JP4925224B2 - 有機化合物及びそれを用いた半導体薄膜電極、光電変換素子、光電気化学太陽電池 - Google Patents
有機化合物及びそれを用いた半導体薄膜電極、光電変換素子、光電気化学太陽電池 Download PDFInfo
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- JP4925224B2 JP4925224B2 JP2008510859A JP2008510859A JP4925224B2 JP 4925224 B2 JP4925224 B2 JP 4925224B2 JP 2008510859 A JP2008510859 A JP 2008510859A JP 2008510859 A JP2008510859 A JP 2008510859A JP 4925224 B2 JP4925224 B2 JP 4925224B2
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- 238000006243 chemical reaction Methods 0.000 title claims description 58
- 239000004065 semiconductor Substances 0.000 title claims description 32
- 239000010409 thin film Substances 0.000 title claims description 26
- 150000002894 organic compounds Chemical class 0.000 title claims description 14
- 125000005647 linker group Chemical group 0.000 claims description 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 125000000623 heterocyclic group Chemical group 0.000 claims description 8
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 5
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical group OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 117
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 78
- 239000000975 dye Substances 0.000 description 75
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 74
- 150000001875 compounds Chemical class 0.000 description 63
- 239000002904 solvent Substances 0.000 description 53
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 44
- 239000000243 solution Substances 0.000 description 41
- 150000001716 carbazoles Chemical class 0.000 description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000012043 crude product Substances 0.000 description 28
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 28
- 238000004440 column chromatography Methods 0.000 description 27
- -1 2-ethyloctyl group Chemical group 0.000 description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 25
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 24
- 125000004432 carbon atom Chemical group C* 0.000 description 24
- 150000001299 aldehydes Chemical class 0.000 description 23
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000012044 organic layer Substances 0.000 description 18
- 238000010992 reflux Methods 0.000 description 18
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 18
- 125000000217 alkyl group Chemical group 0.000 description 15
- 238000004811 liquid chromatography Methods 0.000 description 15
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- 230000015572 biosynthetic process Effects 0.000 description 12
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 11
- 235000019341 magnesium sulphate Nutrition 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 125000001424 substituent group Chemical group 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 10
- QQVDYSUDFZZPSU-UHFFFAOYSA-M chloromethylidene(dimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)=CCl QQVDYSUDFZZPSU-UHFFFAOYSA-M 0.000 description 9
- 229910052740 iodine Inorganic materials 0.000 description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 8
- 0 CC[n]1s(ccc(-c(cc2)ccc2OC)c2)c2c2c1ccc(-c([s]1)c(C)cc1S(*1)=C(*)*=C1C(*1)=C(C*I=C)C[C@]1C=*(C(O)=O)C#N)c2 Chemical compound CC[n]1s(ccc(-c(cc2)ccc2OC)c2)c2c2c1ccc(-c([s]1)c(C)cc1S(*1)=C(*)*=C1C(*1)=C(C*I=C)C[C@]1C=*(C(O)=O)C#N)c2 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000011630 iodine Substances 0.000 description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000012327 Ruthenium complex Substances 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 238000005874 Vilsmeier-Haack formylation reaction Methods 0.000 description 7
- 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 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000022244 formylation Effects 0.000 description 6
- 238000006170 formylation reaction Methods 0.000 description 6
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- 150000002500 ions Chemical class 0.000 description 6
- 229960000956 coumarin Drugs 0.000 description 5
- 235000001671 coumarin Nutrition 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 238000006386 neutralization reaction Methods 0.000 description 4
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- USSDZGUORVTLQJ-UHFFFAOYSA-N 9-ethyl-3-iodocarbazole Chemical compound IC1=CC=C2N(CC)C3=CC=CC=C3C2=C1 USSDZGUORVTLQJ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XGBJCQGPJZKQIF-UHFFFAOYSA-N 2-(3-bromothiophen-2-yl)-3-(3-thiophen-2-ylthiophen-2-yl)thiophene Chemical class BrC1=C(SC=C1)C=1SC=CC=1C=1SC=CC=1C=1SC=CC=1 XGBJCQGPJZKQIF-UHFFFAOYSA-N 0.000 description 2
- JJWJFWRFHDYQCN-UHFFFAOYSA-J 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylate;ruthenium(2+);tetrabutylazanium;dithiocyanate Chemical compound [Ru+2].[S-]C#N.[S-]C#N.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1 JJWJFWRFHDYQCN-UHFFFAOYSA-J 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229910005642 SnTe Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- ZBQUMMFUJLOTQC-UHFFFAOYSA-N dichloronickel;3-diphenylphosphaniumylpropyl(diphenyl)phosphanium Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1[PH+](C=1C=CC=CC=1)CCC[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 ZBQUMMFUJLOTQC-UHFFFAOYSA-N 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 125000002346 iodo group Chemical group I* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
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- RUDATBOHQWOJDD-UHFFFAOYSA-N (3beta,5beta,7alpha)-3,7-Dihydroxycholan-24-oic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)CC2 RUDATBOHQWOJDD-UHFFFAOYSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
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- MXLZUALXSYVAIV-UHFFFAOYSA-N 1,2-dimethyl-3-propylimidazol-1-ium Chemical compound CCCN1C=C[N+](C)=C1C MXLZUALXSYVAIV-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- GKLMJONYGGTHHM-UHFFFAOYSA-N 1-bromo-4-hexoxybenzene Chemical compound CCCCCCOC1=CC=C(Br)C=C1 GKLMJONYGGTHHM-UHFFFAOYSA-N 0.000 description 1
- YRUOEPDZAQDNHR-UHFFFAOYSA-N 1-butyl-2-methylimidazole;hydroiodide Chemical compound [I-].CCCC[N+]=1C=CNC=1C YRUOEPDZAQDNHR-UHFFFAOYSA-N 0.000 description 1
- IKQCDTXBZKMPBB-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;iodide Chemical compound [I-].CCN1C=C[N+](C)=C1 IKQCDTXBZKMPBB-UHFFFAOYSA-M 0.000 description 1
- CZIUVCSYOGFUPH-UHFFFAOYSA-M 1-hexyl-3-methylimidazol-3-ium;iodide Chemical compound [I-].CCCCCC[N+]=1C=CN(C)C=1 CZIUVCSYOGFUPH-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/0075—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of an heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/02—Coumarine dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
- H01M14/005—Photoelectrochemical storage cells
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Description
この太陽電池は、ルテニウム錯体からなる増感剤を用い、ナノ粒子の酸化チタンや酸化亜鉛などの大きいバンドギャップを有する酸化物半導体のナノポーラス薄膜電極、ヨウ素レドックス電解液及び対極から構成される。7〜10%の太陽エネルギー変換効率を示し、比較的高い光電変換効率が得られる点と低コスト製造の可能性から、近年次世代太陽電池の一つとして注目され、研究開発が活発におこなわれている。
これまでに用いられてきた有機色素には、フェニルキサンテン色素、フタロシアニン色素、シアニン色素、メロシアニン色素、ポルフィリン色素、アゾ色素などが挙げられる(非特許文献3,4)。とくに、クマリン色素(非特許文献5)は吸収波長領域がルテニウム錯体とほぼ同等であり、高い光電変換効率を示した。しかしながら、一般的に有機色素を用いた色素増感太陽電池の場合、ルテニウム錯体を用いた太陽電池に比べて、開放電圧が低く、変換効率が低いのが問題点であった。
〈1〉下記一般式(1)で表される有機化合物。
〈2〉〈1〉に記載の有機化合物を有機色素として用いることを特徴とする半導体薄膜電極。
〈3〉〈2〉に記載の半導体薄膜電極を用いることを特徴とする光電変換素子。
〈4〉〈3〉に記載の光電変換素子を用いることを特徴とする光電気化学太陽電池。
置換基としては、例えば、メチル基、ヘキシル基などの直鎖型又はイソブチル基、2−エチルオクチル基などの分岐型の炭素数1〜20、好ましくは1〜12のアルキル基;メトキシ基、ブトキシ基などの炭素数1〜20、好ましくは1〜12アルコキシ基;フェニル基、ナフチル基などの炭素数3〜20、好ましくは5〜12のアリール基;メチルアミノ基、オクチルアミノ基などの炭素数1〜20、好ましくは1〜12のアルキル基を有するモノアルキルアミノ基、ジエチルアミノ基などの炭素数1〜20、好ましくは1〜12のアルキル基を有するジアルキルアミノ基;ピペリジル基などの環構成元素数5〜8、好ましくは5〜6の環状アミノ基;クロロ基、ブロモ基、ヨード基などのハロゲン基;水酸基;ニトロ基;アミノ基が挙げられる。
この連結基としては下記一般式(2)で表されるものを示すことができる。
この連結基としては下記一般式(4)で表されるものを示すことができる。
次に、前記一般式(1)で表される化合物(有機色素)の具体例を以下に示すが、本発明は、これらの化合物に限定されない。
この場合、半導体薄膜電極の基板としては、従来公知のものがそのまま適用することができる。たとえば、フッ素あるいはアンチモンドープの酸化スズ(NESA)、スズドープの酸化インジウム(ITO)、アルミニウムドープの酸化亜鉛などの導電性透明酸化物半導体薄膜をコートしたガラスあるいはプラスチック基板である。好ましくは、フッ素ドープの酸化スズ薄膜コートガラスである。
化合物半導体材料は、例えば、TiO2、ZnO、In2O3、SnO2、ZrO2、Ta2O5、Nb2O5、Fe2O3、Ga2O3、WO3、SrTiO3などの金属酸化物および複合酸化物、AgI、AgBr、CuI、CuBrなどの金属ハロゲン化物、さらに、ZnS、TiS2、ZnO、In2S3、SnS、SnS2、ZrS2、Ag2S、PbS、CdS、TaS2、CuS、Cu2S、WS2、MoS2、CuInS2などの金属硫化物、CdSe、TiSe2、ZrSe2、Bi2Se3、In2Se3、SnSe、SnSe2、Ag2Se、TaSe2、CuSe、Cu2Se、WSe2、MoSe2、CuInSe2、CdTe、TiTe2、ZrTe2、Bi2Te3、In2Te3、SnTe、SnTe2、Ag2Te、TaTe2、CuTe、Cu2Te、WTe2、MoTe2などの金属セレン化物ならび金属テルル化物などを挙げることができるが、これらに限定されない。好ましくは、TiO2、ZnO、SnO2などの酸化物半導体材料である。
前記半導体薄膜電極の膜厚は、通常、0.5〜100μmであり、好ましくは、5〜20μmである。
マグネシウム93mgに2−ブロモ−3−ヘキシルチオフェン903mgのエーテル溶液10mLを滴下し、完全に滴下し終わった後、反応溶液を加熱還流させ、グリニア試薬を調整する。反応溶液を室温に戻し、[1,3−ビス(ジフェニルホスフィノ)プロパン]ニッケルクロリドを19mg加える。その反応溶液に(32)で表される3−ヨウド−9−エチルカルバゾール1.12gのエーテル溶液20mLを滴下し、室温で1時間攪拌する。その後、塩化アンモニウム溶液を加えエーテルにより抽出する。有機層を水及び飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。その粗生成物をカラムクロマトグラフィー(溶媒:へキサン)により精製し、(33)で表される目的生成物であるカルバゾール誘導体を930mg得た。収率は74%であった。
(33)で表される化合物の1H NMRデータ(300MH z,CDCl3):δ8.14 (1H, d, J = 1.5 Hz), 8.10 (1H, d, J = 7.7 Hz), 7.54 (1H, dd, J = 8.3, 1.5 Hz), 7.50-7.41 (3H, m), 7.27-7.25 (1H, m), 7.23 (1H, d, J= 5.2 Hz), 7.01 (1H, d, J = 5.2 Hz), 4.40 (2H, q, J = 7.2 Hz), 2.71 (2H, dd, J = 8.2, 7.4 Hz), 1.67-1.63 (2H, m), 1.47 (3H, t, J = 7.2 Hz), 1.35-1.26 (6H, m), 0.84 (3H, t, J = 6.8 Hz).
(34)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ8.09 (1H, d, J = 7.7 Hz), 8.08 (1H, s), 7.53-7.40 (4H, m), 7.25 (1H, ddd, J = 7.7, 6.8, 1.1 Hz), 6.96 (1H, s), 4.39 (2H, q, J = 7.1 Hz), 2.63 (2H, t, J = 7.7 Hz), 1.65-1.55 (2H, m), 1.47 (3H, t, J = 7.1 Hz), 1.35-1.24 (6H, m), 0.84 (3H, t, J = 6.8 Hz).
(36)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ8.17 (1H, d, J = 1.1 Hz), 8.12 (1H, d, J = 7.7 Hz), 7.56 (1H, dd, J = 8.4, 1.8 Hz), 7.53-7.42 (3H, m), 7.29-7.23 (1H, m), 7.09 (1H, s), 7.04 (1H, d, J = 1.3 Hz), 6.80 (1H, br s), 4.40 (2H, q, J = 7.1 Hz), 2.70 (2H, t, J = 7.8 Hz), 2.60 (2H, t, J = 7.8 Hz), 1.73-1.60 (4H, m), 1.48 (3H, t, J = 7.1 Hz), 1.40-1.24 (12H, m), 0.91 (3H, t, J = 6.6 Hz), 0.86 (3H, t, J = 6.6 Hz).
(37)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ8.17 (1H, d, J = 1.1 Hz), 8.12 (1H, d, J = 7.7 Hz), 7.56 (1H, dd, J = 8.4, 1.8 Hz), 7.53-7.42 (3H, m), 7.29-7.23 (1H, m), 7.09 (1H, s), 7.01 (1H, s), 6.98 (1H, br s), 6.89 (1H, br s), 4.40 (2H, q, J = 7.1 Hz), 2.77-2.67 (4H, m), 2.62 (2H, t, J = 7.8 Hz), 1.74-1.61 (6H, m), 1.48 (3H, t, J = 7.1 Hz), 1.40-1.24 (18H, m), 0.94-0.82 (9H, m).
(38)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ8.19 (1H, s), 8.13 (1H, d, J = 7.7 Hz), 7.57 (1H, d, J = 8.2 Hz), 7.54-7.43 (3H, m), 7.30-7.25 (1H, m), 7.12 (1H, s), 7.04 (1H, s), 7.00 (1H, br s), 6.99 (1H, s), 6.92 (1H, br s), 4.41 (2H, q, J = 7.1 Hz), 2.83-2.69 (6H, m), 2.64 (2H, t, J = 7.7 Hz), 1.78-1.62 (8H, m), 1.49 (3H, t, J = 7.1 Hz), 1.48-1.26 (24H, m), 0.95-0.85 (12H, m).
(39)で表される化合物の1H NMRデータ(400 MHz, THF-d8) δ8.18 (1H, br s), 8.12 (1H, d, J = 7.9 Hz), 7.60-7.51 (3H, m), 7.44 (1H, br t, J = 8.0 Hz), 7.19 (1H, br t, J = 7.8 Hz), 7.17 (1H, s), 7.11 (1H, s), 7.06 (1H, s), 7.04-7.03 (3H, m), 4.47 (2H, q, J = 7.2 Hz), 2.85-2.76 (4H, m), 2.73 (2H, t, J = 7.7 Hz), 2.66-2.58 (4H, m), 1.73-1.60 (10H, m), 1.43 (3H, t, J = 7.0 Hz), 1.42-1.25 (30H, m), 0.94-0.82 (15H, m).
(40)で表される化合物の1H NMRデータ(400 MHz, THF-d8) δ8.19 (1H, br s), 8.12 (1H, d, J = 7.8 Hz), 7.60-7.51 (3H, m), 7.44 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 7.19 (1H, br t, J = 7.4 Hz), 7.18 (1H, s), 7.12 (1H, s), 7.064 (1H, s), 7.061 (1H, s), 7.05 (1H, s), 7.03 (2H, m), 4.47 (2H, q, J = 7.1 Hz), 2.87-2.76 (8H, m), 2.73 (2H, t, J = 7.7 Hz), 2.63 (2H, t, J = 7.7 Hz), 1.77-1.64 (12H, m), 1.43 (3H, t, J = 7.1 Hz), 1.40-1.26 (36H, m), 0.95-0.89 (15H, m), 0.85 (3H, t, J = 6.9 Hz).
(41)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ 10.02 (1H, s), 8.17 (1H, d, J = 1.4 Hz), 8.12 (1H, d, J = 7.7 Hz), 7.55 (1H, dd, J = 8.5, 1.7 Hz), 7.53-7.42 (3H, m), 7.29-7.23 (1H, m), 7.14 (1H, s), 7.05 (2H, br s), 4.40 (2H, q, J = 7.1 Hz), 2.95 (2H, t, J = 7.7 Hz), 2.82 (2H, t, J = 7.7 Hz), 2.71 (2H, t, J = 7.7 Hz), 1.74-1.61 (6H, m), 1.48 (3H, t, J = 7.1 Hz), 1.44-1.24 (18H, m), 0.94-0.83 (9H, m).
(5)で示される色素化合物の1H NMRデータ(300MHz,DMSO-d6):δ 8.23-8.16 (3H, m), 7.65 (1H, d, J = 8.8 Hz), 7.62 (1H, d, J = 8.5 Hz), 7.51-7.44 (2H, m), 7.32 (1H, s), 7.25 (1H, s), 7.23 (1H, s), 7.19 (1H, d, J = 7.4 Hz), 4.45 (2H, q, J = 7.1 Hz), 2.80-2.70 (4H, m), 2.64 (2H, t, J = 7.7 Hz), 1.68-1.52 (6H, m), 1.32 (3H, t, J = 7.7 Hz), 1.38-1.14 (18H, m), 0.83 (3H+3H, t, J = 6.6 Hz), 0.75 (3H, t, J = 6.6 Hz)
DMF1mLに冷却(0度)下、オキシ塩化リン0.1mLを滴下し、室温で1時間攪拌し、Vilsmeier試薬を合成する。(38)で表されるヘキシル置換チオフェン環が4個連なったカルバゾール誘導体270mgのDMF溶液5mLに上記のVilsmeier試薬を室温で滴下し、70度で4時間攪拌する。その後10%の酢酸ナトリウム水溶液30mLを加え中和し、酢酸エチルで抽出を行う。有機層を水及び飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。その粗生成物をカラムクロマトグラフィー(溶媒:へキサン/酢酸エチル=20/1)により粗精製し、さらに液体クロマトグラフィーにより精製し、(42)で表されるアルデヒド誘導体225mgを得た。収率は81%であった。
(42)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ 10.03 (1H, s), 8.18 (1H, d, J = 1.4 Hz), 8.13 (1H, d, J = 7.7 Hz), 7.56 (1H, dd, J = 8.5, 1.7 Hz), 7.54-7.43 (3H, m), 7.30-7.24 (1H, m), 7.13 (1H, s), 7.06 (1H, s), 7.04 (1H, s), 7.01 (1H, s), 4.40 (2H, q, J = 7.1 Hz), 2.96 (2H, t, J = 7.7 Hz), 2.84 (2H, t, J = 7.7 Hz), 2.80 (2H, t, J = 7.7 Hz), 2.72 (2H, t, J = 7.7 Hz), 1.77-1.64 (8H, m), 1.48 (3H, t, J = 7.1 Hz), 1.44-1.26 (24H, m), 0.96-0.84 (12H, m).
(6)で示される色素化合物の1H NMRデータ(300MHz,THF-d8):δ 8.39 (1H, s), 8.16 (1H, s), 8.08 (1H, d, J = 7.7 Hz), 7.56-7.39 (4H, m), 7.17 (1H, d, J = 7.7 Hz), 7.14 (1H, s), 7.05 (2H, s), 6.59 (1H, s), 4.42 (2H, q, J = 6.9 Hz), 2.86-2.66 (8H, m), 1.71-1.60 (8H, m), 1.40 (3H, t, J = 6.9 Hz), 1.40-1.25 (24H, m), 0.95-0.82 (12H, m).
DMF1mLに冷却(0度)下、オキシ塩化リン0.1mLを滴下し、室温で1時間攪拌し、Vilsmeier試薬を合成する。(39)で表されるヘキシル置換チオフェン環が5個連なったカルバゾール誘導体181mgのDMF溶液3mLに上記のVilsmeier試薬を室温で滴下し、70度で4時間攪拌する。その後10%の酢酸ナトリウム水溶液30mLを加え中和し、酢酸エチルで抽出を行う。有機層を水及び飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。その粗生成物をカラムクロマトグラフィー(溶媒:へキサン/酢酸エチル=20/1)により粗精製し、さらに液体クロマトグラフィーにより精製し、(43)で表されるアルデヒド誘導体159mgを得た。収率は84%であった。
(43)で表される化合物の1H NMRデータ(400MHz,CDCl3):δ 10.02 (1H, s), 8.16 (1H, d, J = 1.1 Hz), 8.12 (1H, d, J = 7.4 Hz), 7.56 (1H, dd, J = 8.5, 1.7 Hz), 7.50 (1H, br t, J = 7.7 Hz), 7.45 (1H, d, J = 8.5 Hz), 7.44 (1H, br d, J = 7.7 Hz), 7.26 (1H, m), 7.10 (1H, s), 7.05 (1H, s), 7.02 (1H, s), 7.00 (1H, s), 6.99 (1H, s), 4.41 (2H, q, J = 7.1 Hz), 2.95 (2H, t, J = 7.7 Hz), 2.85-2.76 (6H, m), 2.70 (2H, t, J = 7.7 Hz), 1.76-1.66 (10H, m), 1.48 (3H, t, J = 7.1 Hz), 1.44-1.24 (30H, m), 0.94-0.88 (12H, m), 0.85 (3H, t, J = 7.1 Hz).
(7)で示される色素化合物の1H NMRデータ(300MHz,THF-d8):δ8.41 (1H, s), 8.18 (1H, s), 8.12 (1H, d, J = 7.7 Hz), 7.62-7.50 (4H, m), 7.45-7.40 (1H, m), 7.24 (1H, d, J = 3.4 Hz), 7.25-7.05 (4H, m), 4.47 (2H, q, J = 7.2 Hz), 2.99-2.80 (6H, m), 2.73 (2H, t, J = 7.8 Hz), 1.72-1.55 (5H, m), 1.54-1.25 (30H, m), 0.99-0.75 (12H, m).
DMF1mLに冷却(0度)下、オキシ塩化リン0.1mLを滴下し、室温で1時間攪拌し、Vilsmeier試薬を合成する。(40)で表されるヘキシル置換チオフェン環が6個連なったカルバゾール誘導体253mgのDMF溶液4mLに上記のVilsmeier試薬を室温で滴下し、70度で4時間攪拌する。その後10%の酢酸ナトリウム水溶液30mLを加え中和し、酢酸エチルで抽出を行う。有機層を水及び飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。その粗生成物をカラムクロマトグラフィー(溶媒:へキサン/酢酸エチル=10/1)により粗精製し、さらに液体クロマトグラフィーにより精製し、(44)で表されるアルデヒド誘導体97mgを得た。収率は38%であった。
(44)で表される化合物の1H NMRデータ(400MHz,THF-d8):δ 10.03 (1H, s), 8.18 (1H, d, J = 1.0 Hz), 8.12 (1H, d, J = 7.7 Hz), 7.60-7.51 (3H, m), 7.44 (1H, ddd, J = 8.2, 7.0, 1.1 Hz), 7.19 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 7.19 (1H, s), 7.18 (1H, s), 7.12 (2H, s), 7.09 (1H, s), 7.07 (1H, s), 4.47 (2H, q, J = 7.1 Hz), 3.00 (2H, t, J = 7.8 Hz), 2.90-2.81 (8H, m), 2.73 (2H, t, J = 7.8 Hz), 1.77-1.66 (12H, m), 1.44 (3H, t, J = 7.1 Hz), 1.42-1.26 (36H, m), 0.94-0.88 (12H, m), 0.85 (3H, t, J = 7.0 Hz).
(8)で表される化合物の1H NMRデータ(400MHz,THF-d8):δ 8.41 (1H, s), 8.19 (1H, br s), 8.11 (1H, d, J = 7.7 Hz), 7.60-7.50 (3H, m), 7.43 (1H, ddd, J = 8.2, 7.2, 1.0 Hz), 7.25 (1H, s), 7.19 (1H, br t, J = 7.2 Hz), 7.18 (1H,s), 7.13 (1H, s), 7.12 (1H, s), 7.09 (1H, s), 7.07 (1H, s), 4.46 (2H, q, J = 7.1 Hz), 2.91 (2H, t, J = 7.7 Hz), 2.89-2.80 (8H, m), 2.73 (2H, t, J = 7.7 Hz), 1.77-1.64 (12H, m), 1.43 (3H, t, J = 7.1 Hz), 1.46-1.26 (36H, m), 0.96-0.88 (15H, m), 0.85 (3H, t, J = 7.0 Hz).
(45)で表される9−エチルカルバゾール−3−ボロン酸エステル130mgと(46)で表されるモノブロモ−クウォーターチオフェン誘導体183mgを混合させ、テトラキス(トリフェニホスフィン)パラジウム37mgおよび2mol/L濃度の炭酸ナトリウム水溶液1mL存在下、ジメトキシエタン中、24時間加熱還流を行う。室温に冷却後、酢酸エチルで希釈し、有機層を水及び飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。その粗生成物をカラムクロマトグラフィー(溶媒:へキサン/酢酸エチル=50/1)により粗精製し、さらに液体クロマトグラフィー(溶媒:へキサン/酢酸エチル=50/1)により精製し、(47)で表されるカルバゾール誘導体197mgを得た。収率は90%であった。
(47)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ 8.35 (1H, d, J = 1.7 Hz), 8.18 (1H, br d, J = 7.7 Hz), 7.75 (1H, dd, J = 8.5, 1.7 Hz), 7.52 (1H, ddd, J = 8.2, 7.1, 1.1 Hz), 7.43 (1H, d, J = 8.5 Hz), 7.39 (1H, d, J = 8.5 Hz), 7.33 (1H, dd, J = 5.2, 1.1 Hz), 7.31 (1H, d, J = 3.8 Hz), 7.29 (1H, m), 7.18 (1H, dd, J = 3.6, 1.1 Hz), 7.16 (1H, d, J = 3.8 Hz), 7.10 (1H, dd, J = 5.2, 3.6 Hz), 7.058 (1H, s), 7.055 (1H, s), 4.36 (2H, q, J = 7.1 Hz), 2.85 (2H, t, J = 7.7 Hz), 2.78 (2H, t, J = 7.7 Hz), 1.81-1.65 (4H, m), 1.46 (3H, t, J = 7.1 Hz), 1.42-1.31 (12H, m), 0.96 (3H, t, J = 6.7 Hz), 0.95 (3H, t, J = 6.7 Hz).
(48)で表される化合物の1H NMRデータ(400MHz,CDCl3):δ 9.88 (1H, s), 8.32 (1H, d, J = 1.7 Hz), 8.15 (1H, d, J = 7.7 Hz), 7.74 (1H, dd, J = 8.5, 1.7 Hz), 7.70 (1H, d, J =4.0 Hz), 7.50 (1H, ddd, J = 8.2, 7.1, 1.0 Hz), 7.42 (1H, d, J = 8.2 Hz), 7.41 (1H, d, J = 8.5 Hz), 7.30 (1H, d, J = 3.6 Hz), 7.27 (1H, br t, J = 7.4 Hz), 7.22 (1H, d, J = 4.0 Hz), 7.14 (1H, d, J = 3.6 Hz), 7.07 (1H, s), 7.04 (1H, s), 4.39 (2H, q, J = 7.2 Hz), 2.83 (2H, t, J = 7.8 Hz), 2.76 (2H, t, J = 7.8 Hz), 1.76-1.66 (4H, m), 1.46 (3H, t, J = 7.2 Hz), 1.43-1.30 (12H, m), 0.92 (3H, t, J = 6.7 Hz), 0.90 (3H, t, J = 6.7 Hz).
(9)で表される化合物の1H NMRデータ(400MHz,THF-d8):δ 8.40 (1H, br s), 8.31 (1H, s), 8.07 (1H, d, J = 7.6 Hz), 7.64 (1H, d, J = 7.9 Hz), 7.58 (1H br s), 7.46-7.37 (2H, m), 7.35 (1H, d, J = 7.1 Hz), 7.29 (1H, br s), 7.18-7.08 (3H, m), 7.05 (1H, br s), 7.00 (1H, br s), 4.31 (2H, q, J = 7.1 Hz), 2.82-2.68 (4H, m), 1.78-1.63 (4H, m), 1.50-1.28 (15H, m), 0.91 (3H, t, J = 6.9 Hz), 0.88 (3H, t, J = 6.9 Hz).
(45)で表される9−エチルカルバゾール−3−ボロン酸エステル180mgと(49)で表されるモノブロモ−クウォーターチオフェン誘導体226mgを混合させ、テトラキス(トリフェニホスフィン)パラジウム27mgおよび2mol/L濃度の炭酸ナトリウム水溶液1mL存在下、ジメトキシエタン中、24時間加熱還流を行う。室温に冷却後、酢酸エチルで希釈し、有機層を水及び飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。その粗生成物をカラムクロマトグラフィー(溶媒:へキサン/酢酸エチル=50/1)により粗精製し、さらに液体クロマトグラフィー(溶媒:へキサン/酢酸エチル=20/1)により精製し、(50)で表されるカルバゾール誘導体166mgを得た。収率は61%であった。
(50)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ 8.32 (1H, br s), 8.15 (1H, br d, J = 7.7 Hz), 7.72 (1H, br d, J = 8.0 Hz), 7.50 (1H, br dd, J = 8.0, 7.1 Hz), 7.42 (1H, br d, J = 7.7 Hz), 7.40 (1H, d, J = 8.0 Hz), 7.26 (1H, br dd, J = 8.0, 7.1 Hz), 7.21-7.15 (4H, m), 7.09 (1H, br s), 7.04 (1H, d, J = 3.9 Hz), 6.95 (1H, d, J = 5.2 Hz)), 4.39 (2H, q, J = 7.1 Hz), 2.83-2.77 (4H, m), 1.81-1.61 (4H, m), 1.46 (3H, t, J = 7.1 Hz), 1.41-1.29 (12H, m), 0.93 (3H, t, J = 6.7 Hz), 0.91 (3H, t, J = 6.7 Hz).
(51)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ 9.80 (1H, s), 8.31 (1H, br s), 8.14 (1H, d, J = 7.7 Hz), 7.56 (1H, s), 7.49 (1H, br dd, J = 8.0, 7.1 Hz), 7.41 (1H, d, J = 8.0 Hz), 7.38 (1H, d, J = 8.5 Hz), 7.27 (1H, br dd, J = 8.0, 7.1 Hz), 7.21-7.14 (4H, m), 7.08 (1H, d, J = 3.6 Hz), 4.35 (2H, q, J = 7.1 Hz), 2.83 (2H, t, J = 7.7 Hz), 2.81 (2H, t, J = 7.7 Hz), 1.81-1.63 (4H, m), 1.44 (3H, t, J = 7.1 Hz), 1.42-1.24 (12H, m), 0.95-0.87 (6H, m).
(10)で示される色素化合物の1H NMRデータ(400MHz,DMSO-d8):δ 8.46 (1H, s), 8.23 (1H, d, J = 7.7 Hz), 8.15 (1H, s), 7.70 (1H, dd, J = 8.5, 1.8 Hz), 7.63 (1H, s), 7.60 (1H, d, J = 8.5 Hz), 7.58 (1H, d, J = 8.5 Hz), 7.46 (1H, ddd, J = 8.1, 7.1, 1.0 Hz), 7.45 (1H, s), 7.37, (1H, d, J = 4.0 Hz), 7.36 (1H, d, J = 4.0 Hz), 7.27 (1H, d, J = 4.0 Hz), 7.22 (1H, br t, J = 7.6 Hz), 7.15 (1H, s), 4.41 (2H, q, J = 7.1 Hz), 2.76 (2H, t, J = 7.7 Hz), 2.73 (2H, t, J = 7.7 Hz), 1.72-1.55 (4H, m), 1.42-1.21 (12H, m), 1.30 (3H, t, J = 7.1 Hz), 0.87-0.82 (6H, m).
(52)で表されるカルバゾール誘導体336mgと市販されている(53)のビチオフェンボロン酸エステル243mgを混合させ、テトラキス(トリフェニホスフィン)パラジウム65mgおよび2mol/L濃度の炭酸ナトリウム水溶液1mL存在下、ジメトキシエタン中、24時間加熱還流を行う。室温に冷却後、酢酸エチルで希釈し、有機層を水及び飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。その粗生成物をカラムクロマトグラフィー(溶媒:へキサン/酢酸エチル=50/1)により粗精製し、さらに液体クロマトグラフィー(溶媒:へキサン/酢酸エチル=25/1)により精製し、(54)で表されるカルバゾール誘導体365mgを得た。収率は95%であった。
(54)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ 8.17 (1H, br s), 8.13 (1H, d, J = 7.7 Hz), 7.56 (1H, dd, J = 8.5, 1.7 Hz), 7.54-7.43 (3H, m), 7.29-7.19 (4H, m), 7.14 (1H, d, J = 3.9 Hz), 7.10 (1H, s), 7.05 (1H, d, J = 3.9 Hz), 7.03 (1H, s), 4.41 (2H, q, J = 7.1 Hz), 2.78 (2H, t, J = 7.7 Hz), 2.70 (2H, t, J = 7.7 Hz), 1.76-1.63 (4H, m), 1.48 (3H, t, J = 7.1 Hz), 1.44-1.24 (12H, m), 0.91 (3H, t, J = 6.7 Hz), 0.86 (3H, t, J = 6.7 Hz).
(55)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ 9.86 (1H, s), 8.17 (1H, br s), 8.12 (1H, d, J = 7.7 Hz), 7.66 (1H, d, J = 3.8 Hz), 7.54-7.43 (3H, m), 7.32 (1H, d, J = 3.8 Hz), 7.29-7.23 (2H, m), 7.12 (1H, s), 7.09 (1H, d, J = 3.8 Hz), 7.04 (1H, s), 4.40 (2H, q, J = 7.1 Hz), 2.78 (2H, t, J = 7.7 Hz), 2.71 (2H, t, J = 7.7 Hz), 1.76-1.63 (4H, m), 1.48 (3H, t, J = 7.1 Hz), 1.44-1.24 (12H, m), 0.92 (3H, t, J = 6.6 Hz), 0.86 (3H, t, J = 6.6 Hz).
(11)で示される色素化合物の1H NMRデータ(400MHz,THF-d8):δ 8.35 (1H, s), 8.13 (1H, s), 8.11 (1H, d, J = 7.6 Hz), 7.77 (1H, br s), 7.54-7.49 (3H, m), 7.46 (1H, br s), 7.43 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 7.37 (1H, br s), 7.21-7.16 (3H, m), 7.13 (1H, s), 4.45 (2H, q, J = 7.1 Hz), 2.72 (2H, t, J = 7.7 Hz), 2.72 (2H, t, J = 7.7 Hz), 1.76-1.65 (4H, m), 1.42 (3H, t, J = 7.1 Hz), 1.39-1.25 (12H, m), 0.91 (3H, t, J = 6.9 Hz), 0.84 (3H, t, J = 6.9 Hz).
(56)で表されるカルバゾール誘導体を用いて、前記[0045]で示される臭素化反応及び前記[0046]で示されるスズキカップリング反応を2回ずつ繰り返すことにより、(57)で表されるカルバゾール誘導体を合成することができる。
(57)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ 8.32 (1H, d, J = 1.4 Hz), 8.15 (1H, d, J = 7.7 Hz), 7.73 (1H, br d, J = 8.2 Hz), 7.50 (1H, t, J = 7.7 Hz), 7.42 (1H, d, J = 7.0 Hz), 7.39 (1H, d, J = 8.0 Hz), 7.30-7.25 (2H, m), 7.17 (1H, d, J = 3.6 Hz), 7.10 (1H, d, J = 3.8 Hz), 7.07 (1H, d, J = 3.8 Hz), 7.01 (1H, s), 6.98 (1H, br s), 6.91 (1H, br s), 4.37 (2H, q, J = 7.1 Hz), 2.75 (2H, t, J = 7.7 Hz), 2.62 (2H, t, J = 7.7 Hz), 1.73-1.60 (4H, m), 1.45 (3H, t, J = 7.1 Hz), 1.44-1.26 (12H, m), 0.94-0.89 (6H, m).
(58)で表される化合物の1H NMRデータ(400MHz,CDCl3):δ 10.01 (1H, s), 8.32 (1H, d, J = 1.7 Hz), 8.15 (1H, d, J = 7.6 Hz), 7.73 (1H, dd, J = 8.5, 1.7 Hz), 7.50 (1H, ddd, J = 8.2, 7.0, 1.1 Hz), 7.43 (1H, d, J = 8.2 Hz), 7.42 (1H, d, J = 8.5 Hz), 7.28 (1H, d, J = 3.8 Hz), 7.27 (1H, br t, J = 7.4 Hz), 7.19 (1H, d, J = 3.8 Hz), 7.13 (2H, s), 7.04 (2H, s), 4.40 (2H, q, J = 7.1 Hz), 2.95 (2H, t, J = 7.8 Hz), 2.81 (2H, t, J = 7.8 Hz), 1.75-1.66 (4H, m), 1.46 (3H, t, J = 7.1 Hz), 1.42-1.30 (12H, m), 0.91 (3H, t, J = 7.0 Hz), 0.90 (3H, t, J = 7.0 Hz).
(12)で示される色素化合物の1H NMRデータ(400MHz,DMSO-d6):δ 8.47 (1H, d, J = 1.6 Hz), 8.23 (1H, d, J = 7.6 Hz), 8.14 (1H, s), 7.74 (1H, dd, J = 8.7, 1.5 Hz), 7.62-7.60 (2H, m), 7.50 (1H, dd, J = 3.8 Hz), 7.47 (1H, ddd, J = 8.2, 7.0, 1.2 Hz), 7.36 (1H, d, J = 3.8 Hz), 7.34 (1H, d, J = 3.8 Hz), 7.29 (1H, d, J = 3.8 Hz), 7.28 (1H, s), 7.22 (1H, br t, J = 7.4 Hz), 7.19 (1H, s), 4.43 (2H, q, J = 7.1 Hz), 2.76 (2H, br t, J = 7.6 Hz), 2.72 (2H, br t, J = 7.6 Hz), 1.68-1.52 (4H, m), 1.30 (3H, t, J = 7.1 Hz), 1.37-1.21 (12H, m), 0.85 (3H, t, J = 7.0 Hz), 0.84 (3H, t, J = 7.0 Hz).
マグネシウム204mgに(59)で表される4−ヘキシルオキシブロモベンゼン1.8gのテトラヒドロフラン溶液4mLを滴下し、完全に滴下し終わった後、反応溶液を加熱還流させ、グリニア試薬を調整する。[1,3−ビス(ジフェニルホスフィノ)プロパン]ニッケルクロリド50mg存在下、0度に冷却した(32)で表される3−ヨウド−9−エチルカルバゾール1.0gのテトラヒドロフラン溶液10mLに、先に調整したグリニア試薬を滴下した。滴下後、反応溶液を一晩加熱還流を行った。その後、反応溶液を室温に戻し、塩化アンモニウム溶液を加えて反応を終了させ、酢酸エチルにより抽出する。有機層を水及び飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。その粗生成物をカラムクロマトグラフィー(溶媒:へキサン)により精製し、(60)で表される目的生成物であるカルバゾール誘導体を471mg得た。収率は40%であった。
(60)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ8.28 (1H, d, J = 1.6 Hz), 8.15 (1H, d, J = 7.8 Hz), 7.66 (1H, dd, J = 6.7, 1.8 Hz), 7.64 (2H, d, J = 8.7 Hz), 7.52-7.40 (1H, m), 7.45 (2H, d, J = 8.4 Hz), 7.25 (1H, t, J = 7.3 Hz), 7.02 (2H, d, J = 8.7 Hz), 4.40 (2H, q, J = 7.2 Hz), 4.03 (2H, t, J = 6.6 Hz), 1.90-1.78 (2H, m), 1.55-1.34 (9H, m), 0.94 (3H, t, J = 7.0 Hz).
(61)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ8.36 (1H, d, J = 1.2 Hz), 8.32 (1H, d, J = 1.0 Hz), 7.74 (1H, dd, J = 8.6, 1.7 Hz), 7.70 (1H, dd, J = 8.7, 1.8 Hz), 7.67 (2H, d, J = 8.9 Hz), 7.43 (1H, d, J = 8.6), 7.39 (1H, d, J = 8.6), 7.22 (1H, s), 7.04 (2H, d, J = 8.7 Hz), 7.02 (1H, s), 6.93 (1H, s), 4.36 (2H, q, J = 7.2 Hz), 4.05 (2H, t, J = 6.6 Hz), 2.83 (4H, m), 2.65 (2H, t, J = 7.6 Hz), 1.92-1.60 (8H, m), 1.60-1.28 (27H, m), 1.0-0.87 (12H, m).s
(62)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ 8.37 (1H, d, J = 1.4 Hz), 8.32 (1H, d, J = 1.4 Hz), 7.74 (1H, dd, J = 8.5, 1.7 Hz), 7.70 (1H, dd, J = 8.6, 1.6 Hz), 7.66 (2H, d, J = 8.7 Hz), 7.43 (1H, d, J = 8.5 Hz), 7.39 (1H, d, J = 8.6 Hz), 7.23 (1H, s), 7.04 (1H, s), 7.03 (2H, d, J = 8.7 Hz), 7.04-6.99 (2H, m), 6.29 (1H, s), 4.37 (2H, q, J = 7.2 Hz), 4.04 (2H, t, J = 6.6 Hz), 2.91-2.75 (6H, m), 2.64 (2H, t, J = 7.7 Hz), 1.92-1.63 (9H, m), 1.58-1.26 (34H, m), 1.00-0.85 (15H, m).
(63)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ10.0 (1H, s), 8.35 (1H, d, J = 1.6 Hz), 8.30 (1H, d, J = 1.6 Hz), 7.74 (1H, dd, J = 8.5, 1.7 Hz), 7.68 (1H, dd, J = 8.4, 1.6 Hz), 7.64 (2H, d, J = 8.6 Hz), 7.45 (1H, d, J = 8.5 Hz), 7.40 (1H, d, J = 8.6 Hz), 7.22 (1H, s), 7.05 (1H, s), 7.03 (1H, s), 7.02 (2H, d, J = 8.8 Hz), 4.39 (2H, q, J = 7.2 Hz), 4.03 (2H, t, J = 6.6 Hz), 2.95 (2H, t, J = 7.7 Hz), 2.84 (4H, t, J = 7.8 Hz), 1.89-1.66 (8H, m), 1.55-1.27 (27H, m), 0.98-0.85 (12H, m).
(15)で示される色素化合物の1H NMRデータ(300MHz,CDCl3):δ8.47 (1H, s), 8.41 (1H, s), 8.40 (1H, s), 7.74 (1H, d, J = 8.4 Hz), 7.70 (1H, d, J = 8.6 Hz), 7.65 (2H, d, J = 8.7 Hz), 7.53 (1H, d, J = 4.8 Hz), 7.51 (1H, d, J = 4.8 Hz), 7.36 (1H, s), 7.23 (1H, s), 7.13 (1H, s), 6.99 (2H, d, J = 8.8 Hz), 4.45 (2H, q, J = 7.1 Hz), 4.01 (2H, t, J = 6.5 Hz), 2.95-2.82 (6H, m), 1.85-1.63 (8H, m), 1.58-1.28 (27H, m), 0.98-0.87 (12H, m).
(62)で表されるカルバゾール誘導体のホルミル化は、前記[0048]に示される条件と同様、Vilsmeier反応により行った。178mgのカルバゾール誘導体(62)を用い反応を行い、粗生成物をカラムクロマトグラフィー(溶媒:へキサン/酢酸エチル=20/1)により粗精製し、さらに液体クロマトグラフィー(溶媒:へキサン/酢酸エチル=15/1)により精製し、(64)で表されるアルデヒド誘導体154mgを得た。収率は85%であった。
(64)で表される化合物の1H NMRデータ(300MHz,CDCl3):δ 10.0 (1H, s), 8.35 (1H, br s), 8.30 (1H, br s), 7.74-7.65 (2H, m), 7.64 (2H, d, J = 8.5 Hz), 7.44 (1H, d, J = 8.6 Hz), 7.39 (1H, d, J = 8.6 Hz), 7.21 (1H, s), 7.05 (1H, s), 7.02 (1H, s), 7.02 (2H, d, J = 8.3 Hz), 4.38 (2H, q, J = 7.2 Hz), 4.03 (2H, t, J = 6.5 Hz), 2.95 (2H, t, J = 7.6 Hz), 2.90-2.78 (6H, m), 1.89-1.63 (9H, m), 1.58-1.24 (34H, m), 0.98-0.85 (15H, m).
(16)で示される色素化合物の1H NMRデータ(300MHz,CDCl3):δ8.47 (1H, s), 8.41 (1H, s), 8.40 (1H, s), 7.74 (1H, d, J = 8.3 Hz), 7.70 (1H, d, J = 8.8 Hz), 7.65 (2H, d, J = 7.9 Hz), 7.55-7.48 (2H, m), 7.35 (1H, s), 7.24 (1H, s), 7.13 (1H, s), 7.10 (1H, s), 6.99 (2H, d, J = 8.2 Hz), 4.46 (2H, d, J = 6.9 Hz), 4.01 (2H, t, J = 6.3 Hz), 2.96-2.78 (8H, m), 1.83-1.64 (10H, m), 1.57-1.28 (33H, m), 1.00-0.85 (15H, m).
(67)で表されるアルデヒド誘導体40mgとシアノ酢酸14mgを、ピペリジン0.5mL存在下、アセトニトリル−クロロホルム混合溶媒中で加熱還流を4時間行った。その後反応溶液を室温に戻し、析出してきた結晶を濾過し、クロロホルム−エタノールから再結晶により精製し、(65)で示される色素化合物40mgを得た。収率は87%であった。
(65)で示される色素化合物の1H NMRデータ(300MHz,DMSO-d6):δ 8.50 (1H, s), 8.25 (1H, d, J = 7.7 Hz), 8.12 (1H, s), 7.78 (1H, dd, J = 8.5, 1.7 Hz), 7.72 (1H, d, J = 3.8 Hz), 7.66 (1H, d, J = 8.8 Hz), 7.62 (1H, d, J = 8.5 Hz), 7.53 (1H, d, J = 3.8 Hz), 7.50-7.45 (3H, m), 7.44 (1H, d, J = 3.8 Hz), 7.37 (1H, d, J = 3.8 Hz), 7.23 (1H, t, J = 7.4 Hz), 4.45 (2H, q, J = 7.1 Hz), 1.32 (3H, t, J = 7.1 Hz).
(1)有機色素吸着酸化チタン薄膜電極の作製
チタン・テトライソプロポキシドの加水分解により作製した酸化チタンコロイドをオートクレービングすることにより結晶性の酸化チタンナノ粒子を得た。これに、バインダーとしてエチルセルロース、溶媒としてα−テルピネオールを混合した有機性のペーストを作製した。あるいは、市販の酸化チタンペースト(たとえば、Solaronix社製)を用いても良い。上記酸化チタンペーストをスクリーン印刷法により、酸化スズコート導電性ガラス上に塗布し、空気中500℃で1〜2時間焼成することにより、膜厚が3〜20ミクロンの酸化チタン薄膜電極を得た。この電極を、0.3mMの有機色素溶液(溶媒は、トルエン、t−ブタノール、アセトニトリル1:1:1混合溶媒)に浸漬し、室温で10時間以上放置することにより、有機色素吸着酸化チタン薄膜電極を得た。
前記(1)で作製した酸化チタン薄膜電極(膜厚6ミクロン)に表1記載の色素を吸着させ、白金をスパッタした酸化スズコート導電性ガラスを対極として、ポリエチレンフィルムスペーサーを挟んで重ね合わせ、その隙間に電解液である0.6 Mヨウ化1,2-ジメチル-3-プロピルイミダゾリウム−0.1 Mヨウ化リチウム−0.05 Mヨウ素−0.5 M t-ブチルピリジンのアセトニトリル溶液を注入し、ゼムクリップでとめセルを作製した。セルの光電変換特性の測定は、光源としてキセノンランプとAMフィルターからなるソーラーシミュレーターを用い、光電流電圧特性は、ソースメーターを用いて測定した。
前記(2)で作製した本発明で合成した有機色素を用いた太陽電池における、酸化チタン電極中の電子寿命を、励起レーザー光およびポテンシオスタットを用いたIntensity-modulated photovoltage spectroscopy (IMVS法、例えば、J. Phys. Chem. B, 109, 3480 (2005), J. Phys. Chem. B, 109, 23776 (2005))により評価した。酸化チタン中の電子寿命は、色素からの電離注入量により変化することから、Jsc値が10 mA/cm2の条件での電子寿命値で比較した。
2 レドックス電解液層
3 色素吸着半導体薄膜電極層
4 導電性透明ガラス
Claims (4)
- 請求項1に記載の有機化合物を有機色素として用いることを特徴とする半導体薄膜電極。
- 請求項2に記載の半導体薄膜電極を用いることを特徴とする光電変換素子。
- 請求項3の光電変換素子を用いることを特徴とする光電気化学太陽電池。
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