 125000005110 aryl thio group Chemical group 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- -1 but not limited to Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 2
- MNOJRWOWILAHAV-UHFFFAOYSA-N 3-bromophenol Chemical compound OC1=CC=CC(Br)=C1 MNOJRWOWILAHAV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 2
- 125000003545 alkoxy group Chemical group 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
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- RMBAVIFYHOYIFM-UHFFFAOYSA-M sodium methanethiolate Chemical compound [Na+].[S-]C RMBAVIFYHOYIFM-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- ZYGAMJLTPLERBC-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid propan-2-ol Chemical compound B(O)(O)OC(C)(C)C(C)(C)O.C(C)(C)O ZYGAMJLTPLERBC-UHFFFAOYSA-N 0.000 description 1
- FYELSNVLZVIGTI-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1CC)CC(=O)N1CC2=C(CC1)NN=N2 FYELSNVLZVIGTI-UHFFFAOYSA-N 0.000 description 1
- CACNDVVHWJTZHH-UHFFFAOYSA-N 2-phenylbenzeneselenol Chemical compound [SeH]C1=CC=CC=C1C1=CC=CC=C1 CACNDVVHWJTZHH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910015845 BBr3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- AKBWEOIUSLQOSC-UHFFFAOYSA-N OC(C1=C(C2=CC=CC=C2)C(Br)=CC=C1)=S Chemical compound OC(C1=C(C2=CC=CC=C2)C(Br)=CC=C1)=S AKBWEOIUSLQOSC-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 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
- NGTSCMPNJJGTPR-UHFFFAOYSA-N benzenetellurol Chemical compound [TeH]C1=CC=CC=C1 NGTSCMPNJJGTPR-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QHRVFPPZMPHYHA-UHFFFAOYSA-N bis(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1PC1=CC=CC=C1C QHRVFPPZMPHYHA-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- ONQMBYVVEVFYRP-UHFFFAOYSA-N chloro(triphenyl)germane Chemical compound C=1C=CC=CC=1[Ge](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ONQMBYVVEVFYRP-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OKZIUSOJQLYFSE-UHFFFAOYSA-N difluoroboron Chemical compound F[B]F OKZIUSOJQLYFSE-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- NJVOZLGKTAPUTQ-UHFFFAOYSA-M fentin chloride Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 NJVOZLGKTAPUTQ-UHFFFAOYSA-M 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001296 phosphorescence spectrum Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910000338 selenium disulfide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- SOYQQGMTDUHLAT-UHFFFAOYSA-M sodium;4-bromobenzenethiolate Chemical compound [Na+].[S-]C1=CC=C(Br)C=C1 SOYQQGMTDUHLAT-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005406 washing Methods 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
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
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Abstract
The invention provides a condensed ring compound containing boron atoms and sulfur atoms and a preparation method thereof, wherein the condensed ring compound has a structure shown in a formula I. The condensed ring compound adopts a boron/sulfur hybrid condensed ring unit as a light-emitting unit, and realizes the separation of HOMO and LUMO by utilizing the resonance effect between boron atoms and sulfur atoms, thereby realizing smaller Delta ESTAnd the TADF effect, and meanwhile, the boron/sulfur hybrid fused ring unit has a rigid framework structure, so that the relaxation degree of an excited state structure can be reduced, and the narrow half-peak width is realized. In addition, different substituents are introduced into the skeleton of the boron/sulfur hybrid fused ring unit, so that the half-peak width can be further adjusted. The luminescent compound of the invention is used as a luminescent layer of an electroluminescent device, which can realize narrow electroluminescent half-peak width and high external quantum efficiency of the device under the condition of not needing a filter and a microcavity structure.
Description
Technical Field
The invention belongs to the technical field of organic luminescent materials, and particularly relates to a fused ring compound containing boron atoms and sulfur atoms, and a preparation method and application thereof.
Background
Organic Light Emitting Devices (OLEDs) have the characteristics of rich colors, thin thickness, wide viewing angle, fast response, and the like, and can be used for manufacturing flexible devices, and are considered to be the next generation of flat panel display and solid illumination technologies with the greatest development prospects. OLEDs are generally composed of an ITO anode, a Hole injection layer (TIL), a Hole Transport Layer (HTL), an Emission Layer (EL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and a cathode, and 1 to 2 organic layers may be omitted as needed, and excitons (exiton) are formed by combining holes (Hole) injected through positive and negative electrodes on an organic thin film and electrons (Electron), and energy is released in the form of light emission when the excitons return from an excited state to a stable ground state, thereby emitting light.
Due to the limitation of the spin quantum statistical law, the traditional fluorescent material can only utilize singlet excitons accounting for 25% of the total excitons in the electroluminescent process, and the rest 75% of the triplet excitons are inactivated by means of non-radiative transition, so that the maximum value of the Internal Quantum Efficiency (IQE) of the device is 25%. The phosphorescent metal complex can convert triplet excitons into photons by utilizing the spin-orbit coupling effect of heavy metal atoms, so that the utilization of the triplet excitons is realized, and the internal quantum efficiency of 100% is realized, but the path faces the problem that the phosphorescent metal complex is expensive. TADF (thermally activated delayed fluorescence) materials are third-generation organic luminescent materials following traditional fluorescent and phosphorescent materials, and generally have smaller singlet-triplet energy level difference (delta E)ST) The triplet excited state is transferred to the singlet excited state by utilizing a thermally activated reverse intersystem crossing (RISC) process to emit fluorescence, thereby realizing the full utilization of singlet and triplet excitons and realizing 100 percent internal quantum efficiency. Meanwhile, the material also has higher fluorescence quantum efficiency (PLQY) so as to promote the attenuation of singlet excitons in a light form and improve the efficiency of devices.
The main approach to the current realization of TADF molecules is to introduce electron donor (D) and electron acceptor (a) units such that the highest occupied orbital (HOMO) and lowest unoccupied orbital (LUMO) are separated, thereby achieving a small Δ EST. However, the D-A structure shows larger Stokes shift due to the obvious vibration relaxation of the excited state, and has a wider luminescence spectrum, the half-peak width (FWHM) is generally 70-100 nm, and in practical application, a filter plate is generally adopted or an optical microcavity is generally constructedTo improve color purity, but this results in a decrease in external quantum efficiency of the device or a complicated device structure. The design and synthesis of the luminescent material with narrow half-peak and wide spectral characteristics have important significance.
Therefore, how to develop a light emitting material having both TADF effect and narrow half-peak-width spectral characteristic by reasonable chemical structure design to solve the defect of wide half-peak width faced by the above 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 a boron atom and a sulfur atom, which has a narrow half-peak width, and a preparation method and an application thereof.
The invention provides a condensed ring compound containing boron atoms and sulfur atoms, which has a structure shown in a formula (I):
x is an integer of 0-3, y is an integer of 0-4, z is an integer of 0-4, and x, y and z are not 0 at the same time;
said L1、L2And L3Is independently selected from
-Se-、
-Te-、
The R is1、R2、R3、R1And R2Are respectively and independently selected from hydrogen, halogen, hydroxyl, amino, substituted or unsubstituted alkyl of C1-C30, substituted or unsubstituted haloalkyl of C1-C30, substituted or unsubstituted cycloalkyl of C1-C30 and substituted or unsubstituted alkyl of C1-C30Oxy, substituted or unsubstituted alkylthio of C1-C30, substituted or unsubstituted aryloxy of C1-C30, substituted or unsubstituted arylthio of C1-C30, or a heteroaromatic group selected from an aromatic group having 5-60 aromatic atoms or 5-60 aromatic atoms, the heteroatoms of the heteroaromatic group being independently selected from Si, Ge, N, P, O, S or Se;
the R is1And R2R is1Or R2And R1、R2Or R3Through a single bond, -C-C-, -C ═ N-, -C ═ P-, -C ≡ C-, -O-, -S-, -C (CH)3)2-、
Any one or more of them.
In the present invention, said R1、R2、R3、R1And R2The aryl group is independently selected from hydroxyl, substituted or unsubstituted alkyl of C1-C10, substituted or unsubstituted haloalkyl of C1-C10, substituted or unsubstituted cycloalkyl of C1-C10, substituted or unsubstituted alkoxy of C1-C10, substituted or unsubstituted alkylthio of C1-C10, substituted or unsubstituted aryloxy of C1-C10, substituted or unsubstituted arylthio of C1-C10, or an aromatic group with 5-30 aromatic atoms or a heteroaromatic group with 5-30 aromatic atoms, wherein hetero atoms of the heteroaromatic group are independently selected from Si, Ge, N, P, O, S or Se.
Said- (L)1-R1)、-(L2-R2) And- (L)3-R3) Independently is preferably selected from
One or more of (a).
In the present invention, the fused ring compound is specifically selected from any one or more of the structures represented by the formulae (1-1) to (15-30):
in the present invention, the condensed ring compound containing a boron atom and a sulfur atom is more preferably selected from the group consisting of formula 1-1, formula 1-20, formula 1-46, formula 1-109, formula 2-1, formula 3-2, formula 3-5, formula 3-10, formula 4-7, formula 5-1, formula 5-24, formula 6-4, formula 6-27, formula 6-31, formula 7-1, formula 8-1, formula 9-1, formula 10-1, formula 11-1, formula 12-1, formula 13-1, formula 14-33, formula 14-38, formula 15-12, and formula 15-28.
The invention provides a preparation method of a fused ring compound containing boron atoms and sulfur atoms, which comprises the following steps:
mixing a material having a structure of formula II-1 with a mixture containing- (L)1-R) reacting the material in a solvent to obtain a fused ring compound containing boron atoms and sulfur atoms and having the structure of formula (I);
the M is1、M2And M3Independently selected from halogens, x is an integer of 0-3, y is an integer of 0-4, z is an integer of 0-4, and x, y and z are not 0 at the same time;
said L1Is selected from
-Se-、-Te-、
Or mixing a material having a structure of formula II-2 with a mixture containing- (L)2-R) in a solvent and then oxidizing to obtain a condensed cyclic compound containing boron and sulfur atoms having the structure of formula (I):
the M is1、M2And M3Independently selected from halogens, x is an integer of 0-3, y is an integer of 0-4, z is an integer of 0-4, and x, y and z are not 0 at the same time;
said L2Selected from-S-, -Se-, -Te-;
the R, R1And R2Each independently selected from hydrogen, halogen, hydroxyl, amino, substituted or unsubstituted alkyl of C1-C30, substituted or unsubstituted haloalkyl of C1-C30, substituted or unsubstituted cycloalkyl of C1-C30, substituted or unsubstituted alkoxy of C1-C30, substituted or unsubstituted alkylthio of C1-C30, substituted or unsubstituted aryloxy of C1-C30, substituted or unsubstituted arylthio of C1-C30, or selected from an aromatic group with 5-60 aromatic atoms or a heteroaromatic group with 5-60 aromatic atoms, wherein the heteroatoms of the heteroaromatic group are independently selected from Si, Ge, N, P, O, S or Se;
the R is1And R2R is1And between R, R2And R is selected from the group consisting of-C-, -C-N-, -C-P-, -C.ident.C-, -O-, -S-, -C (CH)3)2-、
Any one or more ofAnd (4) connecting.
The invention provides an organic electroluminescent device, comprising an electroluminescent material; the electroluminescent material comprises the fused ring compound described in any one of the above technical schemes or the fused ring compound prepared by the preparation method described in any one of the above technical schemes.
The above-mentioned fused ring compound of the present invention is preferably used as a light-emitting material in an organic electroluminescent device.
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, and the structure of the organic electroluminescent device of the present invention preferably includes:
a substrate; an anode disposed on the substrate; an organic layer disposed on the anode;
wherein the number of the organic layers is preferably more than or equal to 1, and at least one layer of the organic layers is preferably an organic electroluminescent layer; the organic electroluminescent layer preferably comprises one or more of the above-described light-emitting compounds of the invention;
a cathode disposed on the organic layer.
The substrate of the present invention is not particularly limited in its choice, and may be a substrate of a conventional organic electroluminescent device well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to the application, quality requirements, and product requirements, and the substrate of the present invention is preferably glass or plastic. The thickness of the substrate is preferably 0.3-0.7 mm, and more preferably 0.4-0.6 mm.
According to the invention, the anode is preferably a material susceptible to hole injection, more preferably a conductive metal or conductive metal oxide, and more preferably indium tin oxide.
The organic layers may be 1 or more, and at least one of the organic layers is an organic electroluminescent layer; the organic electroluminescent layer comprises one or more compounds disclosed by the invention. The compound of the invention is preferably used as a luminescent material to directly form an organic electroluminescent layer.
The cathode is preferably a metal including, but not limited to, calcium, magnesium, barium, aluminum, and silver, preferably aluminum.
In order to improve the performance and efficiency of the device, the organic layer between the anode and the organic electroluminescent layer preferably further comprises one or more of a hole injection layer, a hole transport layer and an electron blocking layer. The organic layer between the organic electroluminescent layer and the cathode preferably further comprises a hole blocking layer and an electron injection/transport layer. The materials and thicknesses of the hole injection layer, the hole transport layer, the electron blocking layer, the hole blocking layer, and the electron injection/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 present invention is not particularly limited in the preparation processes of the electrode, the hole injection layer, the hole transport layer, the organic electroluminescent layer, the electron blocking layer, the hole blocking layer and the electron injection/transport layer, and is preferably prepared by processes of vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing and stereolithography.
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 organic layers including at least one organic electroluminescent layer on the anode; forming a cathode on the organic layer;
the organic electroluminescent layer comprises one or more compounds according to the invention.
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. The organic electroluminescent layer and the organic layers below and above the organic electroluminescent layer may be formed on the anode by vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, or stereolithography, without any particular limitation. After the organic layer is formed, a cathode is prepared on the surface thereof, and the cathode is formed by a method known to those skilled in the art, including but not limited to vacuum deposition.
The invention provides a fused ring compound containing boron atoms and sulfur atoms, which has a structure shown in a formula (I). The condensed ring compound adopts a boron/sulfur hybrid condensed ring unit as a light-emitting unit, and realizes the separation of HOMO and LUMO by utilizing the resonance effect between boron atoms and sulfur atoms, thereby realizing smaller Delta ESTAnd the TADF effect, and meanwhile, the boron/sulfur hybrid fused ring unit has a rigid framework structure, so that the relaxation degree of an excited state structure can be reduced, and the narrow half-peak width is realized. In addition, different substituents are introduced into the skeleton of the boron/sulfur hybrid fused ring unit, so that the half-peak width can be further adjusted. The luminescent compound of the invention is used as a luminescent layer of an electroluminescent device, which can realize narrow electroluminescent half-peak width and high external quantum efficiency of the device under the condition of not needing a filter and a microcavity structure. The experimental results show that: the half-peak width of the fused ring compound prepared in the embodiment is 31-46 nm; the maximum external quantum efficiency of the device is 11.2-21.2%, and the half-peak width is 31-46 nm.
Detailed Description
In order to further illustrate the present invention, a fused ring compound containing a boron atom and a sulfur atom, and a method for preparing the same and applications thereof, which are provided by the present invention, will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Under argon atmosphere, m-1(30.0g, 0.11mol) and sodium thiophenolate (43.6g,0.33mol) were added to a 500mL three-necked flask, 180mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 150 ℃, the reaction was stirred under argon atmosphere for 10 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, anhydrous sodium sulfate was added thereto for drying, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain the product m-2(23.0g, yield: 46%).
Elemental analysis Structure (C)18H12Br2S2) Theoretical C, 47.81; h, 2.67; s,14.18 test value C, 47.72; h, 2.73; s, 14.26.
Electrospray mass spectrometry (ESI-MS): theoretical value 452.2; experimental value 452.2 (M)+)。
M-2(5.0g,11.1mmol) and dry o-xylene (80mL) are added to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.6mL,2.5M,11.6mmol) is added dropwise at-30 ℃, and after the addition is completed, the mixture is stirred at-30 ℃ for 2 hours, boron tribromide (3.3g,1.2mL,13.3mmol) is added dropwise to the system, and after the addition is completed for 20 minutes, the mixture is stirred at room temperature for 1 hour. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (3.1g,4.0mL,22.2mmol) 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 the product m-3(1.1g, yield: 26%). Elemental analysis Structure (C)18H10BBrS2) Theoretical value C, 56.73; h, 2.64; b, 2.84; br, 20.97; s,16.82 test value C, 56.65; h, 2.69; b, 2.81; br, 20.99; and S, 16.86.
ESI-MS: theoretical value 380.0; experimental value 380.1 (M)+)。
In a 100mL two-necked flask, m-3(2.0g, 5.25mmol) and diboronic acid ester (2.7g,10.5mmol), Pd were added under an argon atmosphere2(dppf) (0.39g, 0.53mmol), potassium acetate (2.1g, 21.0mmol), 40mL of DMF was taken and added to a flask, and the reaction was stirred at 85 ℃ for 10 hours. Then, the reaction mixture was cooled to room temperature, washed with deionized water, extracted with methylene chloride solution, and the organic phase was separated, dried with 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 BSS-BOO (1.6g, yield: 70%).
Elemental analysis Structure (C)24H22B2O2S2) Theoretical value C, 67.32; h, 5.18; s,14.98 test value C, 67.21; h, 5.13; and S, 15.01.
ESI-MS: theoretical value 428.1; experimental value 429.1([ M + H ]]+)。
The results of examining the photophysical properties of the fused ring compound prepared in example 1 of the present invention are shown in table 1, and table 1 shows the photophysical properties of the fused ring compound prepared in example of the present invention.
Example 2
Under argon atmosphere, m-4(10.0g, 0.05mol) and sodium thiophenolate (16.5g,0.13mol) were added to a 250mL three-necked flask, 80mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 150 ℃, the reaction was stirred under argon atmosphere for 10 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, anhydrous sodium sulfate was added thereto for drying, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain the product m-5(4.5g, yield: 24%).
Elemental analysis Structure (C)18H13BrS2) Theoretical C, 57.91; h, 3.51; s,17.18 test value C, 57.96; h, 3.53; s, 17.18.
ESI-MS: theoretical value 372.0; experimental value 372.1 (M)+)。
M-5(1.5g,4.0mmol) and dry o-xylene (70mL) are added to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (1.7mL,2.5M,4.2mmol) is added dropwise at-30 ℃, stirring is performed for 1 hour at 50 ℃ after the addition is completed, cooling is performed again to-30 ℃, boron tribromide (1.2g,0.5mL,4.8mmol) 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 (1.1g,1.3mL,8.0mmol) 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, an aqueous solution of sodium acetate was added to the reaction system and extracted with ethyl acetate to obtain an organic phase, which was dried over anhydrous sodium sulfate, filtered and the organic solvent removed by rotary evaporation, and the crude product was subjected to column separation to obtain a product m-6(0.48g, 40% yield).
Elemental analysis Structure (C)18H11BS2) Theoretical value C, 71.54; h, 3.67; s,21.22 test value C, 71.48; h, 3.69; s, 21.31.
ESI-MS: theoretical value 302.0; experimental value 302.0 (M)+)。
In a 100mL three-necked flask, m-6(1.0g, 3.3mmol) and N-bromosuccinimide (NBS) (1.4g,8.0mmol) were charged under argon atmosphere, 20mL of Tetrahydrofuran (THF) was charged into the flask, the reaction was stirred at room temperature for 3 hours, then cooled to 0 ℃ and deionized water was added to the reaction system, extraction was performed with dichloromethane, the resulting organic phase was dried over anhydrous sodium sulfate, filtered, concentrated to remove the solvent, and the crude product was column-isolated to give product m-7(1.0g, yield: 68%).
Elemental analysis Structure (C)18H9BBr2S2) Theoretical value C, 47.00; h, 1.97; s,13.94 test value C, 47.14; h, 1.99; s, 13.77.
ESI-MS: theoretical value 457.9; experimental value 458.8([ M + H)]+)。
In a 100mL two-necked flask, under an argon atmosphere, m-7(2.4g, 5.25mmol) and diboronic acid ester (2.7g,10.5mmol), Pd2(dppf) (0.39g, 0.53mmol), potassium acetate (2.1g, 21.0mmol), 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, extracted with dichloromethane solution, and the organic phase was separated, dried with 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 products 1 to 20(1.9g, yield: 67%).
Elemental analysis Structure (C)30H33B3O4S2) Theoretical value C, 65.03; h, 6.00; s,11.57 test value C, 65.17; h, 6.03; s, 11.44.
ESI-MS: theoretical value 554.2; experimental value 555.2([ M + H)]+)。
The photophysical properties of the fused ring compound prepared in example 2 of the present invention were measured and are shown in table 1.
Example 3
Magnesium turnings (0.14g, 5.78mmol) are added to a 100mL two-necked flask under argon atmosphere, m-3(2.0g, 5.25mmol) is dissolved in 30mL of dry THF solution and then added dropwise to the two-necked flask containing the magnesium turnings, the resulting Grignard reagent is filtered and added dropwise slowly to a THF solution of trimethyl borate (0.82g, 7.9mmol) at-70 ℃, after the reaction is completed, the reaction solution is poured slowly into a rapidly stirred ice-water bath, hydrochloric acid is added and stirred for 30min, the mixture is extracted with diethyl ether to obtain an organic phase which is washed with deionized water, dried with anhydrous sodium sulfate to obtain an organic phase which is concentrated and drained, and the crude product is recrystallized with hot n-hexane to obtain products 1-46(1.3g, yield: 71%).
Elemental analysis Structure (C)18H12B2O2S2) Theoretical value C, 62.48; h, 3.50; s,18.53 test value C, 62.41; h, 3.53; s, 18.52.
ESI-MS: theoretical value 346.1; experimental value 346.0 (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
M-3(2.0g, 5.25mmol) and dry tetrahydrofuran (40mL) are added to a 250mL two-necked flask under an argon atmosphere, a butyllithium solution (2.2mL,2.5M,5.5mmol) is added dropwise at-78 ℃, stirring is carried out at-78 ℃ for 30 minutes after the addition is completed, a tetrahydrofuran solution of boron difluoride (1.7g,6.3mmol) is added dropwise to the system, and stirring is carried out at room temperature for 3 hours after the addition is completed for 20 minutes. Deionized water was added to the system, extraction was performed with ether, the resulting organic phase was dried over anhydrous sodium sulfate, and the crude product was separated by column to give products 1 to 109(1.5g, yield: 52%).
Elemental analysis Structure (C)36H32B2S2) Theoretical C, 78.56; h, 5.86; s,11.65 test value C, 78.43; h, 5.83; s, 11.75.
Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS): theoretical value 550.2; experimental value 551.2([ M + H)]+)。
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
In a 100mL two-necked flask, m-3(1.9g, 5.00mmol), KOAc (0.5g, 5.00mmol) and trans-bis [2- (di-o-tolylphosphine) benzyl ] M (M)]Dipalladium (II) acetate (Herrmann I,0.1g), 40mL of DMF was taken and added to the bottle, and PPh was added thereto2P (0.9g, 5.00mmol), heating to 180 deg.C, and stirring under microwave for reaction for 30 min. Then, the reaction solution was cooled to room temperature, washed with deionized water, extracted with dichloromethane solution, the organic phase was extracted with saturated KCl solution and dried with 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 2-1(1.0g, yield: 43%).
Elemental analysis Structure (C)30H20BPS2) Theoretical C, 74.08; h, 4.14; s,13.18 test value C, 74.12; h, 4.10; and S, 13.23.
ESI-MS: theoretical value 486.1; experimental value 486.1 (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
In a 100mL two-necked flask, m-3(1.0g, 2.6mmol) and Cs were placed under an argon atmosphere2CO3(1.3g,3.9mol), SPO (0.8g,3.9mol) was dissolved in 20mL dry DMF and added to a two-necked flask. Adding Pd (OAc) into the reaction system2(6mg, 0.026mmol) and dppf (29mg, 0.052mmol), the reaction was stirred at 120 ℃ for 10 hours. After cooling to room temperature, the reaction was poured into an excess of saturated brine, extracted with dichloromethane, the resulting organic phase was dried over anhydrous sodium sulfate, filtered, concentrated to remove the solvent, and the crude product was column-separated to give the product 3-1(0.5g, yield: 38%).
Elemental analysis Structure (C)30H20BOPS2) Theoretical C, 71.72; h, 4.01; s,12.76 test value C, 71.62; h, 4.07; and S, 12.83.
ESI-MS: theoretical value 502.1; experimental value 503.1([ M + H ]]+)。
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
In a 50mL three-necked flask, m-6(1.0g, 3.3mmol) and N-bromosuccinimide (NBS) (0.7g,4.0mmol) were charged under argon atmosphere, 20mL of Tetrahydrofuran (THF) was charged into the flask, the reaction was stirred at room temperature for 3 hours, then cooled to 0 ℃ and deionized water was added to the reaction system, extraction was performed with dichloromethane, the resulting organic phase was dried over anhydrous sodium sulfate, filtered, concentrated to remove the solvent, and the crude product was column-isolated to give the product m-8(0.8g, yield: 65%).
Elemental analysis Structure (C)18H10BBrS2) Theoretical value C, 56.73; h, 2.64; s,16.82 test value C, 56.79; h, 2.61; s, 16.80.
ESI-MS: theoretical value 380.0; experimental value 380.1 (M)+)。
In a 100mL two-necked flask, m-8(1.0g, 2.6mmol) and Cs were placed under an argon atmosphere2CO3(1.3g,3.9mol), diphenylphosphineoxide (0.8g,3.9mol) was dissolved in 20mL of dry DMF and added to the double-port-fired flaskIn a bottle. Adding Pd (OAc) into the reaction system2(6mg, 0.026mmol) and dppf (29mg, 0.052mmol), the reaction was stirred at 120 ℃ for 10 hours. After cooling to room temperature, the reaction was poured into an excess of saturated brine, extracted with dichloromethane, the resulting organic phase was dried over anhydrous sodium sulfate, filtered, concentrated to remove the solvent, and the crude product was isolated on a column to give the product BSS-PO-2(0.4g, yield: 31%).
Elemental analysis Structure (C)30H20BOPS2) Theoretical C, 71.72; h, 4.01; s,12.76 test value C, 71.61; h, 4.07; and S, 12.84.
ESI-MS: theoretical value 502.1; experimental value 502.1 (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
In a 100mL two-necked flask, m-7(1.2g, 2.6mmol) and Cs were placed under an argon atmosphere2CO3(1.3g,3.9mol), diphenylphosphineoxide (1.6g,7.8mol) was dissolved in 20mL of dry DMF and added to a two-necked flask. Adding Pd (OAc) into the reaction system2(6mg, 0.026mmol) and dppf (29mg, 0.052mmol), the reaction was stirred at 120 ℃ for 10 hours. After cooling to room temperature, the reaction was poured into an excess of saturated brine, extracted with dichloromethane, the resulting organic phase was dried over anhydrous sodium sulfate, filtered, concentrated to remove the solvent, and the crude product was column-separated to give the product 3-5(0.9g, yield: 51%).
Elemental analysis Structure (C)42H29BO2P2S2) Theoretical C, 71.80; h, 4.16; s,9.13 test value C, 71.70; h, 4.19; and S, 9.24.
MALDI-TOF-MS: theoretical value 702.1; experimental value 702.2 (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
Under argon atmosphere, m-1(30.0g, 0.11mol) and sodium m-bromophenylthiobenzoate (69.6g,0.33mol) were charged into a 500mL three-necked flask, 200mL of N-methylpyrrolidone (NMP) was charged into the flask, the temperature was raised to 150 ℃ and the reaction was stirred under argon atmosphere for 10 hours, followed by cooling to room temperature, the reaction mixture was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate was added, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain the product m-9(16.0g, yield: 24%).
Elemental analysis Structure (C)18H10Br4S2) Theoretical value C, 35.44; h, 1.65; s,10.51 test value C, 35.32; h, 1.69; s, 10.67.
MALDI-TOF-MS: theoretical value 605.7; experimental value 605.7 (M)+)。
M-9(5.0g,8.2mmol) and dry o-xylene (80mL) were added to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (3.4mL,2.5M,8.6mmol) was added dropwise at-30 deg.C, stirring was performed at-30 deg.C for 2 hours after the addition was completed, boron tribromide (2.5g,0.9mL,9.8mmol) 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 (2.1g,2.7mL,16.4mmol) 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 give a product m-10(0.5g, yield: 12%).
Elemental analysis Structure (C)18H8BBr3S2) Theoretical value C, 40.12; h, 1.50; s,11.90 test value C, 40.25; h, 1.53; s, 11.95.
MALDI-TOF-MS: theoretical value 535.8; experimental value 535.9 (M)+)。
In a 100mL two-necked flask, m-10(1.4g, 2.6mmol) and Cs were placed under an argon atmosphere2CO3(1.3g,3.9mol), adding diphenylphosphine oxide (1)6g,7.8mol) was dissolved in 20mL of dry DMF and added to a two-necked flask. Adding Pd (OAc) into the reaction system2(6mg, 0.026mmol) and dppf (29mg, 0.052mmol), the reaction was stirred at 120 ℃ for 10 hours. After cooling to room temperature, the reaction was poured into an excess of saturated brine, extracted with dichloromethane, the resulting organic phase was dried over anhydrous sodium sulfate, filtered, concentrated to remove the solvent, and the crude product was column-separated to give the product 3-10(0.9g, yield: 37%).
Elemental analysis Structure (C)54H38BO3P3S2) Theoretical C, 71.85; h, 4.24; s,7.10 test value C, 71.62; h, 4.41; and S, 7.12.
MALDI-TOF-MS: theoretical value 902.2; experimental value 903.2([ M + H)]+)。
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
In a 100mL two-necked flask, m-7(1.2g, 2.6mmol) and Cs were placed under an argon atmosphere2CO3(1.3g,3.9mol), diphenylphosphine (1.8g,7.8mol) was dissolved in 20mL of dry DMF and added to a two-necked flask. Adding Pd (OAc) into the reaction system2(6mg, 0.026mmol) and dppf (29mg, 0.052mmol), the reaction was stirred at 120 ℃ for 10 hours. After cooling to room temperature, the reaction was poured into an excess of saturated brine, extracted with dichloromethane, the resulting organic phase was dried over anhydrous sodium sulfate, filtered, concentrated to remove the solvent, and the crude product was column-separated to give products 4 to 7(0.8g, yield: 40%).
Elemental analysis Structure (C)42H29BP2S4) Theoretical C, 68.66; h, 3.98; s,17.45 test value C, 68.61; h, 3.93; s, 17.49.
MALDI-TOF-MS: theoretical value 734.1; experimental value 735.2([ M + H)]+)。
The condensed ring compound prepared in example 10 was examined for photophysical properties and the results are shown in table 1.
Example 11
In a 100mL two-necked flask, m-3(2.0g, 5.25mmol) and sodium thiomethoxide (0.74g,10.5mmol), Pd were added under an argon atmosphere2(dba)3(0.12g, 0.13mmol), Xantphos ligand (0.15g, 0.26mmol), i-Pr2NEt (1.4g, 10.5mmol) 40mL of 1, 4-dioxane was added to the flask, the temperature was raised to 110 ℃ and the reaction was stirred under argon for 10 hours. Then, the reaction mixture was cooled to room temperature, washed with deionized 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 m-11(1.3g, yield: 70%).
Elemental analysis Structure (C)19H13BS3) Theoretical C, 65.52; h, 3.76; s,27.61 test value C, 65.42; h, 3.79; s, 27.65.
ESI-MS: theoretical value 348.0; experimental value 348.0 (M)+)。
In a 100mL two-necked flask under an argon atmosphere, m-4(2.0g, 5.74mmol) and mCPBA (m-chloroperoxybenzoic acid) (1.0g,5.74mmol) were added, and 40mL of chloroform was added to the flask, and the reaction was stirred at room temperature for 3 hours. The reaction solution was washed with deionized 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 subjected to column separation to give the product BSS-SOM (0.9g, yield: 43%).
Elemental analysis Structure (C)19H13BOS3) Theoretical C, 62.64; h, 3.60; s,26.40 test value C, 62.59; h, 3.65; s, 26.43.
ESI-MS: theoretical value 364.0; experimental value 364.0 (M)+)。
The photophysical properties of the fused ring compound prepared in example 11 of the present invention were measured, and the results are shown in table 1.
Example 12
In a 100mL two-necked flask, m-8(2.0g, 5.25mmol) and thiophenol (1.2g,10.5mmol), Pd were added under an argon atmosphere2(dba)3(0.12g, 0.13mmol), Xantphos ligand (0.15g, 0.26mmol), i-Pr2NEt (1.4g, 10.5mmol) 40mL of 1, 4-dioxane was added to the flask, the temperature was raised to 110 ℃ and the reaction was stirred under argon for 10 hours. Then, the reaction mixture was cooled to room temperature, washed with deionized 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 m-12(1.4g, yield: 66%).
Elemental analysis Structure (C)24H15BS3) Theoretical value C, 70.24; h, 3.68; s,23.44 test value C, 70.20; h, 3.62; and S, 23.48.
ESI-MS: theoretical value 410.0; experimental value 410.1 (M)+)。
In a 100mL two-necked flask under an argon atmosphere, m-12(2.4g, 5.74mmol) and mCPBA (1.0g,5.74mmol) were charged, 40mL of chloroform was added to the flask, and the reaction was stirred at room temperature for 3 hours. The reaction solution was washed with deionized 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 products 5 to 24(1.1g, yield: 46%).
Elemental analysis Structure (C)24H15BOS3) Theoretical C, 67.61; h, 3.55; s,22.56 test value C, 67.67; h, 3.51; s, 22.50.
ESI-MS: theoretical value 426.0; experimental value 426.0 (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
Under argon atmosphere, m-4(10.0g, 0.05mol) and sodium thiophenolate (6.6g,0.05mol), sodium m-bromophenolate (10.6g, 0.05mol) were added to a 500mL three-necked flask, 80mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 150 ℃, the reaction was stirred under argon atmosphere 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 the product m-13(7.0g, yield: 30%).
Elemental analysis Structure (C)24H15BOS3) Theoretical C, 67.61; h, 3.55; s,22.56 test value C, 67.67; h, 3.51; s, 22.50.
ESI-MS: theoretical value 426.0; experimental value 427.0([ M + H)]+)。
In a 250mL two-necked flask, M-13(4.3g,9.4mmol) and dry o-xylene (80mL) were added under argon atmosphere, a butyllithium solution (4.0mL,2.5M,9.9mmol) 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,1.1mL,11.3mmol) 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 (2.4g,3.1mL,18.8mmol) 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 the product m-14(0.6g, yield: 18%). Elemental analysis Structure (C)18H10BBrS2) Theoretical value C, 56.73; h, 2.64; s,16.82 test value C, 56.63; h, 2.69; s, 16.89.
ESI-MS: theoretical value 380.0; experimental value 380.1 (M)+)。
In a 100mL two-necked flask, m-14(2.0g, 5.25mmol) and sodium thiomethoxide (0.74g,10.5mmol), Pd were added under an argon atmosphere2(dba)3(0.12g, 0.13mmol), Xantphos ligand (0.15g, 0.26mmol), i-Pr2NEt (1.4g, 10.5mmol) 40mL of 1, 4-dioxane was added to the flask, the temperature was raised to 110 ℃ and the reaction was stirred under argon for 10 hours. Then cooling to room temperature, washing the reaction solution with deionized water, separating out an organic phase, adding anhydrous sodium sulfate for drying, and removing solvent from the organic phase obtained by filteringThe crude product was column-separated to give the product m-15(1.2g, yield: 63%).
Elemental analysis Structure (C)19H13BS3) Theoretical C, 65.52; h, 3.76; s,27.61 test value C, 65.48; h, 3.77; s, 27.62.
ESI-MS: theoretical value 348.0; experimental value 348.0 (M)+)。
In a 100mL two-necked flask under an argon atmosphere, m-15(2.0g, 5.74mmol) and mCPBA (2.0g,11.48mmol) were added, and 40mL of chloroform was added to the flask, and the reaction was stirred at room temperature for 3 hours. The reaction solution was washed with deionized 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 6-4(1.0g, yield: 47%).
Elemental analysis Structure (C)19H13BO2S3) Theoretical value C, 60.01; h, 3.45; s,25.29 test value C, 60.53; h, 3.48; s, 25.35.
ESI-MS: theoretical value 380.0; experimental value 380.1 (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
Under argon atmosphere, m-4(10.0g, 0.05mol) and sodium thiophenolate (6.6g,0.05mol) were added to a 500mL three-necked flask, and sodium p-bromothiophenolate (10.6g, 0.05mol) 80mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 150 ℃ and the reaction was stirred under argon atmosphere for 10 hours, followed by cooling 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 the product m-16(6.8g, yield: 30%).
Elemental analysis Structure (C)18H12Br2S2) Theoretical C, 47.81; h, 2.67; s,14.18 test value C, 47.71; h, 2.69; s, 14.21.
ESI-MS: theoretical value 449.9; experimental value 449.9 (M)+)。
In a 250mL two-necked flask, M-16(4.3g,9.4mmol) and dry o-xylene (80mL) were added under argon atmosphere, a butyllithium solution (4.0mL,2.5M,9.9mmol) 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,1.1mL,11.3mmol) 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 (2.4g,3.1mL,18.8mmol) 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 give the product m-17(0.6g, yield: 18%).
Elemental analysis Structure (C)18H10BBrS2) Theoretical value C, 56.73; h, 2.64; s,16.82 test value C, 56.77; h, 2.69; s, 16.81.
ESI-MS: theoretical value 380.0; experimental value 380.0 (M)+)。
In a 100mL two-necked flask, m-17(2.0g, 5.25mmol) and thiophenol (1.2g,10.5mmol), Pd were added under an argon atmosphere2(dba)3(0.12g, 0.13mmol), Xantphos ligand (0.15g, 0.26mmol), i-Pr2NEt (1.4g, 10.5mmol) 40mL of 1, 4-dioxane was added to the flask, the temperature was raised to 110 ℃ and the reaction was stirred under argon for 10 hours. Then, the reaction mixture was cooled to room temperature, washed with deionized 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 m-18(1.5g, yield: 70%).
Elemental analysis Structure (C)24H15BS3) Theoretical value C, 70.24; h, 3.68; s,23.44 test value C, 70.10; h, 3.74; and S, 23.47.
ESI-MS: theoretical value 410.0; experimental value 411.0([ M + H ]]+)。
In a 100mL two-necked flask under an argon atmosphere, m-18(2.4g, 5.74mmol) and mCPBA (2.0g,11.48mmol) were charged, 40mL of chloroform was added to the flask, and the reaction was stirred at room temperature for 3 hours. The reaction solution was washed with deionized 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 6 to 27(1.0g, yield: 42%).
Elemental analysis Structure (C)24H15BO2S3) Theoretical value C, 65.16; h, 3.42; s,21.74 test value C, 65.03; h, 3.46; and S, 21.87.
ESI-MS: theoretical value 442.0; experimental value 442.1 (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
Under argon atmosphere, m-1(13.6g, 0.05mol) and sodium thiophenolate (6.6g,0.05mol), sodium m-bromophenolate (10.6g, 0.05mol) were added to a 500mL three-necked flask, 80mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 150 ℃, the reaction was stirred under argon atmosphere 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 the product m-19(15.9g, yield: 60%).
Elemental analysis Structure (C)18H11Br3S2) Theoretical value C, 40.71; h, 2.09; s, test value C of 12.07, 40.79; h, 2.19; s, 11.94.
MALDI-TOF-MS: theoretical value 527.8; experimental value 527.7 (M)+)。
In a 250mL two-necked flask, M-19(5.0g,9.4mmol) and dry o-xylene (80mL) were added under argon atmosphere, a butyllithium solution (4.0mL,2.5M,9.9mmol) 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,1.1mL,11.3mmol) 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 (2.4g,3.1mL,18.8mmol) 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 give a product m-20(0.7g, yield: 17%).
Elemental analysis Structure (C)18H9BBr2S2) Theoretical value C, 47.00; h, 1.97; s,13.94 test value C, 47.03; h, 1.99; s, 14.05.
ESI-MS: theoretical value 457.9; experimental value 458.9([ M + H ]]+)。
In a 100mL two-necked flask, m-20(2.4g, 5.25mmol) and thiophenol (1.2g,10.5mmol), Pd were added under an argon atmosphere2(dba)3(0.12g, 0.13mmol), Xantphos ligand (0.15g, 0.26mmol), i-Pr2NEt (1.4g, 10.5mmol) 40mL of 1, 4-dioxane was added to the flask, the temperature was raised to 110 ℃ and the reaction was stirred under argon for 10 hours. Then, the reaction mixture was cooled to room temperature, washed with deionized 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 m-21(1.9g, yield: 70%).
Elemental analysis Structure (C)30H19BS4) Theoretical C, 69.49; h, 3.69; s,24.73 test value C, 69.34; h, 3.65; and S, 24.80.
MALDI-TOF-MS: theoretical value 518.1; experimental value 518.1 (M)+)。
In a 100mL two-necked flask under an argon atmosphere, m-21(3.0g, 5.74mmol) and mCPBA (2.0g,11.48mmol) were charged, 40mL of chloroform was added to the flask, and the reaction was stirred at room temperature for 3 hours. The reaction solution was washed with deionized 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 6 to 31(1.4g, yield: 41%). Elemental analysis Structure (C)30H19BO4S4) Theoretical value C, 61.86; h, 3.29; s,22.01 test value C, 61.71; h, 3.24; s, 22.13.
MALDI-TOF-MS: theoretical value 582.0; experimental value 582.1 (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
In a 100mL two-necked flask, m-3(2.0g, 5.25mmol) and phenylselenophenol (1.6g,10.5mmol), Pd were added under an argon atmosphere2(dba)3(0.12g, 0.13mmol), Xantphos ligand (0.15g, 0.26mmol), i-Pr2NEt (1.4g, 10.5mmol) 40mL of 1, 4-dioxane was added to the flask, the temperature was raised to 110 ℃ and the reaction was stirred under argon for 10 hours. Then, the reaction mixture was cooled to room temperature, washed with deionized 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 product 7-1(1.2g, yield: 51%).
Elemental analysis Structure (C)24H15BS2Se) theoretical value C, 63.04; h, 3.31; s,14.02 test value C, 63.12; h, 3.30; s, 14.00.
ESI-MS: theoretical value 460.0; experimental value 461.0([ M + H)]+)。
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
In a 100mL two-necked flask under an argon atmosphere, 7-1(2.6g, 5.74mmol) and mCPBA (1.0g,5.74mmol) were added, and 40mL of chloroform was added to the flask, and the reaction was stirred at room temperature for 3 hours. The reaction solution was washed with deionized 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 8-1(1.2g, yield: 45%).
Elemental analysis Structure (C)24H15BOS2Se) theoretical value C, 60.91; h, 3.19; s,13.55 test value C, 60.97; h, 3.15; s, 13.51.
ESI-MS: theoretical value474.0; experimental value 474.0 (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
In a 100mL two-necked flask under an argon atmosphere, 7-1(2.6g, 5.74mmol) and mCPBA (2.0g,11.48mmol) were added, and 40mL of chloroform was added to the flask, and the reaction was stirred at room temperature for 3 hours. The reaction solution was washed with deionized 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 product 9-1(1.2g, yield: 45%).
Elemental analysis Structure (C)24H15BO2S2Se) theoretical value C, 58.92; h, 3.09; s,13.10 test value C, 58.92; h, 3.09; and S, 13.10.
ESI-MS: theoretical value 490.0; experimental value 490.1 (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
In a 100mL two-necked flask, m-3(2.0g, 5.25mmol) and phenyl tellurium phenol (2.2g,10.5mmol), Pd were added under an argon atmosphere2(dba)3(0.12g, 0.13mmol), Xantphos ligand (0.15g, 0.26mmol), i-Pr2NEt (1.4g, 10.5mmol) 40mL of 1, 4-dioxane was added to the flask, the temperature was raised to 110 ℃ and the reaction was stirred under argon for 10 hours. Then, the reaction mixture was cooled to room temperature, washed with deionized 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 10-1(1.1g, yield: 40%).
Elemental analysis junctionStructure (C)24H15BS2Te) theoretical value C, 56.98; h, 2.99; s,12.67 test value C, 56.83; h, 2.99; s, 12.73.
MALDI-TOF-MS: theoretical value 508.0; experimental value 509.0([ M + H)]+)。
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
10-1(2.9g, 5.74mmol) and mCPBA (1.0g,5.74mmol) were placed in a 100mL two-necked flask under an argon atmosphere, 40mL of chloroform was added to the flask, and the reaction was stirred at room temperature for 3 hours. The reaction solution was washed with deionized 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 11-1(1.2g, yield: 41%).
Elemental analysis Structure (C)24H15BOS2Te) theoretical value C, 55.23; h, 2.90; s,12.29 test value C, 55.273; h, 2.91; and S, 12.25.
MALDI-TOF-MS: theoretical value 524.0; experimental value 524.0 (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
10-1(2.9g, 5.74mmol) and mCPBA (2.0g,11.48mmol) were placed in a 100mL two-necked flask under an argon atmosphere, 40mL of chloroform was added to the flask, and the reaction was stirred at room temperature for 3 hours. The reaction solution was washed with deionized 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 12-1(0.96g, yield: 32%).
Elemental analysis Structure (C24H15BO2S2Te) theoretical value C, 53.59; h, 2.81; s,11.92 test value C, 53.52; h, 2.85; and S, 11.90.
MALDI-TOF-MS: theoretical value 540.0; experimental value 540.1 (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
M-3(2.0g, 5.25mmol) and dry tetrahydrofuran (40mL) are added to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (2.2mL,2.5M,5.5mmol) is added dropwise at-78 ℃, stirring is carried out at-78 ℃ for 30 minutes after the addition is completed, a tetrahydrofuran solution of triphenylgermanium chloride (2.1g,6.3mmol) is added dropwise to the system, and stirring is carried out at room temperature for 3 hours after 20 minutes of addition is completed. Deionized water was added to the system, extraction was performed with ether, the obtained organic phase was dried over anhydrous sodium sulfate, and the crude product was separated by column to obtain product 13-1(1.3g, yield: 41%).
Elemental analysis Structure (C)36H25BGeS2) Theoretical value C, 71.45; h, 4.16; s,10.60 test value C, 71.31; h, 4.19; and S, 10.64.
MALDI-TOF-MS: theoretical value 606.1; experimental value 606.1 (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
M-10(2.8g, 5.25mmol) and dry tetrahydrofuran (40mL) are added to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (2.2mL,2.5M,5.5mmol) is added dropwise at-78 ℃, stirring is carried out at-78 ℃ for 30 minutes after the addition is completed, a tetrahydrofuran solution of tributyltin chloride (2.4g,6.3mmol) is added dropwise to the system, and stirring is carried out at room temperature for 3 hours after the addition is completed for 20 minutes. Deionized water was added to the system, extraction was performed with ether, the resulting organic phase was dried over anhydrous sodium sulfate, and the crude product was separated by column to give 14 to 33(1.8g, yield: 30%).
Elemental analysis Structure (C)54H89BS2Sn3) Theoretical C, 55.47; h, 7.67; s,5.48 test value C, 55.31; h, 7.63; s, 5.43.
MALDI-TOF-MS: theoretical value 1172.0; experimental value 1173.1([ M + H)]+)。
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.
Example 24
M-3(2.0g, 5.25mmol) and dry tetrahydrofuran (40mL) are added to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (2.2mL,2.5M,5.5mmol) is added dropwise at-78 ℃, stirring is carried out at-78 ℃ for 30 minutes after the addition is completed, a tetrahydrofuran solution of triphenyltin chloride (2.4g,6.3mmol) is added dropwise to the system, and stirring is carried out at room temperature for 3 hours after 20 minutes of addition is completed. Deionized water was added to the system, extraction was performed with ether, the resulting organic phase was dried over anhydrous sodium sulfate, and the crude product was separated by column to give 14 to 38(1.4g, yield: 40%).
Elemental analysis Structure (C)36H25BS2Sn) theoretical value C, 66.40; h, 3.87; s,9.85 test value C, 66.49; h, 3.89; and S, 9.89.
MALDI-TOF-MS: theoretical value 652.1; experimental value 652.0 (M)+)。
The photophysical properties of the fused ring compound prepared in example 24 of the present invention were measured and the results are shown in table 1.
Example 25
Under argon atmosphere, m-22(35.1g, 0.11mol) and sodium thiophenolate (43.6g,0.33mol) were charged into a 500mL three-necked flask, 180mL of N-methylpyrrolidone (NMP) was charged into the flask, the temperature was raised to 150 ℃, the reaction was stirred under argon atmosphere for 10 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, anhydrous sodium sulfate was added thereto for drying, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain the product m-23(26.0g, yield: 36%).
Elemental analysis Structure (C)18H10Br3IS2) Theoretical C, 32.91; h, 1.53; s,9.76 test value C, 32.74; h, 1.57; and S, 9.89.
MALDI-TOF-MS: theoretical value 653.7; experimental value 654.7([ M + H)]+)。
In a 250mL two-necked flask, M-23(7.3g,11.1mmol) and dry o-xylene (80mL) were added under argon atmosphere, a butyllithium solution (4.6mL,2.5M,11.6mmol) was added dropwise at-30 ℃, after completion of the addition, stirring was performed at-30 ℃ for 2 hours, boron tribromide (3.3g,1.2mL,13.3mmol) was added dropwise to the system, and after completion of the addition, stirring was performed at room temperature for 1 hour after 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (3.1g,4.0mL,22.2mmol) 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 the product m-24(1.0g, yield: 16%).
Elemental analysis Structure (C)18H8BBr2IS2) Theoretical C, 36.90; h, 1.38; s,10.94 test value C, 36.72; h, 1.45; s, 11.0.
MALDI-TOF-MS: theoretical value 583.8; experimental value 583.9 (M)+)。
M-24(3.1g, 5.25mmol) and dry tetrahydrofuran (40mL) were added to a 250mL two-necked flask under an argon atmosphere, a butyllithium solution (2.2mL,2.5M,5.5mmol) was added dropwise at-78 deg.C, stirring was performed at-78 deg.C for 30 minutes after the addition was completed, a tetrahydrofuran solution of tridyborofluoride (1.7g,6.3mmol) was added dropwise to the system, and stirring was returned to room temperature for 3 hours after the addition was completed for 20 minutes. Deionized water was added to the system, extraction was performed with ether, the resulting organic phase was dried over anhydrous sodium sulfate, and the crude product was separated by column to give the product m-25(1.4g, yield: 38%).
Elemental analysis Structure (C)36H30B2Br2S2) Theoretical C, 61.06; h, 4.27; s,9.05 test value C, 61.14; h, 4.28; and S, 9.06.
MALDI-TOF-MS: theoretical value 706.0; experimental value 706.0 (M)+)。
In a 100mL two-necked flask, m-25(1.8g, 2.6mmol) and Cs were placed under an argon atmosphere2CO3(1.3g,3.9mol), diphenylphosphineoxide (0.8g,3.9mol) was dissolved in 20mL of dry DMF and added to a two-necked flask. Adding Pd (OAc) into the reaction system2(6mg, 0.026mmol) and dppf (29mg, 0.052mmol), the reaction was stirred at 120 ℃ for 10 hours. After cooling to room temperature, the reaction was poured into an excess of saturated brine, extracted with dichloromethane, the resulting organic phase was dried over anhydrous sodium sulfate, filtered, concentrated to remove the solvent, and the crude product was column-separated to give 15-12(0.8g, yield: 34%).
Elemental analysis Structure (C)60H50B2O2P2S2) Theoretical C, 75.80; h, 5.30; s,6.74 test value C, 75.53; h, 5.39; and S, 6.95.
MALDI-TOF-MS: theoretical value 950.3; experimental value 951.2([ M + H)]+)。
The photophysical properties of the fused ring compound prepared in example 25 of the present invention were measured and the results are shown in table 1.
Example 26
M-24(3.0g, 5.25mmol) and dry tetrahydrofuran (40mL) were added under argon to a 250mL two-necked flask, a butyllithium solution (2.1mL,2.5M,5.25mmol) was added dropwise at-78 deg.C, after addition was complete, stirring was carried out at-78 deg.C for 30 minutes, isopropanol pinacol borate (1.05mL,5.3mmol) was added dropwise to the system, and after addition was complete for 20 minutes, stirring was returned to room temperature for 3 hours. Deionized water was added to the system, extraction was performed with ether, the resulting organic phase was dried over anhydrous sodium sulfate, and the crude product was separated by column to give the product m-25(1.3g, yield: 43%).
Elemental analysis Structure (C)24H20B2Br2O2S2) Theoretical value C, 49.19; h, 3.44; b, 3.69; br, 27.27; s,10.94 test value C, 49.11; h, 3.47; b, 3.71; br, 27.21; s, 11.04.
MALDI-TOF-MS: theoretical value 584.0; experimental value 584.0 (M)+)。
In a 250mL two-necked flask, M-25(3.1g, 5.25mmol) and dry tetrahydrofuran (40mL) were added under argon atmosphere, a butyllithium solution (2.2mL,2.5M,5.5mmol) was added dropwise at-78 deg.C, stirring was performed at-78 deg.C for 30 minutes after the addition was completed, a tetrahydrofuran solution of tributyltin chloride (2.4g,6.3mmol) was added dropwise to the system, and stirring was returned to room temperature for 3 hours after 20 minutes was completed. Deionized water was added to the system, extraction was performed with ether, the resulting organic phase was dried over anhydrous sodium sulfate, and the crude product was separated by column to give 15 to 28(1.8g, yield: 34%).
Elemental analysis Structure (C)48H74B2O2S2Sn2) Theoretical C, 57.29; h, 7.41; s,6.37 test value C, 57.17; h, 7.34; s, 6.45.
MALDI-TOF-MS: theoretical value 1008.0; experimental value 1009.0([ M + H)]+)。
The photophysical properties of the fused ring compound prepared in example 26 of the present invention were measured, and the results are shown in table 1.
TABLE 1 photophysical properties of fused ring compounds prepared in the examples of the present invention
Note that in the table,. DELTA.ESTIs the difference between the singlet level and the triplet level, obtained by reacting the compound with 10-4A 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 with a HORIBA FluoroMax spectrophotometer (Japan); the delayed fluorescence lifetime is obtained by doping a compound with polystyrene at a concentration of 1 wt% to prepare a sample to be tested, and testing the sample by using a time-resolved fluorescence spectrometer, wherein the testing instrument is an Edinburgh fluorescence spectrometer (FLS-980, UK); half-peak width is the width of the peak at half of the peak height of the fluorescence spectrum at room temperature, i.e. a straight line parallel to the bottom of the peak is drawn through the midpoint of the peak height and the straight line intersects with the two points on both sides of the peak at a distance of 10 deg.C-5The concentration of mol/L was dissolved in a toluene solution to prepare a sample to be measured, and the sample was measured by a fluorescence spectrometer (HORIBA FluoroMax spectrophotometer (Japan)).
As can be seen from Table 1, the fused ring compounds in the examples provided by the present invention have smaller Δ EST(<0.2eV), the delayed fluorescence effect of thermal activation is shown, and the delayed fluorescence life is 47-135 mu s; meanwhile, the luminescent compound provided by the invention also shows narrower half-peak width (<50nm) and overcomes the defect that the half-peak width of the traditional TADF luminescent material is wider (70-100 nm).
Device examples
The process of preparing the device by the organic light-emitting layer by adopting a vacuum evaporation process is as follows: on indium tin oxide supported on a glass substrate, 4X 10-4Sequentially depositing TAPC, TCTA, EML (the luminescent compound and mCP are in a mass ratio of 1: 9), TmPyPB and a LiF/Al cathode under the vacuum degree of Pa to obtain the organic electroluminescent device, wherein the TAPC and the TmPyPB are respectively used as a hole transport layer and an electron transport layer, the TCTA is an exciton blocking layer, and the structural formula of the organic electroluminescent device is as follows:
the specific device structure (device structure a) is:
ITO/TAPC(50nm)/TCTA(5nm)/EML(30nm)/TmPyPB(30nm)/LiF(0.8nm)/Al(100nm)。
the process of preparing the device by adopting the solution processing technology for the organic light-emitting layer is 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 inventive light-emitting compound and mCP at 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 Pa vacuum degree to obtain the organic electroluminescent device, wherein TSPO1 and TmPyPB are respectively used as a hole blocking layer, an electron transport layer and a main material, and the structural formula is as follows:
the specific device structure (device structure B) is:
ITO/PEDOT:PSS(40nm)/EML(30nm)/TSPO1(8nm)/TmPyPB(42nm)/LiF(1nm)/Al(100nm)。
example 27
1-1 in example 1 was used as a target, and 1-1 and mCP were mixed in a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the organic electroluminescent device is prepared by utilizing the structure of the device structure B, the obtained device is tested, and the result is shown in table 2, and the table 2 is the performance parameter of the electroluminescent device prepared by the invention.
Example 28
Taking 1-20 in example 2 as an implementation object, mixing 1-20 and mCP according to a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested, and the result is shown in Table 2.
Example 29
1-46 in example 3 was used as an object, and 1-46 and mCP were mixed in a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested, and the result is shown in Table 2.
Example 30
Taking 1-109 in example 4 as an implementation object, mixing 1-109 and mCP according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 31
2-1 in example 5 was used as a target, and 2-1 and mCP were mixed in a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 32
3-1 in example 6 was used as a target, and 3-1 and mCP were mixed in a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 33
3-2 in example 7 was used as a target, and 3-2 and mCP were mixed in a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 34
3-5 in example 8 was used as an object, and 3-5 and mCP were mixed in a mass ratio of 3-5 to form an organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 35
3-10 in example 9 was used as an object, and 3-10 and mCP were mixed in a mass ratio of 3: 5 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 36
Taking 4-7 in example 10 as an implementation object, mixing 4-7 and mCP according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 37
5-1 in example 11 was used as a target, and 5-1 and mCP were mixed in a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 38
5-24 in example 12 was used as a target, and 5-24 and mCP were mixed in a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 39
Taking 6-4 in example 13 as an implementation object, mixing 6-4 and mCP according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 40
Taking 6-27 in example 14 as an implementation object, mixing 6-27 and mCP according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
EXAMPLE 41
Taking 6-31 in example 15 as an implementation object, mixing 6-31 and mCP according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 42
7-1 in example 16 was used as a target, and 7-1 and mCP were mixed in a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 43
8-1 in example 17 was used as a target, and 8-1 and mCP were mixed in a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 44
9-1 in example 18 was used as a target, and 9-1 and mCP were mixed in a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 45
10-1 in example 19 was used as a target, and 10-1 and mCP were mixed in a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 46
To example 11-1 in example 20, 11-1 and mCP were mixed at a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 47
12-1 in example 21 was used as a target, and 12-1 and mCP were mixed in a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Example 48
13-1 in example 22 was used as a target, and 13-1 and mCP were mixed in a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested, and the result is shown in Table 2.
Example 49
Taking 14-33 in example 23 as an implementation object, mixing 14-33 and mCP according to a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested, and the result is shown in Table 2.
Example 50
Taking 14-38 in example 24 as an implementation object, mixing 14-38 and mCP according to a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested, and the result is shown in Table 2.
Example 51
15-12 in example 25 was used as a target, and 15-12 and mCP were mixed in a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested, and the result is shown in Table 2.
Example 52
Taking 15-28 in example 26 as an implementation object, mixing 15-28 and mCP according to a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested, and the result is shown in Table 2.
Comparative example 1
Taking m-6(BSS) in embodiment 2 as an implementation object, the BSS and the mCP are mixed according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested, and the result is shown in Table 2.
Comparative example 2
Taking m-6(BSS) in embodiment 2 as an implementation object, the BSS and the mCP are mixed according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested, and the result is shown in Table 2.
TABLE 2 Performance parameters of electroluminescent devices prepared with partially fused ring compounds provided by the present invention
Note: the on-voltage in the table is 1cd m in luminance-2The driving voltage of the time device; the maximum external quantum efficiency is obtained according to the current-voltage curve and the electroluminescence spectrum of the device by the 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.
As can be seen from Table 2, the device prepared by the compound provided by the invention has a very narrow electroluminescent spectrum, the half-peak width of the device is less than 50nm, and the problem that the electroluminescent spectrum of the TADF compound with the traditional D-A structure is wide (70-100 nm) is solved. Meanwhile, compared with compounds without substituent groups (comparative example 1 and comparative example 2), the compounds provided by the invention have higher device efficiency in devices.
As is clear from the above examples, the present invention provides a fused ring compound containing a boron atom and a sulfur atom, having a structure represented by formula (I). The condensed ring compound adopts a boron/sulfur hybrid condensed ring unit as a light-emitting unit, and realizes the separation of HOMO and LUMO by utilizing the resonance effect between boron atoms and sulfur atoms, thereby realizing smaller Delta ESTAnd the TADF effect, and meanwhile, the boron/sulfur hybrid fused ring unit has a rigid framework structure, so that the relaxation degree of an excited state structure can be reduced, and the narrow half-peak width is realized. In addition, different substituents are introduced into the skeleton of the boron/sulfur hybrid fused ring unit, so that the half-peak width can be further adjusted. The luminescent compound of the invention is used as a luminescent layer of an electroluminescent device, which can realize narrow electroluminescent half-peak width and high external quantum efficiency of the device under the condition of not needing a filter and a microcavity structure. The experimental results show that: the half-peak width of the fused ring compound prepared in the embodiment is 31-46 nm; the maximum external quantum efficiency of the device is 11.2-21.2%, and the half-peak width is 31-46 nm.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (2)
1. The fused ring compound is characterized by being specifically selected from any one of the structures shown as follows:
2. an organic electroluminescent device comprising an electroluminescent material; the electroluminescent material comprises one of the fused ring compounds of claim 1.
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