WO2020015029A1 - 一种半导体材料及其制备方法与应用 - Google Patents
一种半导体材料及其制备方法与应用 Download PDFInfo
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- WO2020015029A1 WO2020015029A1 PCT/CN2018/099487 CN2018099487W WO2020015029A1 WO 2020015029 A1 WO2020015029 A1 WO 2020015029A1 CN 2018099487 W CN2018099487 W CN 2018099487W WO 2020015029 A1 WO2020015029 A1 WO 2020015029A1
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- WO
- WIPO (PCT)
- Prior art keywords
- benzothiophene
- mixed
- reaction
- molecular structure
- mmol
- Prior art date
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 103
- 239000000463 material Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title abstract description 47
- 125000003118 aryl group Chemical group 0.000 claims abstract description 79
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims description 169
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 122
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 90
- -1 aryl tin Chemical compound 0.000 claims description 84
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 66
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 48
- 101150003085 Pdcl gene Proteins 0.000 claims description 38
- TVBBBGXDQQURHJ-UHFFFAOYSA-N 1-benzothiophene 1-oxide Chemical compound C1=CC=C2S(=O)C=CC2=C1 TVBBBGXDQQURHJ-UHFFFAOYSA-N 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 34
- SRWDQSRTOOMPMO-UHFFFAOYSA-N 3-bromo-1-benzothiophene Chemical compound C1=CC=C2C(Br)=CSC2=C1 SRWDQSRTOOMPMO-UHFFFAOYSA-N 0.000 claims description 33
- 229960000583 acetic acid Drugs 0.000 claims description 33
- 239000012362 glacial acetic acid Substances 0.000 claims description 33
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 239000010409 thin film Substances 0.000 claims description 19
- 230000002950 deficient Effects 0.000 claims description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 5
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001543 aryl boronic acids Chemical class 0.000 claims description 3
- 125000005266 diarylamine group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical class 0.000 claims 1
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 13
- 150000002240 furans Chemical class 0.000 abstract description 8
- 150000003577 thiophenes Chemical class 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 168
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical class C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 153
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 153
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 124
- 239000012074 organic phase Substances 0.000 description 119
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 96
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 91
- 238000004440 column chromatography Methods 0.000 description 91
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 84
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 70
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 70
- 238000003756 stirring Methods 0.000 description 69
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 66
- 239000000243 solution Substances 0.000 description 56
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- 229910052757 nitrogen Inorganic materials 0.000 description 42
- RQYZJTUJRFVHEO-UHFFFAOYSA-N 2,7-dibromo-1-benzothiophene Chemical compound Brc1cc2cccc(Br)c2s1 RQYZJTUJRFVHEO-UHFFFAOYSA-N 0.000 description 40
- 239000007864 aqueous solution Substances 0.000 description 40
- 239000000203 mixture Substances 0.000 description 37
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 36
- 229910000027 potassium carbonate Inorganic materials 0.000 description 35
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 32
- 239000002994 raw material Substances 0.000 description 31
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 25
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 22
- 239000007787 solid Substances 0.000 description 22
- 239000011541 reaction mixture Substances 0.000 description 20
- 238000002506 high-vacuum sublimation Methods 0.000 description 19
- 239000005457 ice water Substances 0.000 description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 16
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 16
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- 239000001632 sodium acetate Substances 0.000 description 16
- 235000017281 sodium acetate Nutrition 0.000 description 16
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 13
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 13
- 235000019345 sodium thiosulphate Nutrition 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- GCQSROWXQJHAJC-UHFFFAOYSA-N 1-benzofuran-2,7-diamine Chemical compound C1=CC(N)=C2OC(N)=CC2=C1 GCQSROWXQJHAJC-UHFFFAOYSA-N 0.000 description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 4
- SBJIDUSVEICMRY-UHFFFAOYSA-N 2,7-diphenyl-[1]benzothiolo[3,2-b][1]benzothiole Chemical compound C1=CC=CC=C1C1=CC=C2C(SC3=CC(=CC=C33)C=4C=CC=CC=4)=C3SC2=C1 SBJIDUSVEICMRY-UHFFFAOYSA-N 0.000 description 4
- UMFNQNWYGHMUHB-UHFFFAOYSA-N 3-phenoxy-1-benzothiophene Chemical compound C=1SC2=CC=CC=C2C=1OC1=CC=CC=C1 UMFNQNWYGHMUHB-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- IUJKWWJXVYSADI-UHFFFAOYSA-N 2-(4-ethylphenyl)-1-benzothiophene Chemical compound C1=CC(CC)=CC=C1C1=CC2=CC=CC=C2S1 IUJKWWJXVYSADI-UHFFFAOYSA-N 0.000 description 3
- PUHYCOWXUUMAEG-UHFFFAOYSA-N C1(=CC=CC2=CC=CC=C12)C=1SC2=C(C1)C=CC=C2C2=CC=CC1=CC=CC=C21 Chemical compound C1(=CC=CC2=CC=CC=C12)C=1SC2=C(C1)C=CC=C2C2=CC=CC1=CC=CC=C21 PUHYCOWXUUMAEG-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 2
- XAWKDYYJKNPXEN-UHFFFAOYSA-N 2,7-bis(4-dodecylphenyl)-1-benzothiophene Chemical compound CCCCCCCCCCCCC1=CC=C(C=C1)C2=CC=CC3=C2SC(=C3)C4=CC=C(C=C4)CCCCCCCCCCCC XAWKDYYJKNPXEN-UHFFFAOYSA-N 0.000 description 2
- BJORIMHABBPUHT-UHFFFAOYSA-N 2,7-bis(4-tridecylphenyl)-1-benzothiophene Chemical compound CCCCCCCCCCCCCC1=CC=C(C=C1)C2=CC=CC3=C2SC(=C3)C4=CC=C(C=C4)CCCCCCCCCCCCC BJORIMHABBPUHT-UHFFFAOYSA-N 0.000 description 2
- ADMUKNAKSUNXOQ-UHFFFAOYSA-N 2,7-dioctyl-1-benzothiophene Chemical compound C1=CC(CCCCCCCC)=C2SC(CCCCCCCC)=CC2=C1 ADMUKNAKSUNXOQ-UHFFFAOYSA-N 0.000 description 2
- OEZURBSSIFUYPE-UHFFFAOYSA-N 2-bromo-3-phenoxy-1-benzothiophene Chemical compound BrC1=C(C2=C(S1)C=CC=C2)OC1=CC=CC=C1 OEZURBSSIFUYPE-UHFFFAOYSA-N 0.000 description 2
- MIQZGCPCMWVWME-UHFFFAOYSA-N 2-bromo-6-(4-decylphenyl)-3-phenoxy-1-benzothiophene Chemical compound CCCCCCCCCCC1=CC=C(C=C1)C2=CC3=C(C=C2)C(=C(S3)Br)OC4=CC=CC=C4 MIQZGCPCMWVWME-UHFFFAOYSA-N 0.000 description 2
- RRIZHUKYGHECIH-UHFFFAOYSA-N 2-naphthalen-1-yl-1-benzothiophene Chemical compound C1=CC=C2C(C3=CC4=CC=CC=C4S3)=CC=CC2=C1 RRIZHUKYGHECIH-UHFFFAOYSA-N 0.000 description 2
- VXNMJAGOXHIGRF-UHFFFAOYSA-N 2-naphthalen-2-yl-1-benzothiophene Chemical compound C1=CC=CC2=CC(C3=CC4=CC=CC=C4S3)=CC=C21 VXNMJAGOXHIGRF-UHFFFAOYSA-N 0.000 description 2
- ZVDWGSVEKOBQLO-UHFFFAOYSA-N 2-phenoxy-1-benzothiophene Chemical compound C=1C2=CC=CC=C2SC=1OC1=CC=CC=C1 ZVDWGSVEKOBQLO-UHFFFAOYSA-N 0.000 description 2
- LBMHPHUSGIEGHJ-UHFFFAOYSA-N 2-phenyl-1-benzothiophene Chemical compound S1C2=CC=CC=C2C=C1C1=CC=CC=C1 LBMHPHUSGIEGHJ-UHFFFAOYSA-N 0.000 description 2
- QXDSVYFLXRPWBJ-UHFFFAOYSA-N 3-(4-decylphenoxy)-1-benzothiophene Chemical compound CCCCCCCCCCC1=CC=C(C=C1)OC2=CSC3=CC=CC=C32 QXDSVYFLXRPWBJ-UHFFFAOYSA-N 0.000 description 2
- FEYHEZFHUFKLTF-UHFFFAOYSA-N 3-(4-dodecylphenoxy)-1-benzothiophene Chemical compound CCCCCCCCCCCCC1=CC=C(C=C1)OC2=CSC3=CC=CC=C32 FEYHEZFHUFKLTF-UHFFFAOYSA-N 0.000 description 2
- DRCOIJBJXVJGNS-UHFFFAOYSA-N 3-(4-octylphenoxy)-1-benzothiophene Chemical compound CCCCCCCCC1=CC=C(C=C1)OC2=CSC3=CC=CC=C32 DRCOIJBJXVJGNS-UHFFFAOYSA-N 0.000 description 2
- UINWFXHCPYUWJH-UHFFFAOYSA-N 3-(4-tridecylphenoxy)-1-benzothiophene Chemical compound CCCCCCCCCCCCCC1=CC=C(C=C1)OC2=CSC3=CC=CC=C32 UINWFXHCPYUWJH-UHFFFAOYSA-N 0.000 description 2
- QGEZFLHLBKCXIK-UHFFFAOYSA-N 3-bromo-6-(4-decylphenyl)-1-benzothiophene Chemical compound CCCCCCCCCCC1=CC=C(C=C1)C2=CC3=C(C=C2)C(=CS3)Br QGEZFLHLBKCXIK-UHFFFAOYSA-N 0.000 description 2
- UXRQSESXVHDPGH-UHFFFAOYSA-N 3-bromo-6-(4-dodecylphenyl)-1-benzothiophene Chemical compound CCCCCCCCCCCCC1=CC=C(C=C1)C2=CC3=C(C=C2)C(=CS3)Br UXRQSESXVHDPGH-UHFFFAOYSA-N 0.000 description 2
- NZKLXNGHNBOGOX-UHFFFAOYSA-N 3-bromo-6-(4-ethylphenyl)-1-benzothiophene Chemical compound CCC1=CC=C(C=C1)C2=CC3=C(C=C2)C(=CS3)Br NZKLXNGHNBOGOX-UHFFFAOYSA-N 0.000 description 2
- LWNWGVOAZUJYCW-UHFFFAOYSA-N 3-bromo-6-(4-heptylphenyl)-1-benzothiophene Chemical compound CCCCCCCC1=CC=C(C=C1)C2=CC3=C(C=C2)C(=CS3)Br LWNWGVOAZUJYCW-UHFFFAOYSA-N 0.000 description 2
- QYNQVGTZNRRZFH-UHFFFAOYSA-N 3-bromo-6-(4-octylphenyl)-1-benzothiophene Chemical compound CCCCCCCCC1=CC=C(C=C1)C2=CC3=C(C=C2)C(=CS3)Br QYNQVGTZNRRZFH-UHFFFAOYSA-N 0.000 description 2
- FAVSXXGUXODROF-UHFFFAOYSA-N 3-bromo-6-(4-pentylphenyl)-1-benzothiophene Chemical compound CCCCCC1=CC=C(C=C1)C2=CC3=C(C=C2)C(=CS3)Br FAVSXXGUXODROF-UHFFFAOYSA-N 0.000 description 2
- URWXKPHCZSKFNR-UHFFFAOYSA-N 3-bromo-6-(4-tridecylphenyl)-1-benzothiophene Chemical compound CCCCCCCCCCCCCC1=CC=C(C=C1)C2=CC3=C(C=C2)C(=CS3)Br URWXKPHCZSKFNR-UHFFFAOYSA-N 0.000 description 2
- ZHQXYSBDQNNVIA-UHFFFAOYSA-N 3-bromo-6-naphthalen-1-yl-1-benzothiophene Chemical compound C1=CC=C2C(=C1)C=CC=C2C3=CC4=C(C=C3)C(=CS4)Br ZHQXYSBDQNNVIA-UHFFFAOYSA-N 0.000 description 2
- BJYWKSSKINMKLW-UHFFFAOYSA-N 3-phenoxy-6-(4-tridecylphenyl)-1-benzothiophene Chemical compound CCCCCCCCCCCCCC1=CC=C(C=C1)C2=CC3=C(C=C2)C(=CS3)OC4=CC=CC=C4 BJYWKSSKINMKLW-UHFFFAOYSA-N 0.000 description 2
- RNLAHQNZWYDUDE-UHFFFAOYSA-N 3-phenoxy-6-phenyl-1-benzothiophene Chemical compound C1=CC=C(C=C1)C2=CC3=C(C=C2)C(=CS3)OC4=CC=CC=C4 RNLAHQNZWYDUDE-UHFFFAOYSA-N 0.000 description 2
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 2
- DWLGVFVYCORKEE-UHFFFAOYSA-N 6-(4-decylphenyl)-3-phenoxy-1-benzothiophene Chemical compound CCCCCCCCCCC1=CC=C(C=C1)C2=CC3=C(C=C2)C(=CS3)OC4=CC=CC=C4 DWLGVFVYCORKEE-UHFFFAOYSA-N 0.000 description 2
- RKGVMCNZCYFELU-UHFFFAOYSA-N 6-(4-dodecylphenyl)-3-phenoxy-1-benzothiophene Chemical compound CCCCCCCCCCCCC1=CC=C(C=C1)C2=CC3=C(C=C2)C(=CS3)OC4=CC=CC=C4 RKGVMCNZCYFELU-UHFFFAOYSA-N 0.000 description 2
- WNAWXYVFZLAKNO-UHFFFAOYSA-N 6-(4-ethylphenyl)-3-phenoxy-1-benzothiophene Chemical compound CCC1=CC=C(C=C1)C2=CC3=C(C=C2)C(=CS3)OC4=CC=CC=C4 WNAWXYVFZLAKNO-UHFFFAOYSA-N 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical compound CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- UMLDUMMLRZFROX-UHFFFAOYSA-N pyridin-2-ylboronic acid Chemical compound OB(O)C1=CC=CC=N1 UMLDUMMLRZFROX-UHFFFAOYSA-N 0.000 description 1
- ABMYEXAYWZJVOV-UHFFFAOYSA-N pyridin-3-ylboronic acid Chemical compound OB(O)C1=CC=CN=C1 ABMYEXAYWZJVOV-UHFFFAOYSA-N 0.000 description 1
- QLULGIRFKAWHOJ-UHFFFAOYSA-N pyridin-4-ylboronic acid Chemical compound OB(O)C1=CC=NC=C1 QLULGIRFKAWHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- YGDICLRMNDWZAK-UHFFFAOYSA-N quinolin-3-ylboronic acid Chemical compound C1=CC=CC2=CC(B(O)O)=CN=C21 YGDICLRMNDWZAK-UHFFFAOYSA-N 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FJRPWCNFWGBGOF-UHFFFAOYSA-N tridecanoyl chloride Chemical compound CCCCCCCCCCCCC(Cl)=O FJRPWCNFWGBGOF-UHFFFAOYSA-N 0.000 description 1
- JUKPJGZUFHCZQI-UHFFFAOYSA-N undecanoyl chloride Chemical compound CCCCCCCCCCC(Cl)=O JUKPJGZUFHCZQI-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
Definitions
- the invention relates to the field of organic semiconductor materials, in particular to a semiconductor material, a preparation method and application thereof.
- OTFTs Organic thin-film transistors
- BTBT Benzothiophene
- BTBT Benzothiophene
- Furan derivatives have potential application prospects in the field of light emission due to their unique properties.
- Furan is one of the simplest heterocyclic aromatic compounds, and has similar chemical structure and electronic properties to thiophene.
- thiophene contains a relatively heavy sulfur atom, which causes fluorescence quenching due to the internal conversion of the spin-orbit coupling caused by the heavy atom.
- Furan semiconductor does not have the problem of fluorescence quenching caused by the spin-orbit coupling. Compared with thiophene semiconductor, it has more excellent fluorescence properties, so it can be used to prepare organic semiconductor light-emitting devices.
- Thiophene derivatives have strong carrier mobility characteristics, while furan derivatives have strong fluorescence properties, both of which have different characteristics due to their different structures.
- the prior art lacks a semiconductor material that has both high carrier mobility and high fluorescence performance.
- an object of the present invention is to provide a semiconductor material, a method for preparing the same, and an application thereof.
- a semiconductor material wherein the molecular structure of the semiconductor material is One of them, wherein Ar1 and Ar2 are all alkyl groups or aryl groups; Ar3, Ar4, Ar5, and Ar6 are all aryl groups; and R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are all aryl groups, and R17, R18, R19, and R20 are all aryl or alkyl groups.
- the semiconductor material, wherein the aryl group includes Among them, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35 and R36 are all aryl or alkyl groups.
- the semiconductor material wherein the molecular structure of the semiconductor material is: wherein, Ar1 and Ar2 are both aromatic groups substituted with N-containing aromatic groups or electron-deficient groups.
- the semiconductor material, wherein the electron-deficient group includes a cyano group, a nitro group, and a halo group.
- the semiconductor material, wherein the N-containing aromatic group includes: Among them, M1, M2, M3, M4, M5, M6, M7, M8, M9, M10, M11, M12, M13, M14, M15, M16, M17, M18, and M19 are independently selected from cyano, nitro, and One of a radical, an aryl group or a nitrogen-containing heterocyclic ring.
- the semiconductor material wherein the molecular structural formula of the semiconductor material includes:
- a method for preparing a semiconductor material comprising the steps of:
- the first intermediate is mixed with diisobutylaluminum hydride, and the reaction produces a molecular structural formula:
- the second intermediate is
- the second intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added
- the third intermediate is mixed with the catalyst PdCl 2 (PPh 3 ) 2 , and the molecular structure of the reaction is:
- the fourth intermediate is:
- the fourth intermediate and the molecular structural formula are The acid chloride is mixed and the reaction produces a molecular structure of The fifth intermediate;
- the fifth intermediate is mixed with potassium hydroxide, a hydration well, and triethylene glycol, and a reduction reaction occurs under heating conditions to generate a molecular structure formula: A semiconductor material, wherein R is an alkyl group.
- a method for preparing a semiconductor material comprising the steps of:
- the first intermediate is mixed with diisobutylaluminum hydride, and the reaction produces a molecular structural formula:
- the second intermediate is
- the second intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added
- the third intermediate is mixed with a PdCl 2 (PPh 3 ) 2 catalyst, and the molecular structure of the reaction is:
- the fourth intermediate is:
- the fourth intermediate is mixed with liquid bromine, and the reaction generates a molecular structure formula:
- the fifth intermediate is mixed with liquid bromine, and the reaction generates a molecular structure formula:
- the fifth intermediate is mixed with arylboronic acid or aryltin and catalyzed by a PdCl 2 (PPh 3 ) 2 catalyst, and the molecular structure is obtained by the reaction:
- a method for preparing a semiconductor material comprising the steps of:
- the first intermediate is mixed with diisobutylaluminum hydride, and the reaction produces a molecular structural formula:
- the second intermediate is
- the second intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added
- the third intermediate is mixed with the catalyst PdCl 2 (PPh 3 ) 2 , and the molecular structure of the reaction is:
- the fourth intermediate is:
- the fourth intermediate is mixed with liquid bromine, and the reaction generates a molecular structure formula:
- the fifth intermediate is mixed with liquid bromine, and the reaction generates a molecular structure formula:
- the fifth intermediate is mixed with one of an N-containing boronic acid, an N-containing aryl tin, an electron-deficient group-substituted aromatic boronic acid or an electron-deficient group-substituted aromatic tin, and passed through PdCl 2 (PPh 3 ) 2 catalyst catalyzed coupling, the molecular structure formula obtained by the reaction is Of semiconductor materials, wherein Ar1 and Ar2 are both aromatic groups substituted with N-containing aromatic groups or electron-deficient groups.
- a method for preparing a semiconductor material comprising the steps of:
- the benzothiophene oxide is mixed with an aryl substituted phenol, and the molecular structure formula is First intermediate
- the first intermediate is mixed with diisobutylaluminum hydride, and the reaction produces a molecular structural formula:
- the second intermediate is
- the second intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added
- the third intermediate is mixed with a PdCl 2 (PPh 3 ) 2 catalyst, and the molecular structure of the reaction is: A semiconductor material, wherein Ar3 is an aryl group.
- a method for preparing a semiconductor material comprising the steps of:
- the first intermediate is mixed with diisobutylaluminum hydride, and the reaction produces a molecular structural formula:
- the second intermediate is
- the second intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added
- the third intermediate is mixed with a PdCl 2 (PPh 3 ) 2 catalyst, and the molecular structure of the reaction is: A semiconductor material, wherein Ar4 is an aryl group.
- a method for preparing a semiconductor material comprising the steps of:
- the first intermediate is mixed with diisobutylaluminum hydride, and the reaction produces a molecular structural formula:
- the second intermediate is
- the second intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added
- the third intermediate is mixed with the catalyst PdCl 2 (PPH 3 ) 2 to form a molecular structure of the reaction:
- the fourth intermediate is mixed with the catalyst PdCl 2 (PPH 3 ) 2 to form a molecular structure of the reaction:
- the fourth intermediate is mixed with the catalyst PdCl 2 (PPH 3 ) 2 to form a molecular structure of the reaction:
- the fourth intermediate is mixed with the catalyst PdCl 2 (PPH 3 ) 2 to form a molecular structure of the reaction:
- the fourth intermediate is mixed with liquid bromine, and the reaction generates a molecular structure formula:
- the fifth intermediate is mixed with liquid bromine, and the reaction generates a molecular structure formula:
- the fifth intermediate is mixed with a diarylamine, and Pd 2 (dba) 3 , HF 4 P (t-Bu) 3 and potassium tert-butoxide are added to carry out a catalytic reaction, and the general molecular structure is Amine derivatives, wherein R1, R2, R3 and R4 are all aryl groups;
- the fifth intermediate is mixed with an aryl borate containing arylamine, and Pd (PPh 3 ) 4 is added to perform a catalytic reaction to generate a molecular structure of the general formula: or An amine derivative, wherein the Ar1, Ar2, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 and R16 are all aryl groups;
- the fifth intermediate is mixed with an aryl-substituted carbazole, and Pd 2 (dba) 3 , HF 4 P (t-Bu) 3 and potassium tert-butoxide are added for a catalytic reaction to generate a general molecular structure.
- Pd 2 (dba) 3 , HF 4 P (t-Bu) 3 and potassium tert-butoxide are added for a catalytic reaction to generate a general molecular structure.
- Amine derivatives in which R17, R18, R19 and R20 are all aryl groups.
- An application of a semiconductor material wherein a semiconductor material is used for preparing an organic thin film transistor device and a light emitting device.
- the present invention combines a thiophene derivative with higher carrier mobility and a furan derivative with higher fluorescence performance, and designs a semiconductor material containing both a thiophene functional group and a furan functional group.
- the molecular structure is One of them, wherein Ar1 and Ar2 are all alkyl groups or aryl groups; Ar3, Ar4, Ar5, and Ar6 are all aryl groups; and R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are all aryl groups, and R17, R18, R19, and R20 are all aryl or alkyl groups.
- the semiconductor material provided by the present invention can effectively solve the problem that high carrier mobility and high fluorescence efficiency of the existing organic semiconductor materials are not compatible.
- the present invention provides a semiconductor material, a preparation method and application thereof.
- the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.
- the present invention provides a semiconductor material whose molecular structure is One of them, wherein Ar1 and Ar2 are all alkyl groups or aryl groups; Ar3, Ar4, Ar5, and Ar6 are all aryl groups; and R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are all aryl groups, and R17, R18, R19, and R20 are all aryl or alkyl groups.
- Furan rings have been widely used to construct ⁇ -conjugated molecules.
- Furan derivatives have the following advantages: (1) Substituting sulfur atoms with oxygen will reduce aromaticity on the one hand, and the molecule has more quinone structure characteristics, making ⁇ - The electrons are better delocalized; on the other hand, the oxidation potential can be lowered, causing the HOMO orbital level to increase, which is conducive to the injection and transport of holes.
- Thiophene contains a relatively heavy sulfur atom, which causes fluorescence quenching due to internal conversion of the orbital coupling caused by the heavy atom, while furan semiconductors do not have the problem of fluorescence quenching due to the orbital coupling, compared with thiophene Semiconductors have more excellent fluorescent properties, so they can be used to prepare organic semiconductor light-emitting devices, including OLEDs and organic light-emitting transistors (OLETs).
- Furan compounds have less aromaticity and smaller ⁇ - ⁇ interactions between molecules, so their solubility is relatively large.
- Furan is a biodegradable material, which can be prepared from biorenewable raw materials, which makes it more suitable for large-scale applications.
- a thiophene derivative has higher carrier mobility and a furan derivative has higher fluorescence performance.
- a semiconductor material containing both a thiophene functional group and a furan functional group is designed.
- the name of the semiconductor material is [ 1] benzothiophene [3,2-b] [1] benzofuran derivatives.
- the semiconductor material provided by the invention has both high carrier mobility and high fluorescence efficiency, and can be used as an active layer of an organic thin film transistor and a light emitting layer in a light emitting device.
- the semiconductor thin film is prepared by vacuum evaporation or spin coating, and further prepared. An organic thin film transistor or light emitting device with high carrier mobility and high fluorescence efficiency is produced.
- the semiconductor material provided by the present invention includes one-side substituted [1] benzothiophene [3,2-b] [1] benzofuran derivative and two-side substituted [1] benzothiophene [3,2- b] [1] benzofuran derivative.
- the molecular structure of the double-side substituted [1] benzothiophene [3,2-b] [1] benzofuran derivative includes Wherein Ar1 and Ar2 are both alkyl or aryl groups, the Ar1 and Ar2 may be the same group or different groups.
- Ar1 and Ar2 are preferably both N-containing aromatic groups or electron-deficient group-substituted aromatic groups.
- the N-containing aromatic groups or electron-deficient group-substituted aromatic groups are introduced due to the introduction of electron-deficient groups.
- the semiconductor material provided by the structural formula provided by the present invention can be used as organic light emitting
- the electronic functional layer of the diode device is made of the semiconductor material into a semiconductor thin film by a vacuum evaporation method or a spin coating method to further prepare an organic light emitting diode device having high electron mobility and high fluorescence efficiency.
- the electron-deficient group includes a cyano group, a nitro group, and a halo group.
- the N-containing aromatic group includes Among them, M1, M2, M3, M4, M5, M6, M7, M8, M9, M10, M11, M12, M13, M14, M15, M16, M17, M18, and M19 are independently selected from cyano, nitro, and alkane One of a radical, an aryl group or a nitrogen-containing heterocyclic ring.
- the molecular structure of the double-substituted [1] benzothiophene [3,2-b] [1] benzofuran derivative further includes: One of them, wherein Ar5 and Ar6 are both aryl groups, and the R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are all Aryl, said R17, R18, R19 and R20 are all aryl or alkyl.
- the aromatic amine group on the [1] benzothiophene [3,2-b] [1] benzofuran can further strengthen the [1] benzothiophene [3,2-b] [ 1]
- the hole mobility and luminous efficiency of benzofuran therefore, the amine derivatives based on [1] benzothiophene [3,2-b] [1] benzofuran provided by the present invention can be used as organic light emitting diodes
- the amine derivative is made into a semiconductor thin film by vacuum evaporation or spin coating, and an organic light emitting diode device with high hole mobility and high fluorescence efficiency is further prepared.
- the molecular structure of the unilaterally substituted [1] benzothiophene [3,2-b] [1] benzofuran derivative is:
- Ar3 and Ar4 are both aryl groups, and preferably, the aryl group is an alkyl-substituted aryl group.
- the aryl group is independently selected from the group consisting of One of them, but not limited to this.
- R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35 and R36 are all aryl or alkyl groups.
- the molecular structure formula of the semiconductor material provided by the present invention specifically includes:
- the present invention provides a molecular structure with the general formula:
- a method for preparing a semiconductor material including steps:
- the first intermediate is mixed with diisobutylaluminum hydride, and the reaction produces a molecular structural formula:
- the second intermediate is
- the second intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added
- the third intermediate is mixed with the catalyst PdCl 2 (PPh 3 ) 2 , and the molecular structure of the reaction is:
- the fourth intermediate is:
- the fourth intermediate and the molecular structural formula are The acid chloride is mixed and the reaction produces a molecular structure of The fifth intermediate;
- the fifth intermediate is mixed with potassium hydroxide, a hydration well, and triethylene glycol, and a reduction reaction occurs under heating conditions to generate a molecular structure formula: A semiconductor material, wherein R is an alkyl group.
- the present invention also provides a general molecular structure of A method for preparing a semiconductor material, including steps:
- the first intermediate is mixed with diisobutylaluminum hydride, and the reaction produces a molecular structural formula:
- the second intermediate is
- the second intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added
- the third intermediate is mixed with a PdCl 2 (PPh 3 ) 2 catalyst, and the molecular structure of the reaction is:
- the fourth intermediate is:
- the fourth intermediate is mixed with liquid bromine, and the reaction generates a molecular structure formula:
- the fifth intermediate is mixed with liquid bromine, and the reaction generates a molecular structure formula:
- the fifth intermediate is mixed with arylboronic acid or aryltin and catalyzed by a PdCl 2 (PPh 3 ) 2 catalyst, and the molecular structure is obtained by the reaction:
- the present invention also provides a general molecular structure of A method for preparing a semiconductor material, including steps:
- the benzothiophene oxide is mixed with an aryl substituted phenol, and the molecular structure formula is First intermediate
- the first intermediate is mixed with diisobutylaluminum hydride, and the reaction produces a molecular structural formula:
- the second intermediate is
- the second intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added
- the third intermediate is mixed with a PdCl 2 (PPh 3 ) 2 catalyst, and the molecular structure of the reaction is: A semiconductor material, wherein Ar3 is an aryl group.
- the present invention also provides a general molecular structure of A method for preparing a semiconductor material, including steps:
- the first intermediate is mixed with diisobutylaluminum hydride, and the reaction produces a molecular structural formula:
- the second intermediate is
- the second intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added
- the third intermediate is mixed with a PdCl 2 (PPh 3 ) 2 catalyst, and the molecular structure of the reaction is: A semiconductor material, wherein Ar4 is an aryl group.
- the present invention also provides a method for preparing a semiconductor material, which includes the following steps:
- the first intermediate is mixed with diisobutylaluminum hydride, and the reaction produces a molecular structural formula:
- the second intermediate is
- the second intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates a molecular structure formula:
- the third intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added
- the third intermediate is mixed with the catalyst PdCl 2 (PPH 3 ) 2 to form a molecular structure of the reaction:
- the fourth intermediate is mixed with the catalyst PdCl 2 (PPH 3 ) 2 to form a molecular structure of the reaction:
- the fourth intermediate is mixed with the catalyst PdCl 2 (PPH 3 ) 2 to form a molecular structure of the reaction:
- the fourth intermediate is mixed with the catalyst PdCl 2 (PPH 3 ) 2 to form a molecular structure of the reaction:
- the fourth intermediate is mixed with liquid bromine, and the reaction generates a molecular structure formula:
- the fifth intermediate is mixed with liquid bromine, and the reaction generates a molecular structure formula:
- the fifth intermediate is mixed with a diarylamine, and Pd 2 (dba) 3 , HF 4 P (t-Bu) 3 and potassium tert-butoxide are added to carry out a catalytic reaction, and the general molecular structure is Amine derivatives, wherein R1, R2, R3 and R4 are all aryl groups;
- the fifth intermediate is mixed with an aryl borate containing arylamine, and Pd (PPh 3 ) 4 is added to perform a catalytic reaction to generate a molecular structure of the general formula: or An amine derivative, wherein the Ar1, Ar2, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 and R16 are all aryl groups;
- the fifth intermediate is mixed with an aryl-substituted carbazole, and Pd 2 (dba) 3 , HF 4 P (t-Bu) 3 and potassium tert-butoxide are added for a catalytic reaction to generate a general molecular structure.
- Pd 2 (dba) 3 , HF 4 P (t-Bu) 3 and potassium tert-butoxide are added for a catalytic reaction to generate a general molecular structure.
- Amine derivatives in which R17, R18, R19 and R20 are all aryl groups.
- the present invention also provides an application of a semiconductor material, wherein the semiconductor material prepared by the present invention is used to prepare an organic thin film transistor or a light emitting device.
- the semiconductor material may be made into a semiconductor thin film by a vacuum evaporation method or a spin coating method as an active layer of an organic thin film transistor or a light emitting layer in a light emitting device.
- the silicon wafer substrate is ultrasonically cleaned with purified water, acetone, and isopropanol, and dried with nitrogen, and then irradiated with UV. Obtain clean silicon wafers. Then immerse it in a 0.1mol / L OTS toluene solution at 65 ° C for 20min; then wash the surface residue with toluene and blow dry with nitrogen to obtain an OTS-modified silicon wafer for use;
- a semiconductor mask is used to mask the silicon wafer, a suitable substrate temperature is selected, and a thin film is prepared under high vacuum. The vapor deposition rate of the semiconductor material is controlled. After the thin film is prepared, the electrode is vapor-deposited with an electrode mask, and Au is used as the electrode material.
- a semiconductor analyzer was used to test the performance of the prepared organic thin film transistor device. Test the Id-Vg and Id-Vd curves, using the following formula
- I d (W / 2L) ⁇ TFT C i (V g -V th ) 2 performs calculation of mobility.
- the specific preparation steps include:
- the specific preparation steps include:
- the specific preparation steps include:
- the specific preparation steps include:
- the specific preparation steps include:
- the specific preparation steps include:
- the specific preparation steps include:
- the preparation method includes the following steps:
- reaction mixture was poured into 100 mL of methanol, filtered, and the solid was washed with hydrochloric acid and water. High vacuum sublimation was used to obtain 2,7-bis (3,5-diphenylamino) phenyl-1-yl [1] benzothiophene [3,2-b] [1] benzofuran.
- Its preparation method includes steps:
- the specific preparation steps include:
- the specific preparation steps include:
- the specific preparation steps include:
- the specific preparation steps include:
- the present invention combines a thiophene derivative with a higher carrier mobility and a furan derivative with higher fluorescence performance.
- a semiconductor material containing both a thiophene functional group and a furan functional group is designed.
- the molecular structure of the material is the molecular structure of the semiconductor material.
- Ar1 and Ar2 are all alkyl groups or aryl groups
- Ar3, Ar4, Ar5, and Ar6 are all aryl groups
- R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are all aryl groups
- R17, R18, R19, and R20 are all aryl or alkyl groups.
- the semiconductor material provided by the present invention can be used as an active layer of an organic thin film transistor and a light emitting layer in a light emitting device.
- the semiconductor thin film can be made by vacuum evaporation or spin coating to further prepare an organic thin film transistor or light emitting device. The problem of high carrier mobility and high fluorescence efficiency of semiconductor materials is not achieved.
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Abstract
一种半导体材料及其制备方法与应用,其中,所述半导体材料的分子结构通式为aa-gg中的一种,其中,所述Ar1和Ar2均为烷基或芳基;所述Ar3、Ar4、Ar5和Ar6均为芳基,所述R1,R2,R3,R4,R5,R6,R7,R8,R9,R10,R11,R12,R13,R14,R15和R16均为芳基,所述R17,R18,R19和R20均为芳基或烷基。结合噻吩衍生物具有较高的载流子迁移率以及呋喃衍生物具有较高荧光性能的特点,设计了一种同时含有噻吩官能团和呋喃官能团的半导体材料,有效解决了现有有机半导体材料不能同时具有高载流子迁移率与高荧光效率的问题。
Description
本发明涉及有机半导体材料领域,尤其涉及一种半导体材料及其制备方法与应用。
有机薄膜晶体管(OTFTs)具有低生产成本和可大面积制造等优势,在柔性器件、智能卡及电子纸等领域将会有广泛的应用。因此,应用于OTFT的有机小分子半导体材料的研究引起了科研工作者的关注。然而,具有高迁移率、空气稳定性及可溶液加工等特征的有机半导体材料仍是这一领域的挑战。[1]苯并噻吩[3,2-b][1]苯并噻吩(BTBT)作为一个经典的半导体母核,因其优异的器件性能而引起了科研工作者广泛的兴趣。
呋喃衍生物因其独特的性质而在发光领域具有潜在的应用前景,呋喃是最简单的杂环芳香化合物之一,与噻吩具有十分相似的化学结构和电子性质。然而,噻吩含有相对重的硫原子,由于重原子产生旋轨偶合作用发生内转换,所以导致荧光淬灭。而呋喃半导体则不存在旋轨偶合作用导致荧光淬灭的问题,相比于噻吩半导体,具有更加出色的荧光性质,因此可以用来制备有机半导体发光器件。
噻吩衍生物具有较强的载流子迁移率特点,而呋喃衍生物具有较强的荧光性能,两者因其各自的结构不同而具有不同的特性。然而,现有技术缺少一种同时具有高载流子迁移率以及高荧光性能的半导体材料。
因此,现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足,本发明的目的在于提供一种半导体材料及其制备方法与应用,旨在解决现有有机半导体材料的高载流子迁移率与高荧光效率不可兼得的问题。
本发明的技术方案如下:
一种半导体材料,其中,所述半导体材料的分子结构通式为
中的一种,其中,所述Ar1和Ar2均为烷基或芳基;所述Ar3、Ar4、Ar5和Ar6均为 芳基,所述R1,R2,R3,R4,R5,R6,R7,R8,R9,R10,R11,R12,R13,R14,R15和R16均为芳基,所述R17,R18,R19和R20均为芳基或烷基。
所述的半导体材料,其中,所述缺电子基团包括氰基、硝基和卤基。
所述的半导体材料,其中,所述含N的芳香基团包括:
其中,M1,M2,M3,M4,M5,M6,M7,M8,M9,M10,M11,M12,M13,M14,M15、M16、M17,M18和M19独立地选自氰基、硝基、烷基、芳基或含氮杂环中的一种。
一种半导体材料的制备方法,其中,包括步骤:
将苯并噻吩与N-溴代丁二酰亚胺混合,反应生成3-溴苯并噻吩;
将所述3-溴苯并噻吩与双氧水混合,反应生成苯并噻吩氧化物;
一种半导体材料的制备方法,其中,包括步骤:
将苯并噻吩与N-溴代丁二酰亚胺混合,反应生成3-溴苯并噻吩;
将所述3-溴苯并噻吩与双氧水混合,反应生成苯并噻吩氧化物;
一种半导体材料的制备方法,其中,包括步骤:
将苯并噻吩与N-溴代丁二酰亚胺混合,反应生成3-溴苯并噻吩;
将所述3-溴苯并噻吩与双氧水混合,反应生成苯并噻吩氧化物;
将所述第五中间体与含N芳基硼酸、含N芳基锡、缺电子基团取代的芳香基硼酸或缺电子基团取代的芳香基锡中的一种混合并通过PdCl
2(PPh
3)
2催化剂催化偶联,反应得到分子结构式为
的半导体材料,其中,Ar1和Ar2均为含N的芳香基团或缺电子基团取代的芳香基团。
一种半导体材料的制备方法,其中,包括步骤:
将苯并噻吩与N-溴代丁二酰亚胺混合,反应生成3-溴苯并噻吩;
将所述3-溴苯并噻吩与双氧水混合,反应生成苯并噻吩氧化物;
一种半导体材料的制备方法,其中,包括步骤:
将芳基取代的苯并噻吩与N-溴代丁二酰亚胺混合,反应生成3-溴芳基取代苯并噻吩;
将所述3-溴芳基取代苯并噻吩与双氧水混合,反应生成芳基取代苯并噻吩氧化物;
一种半导体材料的制备方法,其中,包括步骤:
将苯并噻吩与N-溴代丁二酰亚胺混合,反应生成3-溴苯并噻吩;
将所述3-溴苯并噻吩与双氧水混合,反应生成苯并噻吩氧化物;
或者,将所述第五中间体与含芳胺的芳基硼酸酯混合,并加入Pd(PPh
3)
4进行催化反应,生成分子结构通式为
或
的胺类衍生物,其中,所述Ar1,Ar2,R5,R6,R7,R8,R9,R10,R11,R12,R13,R14,R15和R16均为芳基;
或者,将所述第五中间体与芳基取代的咔唑混合,并加入Pd
2(dba)
3,HF
4P(t-Bu)
3和叔丁醇钾进行催化反应,生成分子结构通式为
的胺类衍生物,其中,R17,R18,R19和R20均为芳基。
一种半导体材料的应用,其中,将一种半导体材料应用于制备有机薄膜晶体管器件和发光器件。
有益效果:本发明结合噻吩衍生物具有较高的载流子迁移率以及呋喃衍生物具有较高荧光性能的特点,设计了一种同时含有噻吩官能团和呋喃官能团的半导体材料,所述半导体材料的分子结构为
中的一种,其中,所述Ar1和Ar2均为烷基或芳基;所述Ar3、Ar4、Ar5和Ar6均为芳基,所述R1,R2,R3,R4,R5,R6,R7,R8,R9,R10,R11,R12,R13,R14,R15和R16均为芳基,所述R17,R18,R19和R20均为芳基或烷基。本发明提供的半导体材料能有效解决现有有机半导体材料高载流子迁移率与高荧光效率不兼得的问题。
本发明提供一种半导体材料及其制备方法与应用,为使本发明的目的、技术方案及效果更加清楚、明确,以下对本发明进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
为解决现有半导体材料高载流子迁移率以及高荧光效率不可兼得的问题,本发明提供了一种半导体材料,其分子结构通式为
中的一种,其中,所述Ar1和Ar2均为烷基或芳基;所述Ar3、Ar4、Ar5和Ar6均为芳基,所述R1,R2,R3,R4,R5,R6,R7,R8,R9,R10,R11,R12,R13,R14,R15和R16均为芳基,所述R17,R18,R19和R20均为芳基或烷基。
呋喃环已经广泛被用于构建π-共轭分子,呋喃衍生物具有以下的优势:(1)用氧取代硫原子一方面会降低芳香性,分子具有更多的醌式结构特征,使得π-电子更好地离域;另一方面可以降低氧化电位,使得HOMO轨道能级升高,因此有利于空穴的注入和传输。(2)噻吩含有相对重的硫原子,由于重原子产生旋轨偶合作用发生内转换,所以导致荧光淬灭,而呋喃半导体则不存在旋轨偶合作用导致荧光淬灭的问题,相比于噻吩半导体,具有更加出色的荧光性质,因此可以用来制备有机半导体发光器件,包括OLEDs和有机发光晶体管(OLETs)。(3)呋喃化合物具有较小的芳香性,分子间π-π相互作用较小,所以溶解度相对较大。(4)呋喃是生物可降解材料,可从生物可再生原料来制备,这使得它更适合大规模应用。
本发明结合噻吩衍生物具有较高的载流子迁移率以及呋喃衍生物具有较高荧光性能的特点,设计了一种同时含有噻吩官能团和呋喃官能团的半导体材料,所述半导体材料的名称为[1]苯并噻吩[3,2-b][1]苯并呋喃衍生物。本发明提供的半导体材料同时具有高载流子迁移率与高荧光效率,可作为有机薄膜晶体管的有源层及发光器件中的发光层,通过真空蒸镀或旋涂法制成半导体薄膜,进一步制备出具有高载流子迁移率和高荧光效率的有机薄膜晶体管或发光器件。
具体来讲,本发明提供的半导体材料包括单侧取代[1]苯并噻吩[3,2-b][1]苯并呋喃衍生物和双侧取代[1]苯并噻吩[3,2-b][1]苯并呋喃衍生物。所述双侧取代[1]苯并噻吩[3,2-b][1]苯并呋喃衍生物的分子结构通式包括
其中Ar1和Ar2均为烷基或芳基,所述Ar1和Ar2可以为相同的基团或不同的基团。
进一步地,当所述半导体材料的分子结构通式为
时,所述Ar1和Ar2优选均为含N的芳香基团或缺电子基团取代的芳香基团,所述含N的芳香基团或缺电子基团取代的芳香基团由于引入了缺电子官能团,从而能够促进[1]苯并噻吩[3,2-b][1]苯并呋喃具有更强的电子迁移率以及发光效率,因此,本发明提供的该结构式的半导体材料能够作为有机发光二极管器件的电子功能层,通过真空蒸镀或旋涂法将所述半导体材料制成半导体薄膜,进一步制备出具有高电子迁移率和高荧光效率的有机发光二极管器件。
优选地,所述缺电子基团包括氰基、硝基和卤基。
更优选地,所述半导体材料中,含N的芳香基团包括
其中,M1,M2,M3,M4,M5,M6,M7,M8,M9,M10,M11,M12,M13,M14,M15、M16、M17,M18和M19独立地选自氰基、硝基、烷基、芳基或含氮杂环中的一种。
进一步地,所述双侧取代[1]苯并噻吩[3,2-b][1]苯并呋喃衍生物的分子结构通式还包括:
中的一种,其中,Ar5和Ar6均为芳基,所述R1,R2,R3,R4,R5,R6,R7,R8,R9,R10,R11,R12,R13,R14,R15和R16均为芳基,所述R17,R18,R19和R20均为芳基或烷基。
在本实施方式中,所述[1]苯并噻吩[3,2-b][1]苯并呋喃上的芳香胺基团能进一步加强[1]苯并噻吩[3,2-b][1]苯并呋喃的空穴迁移率以及发光效率,因此,本发明提供的基于[1]苯并噻吩[3,2-b][1]苯并呋喃的胺类衍生物能够作为有机发光二极管器件的空穴功能层,通过真空蒸镀或旋涂法将所述胺类衍生物制成半导体薄膜,进一步制备出具有高空穴迁移率和高荧光效率的有机发光二极管器件。
优选地,在本发明中,所述芳基独立地选自芳基包括
中的一种,但不限于此。其中,R21,R22,R23,R24,R25,R26,R27,R28,R29,R30,R31,R32,R33,R34,R35和R36均为芳基或烷基。
作为举例,本发明提供的半导体材料的分子结构式具体包括:
将苯并噻吩与N-溴代丁二酰亚胺混合,反应生成3-溴苯并噻吩;
将所述3-溴苯并噻吩与双氧水混合,反应生成苯并噻吩氧化物;
将苯并噻吩与N-溴代丁二酰亚胺混合,反应生成3-溴苯并噻吩;
将所述3-溴苯并噻吩与双氧水混合,反应生成苯并噻吩氧化物;
将苯并噻吩与N-溴代丁二酰亚胺混合,反应生成3-溴苯并噻吩;
将所述3-溴苯并噻吩与双氧水混合,反应生成苯并噻吩氧化物;
将芳基取代的苯并噻吩与N-溴代丁二酰亚胺混合,反应生成3-溴芳基取代苯并噻吩;
将所述3-溴芳基取代苯并噻吩与双氧水混合,反应生成芳基取代苯并噻吩氧化物;
作为其中一实施方式,本发明还提供一种半导体材料的制备方法,其中,包括步骤:
将苯并噻吩与N-溴代丁二酰亚胺混合,反应生成3-溴苯并噻吩;
将所述3-溴苯并噻吩与双氧水混合,反应生成苯并噻吩氧化物;
或者,将所述第五中间体与含芳胺的芳基硼酸酯混合,并加入Pd(PPh
3)
4进行催化反应,生成分子结构通式为
或
的胺类衍生物,其中,所述Ar1,Ar2,R5,R6,R7,R8,R9,R10,R11,R12,R13,R14,R15和R16均为芳基;
或者,将所述第五中间体与芳基取代的咔唑混合,并加入Pd
2(dba)
3,HF
4P(t-Bu)
3和叔丁醇钾进行催化反应,生成分子结构通式为
的胺类衍生物,其中,R17,R18,R19和R20均为芳基。
进一步地,本发明还提供一种半导体材料的应用,其中,将本发明制备的半导体材料用于制备有机薄膜晶体管或发光器件。具体地,可通过真空蒸镀或旋涂法将所述半导体材料制成半导体薄膜,作为有机薄膜晶体管的有源层或发光器件中的发光层。
作为其中一实施方式,以制备有机薄膜晶体管为例,首先分别采用纯净水,丙酮和异丙醇对硅片衬底进行超声清洗,氮气吹干之后,用UV辐射。获得洁净的硅片。然后在0.1mol/L OTS的甲苯溶液中,65℃下浸泡20min;然后用甲苯清洗除去表面的残渣,氮气吹干,获得OTS修饰的硅片,待用;
用半导体掩膜版对所述硅片进行掩膜,选取合适的衬底温度,在高真空下进行薄膜的制备。控制半导体材料蒸镀速率,薄膜制备还之后再用电极掩膜版进行电极的蒸镀,电极材料使用Au。用半导体分析仪对制备的有机薄膜晶体管器件性能进行测试。测试Id-Vg和Id-Vd曲线,利用公式下面公式
I
d=(W/2L)μ
TFTC
i(V
g-V
th)
2进行迁移率的计算。
下面通过具体实施例对本发明一种半导体材料的制备方法做进一步的解释说明:
实施例1
2,7-二戊基[1]苯并噻吩[3,2-b][1]苯并呋喃(C5-BTBF)的合成流程为:
将20g(150mmol)苯并噻吩溶解在150mL氯仿中,0℃下分批加入33.2g(186mmol)N-溴代丁二酰亚胺,加毕,在0℃下反应4h之后升至室温继续搅拌24h。加入60mL氯仿,分别用硫代硫酸钠水溶液,饱和碳酸钠和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析得3-溴苯并噻吩。
将10g(46mmol)3-溴苯并噻吩溶解在80mL二氯甲烷和80mL三氟乙酸溶液中,在室温下搅拌5分钟之后,加入4mL,35%的双氧水,搅拌至原料反应完全,用饱和碳酸钠溶液中和至中性,分液,有机相用饱和碳酸氢钠和水洗涤,无水硫酸镁干燥,浓缩,柱层析的化合物3-溴苯并噻吩-1-氧。
将2.3g(10mmol)3-溴苯并噻吩-1-氧,3.4g(20mmol)苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析得到3-苯氧基苯并噻吩-1-氧。
将2.54g(8mmol)3-苯氧基苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中性,无水硫酸镁干燥,浓缩,柱层析得到3-苯氧基苯并噻吩。
将1.82g.6(6mmol)3-苯氧基苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温,加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-苯氧基苯并噻吩。
将1.51g(4mmol)2-溴-3-苯氧基苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mLN,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸,用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤,无水硫酸镁干燥,浓缩,柱层析得到目标化合物[1]苯并噻吩[3,2-b][1]苯并呋喃。
将2.24g(10mmol)[1]苯并噻吩[3,2-b][1]苯并呋喃溶解在200mL干燥二氯甲烷中,冷冻至-20℃,加入5.3g(40mmol)无水三氯化铝,加毕,冷却至-70℃,加入1.44g(12mmol)戊酰氯,升至室温继续搅拌,TLC检测至反应完全,加入少量水;依次用NaHCO3和水洗涤,干燥,柱层析得到2,7-二戊酰基[1]苯并噻吩[3,2-b][1]苯并呋喃;
将1.96g(5mmol)2,7-二戊酰基[1]苯并噻吩[3,2-b][1]苯并呋喃,1.4g(25mmol)氢氧化钾和100mmol水合肼与50mL三缩乙二醇在100℃下加热1h之后,在210℃继续加热5h,冷却至室温,过滤,固体用水和甲醇洗涤,柱层析纯化得2,7-二戊基[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例2
2,7-二辛基[1]苯并噻吩[3,2-b][1]苯并呋喃(C8-BTBF)的合成流程为:
采用与实施例1相同的步骤制备[1]苯并噻吩[3,2-b][1]苯并呋喃;
将2.24g(10mmol)[1]苯并噻吩[3,2-b][1]苯并呋喃溶解在200mL干燥二氯甲烷中,冷冻至-20℃,加入5.3g(40mmol)无水三氯化铝,加毕,冷却至-70℃,加入1.94g(12mmol)辛酰氯,升至室温继续搅拌,TLC检测至反应完全,加入少量水。依次用NaHCO
3和水洗涤,干燥,柱层析得到2,7-二戊酰基[1]苯并噻吩[3,2-b][1]苯并呋喃;
将2.38g(5mmol)2,7-二辛酰基[1]苯并噻吩[3,2-b][1]苯并呋喃,1.4g(25mmol)氢氧化钾和100mmol水合肼与50mL三缩乙二醇在100℃下加热1h之后,在210℃继续加热5h,冷却至室温,过滤,固体用水和甲醇洗涤,柱层析纯化得2,7-二辛基[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例3
采用与实施例1相同的步骤制备[1]苯并噻吩[3,2-b][1]苯并呋喃;
将2.24g(10mmol)[1]苯并噻吩[3,2-b][1]苯并呋喃溶解在200mL干燥二氯甲烷中,冷冻至-20℃,加入5.3g(40mmol)无水三氯化铝,加毕,冷却至-70℃,加入2.62g(12mmol)十一酰氯,升至室温继续搅拌,TLC检测至反应完全,加入少量水。依次用NaHCO
3和水洗涤。干燥,柱层析得到2,7-二戊酰基[1]苯并噻吩[3,2-b][1]苯并呋喃。
将2.94g(5mmol)2,7-二(十一酰基)[1]苯并噻吩[3,2-b][1]苯并呋喃,1.4g(25mmol)氢氧化钾和100mmol水合肼与50mL三缩乙二醇在100℃下加热1h之后,在210℃继续加热5h,冷却至室温,过滤,固体用水和甲醇洗涤,柱层析纯化得2,7-二(十一烷基)[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例4
采用与实施例1相同的步骤制备[1]苯并噻吩[3,2-b][1]苯并呋喃;
将2.24g(10mmol)[1]苯并噻吩[3,2-b][1]苯并呋喃溶解在200mL干燥二氯甲烷中,冷冻至-20℃,加入5.3g(40mmol)无水三氯化铝,加毕,冷却至-70℃,加入2.78g(12mmol)十三酰氯,升至室温继续搅拌,TLC检测至反应完全,加入少量水。依次用NaHCO
3和水洗涤。干燥,柱层析得到2,7-二戊酰基[1]苯并噻吩[3,2-b][1]苯并呋喃。
将3.08g(5mmol)2,7-二(十三酰基)[1]苯并噻吩[3,2-b][1]苯并呋喃,1.4g(25mmol)氢氧化钾和100mmol水合肼与50mL三缩乙二醇在100℃下加热1h之后,在210℃继续加热5h,冷却至室温,过滤,固体用水和甲醇洗涤,柱层析纯化得2,7-二(十三烷基)[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例5
2,7-二苯基[1]苯并噻吩[3,2-b][1]苯并呋喃的合成流程为:
采用与实施例1相同的步骤制备[1]苯并噻吩[3,2-b][1]苯并呋喃;
将4.48g,20mmol[1]苯并噻吩[3,2-b][1]苯并呋喃溶解在0℃下每100mL含9.6g,60mmol液溴的氯仿溶液,继续滴加液溴的氯仿溶液,至原料反应完全,加入饱和的硫代硫酸钠水溶液还原过量的液溴。有机相用饱和碳酸氢钠水溶液、水洗涤之后干燥,用石油醚作为洗脱剂柱层析得到得2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃。
将1.9g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃和1.83g(15mmol,3当量)苯硼酸溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二苯基[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例6
2,7-二萘基[1]苯并噻吩[3,2-b][1]苯并呋喃(DNa-BTBF)的合成流程为
采用与实施例1相同的步骤制备[1]苯并噻吩[3,2-b][1]苯并呋喃;
将4.48g,20mmol[1]苯并噻吩[3,2-b][1]苯并呋喃溶解在0℃下100mL含9.6g,60mmol液溴的氯仿溶液,继续滴加液溴的氯仿溶液,至原料反应完全,加入饱和的硫代硫酸钠水溶液还原过量的液溴。有机相用饱和碳酸氢钠水溶液、水洗涤之后干燥,用石油醚作为洗脱剂柱层析得到得2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃;
将1.9g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃和2.58g(15mmol,3当量)2-萘硼酸溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二萘基[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例7
2,7-二(4-丁基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(D-C4-Ph-BTBF)的合成流程为:
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃;
将1.9g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃和2.67g(15mmol,3当量)4-丁基苯基溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二萘基[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例8
2,7-二(4-戊基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(D-C5-Ph-BTBF)的合成流程为:
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃;
将1.9g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃和2.88g(15mmol,3当量)4-戊基苯基硼酸溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二(4-戊基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例9
2,7-二(4-庚基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(D-C7-Ph-BTBF)的合成流程为:
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃;
将1.9g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃和3.30g(15mmol,3当量)4-庚基苯基硼酸溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二(4-庚基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例10
2,7-二(4-辛基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(D-C8-Ph-BTBF)的合成流程为:
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃;
将1.9g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃和3.48g(15mmol,3当量)4-辛基苯基硼酸溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反 应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二(4-辛基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例11
2,7-二(4-癸基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(D-C10-Ph-BTBF)的合成流程为:
其具体制备步骤包括:
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃;
将1.9g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃和3.69g(15mmol,3当量)4-癸基苯基硼酸溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二(4-癸基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例12
2,7-二(4-十二烷基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(D-C12-Ph-BTBF)的合成流程为:
其具体制备步骤包括:
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃;
将1.9g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃和4.35g(15mmol,3当量)4-十二烷基苯基硼酸溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二(4-十二烷基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例13
2,7-二(4-十三烷基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(D-C13-Ph-BTBF)的合成流程为:
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃;
将1.9g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃和4.53g(15mmol,3当量)4-十三烷基苯基硼酸溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二(4-十三烷基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例14
7-苯基[1]苯并噻吩[3,2-b][1]苯并呋喃(BTBF-Ph)的合成流程为:
将20g(150mmol)苯并噻吩溶解在150mL氯仿中,0℃下分批加入33.2g(186mmol)N-溴代丁二酰亚胺,加毕,在0℃下反应4h之后升至室温继续搅拌24h。加入60mL氯仿,分别用硫代硫酸钠水溶液,饱和碳酸钠和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析得3-溴苯并噻吩。
将10g(46mmol)3-溴苯并噻吩溶解在80mL二氯甲烷和80mL三氟乙酸溶液中,在室温下搅拌5分钟之后,加入4mL,35%的双氧水,搅拌至原料反应完全,用饱和碳酸钠溶液中和至中性,分液,有机相用饱和碳酸氢钠和水洗涤,无水硫酸镁干燥,浓缩,柱层析的化合物3-溴苯并噻吩-1-氧。
将2.3g(10mmol)3-溴苯并噻吩-1-氧,3.4g(20mmol)3-苯基苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析的3-苯氧基苯并噻吩-1-氧。
将2.54g(8mmol)3-苯氧基苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中性,无水硫酸镁干燥,浓缩,柱层析的3-苯氧基苯并噻吩。
将1.82g.6(6mmol)3-苯氧基苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温,加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-苯氧基苯并噻吩。
将1.51g(4mmol)2-溴-3-苯氧基苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mLN,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸,用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤,无水硫酸镁干燥,浓缩,柱层析的目标化合物7-苯基[1]苯并噻吩[3,2-b][1]苯并呋喃(BTBF-Ph)。
实施例15
将2.3g(10mmol)3-溴苯并噻吩-1-氧,4.4g(20mmol)3-萘基苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析的3-萘氧基苯并噻吩-1-氧。
将2.94g(8mmol)3-萘氧基苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中性,无水硫酸镁干燥,浓缩,柱层析的3-萘氧基苯并噻吩。
将2.11g.6(6mmol)3-萘氧基苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温,加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-萘氧基苯并噻吩。
将1.72g(4mmol)2-溴-3-萘氧基苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mLN,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸,用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤,无水硫酸镁干燥,浓缩,柱层析的目标化合物7-萘基[1]苯并噻吩[3,2-b][1]苯并呋喃(BTBF-Ph)。
实施例16
7-(4-辛基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(BTBF-Ph-C8)的合成流程为:
将2.3g(10mmol)3-溴苯并噻吩-1-氧,5.64g(20mmol)3-(4-辛基苯基)苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析的3-(4-辛基苯氧基)苯并噻吩-1-氧。
将3.44g(8mmol)3-(4-辛基苯氧基)苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中性,无水硫酸镁干燥,浓缩,柱层析的3-(4-辛基苯氧基)苯并噻吩。
将2.48g(6mmol)3-(4-辛基苯氧基)苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温,加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-(4-辛基苯氧基)苯并噻吩。
将1.97g(4mmol)2-溴-3-(4-辛基苯氧基)苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mLN,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸,用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤,无水硫酸镁干燥,浓缩,柱层析的目标化合物7-(4-辛基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(BTBF-Ph-C8)。
实施例17
7-(4-癸基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(BTBF-Ph-C10)的合成流程为:
将2.3g(10mmol)3-溴苯并噻吩-1-氧,6.2g(20mmol)3-(4-癸基苯基)苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析的3-(4-癸基苯氧基)苯并噻吩-1-氧。
将3.66g(8mmol)3-(4-癸基苯氧基)苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中心,无水硫酸镁干燥,浓缩,柱层析的3-(4-癸基苯氧基)苯并噻吩。
将2.65g(6mmol)3-(4-癸基苯氧基)苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温,加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-(4-癸基苯氧基)苯并噻吩。
将2.08g(4mmol)2-溴-3-(4-癸基苯氧基)苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mLN,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸,用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤,无水硫酸镁干燥,浓缩,柱层析的目标化合物7-(4-癸基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(BTBF-Ph-C10)。
实施例18
7-(4-十二烷基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(BTBF-Ph-C12)的合成流程为:
将2.3g(10mmol)3-溴苯并噻吩-1-氧,6.76g(20mmol)3-(4-十二烷基苯基)苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析的3-(4-十二烷基苯氧基)苯并噻吩-1-氧。
将3.88g(8mmol)3-(4-十二烷基苯氧基)苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中心,无水硫酸镁干燥,浓缩,柱层析的3-(4-十二烷基苯氧基)苯并噻吩。
将2.82g(6mmol)3-(4-十二烷基苯氧基)苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温,加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-(4-十二烷基苯氧基)苯并噻吩。
将2.19g(4mmol)2-溴-3-(4-十二烷基苯氧基)苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mLN,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸,用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤,无水硫酸镁干燥,浓缩,柱层析的目标化合物7-(4-十二烷基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(BTBF-Ph-C12)。
实施例19
7-(4-十三烷基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(BTBF-Ph-C13)的合成流程为:
将2.3g(10mmol)3-溴苯并噻吩-1-氧,7.04g(20mmol)3-(4-十三烷基苯基)苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析的3-(4-十三烷基苯氧基)苯并噻吩-1-氧。
将4.0g(8mmol)3-(4-十三烷基苯氧基)苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中性,无水硫酸镁干燥,浓缩,柱层析的3-(4-十三烷基苯氧基)苯并噻吩。
将2.9g(6mmol)3-(4-十三烷基苯氧基)苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温,加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-(4-十三烷基苯氧基)苯并噻吩。
将2.25g(4mmol)2-溴-3-(4-十三烷基苯氧基)苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mLN,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸,用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤,无水硫酸镁干燥,浓缩,柱层析的目标化合物7-(4-十三烷基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(BTBF-Ph-C13)。
实施例20
2-苯基[1]苯并噻吩[3,2-b][1]苯并呋喃(Ph-BTBF)的合成流程为:
将4.2g(20mmol)6-苯基苯并噻吩溶解在30mL氯仿中,0℃下分批加入4.45g(25mmol)N-溴代丁二酰亚胺,加毕,在0℃下反应4h之后升至室温继续搅拌反应至原料消失。分别用硫代硫酸钠水溶液,饱和碳酸钠和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析得3-溴-6-苯基苯并噻吩。
将4.32g(15mmol)3-溴苯并噻吩溶解在30mL二氯甲烷和30mL三氟乙酸溶液中,在室温下搅拌5分钟之后,加入1.0mL,35%的双氧水,搅拌至原料反应完全,用饱和碳酸钠溶液中和至中性,分液,有机相用饱和碳酸氢钠和水洗涤,无水硫酸镁干燥,浓缩,柱层析的化合物3-溴-6-苯基苯并噻吩-1-氧。
将2.87g(10mmol)3-溴-6-苯基苯并噻吩-1-氧,1.88g(20mmol)苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-苯基苯并噻吩-1-氧。
将2.54g(8mmol)3-苯氧基-6-苯基苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中心,无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-苯基苯并噻吩。
将1.81g(6mmol)3-苯氧基-6-苯基苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温,加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-苯氧基-6-苯基苯并噻吩。
将1.52g(4mmol)2-溴-3-苯氧基-6-苯基苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mLN,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸,用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤,无水硫酸镁干燥,浓缩,柱层析的目标化合物2-苯基[1]苯并噻吩[3,2-b][1]苯并呋喃(Ph-BTBF)。
实施例21
2-萘基[1]苯并噻吩[3,2-b][1]苯并呋喃(Na-BTBF)的合成流程为:
将5.2g(20mmol)6-萘基苯并噻吩溶解在30mL氯仿中,0℃下分批加入4.45g(25mmol)N-溴代丁二酰亚胺,加毕,在0℃下反应4h之后升至室温继续搅拌反应至原料消失。分别用硫代硫酸钠水溶液,饱和碳酸钠和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析得3-溴-6-萘基苯并噻吩。
将5.05g(15mmol)3-溴-6-萘基苯并噻吩溶解在30mL二氯甲烷和30mL三氟乙酸溶液中,在室温下搅拌5分钟之后,加入1.0mL,35%的双氧水,搅拌至原料反应完全,用饱和碳酸钠溶液中和至中性,分液,有机相用饱和碳酸氢钠和水洗涤,无水硫酸镁干燥,浓缩,柱层析的化合物3-溴-6-萘基苯并噻吩-1-氧。
将3.53g(10mmol)3-溴-6-萘基苯并噻吩-1-氧,1.88g(20mmol)苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-萘基苯并噻吩-1-氧。
将2.94g(8mmol)3-苯氧基-6-萘基苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中心,无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-萘基苯并噻吩。
将2.11g(6mmol)3-苯氧基-6-萘基苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温,加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-苯氧基-6-萘基苯并噻吩。
将1.72g(4mmol)2-溴-3-苯氧基-6-萘基苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mLN,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸,用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤,无水硫酸镁干燥,浓缩,柱层析的目标化合物2-萘基[1]苯并噻吩[3,2-b][1]苯并呋喃(Na-BTBF)。
实施例22
2-(4-乙基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(C2-Ph-BTBF)的合成流程为:
将4.76g(20mmol)6-(4-乙基苯基)苯并噻吩溶解在30mL氯仿中,0℃下分批加入4.45g(25mmol)N-溴代丁二酰亚胺,加毕,在0℃下反应4h之后升至室温继续搅拌反应至原料消失。分别用硫代硫酸钠水溶液,饱和碳酸钠和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析得3-溴-6-(4-乙基苯基)苯并噻吩。
将4.73g(15mmol)3-溴-6-(4-乙基苯基)苯并噻吩溶解在30mL二氯甲烷和30mL三氟乙酸溶液中,在室温下搅拌5分钟之后,加入1.0mL,35%的双氧水,搅拌至原料反应完全,用饱和碳酸钠溶液中和至中性,分液,有机相用饱和碳酸氢钠和水洗涤,无水硫酸镁干燥,浓缩,柱层析的化合物3-溴-6-(4-乙基苯基)苯并噻吩-1-氧。
将3.31g(10mmol)3-溴-6-(4-乙基苯基)苯并噻吩-1-氧,1.88g(20mmol)苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-(4-乙基苯基)苯并噻吩-1-氧。
将2.77g(8mmol)3-苯氧基-6-(4-乙基苯基)苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中心,无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-(4-乙基苯基)苯并噻吩。
将1.98g(6mmol)3-苯氧基-6-(4-乙基苯基)苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温,加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-苯氧基-6-(4-乙基苯基)苯并噻吩。
将1.63g(4mmol)2-溴-3-苯氧基-6-(4-乙基苯基)苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mLN,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸,用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤,无水硫酸镁干燥,浓缩,柱层析的目标化合物2-(4-乙基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(C2-Ph-BTBF)。
实施例23
2-(4-戊基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(C5-Ph-BTBF)的合成流程为:
其具体制备步骤包括:
将5.6g(20mmol)6-(4-戊基苯基)苯并噻吩溶解在30mL氯仿中,0℃下分批加入4.45g(25mmol)N-溴代丁二酰亚胺,加毕,在0℃下反应4h之后升至室温继续搅拌反应至原料消失。分别用硫代硫酸钠水溶液,饱和碳酸钠和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析得3-溴-6-(4-戊基苯基)苯并噻吩。
将5.37g(15mmol)3-溴-6-(4-戊基苯基)苯并噻吩溶解在30mL二氯甲烷和30mL三氟乙酸溶液中,在室温下搅拌5分钟之后,加入1.0mL,35%的双氧水,搅拌至原料反应完全,用饱和碳酸钠溶液中和至中性,分液,有机相用饱和碳酸氢钠和水洗涤,无水硫酸镁干燥,浓缩,柱层析的化合物3-溴-6-(4-戊基苯基)苯并噻吩-1-氧。
将3.74g(10mmol)3-溴-6-(4-戊基苯基)苯并噻吩-1-氧,1.88g(20mmol)苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-(4-戊基苯基)苯并噻吩-1-氧。
将3.10g(8mmol)3-苯氧基-6-(4-戊基苯基)苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中心,无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-(4-戊基苯基)苯并噻吩。
将2.23g(6mmol)3-苯氧基-6-(4-戊基苯基)苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温,加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-苯氧基-6-(4-戊基苯基)苯并噻吩。
将1.80g(4mmol)2-溴-3-苯氧基-6-(4-戊基苯基)苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mLN,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸,用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤, 无水硫酸镁干燥,浓缩,柱层析的目标化合物2-(4-戊基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(C5-Ph-BTBF)。
实施例24
将6.16g(20mmol)6-(4-庚基苯基)苯并噻吩溶解在30mL氯仿中,0℃下分批加入4.45g(25mmol)N-溴代丁二酰亚胺,加毕,在0℃下反应4h之后升至室温继续搅拌反应至原料消失。分别用硫代硫酸钠水溶液,饱和碳酸钠和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析得3-溴-6-(4-庚基苯基)苯并噻吩。
将5.79g(15mmol)3-溴-6-(4-庚基苯基)苯并噻吩溶解在30mL二氯甲烷和30mL三氟乙酸溶液中,在室温下搅拌5分钟之后,加入1.0mL,35%的双氧水,搅拌至原料反应完全,用饱和碳酸钠溶液中和至中性,分液,有机相用饱和碳酸氢钠和水洗涤,无水硫酸镁干燥,浓缩,柱层析的化合物3-溴-6-(4-庚基苯基)苯并噻吩-1-氧。
将4.02g(10mmol)3-溴-6-(4-庚基苯基)苯并噻吩-1-氧,1.88g(20mmol)苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-(4-庚基苯基)苯并噻吩-1-氧。
将3.33g(8mmol)3-苯氧基-6-(4-庚基苯基)苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中心,无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-(4-庚基苯基)苯并噻吩。
将2.40g(6mmol)3-苯氧基-6-(4-庚基苯基)苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温,加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-苯氧基-6-(4-庚基苯基)苯并噻吩。
将1.91g(4mmol)2-溴-3-苯氧基-6-(4-庚基苯基)苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mLN,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸, 用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤,无水硫酸镁干燥,浓缩,柱层析的目标化合物2-(4-庚基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(C7-Ph-BTBF)。
实施例25
将6.44g(20mmol)6-(4-辛基苯基)苯并噻吩溶解在30mL氯仿中,0℃下分批加入4.45g(25mmol)N-溴代丁二酰亚胺,加毕,在0℃下反应4h之后升至室温继续搅拌反应至原料消失。分别用硫代硫酸钠水溶液,饱和碳酸钠和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析得3-溴-6-(4-辛基苯基)苯并噻吩。
将6.00g(15mmol)3-溴-6-(4-辛基苯基)苯并噻吩溶解在30mL二氯甲烷和30mL三氟乙酸溶液中,在室温下搅拌5分钟之后,加入1.0mL,35%的双氧水,搅拌至原料反应完全,用饱和碳酸钠溶液中和至中性,分液,有机相用饱和碳酸氢钠和水洗涤,无水硫酸镁干燥,浓缩,柱层析的化合物3-溴-6-(4-辛基苯基)苯并噻吩-1-氧。
将4.16g(10mmol)3-溴-6-(4-辛基苯基)苯并噻吩-1-氧,1.88g(20mmol)苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-(4-辛基苯基)苯并噻吩-1-氧。
将3.44g(8mmol)3-苯氧基-6-(4-辛基苯基)苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中心,无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-(4-辛基苯基)苯并噻吩。
将2.48g(6mmol)3-苯氧基-6-(4-辛基苯基)苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温,加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-苯氧基-6-(4-乙基苯基)苯并噻吩。
将1.97g(4mmol)2-溴-3-苯氧基-6-(4-辛基苯基)苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mL N,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸,用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤,无水硫酸镁干燥,浓缩,柱层析的目标化合物2-(4-乙基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(C8-Ph-BTBF)。
实施例26
将7.0g(20mmol)6-(4-癸基苯基)苯并噻吩溶解在30mL氯仿中,0℃下分批加入4.45g(25mmol)N-溴代丁二酰亚胺,加毕,在0℃下反应4h之后升至室温继续搅拌反应至原料消失。分别用硫代硫酸钠水溶液,饱和碳酸钠和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析得3-溴-6-(4-癸基苯基)苯并噻吩。
将6.42g(15mmol)3-溴-6-(4-癸基苯基)苯并噻吩溶解在30mL二氯甲烷和30mL三氟乙酸溶液中,在室温下搅拌5分钟之后,加入1.0mL,35%的双氧水,搅拌至原料反应完全,用饱和碳酸钠溶液中和至中性,分液,有机相用饱和碳酸氢钠和水洗涤,无水硫酸镁干燥,浓缩,柱层析的化合物3-溴-6-(4-癸基苯基)苯并噻吩-1-氧。
将4.44g(10mmol)3-溴-6-(4-癸基苯基)苯并噻吩-1-氧,1.88g(20mmol)苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-(4-癸基苯基)苯并噻吩-1-氧。
将3.66g(8mmol)3-苯氧基-6-(4-癸基苯基)苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中心,无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-(4-癸基苯基)苯并噻吩。
将2.65g(6mmol)3-苯氧基-6-(4-癸基苯基)苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温, 加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-苯氧基-6-(4-癸基苯基)苯并噻吩。
将2.08g(4mmol)2-溴-3-苯氧基-6-(4-癸基苯基)苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mLN,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸,用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤,无水硫酸镁干燥,浓缩,柱层析的目标化合物2-(4-癸基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(C10-Ph-BTBF)。
实施例27
将7.56g(20mmol)6-(4-十二烷基苯基)苯并噻吩溶解在30mL氯仿中,0℃下分批加入4.45g(25mmol)N-溴代丁二酰亚胺,加毕,在0℃下反应4h之后升至室温继续搅拌反应至原料消失。分别用硫代硫酸钠水溶液,饱和碳酸钠和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析得3-溴-6-(4-十二烷基苯基)苯并噻吩。
将6.84g(15mmol)3-溴-6-(4-十二烷基苯基)苯并噻吩溶解在30mL二氯甲烷和30mL三氟乙酸溶液中,在室温下搅拌5分钟之后,加入1.0mL,35%的双氧水,搅拌至原料反应完全,用饱和碳酸钠溶液中和至中性,分液,有机相用饱和碳酸氢钠和水洗涤,无水硫酸镁干燥,浓缩,柱层析的化合物3-溴-6-(4-十二烷基苯基)苯并噻吩-1-氧。
将4.72g(10mmol)3-溴-6-(4-十二烷基苯基)苯并噻吩-1-氧,1.88g(20mmol)苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-(4-十二烷基苯基)苯并噻吩-1-氧。
将3.89g(8mmol)3-苯氧基-6-(4-十二烷基苯基)苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水 溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中心,无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-(4-十二烷基苯基)苯并噻吩。
将2.82g(6mmol)3-苯氧基-6-(4-十二烷基苯基)苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温,加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-苯氧基-6-(4-十二烷基苯基)苯并噻吩。
将2.19g(4mmol)2-溴-3-苯氧基-6-(4-十二烷基苯基)苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mLN,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸,用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤,无水硫酸镁干燥,浓缩,柱层析的目标化合物2-(4-十二烷基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(C12-Ph-BTBF)。
实施例28
将7.84g(20mmol)6-(4-十三烷基苯基)苯并噻吩溶解在30mL氯仿中,0℃下分批加入4.45g(25mmol)N-溴代丁二酰亚胺,加毕,在0℃下反应4h之后升至室温继续搅拌反应至原料消失。分别用硫代硫酸钠水溶液,饱和碳酸钠和水洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析得3-溴-6-(4-十三烷基苯基)苯并噻吩。
将7.05g(15mmol)3-溴-6-(4-十三烷基苯基)苯并噻吩溶解在30mL二氯甲烷和30mL三氟乙酸溶液中,在室温下搅拌5分钟之后,加入1.0mL,35%的双氧水,搅拌至原料反应完全,用饱和碳酸钠溶液中和至中性,分液,有机相用饱和碳酸氢钠和水洗涤,无水硫酸镁干燥,浓缩,柱层析的化合物3-溴-6-(4-十三烷基苯基)苯并噻吩-1-氧。
将4.86g(10mmol)3-溴-6-(4-十三烷基苯基)苯并噻吩-1-氧,1.88g(20mmol)苯酚,2.76g(20mmol)碳酸钾与30mL无水DMF在70℃条件下搅拌反应过夜,降至室温,浓缩,残留物溶解在50mL二氯甲烷中,用饱和食盐水和水 洗涤,有机相用无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-(4-十三烷基苯基)苯并噻吩-1-氧。
将4.0g(8mmol)3-苯氧基-6-(4-十三烷基苯基)苯并噻吩-1-氧溶解在50mL无水甲苯中,在0℃条件下缓慢滴加二异丁基氢化铝(16mmol,13mL,20%的甲苯溶液),加毕,在65℃下搅拌反应至原料消失,冷却至0℃,用2M的氢氧化钠水溶液中和,二氯甲烷萃取三次,合并有机相,有机相用水洗至中心,无水硫酸镁干燥,浓缩,柱层析的3-苯氧基-6-(4-十三烷基苯基)苯并噻吩。
将2.90g(6mmol)3-苯氧基-6-(4-十三烷基苯基)苯并噻吩溶解在30mL冰乙酸中,加入1.2g(6.6mmol)NBS,搅拌10分钟,继续在55℃下搅拌反应2h。冷却至室温,加入80mL冰水,用乙酸乙酯萃取三次,合并有机相,有机相用饱和碳酸钠,饱和食盐水和水洗涤,无水硫酸镁干燥,柱层析得2-溴-3-苯氧基-6-(4-十三烷基苯基)苯并噻吩。
将2.25g(4mmol)2-溴-3-苯氧基-6-(4-十三烷基苯基)苯并噻吩,0.67g(8mmol)醋酸钠溶解在80mLN,N-二甲基乙酰胺中,氮气条件下加入0.14g(0.2mmol)PdCl
2(PPh
3)
2,在140℃条件下搅拌过夜,冷却至室温,加入200mL 1mol/L盐酸,用500mL乙酸乙酯和正己烷(体积比1:1)萃取,有机相用饱和食盐水和水洗涤,无水硫酸镁干燥,浓缩,柱层析的目标化合物2-(4-十三烷基苯基)[1]苯并噻吩[3,2-b][1]苯并呋喃(C13-Ph-BTBF)。
实施例29
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃。
将2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃(1.9g,5mmol)、二苯胺(2.63g,15mmol)溶解于100mL甲苯中,除去体系中的氧之后,加入催化量的Pd
2(dba)
3,HF
4P(t-Bu)
3和叔丁醇钾(1.68g,15mmol),在惰性气体保护下加热反应至原料反应完毕;然后冷却至室温,用饱和食盐水和水洗涤,无水硫酸钠干燥,浓缩,残留物用石油醚和二氯甲烷为洗脱液柱层析得到N
2,N
2,N
7,N
7-四苯基[1]苯并噻吩[3,2-b][1]苯并呋喃-2,7-二胺。
实施例30
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃。
将2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃(1.9g,5mmol)、苯基-1-萘胺(3.28g,15mmol)溶解于100mL甲苯中,除去体系中的氧之后,加入催化量的Pd
2(dba)
3,HF
4P(t-Bu)
3和叔丁醇钾(1.68g,15mmol),在惰性气体保护下加热反应至原料反应完毕;然后冷却至室温,用饱和食盐水和水洗涤,无水硫酸钠干燥,浓缩,残留物用石油醚和二氯甲烷为洗脱液柱层析得N
2,N
7-二苯基-N
2,N
7-二(1-萘基)[1]苯并噻吩[3,2-b][1]苯并呋喃-2,7-二胺。
实施例31
2,7-二(3,5-二苯氨基)苯基-1-基[1]苯并噻吩[3,2-b][1]苯并呋喃的合成流程为:
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃。
将1.9g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃和8.07g(15mmol,3当量)3,5-二苯氨基苯-1-基硼酸频哪醇酯溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二(3,5-二苯氨基)苯基-1-基[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例32
2,7-二(9H-咔唑基)[1]苯并噻吩[3,2-b][1]苯并呋喃-2,7-二胺的合成流程为:
其制备方法包括步骤:
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃。
将2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃(1.9g,5mmol)、咔唑(2.5g,15mmol)溶解于100mL甲苯中,除去体系中的氧之后,加入催化量的Pd
2(dba)
3,HF
4P(t-Bu)
3和叔丁醇钾(1.68g,15mmol),在惰性气体保护下加热反应至原料反应完毕;然后冷却至室温,用饱和食盐水和水洗涤,无水硫酸钠干燥,浓缩,残留物用石油醚和二氯甲烷为洗脱液柱层析得2,7-二(9H-咔唑基)[1]苯并噻吩[3,2-b][1]苯并呋喃-2,7-二胺。
实施例33
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃。
将2.0g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃和1.84g(15mmol,3当量)吡啶-2-硼酸溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二(吡啶-2-基)[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例34
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃;
将2.0g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并噻吩和1.84g(15mmol,3当量)吡啶-3-硼酸溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二(吡啶-3-基)[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例35
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃;
将2.0g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃和1.84g(15mmol,3当量)吡啶-4-硼酸溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二(吡啶-4-基)[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例36
2,7-二(喹啉-3-基)[1]苯并噻吩[3,2-b][1]苯并呋喃的合成流程为:
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃;
将2.0g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃和2.60g(15mmol,3当量)喹啉-3-硼酸溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二(喹啉-3-基)[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例37
2,7-二(喹啉-8-基)[1]苯并噻吩[3,2-b][1]苯并呋喃的合成流程为:
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃;
将2.0g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃和2.60g(15mmol,3当量)喹啉-8-硼酸溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二(喹啉-8-基)[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例38
2,7-二(1,10-邻菲咯啉-3-基)-4-基[1]苯并噻吩[3,2-b][1]苯并呋喃的合成流程为:
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃;
将2.0g(5mmol)2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃和3.36g(15mmol,3当量)1,10-邻菲咯啉-3-硼酸溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二(1,10-邻菲咯啉-3-基)-4-基[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例39
2,7-二-苯并噻唑-4-基[1]苯并噻吩[3,2-b][1]苯并呋喃的合成流程为:
其具体制备步骤包括:
采用与实施例6相同的步骤制备2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃;
氮气保护下,将2,7-二溴[1]苯并噻吩[3,2-b][1]苯并呋喃(3.8g,10mmol),双联频哪醇硼酸酯(7.62g,30mmol),乙酸钾(3.92g,40mmol)和[1,1′-双(二苯基膦)二茂铁]二氯化钯(II)二氯甲烷络合物(0.3mmol,0.25g)溶解在100mL二甲基亚砜,用氮气吹洗15分钟,80℃下加热10h,冷却至室温,倒入冰水中,用二氯甲烷萃取三次,合并有机相,有机相用水洗三次,硫酸镁干燥,浓缩,柱层析纯化得2,7-二频哪醇硼酸酯基[1]苯并噻吩[3,2-b][1]苯并呋喃;
将2.38g(5mmol)2,7-二频哪醇硼酸酯基[1]苯并噻吩[3,2-b][1]苯并呋喃和3.23g(15mmol,3当量)4-溴苯并噻二唑溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二-苯并噻唑-4-基[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例40
采用与实施例39相同的步骤制备2,7-二频哪醇硼酸酯基[1]苯并噻吩[3,2-b][1]苯并呋喃;
将2.38g(5mmol)2,7-二频哪醇硼酸酯基[1]苯并噻吩[3,2-b][1]苯并呋喃和3.23g(15mmol,3当量)5-溴苯并噻二唑溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二-苯并噻唑-5-基[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例41
2,7-二-(2,4-二苯基-1,3,5-三嗪-6-基)[1]苯并噻吩[3,2-b][1]苯并呋喃的合成流程为:
采用与实施例39相同的步骤制备2,7-二频哪醇硼酸酯基[1]苯并噻吩[3,2-b][1]苯并呋喃;
将2.38g(5mmol)2,7-二频哪醇硼酸酯基[1]苯并噻吩[3,2-b][1]苯并呋喃和4.00g(15mmol,3当量)2,4-二苯基-6-氯-1,3,5-三嗪溶解在50mL甲苯中,加入10mL 2M的碳酸钾水溶液,用氮气吹吸30min,加入Pd(PPh
3)
4(2%当量),在氮气环境下110℃下搅拌24h,反应混合物倒入100mL甲醇中,过滤,固体用盐酸和水洗涤。用高真空升华的方式得到2,7-二-苯并噻唑-5-基[1]苯并噻吩[3,2-b][1]苯并呋喃。
实施例42
器件制备及性能测试:
分别采用现有材料DPh-BTBT以及本发明实施例中的DPh-BTBF、BTBF-Ph-C12、D-C12-Ph-BTBF材料来制备同样的有机薄膜晶体管器件,分别测试其载流子迁移率以及荧光量子效率,结果如下所示:
化合物 | 载流子迁移率 | 荧光量子产率 |
DPh-BTBT | 0.36-0.46cm 2V -1s -1 | 18% |
DPh-BTBF | 0.38-0.45cm 2V -1s -1 | 51% |
BTBF-Ph-C12 | 0.33-0.50cm 2V -1s -1 | 42% |
D-C12-Ph-BTBF | 0.40-0.49cm 2V -1s -1 | 52% |
通过上述实验结果可知,本发明制备的[1]苯并噻吩[3,2-b][1]苯并呋喃衍生物与现有
(DPh-BTBT)材料均具有较高的载流子迁移率,但是本发明提供的材料相较于现有DPh-BTBT材料具有更高的荧光效率。
综上所述,本发明结合噻吩衍生物具有较高的载流子迁移率以及呋喃衍生物具有较高荧光性能的特点,设计了一种同时含有噻吩官能团和呋喃官能团的半导体材料,所述半导体材料的分子结构为所述半导体材料的分子结构通式为
中的一种,其中,所述Ar1和Ar2均为烷基或芳基;所述Ar3、Ar4、Ar5和Ar6均为芳基,所述R1,R2,R3,R4,R5,R6,R7,R8,R9,R10,R11,R12,R13,R14,R15和R16均为芳基,所述R17,R18,R19和R20均为芳基或烷基。本发明提供的半导体材料可作为有机薄膜晶体管的有源层及发光器件中的发光层,通过真空蒸镀或旋涂法制成半导体薄膜,进一步制备有机薄膜晶体管或发光器件,旨在解决现有有机半导体材料高载流子迁移率与高荧光效率不兼得的问题。
应当理解的是,本发明的应用不限于上述的举例,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (13)
- 根据权利要求3所述的半导体材料,其特征在于,所述缺电子基团包括氰基、硝基和卤基。
- 一种半导体材料的制备方法,其特征在于,包括步骤:将苯并噻吩与N-溴代丁二酰亚胺混合,反应生成3-溴苯并噻吩;将所述3-溴苯并噻吩与双氧水混合,反应生成苯并噻吩氧化物;
- 一种半导体材料的制备方法,其特征在于,包括步骤:将苯并噻吩与N-溴代丁二酰亚胺混合,反应生成3-溴苯并噻吩;将所述3-溴苯并噻吩与双氧水混合,反应生成苯并噻吩氧化物;
- 一种半导体材料的制备方法,其特征在于,包括步骤:将苯并噻吩与N-溴代丁二酰亚胺混合,反应生成3-溴苯并噻吩;将所述3-溴苯并噻吩与双氧水混合,反应生成苯并噻吩氧化物;
- 一种半导体材料的制备方法,其特征在于,包括步骤:将苯并噻吩与N-溴代丁二酰亚胺混合,反应生成3-溴苯并噻吩;将所述3-溴苯并噻吩与双氧水混合,反应生成苯并噻吩氧化物;或者,将所述第五中间体与含芳胺的芳基硼酸酯混合,并加入Pd(PPh 3) 4进行催化反应,生成分子结构通式为 的胺类衍生物,其中,所述Ar1,Ar2,R5,R6,R7,R8,R9,R10,R11,R12,R13,R14,R15和R16均为芳基;
- 一种半导体材料的应用,其特征在于,将权利要求1-6中任意一种半导体材料应用于制备有机薄膜晶体管器件和发光器件。
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
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CN201810790026.9A CN110734452A (zh) | 2018-07-18 | 2018-07-18 | 一种半导体材料及其制备方法与应用 |
CN201810806814.2 | 2018-07-18 | ||
CN201810789867.8 | 2018-07-18 | ||
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