WO2015122321A1 - 有機半導体材料 - Google Patents
有機半導体材料 Download PDFInfo
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- WO2015122321A1 WO2015122321A1 PCT/JP2015/053004 JP2015053004W WO2015122321A1 WO 2015122321 A1 WO2015122321 A1 WO 2015122321A1 JP 2015053004 W JP2015053004 W JP 2015053004W WO 2015122321 A1 WO2015122321 A1 WO 2015122321A1
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- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000004065 semiconductor Substances 0.000 title claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 327
- 229920000642 polymer Polymers 0.000 claims abstract description 70
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 38
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims abstract description 35
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims abstract description 28
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000005309 thioalkoxy group Chemical group 0.000 claims abstract description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 21
- 125000005843 halogen group Chemical group 0.000 claims abstract description 18
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000007858 starting material Substances 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 35
- -1 tin halide compound Chemical class 0.000 claims description 287
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 170
- 125000004432 carbon atom Chemical group C* 0.000 claims description 97
- 239000003054 catalyst Substances 0.000 claims description 80
- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000002184 metal Substances 0.000 claims description 43
- 238000004519 manufacturing process Methods 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 229910052718 tin Inorganic materials 0.000 claims description 26
- 125000001931 aliphatic group Chemical group 0.000 claims description 23
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 19
- 125000004104 aryloxy group Chemical group 0.000 claims description 16
- 229910052796 boron Inorganic materials 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 230000002140 halogenating effect Effects 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 7
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 143
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 123
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 123
- 239000007787 solid Substances 0.000 description 82
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 75
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 63
- 239000002585 base Substances 0.000 description 61
- 238000005259 measurement Methods 0.000 description 59
- 239000002904 solvent Substances 0.000 description 59
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 58
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 57
- 150000002430 hydrocarbons Chemical group 0.000 description 57
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 48
- 238000001914 filtration Methods 0.000 description 48
- 239000000203 mixture Substances 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 47
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 239000000243 solution Substances 0.000 description 43
- 238000000862 absorption spectrum Methods 0.000 description 40
- 230000015572 biosynthetic process Effects 0.000 description 40
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 36
- 238000003786 synthesis reaction Methods 0.000 description 36
- LNAMMBFJMYMQTO-FNEBRGMMSA-N chloroform;(1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].ClC(Cl)Cl.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 LNAMMBFJMYMQTO-FNEBRGMMSA-N 0.000 description 34
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 32
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 32
- 238000005481 NMR spectroscopy Methods 0.000 description 31
- 238000005160 1H NMR spectroscopy Methods 0.000 description 30
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 30
- 239000012043 crude product Substances 0.000 description 30
- 239000012044 organic layer Substances 0.000 description 30
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- 238000004440 column chromatography Methods 0.000 description 21
- 239000000741 silica gel Substances 0.000 description 21
- 229910002027 silica gel Inorganic materials 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000003446 ligand Substances 0.000 description 20
- 125000005605 benzo group Chemical group 0.000 description 19
- 238000005227 gel permeation chromatography Methods 0.000 description 18
- 229910052763 palladium Inorganic materials 0.000 description 16
- DLQYXUGCCKQSRJ-UHFFFAOYSA-N tris(furan-2-yl)phosphane Chemical compound C1=COC(P(C=2OC=CC=2)C=2OC=CC=2)=C1 DLQYXUGCCKQSRJ-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- 239000010949 copper Substances 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 13
- 238000005859 coupling reaction Methods 0.000 description 13
- 239000010408 film Substances 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 238000000944 Soxhlet extraction Methods 0.000 description 12
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 0 *c1ccccc1 Chemical compound *c1ccccc1 0.000 description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000011630 iodine Substances 0.000 description 11
- 229910052740 iodine Inorganic materials 0.000 description 11
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 10
- 150000001408 amides Chemical class 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 7
- 230000008878 coupling Effects 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- AVRWEULSKHQETA-UHFFFAOYSA-N Thiophene-2 Chemical compound S1C=2CCCCCC=2C(C(=O)OC)=C1NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F AVRWEULSKHQETA-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000004210 ether based solvent Substances 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- IIOSDXGZLBPOHD-UHFFFAOYSA-N tris(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC IIOSDXGZLBPOHD-UHFFFAOYSA-N 0.000 description 6
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003849 aromatic solvent Substances 0.000 description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 description 5
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- UKTDFYOZPFNQOQ-UHFFFAOYSA-N tributyl(thiophen-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CS1 UKTDFYOZPFNQOQ-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- KZDTZHQLABJVLE-UHFFFAOYSA-N 1,8-diiodooctane Chemical compound ICCCCCCCCI KZDTZHQLABJVLE-UHFFFAOYSA-N 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 4
- 229940043279 diisopropylamine Drugs 0.000 description 4
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 4
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 4
- 229910000080 stannane Inorganic materials 0.000 description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
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- LQZMLBORDGWNPD-UHFFFAOYSA-N N-iodosuccinimide Chemical compound IN1C(=O)CCC1=O LQZMLBORDGWNPD-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
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- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
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- 238000011088 calibration curve Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
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- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
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- 230000003993 interaction Effects 0.000 description 2
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- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
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- 150000002576 ketones Chemical class 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
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- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 2
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 2
- HAUKUGBTJXWQMF-UHFFFAOYSA-N lithium;propan-2-olate Chemical compound [Li+].CC(C)[O-] HAUKUGBTJXWQMF-UHFFFAOYSA-N 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
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- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- MXQOYLRVSVOCQT-UHFFFAOYSA-N palladium;tritert-butylphosphane Chemical compound [Pd].CC(C)(C)P(C(C)(C)C)C(C)(C)C.CC(C)(C)P(C(C)(C)C)C(C)(C)C MXQOYLRVSVOCQT-UHFFFAOYSA-N 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
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- RRHPTXZOMDSKRS-PGUQZTAYSA-L (5z)-cycloocta-1,5-diene;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1C\C=C/CCC=C1 RRHPTXZOMDSKRS-PGUQZTAYSA-L 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- VHGDVPCZPQFBLC-UHFFFAOYSA-N 1,2-dichlorobicyclo[2.2.1]hepta-2,5-diene Chemical compound ClC12C(=CC(C=C1)C2)Cl VHGDVPCZPQFBLC-UHFFFAOYSA-N 0.000 description 1
- DCPLDPXQOOHYSU-UHFFFAOYSA-N 1,3-dimethyl-1,3-diazinane Chemical compound CN1CCCN(C)C1 DCPLDPXQOOHYSU-UHFFFAOYSA-N 0.000 description 1
- LVCBYFZCUVYBPP-UHFFFAOYSA-N 1,4-bis(5-bromothiophen-2-yl)-2,5-dioctylpyrrolo[3,4-c]pyrrole-3,6-dione Chemical compound CCCCCCCCN1C(=O)C2=C(C=3SC(Br)=CC=3)N(CCCCCCCC)C(=O)C2=C1C1=CC=C(Br)S1 LVCBYFZCUVYBPP-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- ZEMZPXWZVTUONV-UHFFFAOYSA-N 2-(2-dicyclohexylphosphanylphenyl)-n,n-dimethylaniline Chemical group CN(C)C1=CC=CC=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 ZEMZPXWZVTUONV-UHFFFAOYSA-N 0.000 description 1
- JGFXUYLYPITYGR-UHFFFAOYSA-N 2-(2-diphenylphosphanylphenyl)-n,n-dimethylaniline Chemical group CN(C)C1=CC=CC=C1C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 JGFXUYLYPITYGR-UHFFFAOYSA-N 0.000 description 1
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- GNMFTICJHCZBRF-UHFFFAOYSA-N CC(C)CCCC(C)CCc1ccc(-c([s]c2c3-c4ccc[s]4)nc2c(-c2ccc[s]2)c2c3nc(-c3ccc(CCC(C)CCCC(C)C)[s]3)[s]2)[s]1 Chemical compound CC(C)CCCC(C)CCc1ccc(-c([s]c2c3-c4ccc[s]4)nc2c(-c2ccc[s]2)c2c3nc(-c3ccc(CCC(C)CCCC(C)C)[s]3)[s]2)[s]1 GNMFTICJHCZBRF-UHFFFAOYSA-N 0.000 description 1
- UZDGNWGYJBYERB-UHFFFAOYSA-N CC1(OB(OC1(C)C)C=1SC(=CC=1)[Si](C(C)C)(C(C)C)C(C)C)C Chemical compound CC1(OB(OC1(C)C)C=1SC(=CC=1)[Si](C(C)C)(C(C)C)C(C)C)C UZDGNWGYJBYERB-UHFFFAOYSA-N 0.000 description 1
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- 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 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
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- HTENDICUTNSELD-UHFFFAOYSA-N acetic acid triphenylphosphane Chemical compound CC(O)=O.CC(O)=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HTENDICUTNSELD-UHFFFAOYSA-N 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005104 aryl silyl group Chemical group 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 0.000 description 1
- FAMUPMBATZGWOV-UHFFFAOYSA-M bromo(triphenyl)stannane Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Br)C1=CC=CC=C1 FAMUPMBATZGWOV-UHFFFAOYSA-M 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- PIMYDFDXAUVLON-UHFFFAOYSA-M chloro(triethyl)stannane Chemical compound CC[Sn](Cl)(CC)CC PIMYDFDXAUVLON-UHFFFAOYSA-M 0.000 description 1
- FVFLIQMADUVDSP-UHFFFAOYSA-M chloro(tripropyl)stannane Chemical compound CCC[Sn](Cl)(CCC)CCC FVFLIQMADUVDSP-UHFFFAOYSA-M 0.000 description 1
- ACONPURZGJUVLW-UHFFFAOYSA-N chloroform;palladium Chemical compound [Pd].[Pd].ClC(Cl)Cl ACONPURZGJUVLW-UHFFFAOYSA-N 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- KFGVRWGDTLZAAO-UHFFFAOYSA-N cyclopenta-1,3-diene dicyclohexyl(cyclopenta-1,3-dien-1-yl)phosphane iron(2+) Chemical compound [Fe++].c1cc[cH-]c1.C1CCC(CC1)P(C1CCCCC1)c1ccc[cH-]1 KFGVRWGDTLZAAO-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- BSHICDXRSZQYBP-UHFFFAOYSA-N dichloromethane;palladium(2+) Chemical compound [Pd+2].ClCCl BSHICDXRSZQYBP-UHFFFAOYSA-N 0.000 description 1
- VBDQNUWZQXYUDP-UHFFFAOYSA-L dichloropalladium;ethane-1,2-diamine Chemical compound [Cl-].[Cl-].[Pd+2].NCCN.NCCN VBDQNUWZQXYUDP-UHFFFAOYSA-L 0.000 description 1
- BOUYBUIVMHNXQB-UHFFFAOYSA-N dicyclohexyl(2-dicyclohexylphosphanylethyl)phosphane Chemical compound C1CCCCC1P(C1CCCCC1)CCP(C1CCCCC1)C1CCCCC1 BOUYBUIVMHNXQB-UHFFFAOYSA-N 0.000 description 1
- RSJBEKXKEUQLER-UHFFFAOYSA-N dicyclohexyl(3-dicyclohexylphosphanylpropyl)phosphane Chemical compound C1CCCCC1P(C1CCCCC1)CCCP(C1CCCCC1)C1CCCCC1 RSJBEKXKEUQLER-UHFFFAOYSA-N 0.000 description 1
- WNZGLXFLSFWPMP-UHFFFAOYSA-N dicyclohexyl(4-dicyclohexylphosphanylbutyl)phosphane Chemical compound C1CCCCC1P(C1CCCCC1)CCCCP(C1CCCCC1)C1CCCCC1 WNZGLXFLSFWPMP-UHFFFAOYSA-N 0.000 description 1
- LCSNDSFWVKMJCT-UHFFFAOYSA-N dicyclohexyl-(2-phenylphenyl)phosphane Chemical group C1CCCCC1P(C=1C(=CC=CC=1)C=1C=CC=CC=1)C1CCCCC1 LCSNDSFWVKMJCT-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-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
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 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
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 1
- ANYSGBYRTLOUPO-UHFFFAOYSA-N lithium tetramethylpiperidide Chemical compound [Li]N1C(C)(C)CCCC1(C)C ANYSGBYRTLOUPO-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- AHNJTQYTRPXLLG-UHFFFAOYSA-N lithium;diethylazanide Chemical compound [Li+].CC[N-]CC AHNJTQYTRPXLLG-UHFFFAOYSA-N 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- ULKSWZAXQDJMJT-UHFFFAOYSA-M magnesium;2,2,6,6-tetramethylpiperidin-1-ide;chloride Chemical compound [Cl-].CC1(C)CCCC(C)(C)N1[Mg+] ULKSWZAXQDJMJT-UHFFFAOYSA-M 0.000 description 1
- CQRPUKWAZPZXTO-UHFFFAOYSA-M magnesium;2-methylpropane;chloride Chemical compound [Mg+2].[Cl-].C[C-](C)C CQRPUKWAZPZXTO-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- YICRPERKKBDRSP-UHFFFAOYSA-N methyl 3-amino-4-methylthiophene-2-carboxylate Chemical compound COC(=O)C=1SC=C(C)C=1N YICRPERKKBDRSP-UHFFFAOYSA-N 0.000 description 1
- KZKQGUVWZYKJBN-UHFFFAOYSA-N methyl 5-methylsulfonylpyridine-3-carboxylate Chemical compound COC(=O)C1=CN=CC(S(C)(=O)=O)=C1 KZKQGUVWZYKJBN-UHFFFAOYSA-N 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- GTSFBKGHQLDFHU-UHFFFAOYSA-L methyl(diphenyl)phosphane;palladium(2+);dichloride Chemical compound Cl[Pd]Cl.C=1C=CC=CC=1P(C)C1=CC=CC=C1.C=1C=CC=CC=1P(C)C1=CC=CC=C1 GTSFBKGHQLDFHU-UHFFFAOYSA-L 0.000 description 1
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 1
- HHVIBTZHLRERCL-UHFFFAOYSA-N methylsulphonylmethane Natural products CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- HNNUTDROYPGBMR-UHFFFAOYSA-L palladium(ii) iodide Chemical compound [Pd+2].[I-].[I-] HNNUTDROYPGBMR-UHFFFAOYSA-L 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 1
- BSGYFEXAUOZBKM-UHFFFAOYSA-N potassium sodium propan-2-olate Chemical compound CC([O-])C.[K+].[Na+].CC([O-])C BSGYFEXAUOZBKM-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- MUSFRELEIXGPKU-UHFFFAOYSA-N selanylidenepalladium Chemical compound [Pd]=[Se] MUSFRELEIXGPKU-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NRUVOKMCGYWODZ-UHFFFAOYSA-N sulfanylidenepalladium Chemical compound [Pd]=S NRUVOKMCGYWODZ-UHFFFAOYSA-N 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
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Definitions
- the present invention relates to a polymer compound having a structural unit having a specific benzobisthiazole skeleton, an organic semiconductor material, and a method for producing the same.
- Organic semiconductor materials are one of the most important materials in the field of organic electronics, and can be classified into electron-donating p-type organic semiconductor materials and electron-accepting n-type organic semiconductor materials.
- Various semiconductor elements can be manufactured by appropriately combining p-type organic semiconductor materials and n-type organic semiconductor materials. For example, such elements include excitons formed by recombination of electrons and holes. It is applied to organic electroluminescence that emits light by the action of (exciton), an organic thin film solar cell that converts light into electric power, and an organic thin film transistor that controls the amount of current and voltage.
- organic thin-film solar cells are useful for environmental conservation because they do not release carbon dioxide into the atmosphere, and demand is increasing because they are easy to manufacture with a simple structure.
- the photoelectric conversion efficiency of the organic thin film solar cell is still not sufficient.
- FF fill factor
- the open circuit voltage (Voc) is proportional to the energy difference between the HOMO (highest occupied orbital) level of the p-type organic semiconductor and the LUMO (lowest unoccupied orbital) level of the n-type organic semiconductor, the open circuit voltage (Voc) ) Needs to be deepened (reduced) in the HOMO level of the p-type organic semiconductor.
- the short circuit current density (Jsc) correlates with the amount of energy received by the organic semiconductor material.
- the short circuit current density (Jsc) of the organic semiconductor material from the visible region to the near infrared region. It is necessary to absorb light in a wide wavelength range. Of the light that can be absorbed by the organic semiconductor material, the wavelength of the light with the lowest energy (the longest wavelength) is the absorption edge wavelength, and the energy corresponding to this wavelength corresponds to the band gap energy. Therefore, in order to absorb light in a wider wavelength range, it is necessary to narrow the band gap (energy difference between the HOMO level and the LUMO level of the p-type organic semiconductor).
- Patent Document 1 proposes a compound having a benzobisthiazole skeleton, but the conversion efficiency is not clear.
- An object of the present invention is to provide an organic semiconductor material excellent in photoelectric conversion efficiency. Another object of the present invention is to provide a raw material compound that can introduce more various skeletons and substituents because the organic semiconductor material is closely related to the chemical structure and the conversion efficiency. Furthermore, it is providing the manufacturing method of such an organic-semiconductor material and its raw material compound.
- the present inventors In order to improve the conversion efficiency, that is, to improve the short-circuit current density (Jsc) while improving the open circuit voltage (Voc), the present inventors have absorbed light in a wide wavelength range in the p-type organic semiconductor. At the same time, it has been found useful to make the HOMO level appropriately deep. And as a result of earnestly examining paying attention to the correlation between the conversion efficiency and the chemical structure in the p-type organic semiconductor material, by using an organic semiconductor polymer having a specific structure, the entire visible light region has a wide light absorption. At the same time, it was found that the short circuit current density (Jsc) can be improved while improving the open circuit voltage (Voc) because the HOMO level and the LUMO level can be adjusted to appropriate ranges. And when such an organic-semiconductor polymer was used, it discovered that a charge separation could be easily caused between a p-type organic semiconductor and an n-type organic semiconductor, and completed this invention.
- the polymer compound according to the present invention includes a benzobisthiazole structural unit represented by the formula (1).
- T 1 and T 2 are each independently a thiophene ring, hydrocarbon group or organosilyl group optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group or an organosilyl group. It represents a thiazole ring which may be substituted, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group.
- B 1 and B 2 represent a thiophene ring that may be substituted with a hydrocarbon group, a thiazole ring that may be substituted with a hydrocarbon group, or an ethynylene group.
- T 1 and T 2 are each preferably a group represented by any of the following formulas (t1) to (t5).
- R 13 to R 14 each independently represents a hydrocarbon group having 6 to 30 carbon atoms.
- R 15 to R 16 each independently represent a hydrocarbon group having 6 to 30 carbon atoms or a group represented by * -Si (R 18 ) 3 .
- R 15 ′ represents a hydrogen atom, a hydrocarbon group having 6 to 30 carbon atoms, or a group represented by * —Si (R 18 ) 3 .
- R 17 each independently represents a hydrocarbon group having 6 to 30 carbon atoms, * —O—R 19 , * —S—R 20 , * —Si (R 18 ) 3 , or * —CF 3 .
- R 18 each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a plurality of R 18 may be the same or different.
- R 19 to R 20 each represents a hydrocarbon group having 6 to 30 carbon atoms. * Represents a bond. ]
- B 1 and B 2 are each preferably a group represented by any of the following formulas (b1) to (b3).
- R 21 , R 22 and R 21 ′ represent a hydrogen atom or a hydrocarbon group having 6 to 30 carbon atoms. * Represents a bond, and in particular, * on the left side represents a bond bonded to the benzene ring of the benzobisthiazole compound. ]
- the polymer compound of the present invention is preferably a donor-acceptor type semiconductor polymer.
- An organic semiconductor material containing the polymer compound of the present invention is also included in the technical scope of the present invention.
- this invention contains the benzobis thiazole compound represented by Formula (5).
- T 1 , T 2 , B 1 and B 2 each represent the same group as described above.
- R 1 to R 4 each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
- M 1 and M 2 each independently represent a boron atom or a tin atom.
- R 1 and R 2 may form a ring together with M 1
- R 3 and R 4 may form a ring together with M 2 .
- m and n each represents an integer of 1 or 2. When m and n are 2, the plurality of R 1 and R 3 may be the same or different.
- the present invention also includes a benzobisthiazole compound represented by the formula (4).
- a benzobisthiazole compound represented by the formula (4).
- T 1 , T 2 , B 1 and B 2 each represent the same group as described above.
- the present invention further includes a benzobisthiazole compound represented by the formula (3).
- T 1 and T 2 each represent the same group as described above.
- X 1 and X 2 represent a halogen atom.
- the present invention includes a benzobisthiazole compound represented by the formula (2).
- T 1 and T 2 each represent the same group as described above. ]
- the method for producing the polymer compound of the present invention comprises 2,6-diiodobenzo [1,2-d: 4,5-d ′] bisthiazole and 2,6-dibromobenzo [1,2-d: 4, One compound selected from the group consisting of 5-d ′] bisthiazole as a starting material, A compound represented by formula (2),
- T 1 , T 2 , X 1 and X 2 each represent the same group as described above.
- T 1 , T 2 , B 1 and B 2 each represent the same group as described above. ] It is characterized by going through.
- the method for producing a polymer compound of the present invention preferably includes the following first step, second step, and third step.
- a metal catalyst one compound selected from the group consisting of formula (6) and / or formula (7)
- T 1 and T 2 each represent the same group as described above.
- R 5 and R 6 each independently represents a hydrogen atom or * -M 3 (R 7 ) k R 8 .
- R 7 and R 8 each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
- M 3 represents a boron atom or a tin atom. * Represents a bond.
- R 7 and R 8 may form a ring together with M 3 .
- k represents an integer of 1 or 2. When k is 2, the plurality of R 7 may be the same or different.
- Step of obtaining a compound represented by formula (2) by reacting the compound represented by formula (2) Second step: reacting the compound represented by formula (2) with a base and a halogenating reagent to formula (3)
- Step 3 for obtaining a compound represented by formula (3) A compound represented by formula (3) is reacted with a compound represented by formula (8) and / or formula (9) in the presence of a metal catalyst.
- B 1 and B 2 each represent the same group as described above.
- R 9 to R 12 are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 6 to 10 carbon atoms. Represents an aryloxy group.
- M 4 and M 5 each represent a boron atom, a tin atom, or a silicon atom.
- R 9 and R 10 may form a ring together with M 4
- R 11 and R 12 may form a ring together with M 5 .
- p and q represent an integer of 1 or 2. When p is 2, the plurality of R 9 may be the same or different. When q is 2, the plurality of R 11 may be the same or different. ]
- the method for producing a polymer compound of the present invention preferably further undergoes a compound represented by the following formula (5).
- T 1 , T 2 , B 3 , B 4 , R 1 to R 4 , M 1 , M 2 , m, and n each represent the same group as described above.
- the polymer compound production method of the present invention preferably further includes the following fourth step.
- Fourth step a step of obtaining a compound represented by the formula (5) by reacting a compound represented by the formula (4) with a base and a tin halide compound.
- the benzobisthiazole compound of the present invention can form a planar cruciform skeleton by intramolecular SN interaction.
- ⁇ conjugation is extended to a planar cross-shaped skeleton, so that it exhibits multiband light absorption derived from a plurality of ⁇ - ⁇ * transitions and can absorb a wide range of light from the visible region to the near infrared region.
- Voc open circuit voltage
- Jsc short circuit current density
- substituents can be introduced as substituents into the benzobisthiazole skeleton, and the characteristics of the material (for example, crystallinity, film-forming property, absorption wavelength) are controlled. it can.
- FIG. 1 shows an ultraviolet-visible absorption spectrum of the polymer compound of Example 22.
- FIG. 2 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 23.
- FIG. 3 shows an ultraviolet-visible absorption spectrum of the polymer compound of Example 24.
- FIG. 4 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 25.
- FIG. 5 shows an ultraviolet-visible absorption spectrum of the polymer compound of Example 26.
- 6 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 27.
- FIG. FIG. 7 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 28.
- FIG. 8 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 29.
- FIG. 9 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 30.
- FIG. 10 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 31.
- FIG. 11 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 32.
- 12 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 37.
- FIG. 13 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 38.
- FIG. 14 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 39.
- FIG. 15 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 40.
- FIG. 16 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 41.
- FIG. 17 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 46.
- FIG. 18 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 47.
- FIG. 19 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 49.
- Polymer Compound The polymer compound of the present invention has a benzobisthiazole structural unit represented by the formula (1).
- T 1 and T 2 are each independently a thiophene ring, hydrocarbon group or organosilyl group optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group or an organosilyl group. It represents a thiazole ring which may be substituted, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group.
- B 1 and B 2 represent a thiophene ring that may be substituted with a hydrocarbon group, a thiazole ring that may be substituted with a hydrocarbon group, or an ethynylene group.
- the polymer compound of the present invention has the benzobisthiazole structural unit represented by the formula (1), the band gap can be narrowed while deepening the HOMO level, which is advantageous for increasing the photoelectric conversion efficiency.
- the polymer compound of the present invention is preferably a donor-acceptor type semiconductor polymer.
- the donor-acceptor type semiconductor polymer compound means a polymer compound in which donor units and acceptor units are alternately arranged.
- the donor unit means an electron donating structural unit, and the acceptor unit means an electron accepting structural unit.
- the donor-acceptor type semiconductor polymer is preferably a polymer compound in which the structural unit represented by the formula (1) and other structural units are alternately arranged.
- the organosilyl group means a monovalent group in which one or more hydrocarbon groups are substituted on Si atoms, and the number of hydrocarbon groups substituted on Si atoms is two or more. It is preferable that it is 3 and it is more preferable that it is three.
- T 1 and T 2 may be the same or different from each other, but are preferably the same from the viewpoint of easy production.
- T 1 and T 2 are preferably groups represented by the following formulas (t1) to (t5), respectively.
- the alkoxy group of T 1 and T 2 is preferably a group represented by the following formula (t1)
- the thioalkoxy group is preferably a group represented by the following formula (t2).
- a group represented by the following formula (t3) is preferable, and as the thiazole ring optionally substituted with a hydrocarbon group or an organosilyl group, the following formula ( The group represented by t4) is preferable, and the phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group is represented by the following formula (t5). ) Is preferred.
- T 1 and T 2 are groups represented by the following formulas (t1) to (t5), it is possible to absorb short-wavelength light and to have high planarity, so that ⁇ - ⁇ stacking is efficiently performed. Therefore, photoelectric conversion efficiency can be further increased.
- R 13 to R 14 each independently represents a hydrocarbon group having 6 to 30 carbon atoms.
- R 15 to R 16 each independently represent a hydrocarbon group having 6 to 30 carbon atoms or a group represented by * -Si (R 18 ) 3 .
- R 15 ′ represents a hydrogen atom, a hydrocarbon group having 6 to 30 carbon atoms, or a group represented by * —Si (R 18 ) 3 .
- R 17 each independently represents a hydrocarbon group having 6 to 30 carbon atoms, * —O—R 19 , * —S—R 20 , * —Si (R 18 ) 3 , or * —CF 3 .
- R 18 each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a plurality of R 18 may be the same or different.
- R 19 to R 20 each represents a hydrocarbon group having 6 to 30 carbon atoms. * Represents a bond. ]
- the hydrocarbon group having 6 to 30 carbon atoms of R 13 to R 17 , R 19 to R 20 and R 15 ′ is preferably a branched hydrocarbon group. More preferably, it is a branched chain saturated hydrocarbon group.
- the hydrocarbon groups of R 13 to R 17 , R 19 to R 20 and R 15 ′ have a branch, so that the solubility in an organic solvent can be increased, and the polymer compound of the present invention has an appropriate crystallinity. Obtainable.
- the larger the carbon number of the hydrocarbon group of R 13 to R 17 , R 19 to R 20 , and R 15 ′ the more the solubility in organic solvents can be improved.
- the carbon number of the hydrocarbon group of R 13 to R 17 , R 19 to R 20 and R 15 ′ is preferably 8 to 25, more preferably 8 to 20, and still more preferably 8 to 16. is there.
- Examples of the hydrocarbon group having 6 to 30 carbon atoms represented by R 13 to R 17 , R 19 to R 20 and R 15 ′ include an alkyl group having 6 carbon atoms such as an n-hexyl group; an n-heptyl group An alkyl group having 7 carbon atoms such as n-octyl group, 1-n-butylbutyl group, 1-n-propylpentyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1 An alkyl group having 8 carbon atoms such as a methylheptyl group, a 2-methylheptyl group, a 6-methylheptyl group, a 2,4,4-trimethylpentyl group or a 2,5-dimethylhexyl group; an n-nonyl group, 1- n-propylhexyl group, 2-n-
- Alkyl group Alkyl group; and the like.
- An alkyl group having 8 to 20 carbon atoms is preferable, an alkyl group having 8 to 16 carbon atoms is more preferable, a branched alkyl group having 8 to 16 carbon atoms is further preferable, and 2-ethylhexyl is particularly preferable.
- R 13 to R 17 , R 19 to R 20 , and R 15 ′ are the above groups, the polymer compound of the present invention has improved solubility in an organic solvent and has appropriate crystallinity.
- the number of carbon atoms of the aliphatic hydrocarbon group of R 18 is preferably Is 1 to 18, more preferably 1 to 8.
- the aliphatic hydrocarbon group for R 18 include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group, an octyl group, and an octadecyl group.
- the number of carbon atoms of the aromatic hydrocarbon group for R 18 is preferably 6 to 8, more preferably 6 to 7, and particularly preferably 6.
- R 18 examples include a phenyl group.
- R 18 is preferably an aliphatic hydrocarbon group, more preferably a branched aliphatic hydrocarbon group, and particularly preferably an isopropyl group.
- the plurality of R 18 may be the same or different, but are preferably the same.
- R 15 to R 17 and R 15 ′ are a group represented by * —Si (R 18 ) 3
- the polymer compound of the present invention has improved solubility in an organic solvent.
- the groups represented by * -Si (R 18 ) 3 in R 15 to R 17 and R 15 ′ are specifically a trimethylsilyl group, an ethyldimethylsilyl group, Alkylsilyl groups such as isopropyldimethylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, triethylsilyl group, triisobutylsilyl group, tripropylsilyl group, tributylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group; And arylsilyl groups such as triphenylsilyl group and tert-butylchlorodiphenylsilyl group.
- an alkylsilyl group is preferable, and a trimethylsilyl group and a triisopropylsilyl group are particularly preferable.
- R 17 is a halogen atom
- any of fluorine, chlorine, bromine and iodine can be used.
- R 15 ′ is a hydrogen atom, a hydrocarbon group having 6 to 30 carbon atoms exemplified as R 15 , or a group similar to the group represented by * —Si (R 18 ) 3 .
- groups represented by formulas (t1), (t3), and (t5) are preferable from the viewpoint of excellent planarity as a whole structural unit represented by formula (1). More preferred is a group represented by the formula (t3), and further preferred are groups represented by the following formulas (t3-1) to (t3-16). In the formula, * represents a bond.
- an electron donating group or an electron withdrawing group can be used.
- the electron donating group include groups represented by formulas (t1) to (t3).
- R 13 to R 15 and R 15 ′ represent the same groups as described above.
- R 17 each independently represents a hydrocarbon group having 6 to 30 carbon atoms, * —O—R 19 or * —S—R 20 . * Represents a bond.
- Examples of the electron withdrawing group that can be used as T 1 and T 2 include groups represented by formulas (t4) to (t5).
- R 16 represents the same group as described above.
- R 17 represents a halogen atom or a trifluoromethyl group. * Represents a bond.
- B 1 and B 2 may be the same or different from each other, but are the same from the viewpoint of easy production. Preferably there is.
- B 1 and B 2 are each preferably a group represented by any of the following formulas (b1) to (b3).
- B 1 and B 2 are groups represented by the following formulas (b1) to (b3), the obtained polymer compound has good planarity, and the photoelectric conversion efficiency can be further improved.
- R 21 , R 22 and R 21 ′ represent a hydrogen atom or a hydrocarbon group having 6 to 30 carbon atoms. * Represents a bond, and in particular, * on the left side represents a bond bonded to the benzene ring of the benzobisthiazole compound. ]
- Examples of the hydrocarbon group having 6 to 30 carbon atoms of R 21 , R 22 and R 21 ′ are exemplified as the hydrocarbon group having 6 to 30 carbon atoms of R 13 to R 17 , R 19 to R 20 and R 15 ′ .
- a group can be preferably used. It is preferable that R 21 , R 22 , and R 21 ′ are hydrogen atoms because a donor-acceptor type semiconductor polymer can be easily formed. In addition, it is preferable that R 21 , R 22 , and R 21 ′ are hydrocarbon groups having 6 to 30 carbon atoms because the photoelectric conversion efficiency may be further improved.
- B 1 and B 2 are more preferably groups represented by the formulas (b1) and (b2).
- B 1 and B 2 are groups represented by the formulas (b1) and (b2)
- an interaction between an S atom and an N atom occurs in the benzobisthiazole structural unit (1), and planarity is further improved.
- B 1 and B 2 specifically, a group represented by the following formula is preferable.
- * represents a bond
- * on the left side is bonded to the benzene ring of benzobisthiazole.
- examples of the structural unit represented by the formula (1) include groups represented by the following formulas (1-1) to (1-48).
- R 30 to R 60 are each independently the same as the hydrocarbon group having 6 to 30 carbon atoms of R 13 to R 17 , R 19 to R 20 , and R 15 ′ .
- a 30 and A 31 each independently represent a group similar to T 1 and T 2 .
- the groups represented by the above formulas (c1) to (c18) are groups that act as acceptor units, and the groups represented by the formulas (c20) to (c31) are groups that act as donor units. It is.
- the group represented by the formula (c19) may act as an acceptor unit or may act as a donor unit depending on the types of A 30 and A 31 .
- the weight average molecular weight and number average molecular weight of the polymer compound of the present invention are generally 2,000 or more and 500,000 or less, more preferably 3,000 or more and 200,000 or less.
- the weight average molecular weight and number average molecular weight of the polymer compound of the present invention can be calculated based on a calibration curve prepared using polystyrene as a standard sample using gel permeation chromatography.
- the ionization potential of the polymer compound of the present invention is preferably 4 eV or more, more preferably 4.5 eV or more, still more preferably 5 eV or more, and particularly preferably 5.1 eV or more.
- the upper limit of ionization potential is not specifically limited, For example, it is 7 eV or less, it is preferable that it is 6.5 eV or less, and it is preferable that it is 6.2 eV or less.
- the HOMO level is appropriately deepened (lowered), so that both a high open-circuit voltage (Voc) and a short-circuit current density (Jsc) can be obtained. It becomes possible, and higher photoelectric conversion efficiency can be obtained.
- Compound 2-1 Compound Represented by Formula (5)
- the present invention includes a compound represented by the following formula (5) (hereinafter sometimes referred to as “compound (5)”).
- T 1 and T 2 are each independently a thiophene ring, hydrocarbon group or organosilyl group optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group or an organosilyl group. It represents a thiazole ring which may be substituted, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group.
- B 3 and B 4 represent a thiophene ring which may be substituted with an alkyl group or a thiazole ring which may be substituted with an alkyl group.
- R 1 to R 4 each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
- M 1 and M 2 each independently represent a boron atom or a tin atom.
- R 1 and R 2 may form a ring together with M 1
- R 3 and R 4 may form a ring together with M 2 .
- m and n each represents an integer of 1 or 2. When m and n are 2, the plurality of R 1 and R 3 may be the same or different. ]
- B 3 and B 4 may be the same or different from each other, but are preferably the same from the viewpoint of easy production.
- B 3 and B 4 are preferably groups represented by the above formulas (b1) to (b2).
- the number of carbon atoms of the aliphatic hydrocarbon group of R 1 to R 4 is preferably 1 to 5, and more preferably 1 to 4.
- a methyl group, an ethyl group, a propyl group, and a butyl group are preferable, and a methyl group and a butyl group are more preferable.
- the number of carbon atoms of the alkoxy group of R 1 to R 4 is preferably 1 to 3, and more preferably 1 to 2.
- alkoxy group for R 1 to R 4 a methoxy group, an ethoxy group, a propoxy group and the like are preferable, and a methoxy group and an ethoxy group are more preferable.
- the number of carbon atoms of the aryloxy group of R 1 to R 4 is preferably 6 to 9, and more preferably 6 to 8.
- Examples of the aryloxy group for R 1 to R 4 include a phenyloxy group, a benzyloxy group, a phenylenebis (methyleneoxy) group, and the like.
- R 1 to R 4 are preferably a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms, m, n Is preferably 1.
- * -M 1 (R 1 ) m R 2 and * -M 2 (R 3 ) n R 4 when M 1 and M 2 are boron atoms include groups represented by the following formulae. . * Represents a bond.
- R 1 to R 4 are preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and m and n are preferably 2.
- Examples of * -M 1 (R 1 ) m R 2 and * -M 2 (R 3 ) n R 4 when M 1 and M 2 are tin atoms include groups represented by the following formulae. . However, * represents a bond.
- the compound (5) is an intermediate compound used for the synthesis of the polymer compound of the present invention. Since this compound (5) has the above-mentioned predetermined group, it has high temporal stability and can react efficiently to form the polymer compound of the present invention.
- the compound represented by a following formula can be illustrated, for example.
- the compounds represented by the formulas (5-33) to (5-64) in which the methyl group on the tin atom is substituted with a butyl group are also represented by the compounds ( A preferred example is 5).
- the present invention includes a compound represented by the following formula (4) (hereinafter sometimes referred to as “compound (4)”).
- T 1 , T 2 , B 1 and B 2 each represent the same group as described above.
- Compound (4) is a raw material of the compound (5). That is, the compound (4) corresponds to an intermediate of the compound (5). Since this compound (4) has the above-mentioned predetermined group, it has high temporal stability and has an efficient reactivity. Examples of the compound (4) include the following compounds.
- Compound Represented by Formula (3) The present invention includes a compound represented by the following formula (3) (hereinafter sometimes referred to as “compound (3)”).
- T 1 , T 2 , X 1 and X 2 each represent the same group as described above.
- halogen atom for X examples include chlorine, bromine and iodine. Either can be used, but iodine is particularly preferred from the viewpoint of the balance between reactivity and stability.
- the compound (3) is a raw material for the compound (4). That is, the compound (3) corresponds to an intermediate of the compound (6). Since this compound (3) has the above-mentioned predetermined group, it has high aging stability and high solubility in an organic solvent, and thus has an efficient reactivity. Furthermore, by using the compound (3), various skeletons and substituents can be introduced into the polymer compound of the present invention. Examples of the compound (3) include the following compounds.
- a compound represented by the following formula (3 ′) (hereinafter sometimes referred to as “compound (3 ′)”) is also produced.
- compound (3 ′) in formulas (1), (4) and (5), only at one of the two substitutable positions present on the benzene ring of benzobisthiazole, A compound in which the groups represented by B 1 and B 2 are substituted can be obtained.
- Such a compound is useful, for example, for the terminal portion of the polymer compound of the present invention.
- T 1 , T 2 and X 1 each represent the same group as described above.
- Examples of the compound (3 ′) include compounds represented by the following formula.
- Compound Represented by Formula (2) The present invention includes a compound represented by the following formula (2) (hereinafter sometimes referred to as “compound (2)”).
- T 1 and T 2 each represent the same group as described above.
- the compound (2) is a raw material for the compound (3). That is, the compound (2) corresponds to an intermediate of the compound (5). Since this compound (2) has the above-mentioned predetermined group, it has high temporal stability and has an efficient reactivity. Furthermore, by using the compound (2), various skeletons and substituents can be introduced into the polymer compound of the present invention. Examples of the compound (2) include the following compounds.
- the polymer compound represented by the formula (1) of the present invention includes 2,6-diiodobenzo [1,2-d: 4,5-d ′] bisthiazole and 2,6-dibromobenzo [1 , 2-d: 4,5-d ′] bisthiazole as a starting material, a compound represented by formula (2),
- T 1 , T 2 , X 1 and X 2 each represent the same group as described above.
- T 1 , T 2 , B 1 and B 2 each represent the same group as described above. ] It is manufactured by the manufacturing method characterized by passing through.
- the method for producing a polymer compound of the present invention further comprises a compound represented by formula (5)
- T 1 , T 2 , B 3 , B 4 , R 1 to R 4 , M 1 , M 2 , m, and n each represent the same group as described above. ] It is preferable to go through.
- the manufacturing method of this invention includes the following 1st process.
- a metal catalyst one compound selected from the group consisting of formula (6) and / or formula (7)
- T 1 and T 2 each represent the same group as described above.
- R 5 and R 6 each independently represents a hydrogen atom or * -M 3 (R 7 ) k R 8 .
- R 7 and R 8 each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
- M 3 represents a boron atom or a tin atom. * Represents a bond.
- R 7 and R 8 may form a ring together with M 3 .
- k represents an integer of 1 or 2. When k is 2, the plurality of R 7 may be the same or different.
- 2,6-diiodobenzo [1,2-d: 4,5-d ′] bisthiazole and 2,6-dibromobenzo [1,2-d: 4,5-d ′] bis As one compound selected from the group consisting of thiazole (hereinafter sometimes referred to as “2,6-dihalogenated benzobisthiazole”), 2,6-diiodobenzo [1,2-d: 4,5- d ′] bisthiazole is preferred.
- the compound represented by the formula (6) and / or (7) to be reacted with 2,6-dihalogenated benzobisthiazole hereinafter sometimes referred to as “compound (6)” or “compound (7)”).
- the carbon number of the aliphatic hydrocarbon group of R 7 and R 8 when R 5 and R 6 are M 3 (R 7 ) k R 8 is preferably 1 to 5, more preferably 1 to 4.
- Examples of the aliphatic hydrocarbon group for R 7 and R 8 include a methyl group, an ethyl group, a propyl group, and a butyl group.
- the number of carbon atoms of the alkoxy group of R 7 and R 8 is preferably 1 to 3, more preferably 1 to 2.
- the alkoxy group for R 7 and R 8 is preferably a methoxy group, an ethoxy group, a propoxy group, or the like, more preferably a methoxy group or an ethoxy group.
- the number of carbon atoms of the aryloxy group of R 7 and R 8 is preferably 6 to 9, and more preferably 6 to 8.
- Examples of the aryloxy group for R 7 and R 8 include a phenyloxy group, a benzyloxy group, and a phenylenebis (methyleneoxy) group.
- R 7 and R 8 are * -M 3 (R 7 ) k R 8 and M 3 is a boron atom
- R 7 and R 8 are a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or carbon It is preferably an aryloxy group of several 6 to 10, and k is preferably 1.
- * -M 3 (R 7 ) k R 8 when M 3 is a boron atom include groups represented by the following formulae. * Represents a bond.
- R 7 and R 8 When R 5 and R 6 are * -M 3 (R 7 ) k R 8 and M 3 is a tin atom, R 7 and R 8 must be an aliphatic hydrocarbon group having 1 to 6 carbon atoms. And k is preferably 2. Examples of * -M 3 (R 7 ) k R 8 in the case where M 3 is a tin atom include groups represented by the following formulae. * Represents a bond.
- R 5 and R 6 can be appropriately selected according to the types of T 1 and T 2 .
- T 1 and T 2 are groups represented by formulas (t1) and (t2)
- R 5 and R 6 are preferably hydrogen atoms.
- T 1 and T 2 are groups represented by formulas (t3) to (t5)
- R 5 and R 6 are groups represented by * -M 3 (R 7 ) k R 8.
- the group represented by * -Sn (R 7 ) 2 R 8 is more preferable.
- Examples of the compounds (6) and (7) include compounds represented by the following formula.
- the compounds (6) and (7) may be the same or different depending on the target compound, but are preferably the same from the viewpoint of suppressing the formation of by-products.
- the molar ratio of 2,6-dihalogenated benzobisthiazole to the total of compounds (6) and (7) (2,6-dihalogenated benzobisthiazole: total of compounds (6) and (7) ) Is generally about 1: 1 to 1:10 and is not particularly limited, but is preferably 1: 1.5 to 1: 8, more preferably 1: 2 to 1: 6, from the viewpoint of yield and reaction efficiency. More preferably, 1: 2 to 1: 5.
- the metal catalyst used in the reaction of 2,6-dihalogenated benzobisthiazole with compound (6) and / or compound (7) includes a palladium catalyst, a nickel catalyst, an iron catalyst, copper And transition metal catalysts such as rhodium catalysts, rhodium catalysts, and ruthenium catalysts.
- a copper catalyst and a palladium catalyst are preferable.
- the valence of palladium is not particularly limited, and may be zero or divalent.
- the palladium-based catalyst examples include palladium (II) chloride, palladium (II) bromide, palladium (II) iodide, palladium (II) oxide, palladium (II) sulfide, palladium (II) telluride, palladium hydroxide ( II), palladium selenide (II), palladium cyanide (II), palladium acetate (II), palladium trifluoroacetate (II), palladium acetylacetonate (II), diacetate bis (triphenylphosphine) palladium (II) ), Tetrakis (triphenylphosphine) palladium (0), dichlorobis (triphenylphosphine) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (benzonitrile) palladium (II), dichloro [1,2 Bis (diphenyl
- the copper catalyst examples include copper, copper fluoride (I), copper chloride (I), copper bromide (I), copper iodide (I), copper fluoride (II), copper chloride (II), odor Copper halide compounds such as copper (II) iodide, copper (II) iodide; copper (I) oxide, copper (I) sulfide, copper oxide (II), copper sulfide (II), copper acetate (I), acetic acid Examples include copper (II) and copper (II) sulfate.
- the metal catalyst can be appropriately selected according to the types of T 1 and T 2.
- T 1 and T 2 are groups represented by the formulas (t1) and (t2)
- a copper-based catalyst is preferable, a copper halide compound is more preferable, and copper (I) iodide is most preferable. It is preferable that a base coexists.
- the metal catalyst is preferably a palladium catalyst, and dichlorobis (triphenyl) Phosphine) palladium (II), tris (dibenzylideneacetone) dipalladium (0), and tris (dibenzylideneacetone) dipalladium (0) chloroform adduct are particularly preferred.
- the molar ratio of 2,6-dihalogenated benzobisthiazole to metal catalyst is generally about 1: 0.0001 to 1: 0.5. Although not particularly limited, it is preferably 1: 0.001 to 1: 0.4, more preferably 1: 0.005 to 1: 0.3, and 1: 0.01 to 1 from the viewpoint of yield and reaction efficiency. 1: 0.2 is more preferable.
- a specific ligand may be coordinated with a metal catalyst such as a copper catalyst or a palladium catalyst.
- the ligands include trimethylphosphine, triethylphosphine, tri (n-butyl) phosphine, tri (isopropyl) phosphine, tri (tert-butyl) phosphine, tri-tert-butylphosphonium tetrafluoroborate, bis (tert-butyl) ) Methylphosphine, tricyclohexylphosphine, diphenyl (methyl) phosphine, triphenisphosphine, tris (o-tolyl) phosphine, tris (m-tolyl) phosphine, tris (p-tolyl) phosphine, tris (2-furyl) phosphine, Tris (2-methoxyphenyl) phosphine, Tris (3-methoxy
- triphenylphosphine tris (o-tolyl) phosphine, and tris (2-furyl) phosphine are preferable.
- the molar ratio of the metal catalyst to the ligand is generally about 1: 0.5 to 1:10. Although not particularly limited, it is preferably 1: 1 to 1: 8, more preferably 1: 1 to 1: 7, and even more preferably 1: 1 to 1: 5 from the viewpoint of yield and reaction efficiency.
- a base when reacting compound (6) and / or compound (7) with 2,6-dihalogenated benzobisthiazole in the presence of a metal catalyst, a base may coexist.
- T 1 and T 2 are groups represented by the formulas (t1) and (t2)
- it is preferable that a base coexists.
- T 1 and T 2 are groups represented by the formulas (t3) to (t5)
- the presence or absence of the base is determined depending on the types of R 5 and R 6. can do.
- R 5 and R 6 are groups represented by * -M 3 (R 7 ) k R 8 and M 3 is a boron atom
- R 7 and R 8 and M 3 is a boron atom
- M 3 is tin.
- a base does not have to coexist.
- Examples of the base include lithium metal hydride, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate and other alkali metal salt compounds; magnesium hydroxide, calcium hydroxide, barium hydroxide, Alkaline earth metal salt compounds such as magnesium carbonate, calcium carbonate, barium carbonate; lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium isopropoxide, sodium isopropoxide Potassium isopropoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, lithium tert-amyl alkoxide, sodium tert-amyl alkoxide It alkoxy alkali metal compounds such as potassium tert- amyl alkoxide; lithium hydride, sodium hydride, metal hydride compounds such as potassium hydride.
- an alkoxyalkali metal compound is preferable, and lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate, and cesium carbonate are more preferable.
- the molar ratio of 2,6-dihalogenated benzobisthiazole and base (2,6-dihalogenated benzobisthiazole: base) is generally about 1: 1 to 1:10 and is not particularly limited. From the viewpoint of yield and reaction efficiency, 1: 1.5 to 1: 8 is preferable, 1: 1.8 to 1: 6 is more preferable, and 1: 2 to 1: 5 is more preferable.
- the solvent for reacting compound (6) and / or compound (7) with 2,6-dihalogenated benzobisthiazole in the presence of a metal catalyst is not particularly limited as long as it does not affect the reaction.
- ether solvents, aromatic solvents, ester solvents, hydrocarbon solvents, halogen solvents, ketone solvents, amide solvents, and the like can be used.
- ether solvent examples include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, t-butyl methyl ether, and dioxane.
- aromatic solvent examples include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene.
- ester solvent examples include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate.
- Examples of the hydrocarbon solvent include pentane, hexane, and heptane.
- Examples of the halogen solvent include dichloromethane, chloroform, dichloroethane, and dichloropropane.
- Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
- Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl3,4,5,6-tetrahydro- (1H ) -Pyrimidine.
- a nitrile solvent such as acetonitrile, a sulfoxide solvent such as dimethyl sulfoxide, and a sulfone solvent such as sulfolane can be used.
- a nitrile solvent such as acetonitrile, a sulfoxide solvent such as dimethyl sulfoxide, and a sulfone solvent such as sulfolane
- tetrahydrofuran, dioxane, and N, N-dimethylformamide are particularly preferable.
- the amount of solvent used in the first step is generally 1 mL or more and 50 mL or less with respect to 1 g of 2,6-dihalogenated benzobisthiazole, and is not particularly limited, but is 5 mL or more from the viewpoint of yield and reaction efficiency. 40 mL or less, preferably 8 mL or more and 35 mL or less, more preferably 10 mL or more and 30 mL or less.
- the reaction temperature is not particularly limited, but is preferably 0 ° C. or higher and 200 ° C. or lower, more preferably 30 ° C. or higher and 180 ° C. or lower, and 40 ° C. or higher from the viewpoint of increasing the reaction yield. More preferably, it is 150 ° C. or lower.
- Second Step a step of obtaining a compound represented by the formula (3) by reacting a compound represented by the formula (2) with a base and a halogenating reagent.
- Examples of the base to be reacted with the compound (2) in the second step include alkyl lithium, alkyl metal amide, alkyl magnesium, magnesium complex, and alkali metal hydride.
- alkyl lithium examples include n-butyl lithium, sec-butyl lithium, and tert-butyl lithium.
- alkyl metal amide examples include lithium diisopropylamide, lithium diethylamide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, lithium-2,2,6,6-tetramethylpiperidide , Lithium amide, sodium amide, potassium amide.
- alkylmagnesium and the magnesium complex examples include tert-butylmagnesium chloride, ethylmagnesium chloride, 2,2,6,6-tetramethylpiperidinylmagnesium chloride, and lithium chloride complex.
- alkali metal hydride examples include lithium hydride, sodium hydride, and potassium hydride.
- alkyl metal amides are preferable from the viewpoint of regioselectivity, and n-butyllithium and lithium diisopropylamide are particularly preferable.
- the molar ratio of the compound (2) to the base is generally about 1: 1.8 to 1: 3.0, and is not particularly limited. In view of the above, 1: 1.9 to 1: 2.6 is preferable, 1: 2.0 to 1: 2.4 is more preferable, and 1: 2.0 to 1: 2.2 is more preferable.
- examples of the halogenating reagent to be reacted with the compound (2) together with a base include halogen molecules and N-halogenated succinimide.
- examples of the halogen molecule include chlorine, bromine and iodine.
- examples of the N-halogenated succinimide include N-chlorosuccinimide, N-bromosuccinimide, and N-iodosuccinimide. From the viewpoint of availability and reactivity, halogen molecules are preferable, and iodine is particularly preferable.
- the molar ratio of the compound (2) to the halogenating reagent is generally about 1: 1.5 to 1: 20.0 and is not particularly limited. From the viewpoint of rate and reaction efficiency, it is preferably 1: 1.7 to 1: 17.0, more preferably 1: 1.9 to 1: 15.0, and even more preferably 1: 2.0 to 1: 10.0. .
- the molar ratio of base to halogenating reagent is, for example, about 1: 0.5 to 1: 2.0, preferably 1: 0.6 to 1: 1.7, and 1: 0. 7 to 1: 1.5 is more preferable, and 1: 0.8 to 1: 1.2 is more preferable.
- the base and the halogenating reagent may be reacted at the same time, but from the viewpoint of reaction efficiency, it is preferable to first react the basic compound and then react with the halogenating reagent.
- the solvent for reacting the compound (2) with the base and the halogenating reagent is not particularly limited, but ether solvents and hydrocarbon solvents can be used.
- ether solvents include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, t-butyl methyl ether, and dioxane.
- the hydrocarbon solvent include pentane, hexane, heptane, benzene, toluene, and xylene. Of these, ether solvents are preferable, and tetrahydrofuran is particularly preferable.
- a solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
- the amount of the solvent used in the second step is generally 3 mL or more and about 150 mL with respect to 1 g of the compound (2) and is not particularly limited, but is preferably 5 mL or more and 120 mL or less from the viewpoint of yield and reaction efficiency. 8 mL or more and 100 mL or less are more preferable, and 10 mL or more and 80 mL or less are more preferable.
- the temperature at which the compound (2) is reacted with the base and the halogenating reagent is preferably room temperature or lower, more preferably ⁇ 30 ° C. or lower, from the viewpoint of suppressing the formation of by-products. Preferably, it is ⁇ 35 ° C. or lower.
- Third Step The production method of the present invention preferably includes the following third step.
- Third step The compound represented by the formula (3) is reacted with a compound represented by the following formula (8) and / or the formula (9) in the presence of a metal catalyst to represent the compound represented by the formula (4). To obtain a compound represented by the formula (3)
- B 1 and B 2 each represent the same group as described above.
- R 9 to R 12 are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 6 to 10 carbon atoms. Represents an aryloxy group.
- M 4 and M 5 each represent a boron atom, a tin atom, or a silicon atom.
- R 9 and R 10 may form a ring together with M 4
- R 11 and R 12 may form a ring together with M 5 .
- p and q represent an integer of 1 or 2. When p is 2, the plurality of R 9 may be the same or different. When q is 2, the plurality of R 11 may be the same or different. ]
- * -M 4 (R 9 ) p R 10 and * -M 5 (R 11 ) q R 12 are the compounds (6)
- the groups exemplified when R 11 and R 12 in (7) are * -M 3 (R 13 ) k R 14 , and in formulas (1) to (t5), R 15 to R 17 , R 15 ′ Preferred examples are the same groups as those exemplified when is * -Si (R 18 ) 3 .
- * -M 4 (R 9 ) p R 10 , * -M 5 (R 11 ) q R 12 is, for example, a group represented by the following formula: It can be preferably used. * Represents a bond.
- * -M 4 (R 9 ) p R 10 and * -M 5 (R 11 ) q R 12 are, for example, groups represented by the following formulae: Is mentioned. * Represents a bond.
- * -M 4 (R 9 ) p R 10 , * -M 5 (R 11 ) q R 12 is preferably an alkylsilyl group, such as a trimethylsilyl group or triisopropylsilyl group The group is particularly preferred.
- B 1 and B 2 may be a thiophene ring optionally substituted with a hydrocarbon group (preferably a group represented by the formula (b1)) or a thiazole ring optionally substituted with a hydrocarbon group (preferably Is a group represented by the formula (b2), it is preferable that M 4 and M 5 are a boron atom or a tin atom.
- B 1 and B 2 are an ethynylene group (preferably a group represented by the formula (b3))
- M 4 and M 5 are preferably silicon atoms.
- Examples of the compounds (8) and (9) include compounds represented by the following formulas.
- Compounds (8) and (9) may be the same or different depending on the target compound, but are preferably the same from the viewpoint of suppressing the formation of by-products.
- the molar ratio of compound (3) to the sum of compounds (8) and (9) is generally 1: 1 to 1: Although it is about 10 and is not particularly limited, it is preferably 1: 1.5 to 1: 8, more preferably 1: 2 to 1: 6, and still more preferably 1: 2 to 1: 5 from the viewpoint of yield and reaction efficiency. .
- the same metal catalyst as exemplified as the metal catalyst used in the first step is preferably used as the metal catalyst used when the compound (3) is reacted with the compounds (8) and / or (9).
- Transition metal catalysts such as palladium catalysts, nickel catalysts, iron catalysts, copper catalysts, rhodium catalysts, ruthenium catalysts, and the like.
- the metal catalyst used is preferably a palladium-based catalyst, such as dichlorobis (triphenylphosphine) palladium (II), tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0 ) Chloroform adduct is particularly preferred.
- the metal catalyst is preferably a copper-based catalyst when B 1 and B 2 in the formulas (8) and (9) are ethynylene groups (preferably groups represented by the formula (b3)).
- copper-based catalysts copper (II) iodide is particularly preferable.
- the molar ratio of the compound (3) to the metal catalyst is generally about 1: 0.0001 to 1: 0.5 and is not particularly limited. From the viewpoint of reaction efficiency, it is preferably 1: 0.001 to 1: 0.4, more preferably 1: 0.005 to 1: 0.3, and still more preferably 1: 0.01 to 1: 0.2.
- a specific ligand may be coordinated to a metal catalyst such as a copper catalyst or a palladium catalyst, and the ligand is the same as the ligand used in the first step.
- a metal catalyst such as a copper catalyst or a palladium catalyst
- the ligand is the same as the ligand used in the first step.
- the molar ratio of the metal catalyst to the ligand is generally about 1: 0.5 to 1:10. Although not particularly limited, it is preferably 1: 1 to 1: 8, more preferably 1: 1 to 1: 7, and even more preferably 1: 1 to 1: 5 from the viewpoint of yield and reaction efficiency.
- the compound (3), the presence of a metal catalyst, in the reaction of compound (8) and / or the compound (9) may be allowed to coexist bases of M 4, M 5
- the presence or absence of a base can be determined depending on the type. For example, when M 4 and M 5 are a boron atom and a silicon atom, it is preferable to make a base coexist, and when M 4 and M 5 are a tin atom, it is not necessary to make a base coexist.
- the base those similar to those exemplified as the base used in the first step can be preferably used.
- the base in addition to the base used in the first step, trimethylamine, triethylamine, tripropylamine, diisopropylethylamine, tributylamine, tripentylamine, trihexylamine, trioctylamine, triallylamine, pyridine, 2-methyl Pyridine, 3-methylpyridine, 4-methylpyridine, N-methylmorpholine, N, N-dimethylcyclohexylamine, N, N-dimethylaniline, N-methylimidazole, 1,4-diazabicyclo [2.2.2] octane Tertiary amines such as 1,8-diazabicyclo [5.4.0] undec-7-ene; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, dipentylamine, dihexylamine, dicycl
- Base can be selected depending on the kind of M 4, M 5, when M 4, M 5 is boron atom is preferably the base exemplified as the base used in the first step, more preferably, alkoxy alkali Metal compounds, more preferably lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate, and cesium carbonate.
- the base is preferably an amine, more preferably a secondary amine or a tertiary amine, and particularly preferably diisopropylamine, diisopropylethylamine, or triethylamine.
- the molar ratio of the compound (3) to the base is generally about 1: 1 to 1:50 and is not particularly limited, but is 1 from the viewpoint of yield and reaction efficiency. : 1.5 to 1:40 is preferable, 1: 1.8 to 1:35 is more preferable, and 1: 2 to 1:30 is more preferable.
- the molar ratio of compound (3) to base is preferably 1: 1 to 1:10, and 1: 1.5 to 1: 8 is more preferable, 1: 1.8 to 1: 6 is more preferable, and 1: 2 to 1: 5 is particularly preferable.
- the molar ratio of the compound (3) to the base is preferably 1: 1 to 1:50, more preferably 1: 5 to 1. : 40, more preferably 1: 8 to 1:35, and particularly preferably 1:10 to: 35.
- the same solvent as used in the first step is preferably used as a solvent for reacting compound (3) with compound (8) and / or compound (9) in the presence of a metal catalyst.
- a metal catalyst be able to.
- tetrahydrofuran, dioxane, and N, N-dimethylformamide are particularly preferable.
- the amount of the solvent used in the third step is generally not less than 1 mL and not more than 50 mL with respect to 1 g of compound (3), but is preferably 5 mL or more and 40 mL or less from the viewpoint of yield and reaction efficiency. 8 mL or more and 35 mL or less is more preferable, and 10 mL or more and 30 mL or less is more preferable.
- M 4 and M 5 are silicon atoms
- the total amount of the solvent and the base (preferably amine) used is generally 1 mL or more and 50 mL or less with respect to 1 g of the compound (3).
- the amount of the solvent used is, for example, 100% by volume or less, more preferably 80% by volume or less, and still more preferably 60% in a total of 100% by volume of the solvent and the base. % By volume or less. Further, the amount of the solvent used may be 40% by volume or less, more preferably 20% by volume or less in 100% by volume of the solvent and the base in total, and 0% by volume, that is, completely used. Not necessary.
- the reaction temperature is not particularly limited, but is preferably 0 ° C. or higher and 200 ° C. or lower, more preferably 30 ° C. or higher and 180 ° C. or lower, and 40 ° C. or higher from the viewpoint of increasing the reaction yield. More preferably, it is 150 ° C. or lower.
- B 1 and B 2 in formulas (8) and (9) are ethynylene groups (preferably groups represented by formula (b3)), and M 4 and M 5 are silicon atoms.
- the compound obtained by reacting compound (3) with compounds (8) and (9) has the following reaction formula:
- T 1 , T 2 , R 9 to R 12 , X 1 and X 2 each represent the same group as described above.
- the production method of the present invention preferably further includes a deorganosilyl group step.
- the deorganosilyl group step the following deorganosilyl group step 1 or deorganosilyl group step 2 is preferable.
- Deorganosilyl group step 1 * -Si (R 9 ) p R 10 , * -Si (R 11 ) q A compound having a group derived from R 12 is reacted with a base in an alcohol solvent to obtain *- Step of eliminating a group derived from Si (R 9 ) p R 10 , * -Si (R 11 ) q R 12
- Deorganosilyl group Step 2 * -Si (R 9 ) p R 10 , * -Si A compound having a group derived from (R 11 ) q R 12 is reacted with a fluorine compound to form a group derived from * -Si (R 9 ) p R 10 , * -Si (R 11 ) q R 12. Desorption process
- the deorganosilyl group step may be performed on the compound obtained by reacting the compound (3) with the compounds (8) and (9), and a coupling step described later. You may carry out with respect to the high molecular compound obtained by. That is, the deorganosilyl group step may be performed between the third step and the coupling step, or may be performed after the coupling step.
- B 1 and B 2 are an ethynylene group (preferably a group represented by the formula (b3))
- the fourth step may not be performed in the production method of the present invention.
- Deorganosilyl group step 1 Examples of the base used in the deorganosilyl group step 1 include alkali metal salt compounds such as sodium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; magnesium hydroxide, calcium hydroxide, barium hydroxide Alkaline earth metal salt compounds such as magnesium carbonate, calcium carbonate, barium carbonate; lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium isopropoxide, sodium isopropoxy Potassium isopropylpropoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, lithium tert-amyl alkoxide, sodium tert-amylal Kishido, alkoxy alkali metal compounds such as potassium tert- amyl alkoxides.
- alkali metal salt compounds such as sodium hydroxide
- the molar ratio (compound: base) of the compound and base obtained by reacting compound (3) with compounds (8) and (9) is generally from 1: 0.01 to 1: Although it is about 10 and is not particularly limited, it is preferably from 1: 0.03 to 1: 8, more preferably from 1: 0.05 to 1: 6, and from 1: 0.1 to 1: from the viewpoint of yield and reaction efficiency. 5 is more preferable.
- the reaction proceeds even if the base has a molar amount equivalent to that of the catalyst.
- Examples of the alcohol solvent used in the deorganosilyl group step 1 include methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol, tert-butanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, 2-ethylhexanol, and the like. And methanol and ethanol are particularly preferable.
- the same solvent as used in the first step may be used together. Examples of such a solvent include ether solvents such as tetrahydrofuran, and aromatic solvents such as toluene.
- amide solvents such as dimethylformamide.
- Use of such a solvent is preferable because a compound having a group derived from * -Si (R 9 ) p R 10 and * -Si (R 11 ) q R 12 is easily dissolved.
- the amount of the alcohol solvent used is generally 1 mL or more and 50 mL or less with respect to 1 g of the compound obtained by reacting the compound (3) with the compounds (8) and (9). Although it is about and is not particularly limited, from the viewpoint of yield and reaction efficiency, 5 mL or more and 40 mL or less are preferable, 8 mL or more and 35 mL or less are more preferable, and 10 mL or more and 30 mL or less are more preferable.
- the reaction temperature is not particularly limited, but it is preferably 0 ° C. or higher and 200 ° C. or lower, more preferably 10 ° C. or higher and 180 ° C. or lower from the viewpoint of increasing the reaction yield. More preferably, the temperature is 20 ° C. or higher and 150 ° C. or lower.
- the fluorine compound used in the deorganosilyl group step 2 includes lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, magnesium fluoride, calcium fluoride, barium fluoride, ammonium fluoride, tetramethylammonium fluoride.
- Tetraethylammonium fluoride Tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, tetrapentylammonium fluoride, tetrahexylammonium fluoride, etc.
- sodium fluoride, potassium fluoride, tetraethylammonium fluoride, tetrabutyl Ammonium fluoride is preferred.
- the molar ratio of the compound obtained by reacting the compound (3) with the compounds (8) and (9) and the fluorine compound is generally 1: 1 to 1: Although it is about 10 and is not particularly limited, it is preferably 1: 1.5 to 1: 8, more preferably 1: 1.8 to 1: 6, and 1: 2 to 1: 5 from the viewpoint of yield and reaction efficiency. Further preferred.
- the same solvent as that used in the first step can be preferably used.
- tetrahydrofuran, dioxane, and N, N-dimethylformamide are particularly preferable.
- the amount of the solvent used is generally 1 mL or more and 50 mL or less with respect to 1 g of the compound obtained by reacting the compound (3) with the compounds (8) and (9).
- the amount of the solvent used is generally 1 mL or more and 50 mL or less with respect to 1 g of the compound obtained by reacting the compound (3) with the compounds (8) and (9).
- 5 mL or more and 40 mL or less are preferable, 8 mL or more and 35 mL or less are more preferable, and 10 mL or more and 30 mL or less are more preferable.
- the reaction temperature is not particularly limited, but it is preferably 0 ° C. or higher and 200 ° C. or lower, more preferably 10 ° C. or higher and 180 ° C. or lower from the viewpoint of increasing the reaction yield. More preferably, the temperature is 20 ° C. or higher and 150 ° C. or lower.
- the production method of the present invention preferably includes the following fourth step.
- Fourth step A step of reacting a compound represented by the formula (4) with a base and a tin halide compound to obtain a compound represented by the formula (5).
- the compound (4) In Formula (4), B 1 and B 2 may be substituted with a thiophene ring (preferably a group represented by Formula (b1)) which may be substituted with a hydrocarbon group, or a hydrocarbon group.
- a good thiazole ring preferably a group represented by the formula (b2)
- any of the bases exemplified in the second step can be used.
- an alkyl metal amide is preferable, and lithium diisopropylamide is particularly preferable.
- the molar ratio of the compound (4) to the base is generally about 1: 1 to 1: 5 and is not particularly limited, but is 1 from the viewpoint of yield and reaction efficiency. : 1.1 to 1: 4 is preferable, 1: 1.5 to 1: 3 is more preferable, and 1: 1.8 to 1: 2.5 is more preferable.
- examples of the tin halide compound to be reacted with the compound (4) together with a base include a halogenated alkyltin compound, a halogenated cycloalkyltin compound, and a halogenated aryltin compound.
- examples of the halogenated alkyltin compounds include triethyltin chloride, tripropyltin chloride, tributyltin chloride, trimethyltin bromide, triethyltin bromide, tripropyltin bromide, and tributyltin bromide.
- halogenated cycloalkyl tin compound examples include tricyclohexyl tin chloride and tricyclohexyl tin bromide.
- halogenated aryl tin compound examples include triphenyl tin chloride, tribenzyl tin chloride, triphenyl tin bromide, and tribenzyl tin bromide.
- a halogenated alkyltin compound is preferable, and trimethyltin chloride and tributyltin chloride are more preferable.
- the molar ratio of the compound (4) to the halogenated silane compound is generally about 1: 1 to 1: 5 and is not particularly limited. From the viewpoint of reaction efficiency, 1: 1.1 to 1: 4 is preferable, 1: 1.5 to 1: 3 is more preferable, and 1: 1.8 to 1: 2.5 is more preferable.
- the molar ratio of the base and the tin halide compound is, for example, about 1: 0.5 to 1: 2.0, preferably 1: 0.6 to 1: 1.7. The ratio is more preferably 1: 0.7 to 1: 1.5, and further preferably 1: 0.8 to 1: 1.2.
- the base and the tin halide compound may be reacted with the compound (4) at the same time, from the viewpoint of the reaction yield, the compound (4) is first reacted with the base and then the tin halide compound is reacted. preferable.
- the temperature at which the compound (4) is reacted with the base and then the tin halide compound is added is preferably room temperature or lower, and preferably 0 ° C. or lower from the viewpoint of suppressing the formation of by-products. More preferred.
- a solvent for reacting the compound (4) with a base and a tin halide compound is not particularly limited, but an ether solvent, a hydrocarbon solvent, or the like can be used.
- the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, t-butyl methyl ether, and dioxane.
- the hydrocarbon solvent include pentane, hexane, heptane, benzene, toluene, and xylene. Of these, tetrahydrofuran is preferred.
- a solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
- the amount of solvent used in the fourth step is generally 1 mL or more and 70 mL or less with respect to 1 g of compound (4), and is not particularly limited, but is preferably 5 mL or more and 60 mL or less from the viewpoint of yield and reaction efficiency. 10 mL or more and 50 mL are more preferable, and 20 mL or more and 45 mL or less are more preferable.
- the coupling reaction can be performed by reacting the compound (4) or the compound (5) with any of the compounds represented by the following formulas (C1) to (C31) in the presence of a metal catalyst.
- R is R 30 ⁇ R 60 are each independently same groups as the hydrocarbon group of R 13 ⁇ R 17, R 19 ⁇ 6 to 30 carbon atoms in R 20 A 30 and A 31 each independently represent the same group as T 1 and T 2, and Y represents a halogen atom.
- the compounds represented by the above formulas (C1) to (C18) are compounds that form acceptor units, and the compounds represented by formulas (C20) to (C31) are compounds that form donor units. It is.
- the compound represented by the formula (C19) may form an acceptor unit or a donor unit depending on the types of A 30 and A 31 .
- the compound of the present invention subjected to the coupling reaction can be selected according to the types of B 1 and B 2 in the formulas (4) and (5), and B 1 and B 2 are substituted with a hydrocarbon group.
- a thiophene ring preferably a group represented by the formula (b1)
- a thiazole ring preferably a group represented by the formula (b2)
- the compound (5) is preferably used, and when B 1 and B 2 are an ethynylene group (preferably a group represented by the formula (b3)), the compound (4) is preferably used.
- the molar ratio between the compound (4) or the compound (5) and any one of the compounds represented by the formulas (C1) to (C26) is preferably in the range of 1:99 to 99: 1, and 20:80 It is preferably in the range of ⁇ 80: 20, more preferably in the range of 40:60 to 60:40.
- a transition metal catalyst is preferable, and examples of the transition metal catalyst include a palladium catalyst, a nickel catalyst, an iron catalyst, a copper catalyst, a rhodium catalyst, and a ruthenium catalyst. Among these, a palladium-based catalyst is preferable.
- the palladium of the palladium-based catalyst may be zero-valent or divalent.
- any of the palladium-based catalysts exemplified in the first step can be used, and these catalysts may be used alone or in combination of two or more.
- tris (dibenzylideneacetone) dipalladium (0) and tris (dibenzylideneacetone) dipalladium (0) chloroform adduct are particularly preferable.
- the molar ratio of the compound represented by formula (4) or (5) to the metal catalyst is generally from 1: 0.0001 to 1: 0. Although not particularly limited, it is preferably 1: 0.001 to 1: 0.3, more preferably 1: 0.005 to 1: 0.2, and 1: 0. More preferably, the ratio is .01 to 1: 0.1.
- a specific ligand may be coordinated with the metal catalyst.
- the ligand any of the ligands exemplified in the first step can be used, and a catalyst coordinated with any of these ligands may be used in the reaction.
- a ligand may be used individually by 1 type and may be used in mixture of 2 or more types. Of these, triphenylphosphine, tris (o-tolyl) phosphine, and tris (2-methoxyphenyl) phosphine are preferable.
- the molar ratio of the metal catalyst to the ligand is generally about 1: 0.5 to 1:10. Although not particularly limited, it is preferably 1: 1 to 1: 8, more preferably 1: 1 to 1: 7, and even more preferably 1: 1 to 1: 5 from the viewpoint of yield and reaction efficiency.
- the solvent for reacting compound (4) or compound (5) with any of the compounds represented by formulas (C1) to (C26) is not particularly limited as long as it does not affect the reaction.
- Conventionally known solvents can be used.
- ether solvents, aromatic solvents, ester solvents, hydrocarbon solvents, halogen solvents, ketone solvents, amide solvents and the like can be used.
- ether solvent examples include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, tert-butyl methyl ether, and dioxane.
- aromatic solvent examples include benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, and tetralin.
- ester solvent examples include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate.
- hydrocarbon solvent examples include pentane, hexane, heptane, octane, and decalin.
- halogen solvent examples include dichloromethane, chloroform, dichloroethane, and dichloropropane.
- ketone solvent examples include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
- amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro- (1H ) -Pyrimidinone.
- nitrile solvents such as acetonitrile, sulfoxide solvents such as dimethyl sulfoxide, and sulfone solvents such as sulfolane can be used.
- sulfoxide solvents such as dimethyl sulfoxide
- sulfone solvents such as sulfolane
- tetrahydrofuran, toluene, chlorobenzene, and N, N-dimethylformamide are preferable, and chlorobenzene is particularly preferable.
- a solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
- the amount of the solvent used relative to 1 g in total of the compound (4) or compound (5) and the compounds represented by formulas (C1) to (C26) is generally about 1 mL or more and 150 mL or less, and is not particularly limited. However, from the viewpoint of yield and reaction efficiency, 5 mL or more and 100 mL or less are preferable, 8 mL or more and 90 mL or less are more preferable, and 10 mL or more and 80 mL or less are more preferable.
- NMR spectrum measurement About the benzobis thiazole compound, NMR spectrum measurement was performed using the NMR spectrum measuring apparatus (Agilent (formerly Varian), "400MR”, and Bruker, "AVANCE 500").
- the molecular weight of the benzobisthiazole compound was measured using gel permeation chromatography (GPC).
- GPC Gel permeation chromatography
- the benzobisthiazole compound was dissolved in a mobile phase solvent (chloroform) so as to have a concentration of 0.5 g / L, measured under the following conditions, and based on a calibration curve prepared using polystyrene as a standard sample. By conversion, the number average molecular weight and the weight average molecular weight of the benzobisthiazole compound were calculated.
- the GPC conditions in the measurement are as follows.
- HLC-8320GPC manufactured by Tosoh Corporation
- TSKgel registered trademark
- SuperHM-H′2 + TSKgel registered trademark
- SuperH2000 manufactured by Tosoh Corporation
- IR spectrum The IR spectrum of the benzobisthiazole compound was measured using an infrared spectrometer (manufactured by JASCO, “FT / IR-6100”).
- UV-visible absorption spectrum The obtained benzobisthiazole compound was dissolved in chloroform so as to have a concentration of 0.03 g / L, and an ultraviolet / visible spectrometer (“UV-2450”, “UV-3150” manufactured by Shimadzu Corporation) was dissolved. )) And UV-visible absorption spectrum measurement was performed using a cell having an optical path length of 1 cm.
- a benzobisthiazole compound was formed on a glass substrate so as to have a thickness of 50 nm to 100 nm.
- the ionization potential of this membrane was measured with an ultraviolet photoelectron analyzer (“AC-3” manufactured by Riken Keiki Co., Ltd.) at room temperature and normal pressure.
- tributyltin chloride (352 ⁇ L, 1.30 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, water was added and extracted twice with toluene. The organic layer was washed with water and then dried over anhydrous magnesium sulfate.
- a donor material: acceptor Material 1: 2 (weight) (total concentration 24 mg / mL) and 1,8-diiodooctane (0.03 mL / mL) were dissolved in chlorobenzene and passed through a 0.45 ⁇ m filter to obtain a mixed solution.
- the glass substrate on which the ITO film was formed was surface treated by ozone UV treatment, and then PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) was applied with a spin coater did.
- PEDOT-PSS [poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)
- the mixed solution of the above donor material and acceptor material was formed into a film with a spin coater and dried under reduced pressure at room temperature.
- an ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated to produce a film converted to titanium oxide by moisture in the atmosphere.
- aluminum as an electrode was deposited to obtain a device.
- the glass substrate on which the ITO film was formed was surface treated by ozone UV treatment, and then PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) was applied with a spin coater did.
- PEDOT-PSS [poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)
- the mixed solution of the above donor material and acceptor material was formed into a film with a spin coater and dried under reduced pressure at room temperature.
- an ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated to produce a film converted to titanium oxide by moisture in the atmosphere.
- aluminum which is an electrode was vapor-deposited to make a device.
- tributyltin chloride (352 ⁇ L, 1.30 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, water was added and extracted twice with toluene. The organic layer was washed with water and then dried over anhydrous magnesium sulfate.
- a device was prepared in the same manner as in Example 30 except that P-THHDT-DBTH-HTT obtained as described above was used instead of P-THDT-DBTH-EH-IMTH. Produced.
- the obtained device was subjected to characteristic evaluation using a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm 2 , manufactured by Spectrometer Co., Ltd.).
- Jsc short-circuit current density
- Voc open-circuit voltage
- FF fill factor
- conversion efficiency is 1.62%. confirmed.
- the glass substrate on which the ITO film was formed was surface treated by ozone UV treatment, and then PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) was applied with a spin coater did.
- PEDOT-PSS [poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)
- the mixed solution of the above donor material and acceptor material was formed into a film with a spin coater and dried under reduced pressure at room temperature.
- an ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated to produce a film converted to titanium oxide by moisture in the atmosphere.
- aluminum as an electrode was deposited to obtain a device.
- the obtained device was subjected to characteristic evaluation using a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm 2 , manufactured by Spectrometer Co., Ltd.).
- Jsc short-circuit current density
- Voc open end voltage
- FF curve factor
- tributyltin chloride 75 ⁇ L, 0.28 mmol was added, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, water was added and extracted twice with toluene. The organic layer was washed with water and then dried over anhydrous magnesium sulfate.
- P-THTIPSTH-DBTH-O-IMTH obtained as described above as a donor material and PCBM (C61) (phenyl C61-butyric acid methyl ester) as an acceptor material
- a donor material: acceptor Material 1: 1.5 (mass) (total concentration 20 mg / mL) and 1,8-diiodooctane (0.03 mL / mL) dissolved in chlorobenzene and mixed through a 0.45 ⁇ m filter It was.
- the glass substrate on which the ITO film was formed was surface treated by ozone UV treatment, and then PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) was applied with a spin coater did.
- PEDOT-PSS [poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)
- the mixed solution of the donor material / acceptor material was formed into a film with a spin coater and annealed at 150 ° C.
- an ethanol solution about 0.3% by volume
- tetraisopropyl orthotitanate was spin-coated to produce a film converted into titanium oxide by moisture in the atmosphere.
- aluminum which is an electrode was vapor-deposited to make a device.
- the obtained device was subjected to characteristic evaluation using a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm 2 , manufactured by Spectrometer Co., Ltd.).
- Jsc short-circuit current density
- Voc open-circuit voltage
- FF curve factor
- the polymer compound of the present invention has high photoelectric conversion efficiency, it is useful for organic electro devices such as organic electroluminescence elements and organic thin film transistor elements.
Abstract
Description
[式(1)中、T1、T2は、それぞれ独立に、アルコキシ基、チオアルコキシ基、炭化水素基もしくはオルガノシリル基で置換されていてもよいチオフェン環、炭化水素基もしくはオルガノシリル基で置換されていてもよいチアゾール環、または、炭化水素基、アルコキシ基、チオアルコキシ基、オルガノシリル基、ハロゲン原子、もしくは、トリフルオロメチル基で置換されていてもよいフェニル基を表す。また、B1、B2は、炭化水素基で置換されていてもよいチオフェン環、炭化水素基で置換されていてもよいチアゾール環、または、エチニレン基を表す。]
[式(t1)~(t5)中、R13~R14は、それぞれ独立に、炭素数6~30の炭化水素基を表す。R15~R16は、それぞれ独立に、炭素数6~30の炭化水素基、または、*-Si(R18)3で表される基を表す。R15'は、水素原子、炭素数6~30の炭化水素基、*-Si(R18)3で表される基を表す。R17は、それぞれ独立に、炭素数6~30の炭化水素基、*-O-R19、*-S-R20、*-Si(R18)3、または、*-CF3を表す。R18は、それぞれ独立に、炭素数1~20の脂肪族炭化水素基、または、炭素数6~10の芳香族炭化水素基を表し、複数のR18は、同一でも異なっていてもよい。R19~R20は、炭素数6~30の炭化水素基を表す。*は結合手を表す。]
[式(b1)~(b3)中、R21、R22、R21'は、水素原子または炭素数6~30の炭化水素基を表す。*は結合手を表し、特に左側の*は、ベンゾビスチアゾール化合物のベンゼン環に結合する結合手を表すものとする。]
[式(5)中、T1、T2、B1、B2は、それぞれ上記と同様の基を表す。R1~R4は、それぞれ独立に、炭素数1~6の脂肪族炭化水素基、水酸基、炭素数1~6のアルコキシ基、または、炭素数6~10のアリールオキシ基を表す。M1、M2は、それぞれ独立に、ホウ素原子または錫原子を表す。R1、R2は、M1とともに環を形成していてもよく、R3、R4は、M2とともに環を形成していてもよい。m、nは、それぞれ、1または2の整数を表す。また、m、nが2のとき、複数のR1、R3は、それぞれ同一でも、異なっていてもよい。]
式(2)で表される化合物、
第一工程:2,6-ジヨードベンゾ[1,2-d:4,5-d’]ビスチアゾール、および、2,6-ジブロモベンゾ[1,2-d:4,5-d’]ビスチアゾールからなる群より選ばれた1の化合物に、金属触媒の存在下、式(6)および/または式(7)
[式(6)、(7)中、T1、T2は、それぞれ上記と同様の基を表す。R5、R6は、それぞれ独立に、水素原子、または、*-M3(R7)kR8を表す。R7、R8は、それぞれ独立に、炭素数1~6の脂肪族炭化水素基、水酸基、炭素数1~6のアルコキシ基、または、炭素数6~10のアリールオキシ基を表す。M3は、ホウ素原子または錫原子を表す。*は結合手を表す。R7、R8は、M3とともに環を形成していてもよい。kは1または2の整数を表す。また、kが2のとき、複数のR7は、それぞれ同一でも、異なっていてもよい。]
で表される化合物を反応させて、式(2)で表される化合物を得る工程
第二工程:式(2)で表される化合物に塩基とハロゲン化試薬とを反応させて、式(3)で表される化合物を得る工程
第三工程:式(3)で表される化合物に、金属触媒の存在下、下記式(8)および/または式(9)で表される化合物を反応させて、式(4)で表される化合物を得る工程
[式(8)、(9)中、B1、B2は、それぞれ上記と同様の基を表す。R9~R12は、それぞれ独立に、炭素数1~6の脂肪族炭化水素基、水酸基、炭素数1~6のアルコキシ基、炭素数6~10のアリール基、または、炭素数6~10のアリールオキシ基を表す。M4、M5は、ホウ素原子、錫原子、または、ケイ素原子を表す。R9、R10は、M4とともに環を形成していてもよく、R11、R12は、M5とともに環を形成していてもよい。p、qは1または2の整数を表す。pが2のとき、複数のR9は、それぞれ同一でも、異なっていてもよい。また、qが2のとき、複数のR11は、それぞれ同一でも、異なっていてもよい。]
第四工程:式(4)で表される化合物に、塩基とハロゲン化錫化合物とを反応させて、式(5)で表される化合物を得る工程
本発明の高分子化合物は、式(1)で表されるベンゾビスチアゾール構造単位を有する。
なお、本明細書において、オルガノシリル基は、Si原子に1個以上の炭化水素基が置換した1価の基を意味するものとし、Si原子に置換する炭化水素基の数は、2個以上であることが好ましく、3個であることがさらに好ましい。
式(1)で表されるベンゾビスチアゾール構造単位においては、T1、T2は、それぞれ、下記式(t1)~(t5)で表される基であることが好ましい。具体的には、T1、T2のアルコキシ基としては、下記式(t1)で表される基が好ましく、チオアルコキシ基としては、下記式(t2)で表される基が好ましく、炭化水素基もしくはオルガノシリル基で置換されていてもよいチオフェン環としては下記式(t3)で表される基が好ましく、炭化水素基もしくはオルガノシリル基で置換されていてもよいチアゾール環としては下記式(t4)で表される基が好ましく、炭化水素基、アルコキシ基、チオアルコキシ基、オルガノシリル基、ハロゲン原子、もしくは、トリフルオロメチル基で置換されていてもよいフェニル基としては、下記式(t5)で表される基が好ましい。T1、T2が下記式(t1)~(t5)で表される基であると、短波長の光を吸収することができるとともに、高い平面性を有することから効率的にπ-πスタッキングが形成されるため、より一層光電変換効率を高めることができる。
[式(t1)~(t5)中、R13~R14は、それぞれ独立に、炭素数6~30の炭化水素基を表す。R15~R16は、それぞれ独立に、炭素数6~30の炭化水素基、または、*-Si(R18)3で表される基を表す。R15'は、水素原子、炭素数6~30の炭化水素基、*-Si(R18)3で表される基を表す。R17は、それぞれ独立に、炭素数6~30の炭化水素基、*-O-R19、*-S-R20、*-Si(R18)3、または、*-CF3を表す。R18は、それぞれ独立に、炭素数1~20の脂肪族炭化水素基、または、炭素数6~10の芳香族炭化水素基を表し、複数のR18は、同一でも異なっていてもよい。R19~R20は、炭素数6~30の炭化水素基を表す。*は結合手を表す。]
[式(t1)~(t3)中、*は結合手を表し、R13~R15、R15'は、前記と同様の基を表す。R17は、それぞれ独立に、炭素数6~30の炭化水素基、*-O-R19、*-S-R20を表す。*は結合手を表す。]
[式(b1)~(b3)中、R21、R22、R21'は、水素原子または炭素数6~30の炭化水素基を表す。*は結合手を表し、特に左側の*は、ベンゾビスチアゾール化合物のベンゼン環に結合する結合手を表すものとする。]
R21、R22、R21'が水素原子であると、ドナー-アクセプター型半導体ポリマーの形成が容易であるため、好ましい。また、R21、R22、R21'が炭素数6~30の炭化水素基であると、より一層光電変換効率を高められる可能性があるため好ましい。
本発明は、下記式(5)で表される化合物(以下、「化合物(5)」ということがある。)を含む。
[式(5)中、T1、T2は、それぞれ独立に、アルコキシ基、チオアルコキシ基、炭化水素基もしくはオルガノシリル基で置換されていてもよいチオフェン環、炭化水素基もしくはオルガノシリル基で置換されていてもよいチアゾール環、または、炭化水素基、アルコキシ基、チオアルコキシ基、オルガノシリル基、ハロゲン原子、もしくは、トリフルオロメチル基で置換されていてもよいフェニル基を表す。また、B3、B4は、アルキル基で置換されていてもよいチオフェン環、または、アルキル基で置換されていてもよいチアゾール環を表す。R1~R4は、それぞれ独立に、炭素数1~6の脂肪族炭化水素基、水酸基、炭素数1~6のアルコキシ基、または、炭素数6~10のアリールオキシ基を表す。M1、M2は、それぞれ独立に、ホウ素原子または錫原子を表す。R1、R2は、M1とともに環を形成していてもよく、R3、R4は、M2とともに環を形成していてもよい。m、nは、それぞれ、1または2の整数を表す。また、m、nが2のとき、複数のR1、R3は、それぞれ同一でも、異なっていてもよい。]
本発明は、下記式(4)で表される化合物(以下、「化合物(4)」ということがある。)を含む。
本発明は、下記式(3)で表される化合物(以下、「化合物(3)」ということがある。)を含む。
本発明は、下記式(2)で表される化合物(以下、「化合物(2)」ということがある。)を含む。
本発明の式(1)で表される高分子化合物は、2,6-ジヨードベンゾ[1,2-d:4,5-d’]ビスチアゾール、および、2,6-ジブロモベンゾ[1,2-d:4,5-d’]ビスチアゾールからなる群より選ばれた1の化合物を出発原料とし、式(2)で表される化合物、
本発明の製造方法は、下記第一工程を含むことが好ましい。
第一工程:2,6-ジヨードベンゾ[1,2-d:4,5-d’]ビスチアゾール、および、2,6-ジブロモベンゾ[1,2-d:4,5-d’]ビスチアゾールからなる群より選ばれた1の化合物に、金属触媒の存在下、式(6)および/または式(7)
[式(6)、(7)中、T1、T2は、それぞれ上記と同様の基を表す。R5、R6は、それぞれ独立に、水素原子、または、*-M3(R7)kR8を表す。R7、R8は、それぞれ独立に、炭素数1~6の脂肪族炭化水素基、水酸基、炭素数1~6のアルコキシ基、または、炭素数6~10のアリールオキシ基を表す。M3は、ホウ素原子または錫原子を表す。*は結合手を表す。R7、R8は、M3とともに環を形成していてもよい。kは1または2の整数を表す。また、kが2のとき、複数のR7は、それぞれ同一でも、異なっていてもよい。]
で表される化合物を反応させて、式(2)で表される化合物を得る工程
また、2,6-ジハロゲン化ベンゾビスチアゾールと反応させる式(6)および/または(7)で表される化合物(以下、「化合物(6)」、「化合物(7)」ということがある。)としては、T1、T2がそれぞれ前記と同様の基であり、R5、R6が、水素原子、または、*-M3(R7)kR8である化合物が好ましい。*は結合手を表す。
なお、パラジウムの価数は特に限定されず、0価であっても2価であってもよい。
これらの中でも、テトラヒドロフラン、ジオキサン、N,N-ジメチルホルムアミドが特に好ましい。
本発明の製造方法は、下記第二工程を含むことが好ましい。
第二工程:式(2)で表される化合物に塩基とハロゲン化試薬とを反応させて、式(3)で表される化合物を得る工程
塩基とハロゲン化試薬のモル比(塩基:ハロゲン化試薬)は、例えば1:0.5~1:2.0程度であり、1:0.6~1:1.7が好ましく、1:0.7~1:1.5がより好ましく、1:0.8~1:1.2がさらに好ましい。
本発明の製造方法は、下記第三工程を含むことが好ましい。
第三工程:式(3)で表される化合物に、金属触媒の存在下、下記式(8)および/または式(9)で表される化合物を反応させて、式(4)で表される化合物を得る工程
[式(8)、(9)中、B1、B2は、それぞれ上記と同様の基を表す。R9~R12は、それぞれ独立に、炭素数1~6の脂肪族炭化水素基、水酸基、炭素数1~6のアルコキシ基、炭素数6~10のアリール基、または、炭素数6~10のアリールオキシ基を表す。M4、M5は、ホウ素原子、錫原子、または、ケイ素原子を表す。R9、R10は、M4とともに環を形成していてもよく、R11、R12は、M5とともに環を形成していてもよい。p、qは1または2の整数を表す。pが2のとき、複数のR9は、それぞれ同一でも、異なっていてもよい。また、qが2のとき、複数のR11は、それぞれ同一でも、異なっていてもよい。]
また、M4、M5がケイ素原子である場合、溶媒と塩基(好ましくはアミン)の合計の使用量は、化合物(3)の1gに対して、一般に1mL以上、50mL以下程度であり特に限定されないが、収率や反応効率の観点から5mL以上、40mL以下が好ましく、8mL以上、35mL以下がより好ましく、10mL以上、30mL以下がさらに好ましい。さらに、M4、M5がケイ素原子である場合、溶媒の使用量は、溶媒と塩基の合計100体積%中、例えば100体積%以下であり、より好ましくは80体積%以下、さらに好ましくは60体積%以下である。さらに、溶媒の使用量は、溶媒と塩基の合計100体積%中、40体積%以下であってもよく、より好ましくは20体積%以下であってもよく、0体積%、すなわち、全く使用しなくともよい。
脱オルガノシリル基工程1:*-Si(R9)pR10、*-Si(R11)qR12に由来する基を有する化合物に、アルコール系溶媒中、塩基を反応させて、*-Si(R9)pR10、*-Si(R11)qR12に由来する基をを脱離する工程
脱オルガノシリル基工程2:*-Si(R9)pR10、*-Si(R11)qR12に由来する基を有する化合物に、フッ素化合物を反応させて、*-Si(R9)pR10、*-Si(R11)qR12に由来する基をを脱離する工程
脱オルガノシリル基工程1において用いられる塩基としては、水酸化ナトリウム、水酸化セシウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸セシウム等のアルカリ金属塩化合物;水酸化マグネシウム、水酸化カルシウム、水酸化バリウム、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム等のアルカリ土類金属塩化合物;リチウムメトキシド、ナトリウムメトキシド、カリウムメトキシド、リチウムエトキシド、ナトリウムエトキシド、カリウムエトキシド、リチウムイソプロポキシド、ナトリウムイソプロポキシド、カリウムイソプロポキシド、リチウムtert-ブトキシド、ナトリウムtert-ブトキシド、カリウムtert-ブトキシド、リチウムtert-アミルアルコキシド、ナトリウムtert-アミルアルコキシド、カリウムtert-アミルアルコキシド等のアルコキシアルカリ金属化合物が挙げられる。中でも、塩基としては、アルコキシアルカリ金属化合物が好ましく炭酸ナトリウム、炭酸カリウム、炭酸セシウムがより好ましい。
脱オルガノシリル基工程2において用いられるフッ素化合物としては、フッ化リチウム、フッ化ナトリウム、フッ化カリウム、フッ化セシウム、フッ化マグネシウム、フッ化カルシウム、フッ化バリウム、フッ化アンモニウム、テトラメチルアンモニウムフルオリド、テトラエチルアンモニウムフルオリド、テトラプロピルアンモニウムフルオリド、テトラブチルアンモニウムフルオリド、テトラペンチルアンモニウムフルオリド、テトラヘキシルアンモニウムフルオリド等が挙げられ、フッ化ナトリウム、フッ化カリウム、テトラエチルアンモニウムフルオリド、テトラブチルアンモニウムフルオリドが好ましい。
本発明の製造方法は、下記第四工程を含むことが好ましい。
第四工程:式(4)で表される化合物に、塩基とハロゲン化錫化合物とを反応させて、式(5)で表される化合物を得る工程 なお、本発明において、化合物(4)が、式(4)において、B1、B2が炭化水素基で置換されていてもよいチオフェン環(好ましくは、式(b1)で表される基)、または、炭化水素基で置換されていてもよいチアゾール環(好ましくは、式(b2)で表される基)である場合、第四工程を含むことが好ましい。
塩基とハロゲン化錫化合物とのモル比(塩基:ハロゲン化錫化合物)は、例えば1:0.5~1:2.0程度であり、1:0.6~1:1.7が好ましく、1:0.7~1:1.5がより好ましく、1:0.8~1:1.2がさらに好ましい。
さらに、カップリング反応によって、本発明の構造単位と、本発明の構造単位と組合せてドナー-アクセプター型高分子化合物を形成する構造単位とを、交互に配置することによって、本発明の高分子化合物を製造することができる。
実施例で用いた測定方法は、下記の通りである。
ベンゾビスチアゾール化合物について、NMRスペクトル測定装置(Agilent社(旧Varian社)製、「400MR」、および、Bruker社製、「AVANCE 500」)を用いて、NMRスペクトル測定を行った。
ベンゾビスチアゾール化合物について、質量分析装置(Bruker Daltnics社製、「MicrOTOF」)を用いて、高分解能マススペクトル測定を行った。
ベンゾビスチアゾール化合物について、ゲル浸透クロマトグラフィー(GPC)を用い、分子量測定を行った。測定に際しては、ベンゾビスチアゾール化合物を0.5g/Lの濃度となるように移動相溶媒(クロロホルム)に溶解して、下記条件で測定を行い、ポリスチレンを標準試料として作成した較正曲線に基づいて換算することによって、ベンゾビスチアゾール化合物の数平均分子量、重量平均分子量を算出した。測定におけるGPC条件は、下記の通りである。
移動相:クロロホルム流速:0.6mL/min
装置:HLC-8320GPC(東ソー社製)
カラム:TSKgel(登録商標)、SuperHM-H’2 + TSKgel(登録商標)、SuperH2000(東ソー社製)
ベンゾビスチアゾール化合物について、赤外分光装置(JASCO社製、「FT/IR-6100」)を用い、IRスペクトル測定を行った。
0.03g/Lの濃度になる様に、得られたベンゾビスチアゾール化合物をクロロホルムに溶解し、紫外・可視分光装置(島津製作所社製、「UV-2450」、「UV-3150」)、および、光路長1cmのセルを用いて紫外可視吸収スペクトル測定を行った。
ベンゾビスチアゾール化合物について、融点測定装置(Buchi社製、「M-560」)を用い、融点測定を行った。
ガラス基板上にベンゾビスチアゾール化合物を50nm~100nmの厚みになるように成膜した。この膜について、常温常圧下、紫外線光電子分析装置(理研計器社製、「AC-3」)によりイオン化ポテンシャルを測定した。
1H-NMR測定により、目的とする化合物が生成したことを確認した。
1H-NMR測定により、目的とする化合物が生成したことを確認した。
1H-NMR測定により、目的とする化合物が生成したことを確認した。
1H-NMR測定により、目的とする化合物が生成したことを確認した。
1H-NMR測定により、目的とする化合物が生成したことを確認した。
1H-NMR測定により、目的とする化合物が生成したことを確認した。
1H-NMR測定により、目的とする化合物が生成したことを確認した。
1H-NMR測定により、目的とする化合物が生成したことを確認した。
1H-NMR測定により、目的とする化合物が生成したことを確認した。
2,6-ビス[5-(3,7-ジメチルオクチル)チオフェン-2-イル]-4,8-ジチオフェン-2-イル-ベンゾ[1,2-d;4,5-d’]ビスチアゾール(DTH-DBTH-DMOTH)の合成
1H-NMR測定により、目的とする化合物が生成したことを確認した。
1H-NMR測定により、目的とする化合物が生成したことを確認した。
1H-NMR測定により、目的とする化合物が生成したことを確認した。
1H-NMR測定により、目的とする化合物が生成したことを確認した。
1H-NMR測定により、目的とする化合物が生成したことを確認した。
2,6-ビス[5-(3,7-ジメチルオクチル)チオフェン-2-イル]-4,8-ビス(5-トリブチルスタンニルチオフェン-2-イル)-ベンゾ[1,2-d;4,5-d’]ビスチアゾール(DTH-DBTH-DMOTH-DSB)の合成
1H-NMR測定により、目的とする化合物が生成したことを確認した。
2,6-ビス[5-(2-エチルヘキシル)チオフェン-2-イル]-4,8-ビス(5-トリメチルスタンニルチオフェン-2-イル)-ベンゾ[1,2-d;4,5-d’]ビスチアゾール(DTH-DBTH-EHTH-DSM)の合成
1H-NMR測定により、目的とする化合物が生成したことを確認した。
2,6-ビス[5-(2-ブチルオクチル)チオフェン-2-イル]-4,8-ビス(5-トリメチルスタンニルチオフェン-2-イル)-ベンゾ[1,2-d;4,5-d’]ビスチアゾール(DTH-DBTH-BOTH-DSM)
1H-NMR測定により、目的とする化合物が生成したことを確認した。
2,6-ビス[5-(2-ヘキシルデシル)チオフェン-2-イル]-4,8-ビス(5-トリメチルスタンニルチオフェン-2-イル)-ベンゾ[1,2-d;4,5-d’]ビスチアゾール(DTH-DBTH-HDTH-DSM)
1H-NMR測定により、目的とする化合物が生成したことを確認した。
2,6-ビス[5-(2-ヘキシルデシル)チオフェン-2-イル]-4,8-ビス(5-トリブチルスタンニルチオフェン-2-イル)-ベンゾ[1,2-d;4,5-d’]ビスチアゾール(DTH-DBTH-HDTH-DSB)
1H-NMR測定により、目的とする化合物が生成したことを確認した。
2,6-ビス[5-(2-デシルテトラデシル)チオフェン-2-イル]-4,8-ビス(5-トリメチルスタンニルチオフェン-2-イル)-ベンゾ[1,2-d;4,5-d’]ビスチアゾール(DTH-DBTH-TDTH-DSM)
1H-NMR測定により、目的とする化合物が生成したことを確認した。
イオン化ポテンシャル:5.24eV(HOMO -5.24eV)
イオン化ポテンシャル:5.36eV(HOMO -5.36eV)
GPC測定結果 Mw(重量平均分子量):68000
Mn(数平均分子量):21100
前記のように得られたP-THDT-DBTH-EH-IMTHを
ドナー材料、PCBM(C61)(フェニルC61-酪酸メチルエステル)をアクセプター材料として用いて、ドナー材料:アクセプター材料=1:2(重量)(合計濃度24mg/mL)、および1,8-ジヨードオクタン(0.03mL/mL)をクロロベンゼンに溶解させて0.45μmのフィルターに通して混合溶液とした。
ITOが成膜されたガラス基板をオゾンUV処理して表面処理を行った後に、PEDOT-PSS([ポリ(3,4-エチレンジオキシチオフェン)-ポリ(スチレンスルホン酸))をスピンコーターで塗布した。次に、上記のドナー材料・アクセプター材料の混合溶液をスピンコーターで成膜して室温で減圧乾燥した。その上に、オルトチタン酸テトライソプロピルのエタノール溶液(約0.3v%)をスピンコートして雰囲気中の水分により酸化チタンに変換した膜を作製した。その後、電極であるアルミニウムを蒸着してデバイスとした。
得られたデバイスにソーラーシミュレーター(CEP2000、AM1.5Gフィルター、放射強度100mW/cm2、分光計器製)を用いて特性評価を行った。その結果、Jsc(短絡電流密度)=8.64mA/cm2、Voc(開放端電圧)=0.86V、FF(曲線因子)=0.58で変換効率4.34%であることが確認された。
イオン化ポテンシャル:5.25eV(HOMO -5.25eV)
GPC測定結果 Mw(重量平均分子量):34000
Mn(数平均分子量):12700
P-THDT-DBTH-EH-IMTHの代わりに、前記のように得られたP-THDT-DBTH-O-IMTHを用いたこと以外は実施例23と同様にして、デバイスを作製した。得られたデバイスにソーラーシミュレーター(CEP2000、AM1.5Gフィルター、放射強度100mW/cm2、分光計器製)を用いて特性評価を行った。その結果、Jsc(短絡電流密度)=7.51mA/cm2、Voc(開放端電圧)=0.79V、FF(曲線因子)=0.70で変換効率4.13%であることが確認された。
イオン化ポテンシャル:5.25eV(HOMO -5.25eV)
GPC測定結果 Mw(重量平均分子量):15900
Mn(数平均分子量):8100
P-THDT-DBTH-EH-IMTHの代わりに、前記のように得られたP-TEHT-DBTH-HD-IMTHを用いたこと以外は実施例23と同様にして、デバイスを作製した。得られたデバイスにソーラーシミュレーター(CEP2000、AM1.5Gフィルター、放射強度100mW/cm2、分光計器製)を用いて特性評価を行った。その結果、Jsc(短絡電流密度)=5.55mA/cm2、Voc(開放端電圧)=0.78V、FF(曲線因子)=0.64で変換効率2.81%であることが確認された。
イオン化ポテンシャル:5.23eV(HOMO -5.23eV)
イオン化ポテンシャル:5.27eV(HOMO -5.27eV)
イオン化ポテンシャル:5.11eV(HOMO -5.11eV)
イオン化ポテンシャル:5.55eV(HOMO -5.55eV)
GPC測定結果 Mw(重量平均分子量):4500
Mn(数平均分子量):3300
イオン化ポテンシャル:5.10eV(HOMO -5.10eV)
GPC測定結果 Mw(重量平均分子量):6100
Mn(数平均分子量):3600
前記のように得られたP-THDT-DBTH-DMO-DPPをドナー材料、PCBM(C61)(フェニルC61-酪酸メチルエステル)をアクセプター材料として用いて、ドナー材料:アクセプター材料=1:2(重量)(合計濃度24mg/mL)、および1,8-ジヨードオクタン(0.03mL/mL)をオルトジクロロベンゼンに溶解させて0.45μmのフィルターに通して混合溶液とした。
ITOが成膜されたガラス基板をオゾンUV処理して表面処理を行った後に、PEDOT-PSS([ポリ(3,4-エチレンジオキシチオフェン)-ポリ(スチレンスルホン酸))をスピンコーターで塗布した。次に、上記のドナー材料・アクセプター材料の混合溶液をスピンコーターで成膜して室温で減圧乾燥した。その上に、オルトチタン酸テトライソプロピルのエタノール溶液(約0.3v%)をスピンコートして雰囲気中の水分により酸化チタンに変換した膜を作製した。その後、電極であるアルミニウムを蒸着してデバイスとした。
得られたデバイスにソーラーシミュレーター(CEP2000、AM1.5Gフィルター、放射強度100mW/cm2、分光計器製)を用いて特性評価を行った。その結果、Jsc(短絡電流密度)=6.66mA/cm2、Voc(開放端電圧)=0.45V、FF(曲線因子)=0.62で変換効率2.02%であることが確認された。
イオン化ポテンシャル:5.10eV(HOMO -5.10eV)
GPC測定結果 Mw(重量平均分子量):6700
Mn(数平均分子量):4800
イオン化ポテンシャル:5.30eV(HOMO -5.30eV)
GPC測定結果 Mw(重量平均分子量):20200
Mn(数平均分子量):10300
2,6-ビス[5-(3,7-ジメチルオクチル)チオフェン-2-イル]-4,8-ビスチアゾール-2-イル-ベンゾ[1,2-d;4,5-d’]ビスチアゾール(DTHA-DBTH-DMOTH)の合成
1H-NMR測定により、目的とする化合物が生成したことを確認した。
1H-NMR測定により、目的とする化合物が生成したことを確認した。
2,6-ビス[5-(3,7-ジメチルオクチル)チオフェン-2-イル]-4,8-ビス(5-トリブチルスタンニルチアゾール-2-イル)-ベンゾ[1,2-d;4,5-d’]ビスチアゾール(DTHA-DBTH-DMOTH-DSB)の合成
1H-NMR測定により、目的とする化合物が生成したことを確認した。
2,6-ビス[5-(2-ヘキシルデシル)チオフェン-2-イル]-4,8-ビス(5-トリブチルスタンニルチアゾール-2-イル)-ベンゾ[1,2-d;4,5-d’]ビスチアゾール(DTHA-DBTH-DMOTH-DSB)の合成
1H-NMR測定により、目的とする化合物が生成したことを確認した。
P-THDMOT-DBTH-O-IMTHの合成
イオン化ポテンシャル:5.62eV(HOMO -5.62eV)
イオン化ポテンシャル:5.61eV(HOMO -5.61eV)
GPC測定結果 Mw(重量平均分子量):20300
Mn(数平均分子量):8800
イオン化ポテンシャル:5.42eV(HOMO -5.42eV)
イオン化ポテンシャル:5.61eV(HOMO -5.61eV)
GPC測定結果 Mw(重量平均分子量):8400
Mn(数平均分子量):1600
P-THDT-DBTH-EH-IMTHの代わりに、前記のように得られたP-THHDT-DBTH-HTTを用いたこと以外は実施例30と同様にして、デバイスを作製した。得られたデバイスにソーラーシミュレーター(CEP2000、AM1.5Gフィルター、放射強度100mW/cm2、分光計器製)を用いて特性評価を行った。その結果、Jsc(短絡電流密度)= 4.67 mA/cm2、Voc(開放端電圧) = 0.59 V、FF(曲線因子) = 0.59で変換効率1.62%であることが確認された。
イオン化ポテンシャル:5.24eV(HOMO -5.24eV)
GPC測定結果 Mw(重量平均分子量):15200
Mn(数平均分子量):6500
前記のように得られたP-THHDT-DBTH-EH-BDTをドナー材料、PCBM(C61)(フェニルC61-酪酸メチルエステル)をアクセプター材料として用いて、ドナー材料:アクセプター材料=1:2(重量)(合計濃度30mg/mL)、および1,8-ジヨードオクタン(0.03mL/mL)をオルトジクロロベンゼンに溶解させて0.45μmのフィルターに通して混合溶液とした。
ITOが成膜されたガラス基板をオゾンUV処理して表面処理を行った後に、PEDOT-PSS([ポリ(3,4-エチレンジオキシチオフェン)-ポリ(スチレンスルホン酸))をスピンコーターで塗布した。次に、上記のドナー材料・アクセプター材料の混合溶液をスピンコーターで成膜して室温で減圧乾燥した。その上に、オルトチタン酸テトライソプロピルのエタノール溶液(約0.3v%)をスピンコートして雰囲気中の水分により酸化チタンに変換した膜を作製した。その後、電極であるアルミニウムを蒸着してデバイスとした。
得られたデバイスにソーラーシミュレーター(CEP2000、AM1.5Gフィルター、放射強度100mW/cm2、分光計器製)を用いて特性評価を行った。その結果、Jsc(短絡電流密度)= 3.65 mA/cm2、Voc(開放端電圧) = 0.74 V、FF(曲線因子) = 0.47で変換効率1.26%であることが確認された。
1H-NMR測定により、目的とする化合物が生成したことを確認した。
1H-NMR測定、高分解能マススペクトル測定により、目的とする化合物が生成したことを確認した。
計算値:C34H46I2N2S4Si2+H: 921.0245
測定値: 921.02444
4,8-ビス-(チオフェン-2-イル)-2,6-ビス-(5-トリイソプロピルシラニルチオフェン-2-イル)-ベンゾ[1,2-d;4,5-d’]ビスチアゾール(DBTH-TIPSTH-THA)の合成
1H-NMR測定、13C-NMR測定、IRスペクトル測定、融点測定、高分解能マススペクトル測定により、目的とする化合物が生成したことを確認した。
13C NMR (125MHz, CDCl3): δ165.74, 161.98, 148.32, 142.31, 142.10, 141.29, 136.67, 131.61, 130.24, 122.81, 121.00, 17.85, 4.11.
IR (KBr): 2941, 1864, 1539, 1474, 1460, 1323, 999, 976, 659 cm-1.
融点:285℃で分解
高分解能マススペクトル分析(APCI:大気圧化学イオン化法)
計算値:C40H51N4S6Si2+H:835.1971
測定値:835.1999
4,8-ビス(5-トリブチルスタンニルチオフェン-2-イル)-2,6-ビス(5-トリイソプロピルシラニルチオフェン-2-イル)-ベンゾ[1,2-d;4,5-d’]ビスチアゾール(DBTH-TIPSTH-THA-DSB)の合成
1H-NMR測定により、目的とする化合物が生成したことを確認した。
Mw(重量平均分子量):31800
Mn(数平均分子量):3300
イオン化ポテンシャル:5.65eV(HOMO -5.65eV)
前記のように得られたP-THTIPSTH-DBTH-O-IMTHをドナー材料、PCBM(C61)(フェニルC61-酪酸メチルエステル)をアクセプター材料として用いて、ドナー材料:アクセプター材料=1:1.5(質量)(合計濃度20mg/mL)、および、1,8-ジヨードオクタン(0.03mL/mL)をクロロベンゼンに溶解させて0.45μmのフィルターに通して混合溶液とした。
イオン化ポテンシャル:5.13eV(HOMO -5.13eV)
1H-NMR測定により、目的とする化合物が生成したことを確認した。
GPC測定結果 Mw(重量平均分子量):8700
Mn(数平均分子量):5700
イオン化ポテンシャル:6.18eV(HOMO -6.18eV)
Claims (13)
- 式(1)で表されるベンゾビスチアゾール構造単位を含むことを特徴とする高分子化合物。
[式(1)中、
T1、T2は、それぞれ独立に、アルコキシ基、チオアルコキシ基、炭化水素基もしくはオルガノシリル基で置換されていてもよいチオフェン環、炭化水素基もしくはオルガノシリル基で置換されていてもよいチアゾール環、または、炭化水素基、アルコキシ基、チオアルコキシ基、オルガノシリル基、ハロゲン原子、もしくは、トリフルオロメチル基で置換されていてもよいフェニル基を表す。
また、B1、B2は、炭化水素基で置換されていてもよいチオフェン環、炭化水素基で置換されていてもよいチアゾール環、または、エチニレン基を表す。] - T1、T2が、それぞれ、下記式(t1)~(t5)のいずれかで表される基である請求項1に記載の高分子化合物。
[式(t1)~(t5)中、
R13~R14は、それぞれ独立に、炭素数6~30の炭化水素基を表す。
R15~R16は、それぞれ独立に、炭素数6~30の炭化水素基、または、*-Si(R18)3で表される基を表す。
R15'は、水素原子、炭素数6~30の炭化水素基、*-Si(R18)3で表される基を表す。
R17は、それぞれ独立に、炭素数6~30の炭化水素基、*-O-R19、*-S-R20、*-Si(R18)3、または、*-CF3を表す。
R18は、それぞれ独立に、炭素数1~20の脂肪族炭化水素基、または、炭素数6~10の芳香族炭化水素基を表し、複数のR18は、同一でも異なっていてもよい。
R19~R20は、炭素数6~30の炭化水素基を表す。
*は結合手を表す。] - ドナー-アクセプター型半導体ポリマーである請求項1~3のいずれか一項に記載の高分子化合物。
- 請求項1~4のいずれか一項に記載の高分子化合物を含む有機半導体材料。
- 式(5)で表されるベンゾビスチアゾール化合物。
[式(5)中、
T1、T2は、それぞれ独立に、アルコキシ基、チオアルコキシ基、炭化水素基もしくはオルガノシリル基で置換されていてもよいチオフェン環、炭化水素基もしくはオルガノシリル基で置換されていてもよいチアゾール環、または、炭化水素基、アルコキシ基、チオアルコキシ基、オルガノシリル基、ハロゲン原子、もしくは、トリフルオロメチル基で置換されていてもよいフェニル基を表す。
また、B3、B4は、アルキル基で置換されていてもよいチオフェン環、または、アルキル基で置換されていてもよいチアゾール環を表す。
R1~R4は、それぞれ独立に、炭素数1~6の脂肪族炭化水素基、水酸基、炭素数1~6のアルコキシ基、または、炭素数6~10のアリールオキシ基を表す。
M1、M2は、それぞれ独立に、ホウ素原子または錫原子を表す。
R1、R2は、M1とともに環を形成していてもよく、R3、R4は、M2とともに環を形成していてもよい。
m、nは、それぞれ、1または2の整数を表す。また、m、nが2のとき、複数のR1、R3は、それぞれ同一でも、異なっていてもよい。] - 請求項1~4のいずれか一項に記載の高分子化合物の製造方法であって、
2,6-ジヨードベンゾ[1,2-d:4,5-d’]ビスチアゾール、および、2,6-ジブロモベンゾ[1,2-d:4,5-d’]ビスチアゾールからなる群より選ばれた1の化合物を出発原料とし、
式(2)で表される化合物、
[式(2)中、
T1、T2は、それぞれ独立に、アルコキシ基、チオアルコキシ基、炭化水素基もしくはオルガノシリル基で置換されていてもよいチオフェン環、炭化水素基もしくはオルガノシリル基で置換されていてもよいチアゾール環、または、炭化水素基、アルコキシ基、チオアルコキシ基、オルガノシリル基、ハロゲン原子、もしくは、トリフルオロメチル基で置換されていてもよいフェニル基を表す。]
式(3)で表される化合物、
[式(3)中、
T1、T2は、それぞれ上記と同様の基を表す。
X1、X2は、ハロゲン原子を表す。]
式(4)で表される化合物、
[式(4)中、
T1、T2は、それぞれ上記と同様の基を表す。
また、B1、B2は、炭化水素基で置換されていてもよいチオフェン環、炭化水素基で置換されていてもよいチアゾール環、または、エチニレン基を表す。]
を経ることを特徴とする製造方法。 - 下記第一工程、第二工程、および、第三工程を含む請求項10に記載の製造方法。
第一工程:2,6-ジヨードベンゾ[1,2-d:4,5-d’]ビスチアゾール、および、2,6-ジブロモベンゾ[1,2-d:4,5-d’]ビスチアゾールからなる群より選ばれた1の化合物に、金属触媒の存在下、式(6)および/または式(7)
[式(6)、(7)中、
T1、T2は、それぞれ上記と同様の基を表す。
R5、R6は、それぞれ独立に、水素原子、または、*-M3(R7)kR8を表す。
R7、R8は、それぞれ独立に、炭素数1~6の脂肪族炭化水素基、水酸基、炭素数1~6のアルコキシ基、または、炭素数6~10のアリールオキシ基を表す。
M3は、ホウ素原子または錫原子を表す。*は結合手を表す。
R7、R8は、M3とともに環を形成していてもよい。
kは1、または、2の整数を表す。また、kが2のとき、複数のR7は、それぞれ同一でも、異なっていてもよい。]で表される化合物を反応させて、式(2)で表される化合物を得る工程
第二工程:式(2)で表される化合物に塩基とハロゲン化試薬とを反応させて、式(3)で表される化合物を得る工程
第三工程:式(3)で表される化合物に、金属触媒の存在下、下記式(8)および/または式(9)で表される化合物を反応させて、式(4)で表される化合物を得る工程
[式(8)、(9)中、 B1、B2は、それぞれ上記と同様の基を表す。
R9~R12は、それぞれ独立に、炭素数1~6の脂肪族炭化水素基、水酸基、炭素数1~6のアルコキシ基、炭素数6~10のアリール基、または、炭素数6~10のアリールオキシ基を表す。
M4、M5は、ホウ素原子、錫原子、または、ケイ素原子を表す。
R9、R10は、M4とともに環を形成していてもよく、R11、R12は、M5とともに環を形成していてもよい。
p、qは1または2の整数を表す。pが2のとき、複数のR9は、それぞれ同一でも、異なっていてもよい。また、qが2のとき、複数のR11は、それぞれ同一でも、異なっていてもよい。] - さらに下記第四工程を含む請求項12に記載の製造方法。
第四工程:式(4)で表される化合物に、塩基とハロゲン化錫化合物とを反応させて、式(5)で表される化合物を得る工程
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WO2019043451A1 (ja) * | 2017-08-31 | 2019-03-07 | 東洋紡株式会社 | n型半導体として使用可能な化合物 |
JP2019043878A (ja) * | 2017-08-31 | 2019-03-22 | 東洋紡株式会社 | n型半導体として使用可能な化合物 |
WO2020218189A1 (ja) * | 2019-04-26 | 2020-10-29 | 東洋紡株式会社 | 高分子化合物 |
WO2022054459A1 (ja) * | 2020-09-09 | 2022-03-17 | 東洋紡株式会社 | N-アルキルチエノピロールジオン化合物 |
CN115584017A (zh) * | 2022-09-30 | 2023-01-10 | 武汉工程大学 | 一类联二噻唑类宽带隙聚合物及其在光电器件中的应用 |
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EP3106484A1 (en) | 2016-12-21 |
KR102218245B1 (ko) | 2021-02-22 |
US10211401B2 (en) | 2019-02-19 |
EP3106484A4 (en) | 2017-10-04 |
JP6500786B2 (ja) | 2019-04-17 |
CN105992787B (zh) | 2020-03-03 |
JPWO2015122321A1 (ja) | 2017-03-30 |
CN105992787A (zh) | 2016-10-05 |
KR20160122743A (ko) | 2016-10-24 |
KR20200108921A (ko) | 2020-09-21 |
US20170069845A1 (en) | 2017-03-09 |
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