JP2007277513A - Solution of binuclear metal complex pigment, photoelectric conversion device using the solution and photochemical cell - Google Patents
Solution of binuclear metal complex pigment, photoelectric conversion device using the solution and photochemical cell Download PDFInfo
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- JP2007277513A JP2007277513A JP2006247931A JP2006247931A JP2007277513A JP 2007277513 A JP2007277513 A JP 2007277513A JP 2006247931 A JP2006247931 A JP 2006247931A JP 2006247931 A JP2006247931 A JP 2006247931A JP 2007277513 A JP2007277513 A JP 2007277513A
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- Prior art keywords
- metal complex
- group
- dye solution
- dye
- substituted
- Prior art date
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 54
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 35
- 239000000049 pigment Substances 0.000 title abstract description 5
- 239000003446 ligand Substances 0.000 claims abstract description 43
- 239000004065 semiconductor Substances 0.000 claims abstract description 26
- 150000002500 ions Chemical class 0.000 claims abstract description 18
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 125000004429 atom Chemical group 0.000 claims abstract description 7
- 239000000975 dye Substances 0.000 claims description 68
- 239000000434 metal complex dye Substances 0.000 claims description 42
- 125000001424 substituent group Chemical group 0.000 claims description 38
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 31
- 125000003545 alkoxy group Chemical group 0.000 claims description 23
- 239000010419 fine particle Substances 0.000 claims description 23
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- -1 R 56 Chemical compound 0.000 claims description 14
- 125000004122 cyclic group Chemical group 0.000 claims description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims description 12
- 239000013522 chelant Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052762 osmium Inorganic materials 0.000 claims description 6
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 230000031700 light absorption Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 60
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 39
- 125000000217 alkyl group Chemical group 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 21
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 150000001721 carbon Chemical group 0.000 description 13
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 13
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 238000002835 absorbance Methods 0.000 description 8
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- YQZGQXPHGLAEHA-UHFFFAOYSA-N 2-pyridin-2-ylquinoline Chemical compound N1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 YQZGQXPHGLAEHA-UHFFFAOYSA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- 229910001887 tin oxide Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000012047 saturated solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- WPTCSQBWLUUYDV-UHFFFAOYSA-N 2-quinolin-2-ylquinoline Chemical compound C1=CC=CC2=NC(C3=NC4=CC=CC=C4C=C3)=CC=C21 WPTCSQBWLUUYDV-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 0 C*c1cc(-c2cc(*)cc*2C)*(C*2ccc(*)cc2-c2*(*)ccc(*)c2)cc1 Chemical compound C*c1cc(-c2cc(*)cc*2C)*(C*2ccc(*)cc2-c2*(*)ccc(*)c2)cc1 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- GCRLVKBHFZOVLQ-UHFFFAOYSA-H hexachloroosmium Chemical compound Cl[Os](Cl)(Cl)(Cl)(Cl)Cl GCRLVKBHFZOVLQ-UHFFFAOYSA-H 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical class [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- ISHFYECQSXFODS-UHFFFAOYSA-M 1,2-dimethyl-3-propylimidazol-1-ium;iodide Chemical compound [I-].CCCN1C=C[N+](C)=C1C ISHFYECQSXFODS-UHFFFAOYSA-M 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 description 2
- VMISXESAJBVFNH-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid;ruthenium(2+);diisothiocyanate Chemical compound [Ru+2].[N-]=C=S.[N-]=C=S.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 VMISXESAJBVFNH-UHFFFAOYSA-N 0.000 description 2
- YYZBPKCINJVSGH-UHFFFAOYSA-N 3-iodopropanenitrile Chemical compound ICCC#N YYZBPKCINJVSGH-UHFFFAOYSA-N 0.000 description 2
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- ZYSSNSIOLIJYRF-UHFFFAOYSA-H Cl[Ir](Cl)(Cl)(Cl)(Cl)Cl Chemical compound Cl[Ir](Cl)(Cl)(Cl)(Cl)Cl ZYSSNSIOLIJYRF-UHFFFAOYSA-H 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- XZQYTGKSBZGQMO-UHFFFAOYSA-I Rhenium(V) chloride Inorganic materials Cl[Re](Cl)(Cl)(Cl)Cl XZQYTGKSBZGQMO-UHFFFAOYSA-I 0.000 description 2
- 229910021637 Rhenium(VI) chloride Inorganic materials 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005314 correlation function Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- GSGIQJBJGSKCDZ-UHFFFAOYSA-H hexachlororhenium Chemical compound Cl[Re](Cl)(Cl)(Cl)(Cl)Cl GSGIQJBJGSKCDZ-UHFFFAOYSA-H 0.000 description 2
- QTNLQPHXMVHGBA-UHFFFAOYSA-H hexachlororhodium Chemical compound Cl[Rh](Cl)(Cl)(Cl)(Cl)Cl QTNLQPHXMVHGBA-UHFFFAOYSA-H 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- CHGSZSOJDJQCGO-UHFFFAOYSA-N ruthenium(2+);hexacyanide Chemical compound [Ru+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] CHGSZSOJDJQCGO-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- UXMRNSHDSCDMLG-UHFFFAOYSA-J tetrachlororhenium Chemical compound Cl[Re](Cl)(Cl)Cl UXMRNSHDSCDMLG-UHFFFAOYSA-J 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- MWEXRLZUDANQDZ-RPENNLSWSA-N (2s)-3-hydroxy-n-[11-[4-[4-[4-[11-[[2-[4-[(2r)-2-hydroxypropyl]triazol-1-yl]acetyl]amino]undecanoyl]piperazin-1-yl]-6-[2-[2-(2-prop-2-ynoxyethoxy)ethoxy]ethylamino]-1,3,5-triazin-2-yl]piperazin-1-yl]-11-oxoundecyl]-2-[4-(3-methylsulfanylpropyl)triazol-1-y Chemical compound N1=NC(CCCSC)=CN1[C@@H](CO)C(=O)NCCCCCCCCCCC(=O)N1CCN(C=2N=C(N=C(NCCOCCOCCOCC#C)N=2)N2CCN(CC2)C(=O)CCCCCCCCCCNC(=O)CN2N=NC(C[C@@H](C)O)=C2)CC1 MWEXRLZUDANQDZ-RPENNLSWSA-N 0.000 description 1
- MBOIBXSDCWRKJR-UHFFFAOYSA-N 1,10-phenanthroline-4,7-dicarboxylic acid Chemical compound C1=CC2=C(C(O)=O)C=CN=C2C2=C1C(C(=O)O)=CC=N2 MBOIBXSDCWRKJR-UHFFFAOYSA-N 0.000 description 1
- JBOIAZWJIACNJF-UHFFFAOYSA-N 1h-imidazole;hydroiodide Chemical compound [I-].[NH2+]1C=CN=C1 JBOIAZWJIACNJF-UHFFFAOYSA-N 0.000 description 1
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 1
- VEZJRJGLFIXQHG-UHFFFAOYSA-N 2-(1h-benzimidazol-2-yl)-1h-benzimidazole Chemical compound C1=CC=C2NC(C=3NC4=CC=CC=C4N=3)=NC2=C1 VEZJRJGLFIXQHG-UHFFFAOYSA-N 0.000 description 1
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical compound C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 description 1
- HKOAFLAGUQUJQG-UHFFFAOYSA-N 2-pyrimidin-2-ylpyrimidine Chemical compound N1=CC=CN=C1C1=NC=CC=N1 HKOAFLAGUQUJQG-UHFFFAOYSA-N 0.000 description 1
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- AFYNADDZULBEJA-UHFFFAOYSA-N bicinchoninic acid Chemical compound C1=CC=CC2=NC(C=3C=C(C4=CC=CC=C4N=3)C(=O)O)=CC(C(O)=O)=C21 AFYNADDZULBEJA-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- AHKYNYDHPKXRCM-UHFFFAOYSA-N c(cc1)cc2c1nc(-c1nc3ccccc3[n-]1)[n-]2 Chemical compound c(cc1)cc2c1nc(-c1nc3ccccc3[n-]1)[n-]2 AHKYNYDHPKXRCM-UHFFFAOYSA-N 0.000 description 1
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- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
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- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
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- FZHCFNGSGGGXEH-UHFFFAOYSA-N ruthenocene Chemical compound [Ru+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 FZHCFNGSGGGXEH-UHFFFAOYSA-N 0.000 description 1
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
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- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
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- IEKWPPTXWFKANS-UHFFFAOYSA-K trichlorocobalt Chemical compound Cl[Co](Cl)Cl IEKWPPTXWFKANS-UHFFFAOYSA-K 0.000 description 1
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Images
Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
Description
本発明は、高い吸光係数を有する、電子移動に優れた耐熱性に優れた金属錯体色素を溶解した耐光性、耐酸化還元性に優れた金属錯体色素溶液を用いることによって作製された、光増感された酸化物半導体を用いた光電変換素子、ならびにそれを用いた光化学電池に関する。 The present invention is a photosensitizer produced by using a metal complex dye solution having a high extinction coefficient, an excellent metal complex dye having excellent electron transfer, and excellent light resistance and redox resistance. The present invention relates to a photoelectric conversion element using a sensed oxide semiconductor, and a photochemical battery using the photoelectric conversion element.
太陽電池はクリーンな再生型エネルギー源として大きく期待されており、単結晶シリコン系、多結晶シリコン系、アモルファスシリコン系の太陽電池やテルル化カドミウム、セレン化インジウム銅などの化合物からなる太陽電池の実用化をめざした研究がなされている。しかし、家庭用電源として普及させるためには、いずれの電池も製造コストが高いことや原材料の確保が困難なことやリサイクルの問題、また大面積化が困難であるなど克服しなければならない多くの問題を抱えている。そこで、大面積化や低価格化を目指し有機材料を用いた太陽電池が提案されてきたが、いずれも変換効率が１％程度と実用化にはほど遠いものであった。 Solar cells are highly expected as a clean renewable energy source. Practical use of single-crystal silicon-based, polycrystalline silicon-based, amorphous silicon-based solar cells and solar cells composed of compounds such as cadmium telluride and indium copper selenide Research has been conducted with the aim of making it easier. However, in order to disseminate it as a household power source, many of the batteries that must be overcome, such as high manufacturing costs, difficulty in securing raw materials, recycling problems, and difficulty in increasing the area. I have a problem. Thus, solar cells using organic materials have been proposed with the aim of increasing the area and reducing the price, but all have a conversion efficiency of about 1%, which is far from practical use.
こうした状況の中、１９９１年にグレッツェルらによりＮａｔｕｒｅに色素によって増感された半導体微粒子を用いた光電変換素子および太陽電池、ならびにこの太陽電池の作製に必要な材料および製造技術が開示された。（例えば、Ｎａｔｕｒｅ、第３５３巻、７３７頁、１９９１年（非特許文献１）、特開平１−２２０３８０号公報（特許文献１）など）。この電池はルテニウム色素によって増感された多孔質チタニア薄膜を作用電極とする湿式太陽電池である。この太陽電池の利点は、安価な材料を高純度に精製する必要がなく用いられるため、安価な光電変換素子として提供できること、さらに用いられる色素の吸収がブロードであり、広い可視光の波長域にわたって太陽光を電気に変換できることである。しかしながら実用化のためにはさらなる変換効率の向上が必要であり、より高い吸光係数を有し、より高波長域まで光を吸収する色素の開発が望まれている。 Under such circumstances, in 1991, Gretzel et al. Disclosed a photoelectric conversion element and a solar cell using semiconductor fine particles sensitized with a dye in Nature, and materials and manufacturing techniques necessary for the production of the solar cell. (For example, Nature, Volume 353, page 737, 1991 (Non-Patent Document 1), JP-A-1-220380 (Patent Document 1), etc.). This battery is a wet solar cell using a porous titania thin film sensitized with a ruthenium dye as a working electrode. The advantage of this solar cell is that it can be used as an inexpensive photoelectric conversion element because it is not necessary to purify an inexpensive material with high purity, and further, the absorption of the dye used is broad, and over a wide visible light wavelength range. It can convert sunlight into electricity. However, further improvement in conversion efficiency is necessary for practical use, and development of a dye having a higher extinction coefficient and absorbing light up to a higher wavelength region is desired.
本出願人による特開２００３−２６１５３６号公報（特許文献２）には、光電変換素子として有用な金属錯体色素であるジピリジル配位子含有金属単核錯体が開示されている。
また、色素増感太陽電池の最新技術（株式会社シーエムシー、２００１年５月２５日発行、１１７頁）（非特許文献２）には、多核β−ジケトナート錯体色素が開示されている。
また、特開２００４−３５９６７７号公報（特許文献３）には、光などの活性光線のエネルギーを受けて電子を取り出す光電変換機能の優れた新規な複核錯体として、複数の金属と複数の配位子を有し、その複数の金属に配位する橋かけ配位子（ＢＬ）が複素共役環を有する配位構造と複素共役環を有しない配位構造を有する複核錯体が開示されている。また、特開２０００−３２３１９１にはアシルオキシ基、アシルチオオキシ基等を有する対称な複核錯体が開示されている。（特許文献４）
また、１９９９年にグレッツェルらによりInorg. Chem.１９９９、３８、６２９８−６３０５（非特許文献３）に色素によって増感された半導体微粒子を用いた太陽電池に関して、溶液の調整法が開示された。
JP 2003-261536 (Patent Document 2) by the present applicant discloses a dipyridyl ligand-containing metal mononuclear complex which is a metal complex dye useful as a photoelectric conversion element.
In addition, the latest technology of dye-sensitized solar cells (CMC Co., Ltd., issued on May 25, 2001, page 117) (Non-Patent Document 2) discloses polynuclear β-diketonate complex dyes.
In addition, Japanese Patent Application Laid-Open No. 2004-359677 (Patent Document 3) describes a plurality of metals and a plurality of coordinations as a novel multinuclear complex having an excellent photoelectric conversion function for extracting electrons by receiving the energy of actinic rays such as light. A binuclear complex having a coordination structure in which a bridging ligand (BL) having a conjugated group and a metal coordinated to a plurality of metals has a heteroconjugated ring and a coordination structure not having a heteroconjugated ring is disclosed. JP 2000-323191 discloses a symmetric binuclear complex having an acyloxy group, an acylthiooxy group and the like. (Patent Document 4)
In 1999, Gretzel et al., Inorg. Chem. 1999, 38, 6298-6305 (Non-patent Document 3) disclosed a method for preparing a solution for a solar cell using semiconductor fine particles sensitized with a dye.
光電変換素子として、有用かつ新規な金属錯体色素が望まれている。
本発明の目的は、金属錯体色素の多核化により吸光係数の向上を目指し、電子遷移の方向を電解液側から多孔質半導体へ調整することでスムーズな電子移動を実現させ、効率良く半導体微粒子を光増感し得る耐熱性に優れた色素を溶解した耐光性、耐酸化還元性に優れた金属錯体色素溶液とこの溶液を用いることにより作製した半導体微粒子を含むことを特徴とする耐光性の高い光電変換素子ならびこの光電変換素子からなる光化学電池を提供することである。 The purpose of the present invention is to improve the light absorption coefficient by making the metal complex dye multinuclear, and by adjusting the direction of electron transition from the electrolyte side to the porous semiconductor, it realizes smooth electron transfer, and efficiently produces semiconductor fine particles. High light resistance characterized by including a light- and dye-dissolved metal complex dye solution in which a dye having excellent heat resistance capable of photosensitization is dissolved and semiconductor fine particles prepared by using this solution It is to provide a photoelectric conversion element and a photochemical battery comprising the photoelectric conversion element.
本発明は、一般式：（Ｌ１）２Ｍ１（ＢＬ）Ｍ２（Ｌ２）２（Ｘ）ｎで示される非対称な二核金属錯体を溶解した金属錯体色素溶液に関する。（但し、Ｍ１及びＭ２は、遷移金属であって、同一でも異なっていてもよく、Ｌ１及びＬ２は、多座配位可能なキレート型配位子であって、Ｌ１とＬ２は異なるものであり、二つのＬ１は異なるものであってもよく、二つのＬ２も異なるものであってもよく、ＢＬはヘテロ原子を含む環状構造を少なくとも二つ有する架橋配位子であって、Ｍ１及びＭ２に配位する配位原子がこの環状構造に含まれるヘテロ原子である。Ｘは対イオンである。ｎは錯体の電荷を中和するのに必要な対イオンの数を表す。）
The present invention relates to a metal complex dye solution in which an asymmetric binuclear metal complex represented by the general formula: (L 1 ) 2 M 1 (BL) M 2 (L 2 ) 2 (X) n is dissolved. (However, M 1 and M 2 are transition metals and may be the same or different, and L 1 and L 2 are multidentate chelate-type ligands, and L 1 and
また、本発明は、Ｌ１及びＬ２が二座もしくは三座もしくは四座配位可能なキレート型配位子であることを特徴とする上記の二核金属錯体を溶解した金属錯体色素溶液に関する。 The present invention also relates to a metal complex dye solution in which the above binuclear metal complex is dissolved, wherein L 1 and L 2 are chelate type ligands capable of bidentate, tridentate or tetradentate coordination.
本発明は分解に起因するガス発生温度が280℃以上であることを特徴とした二核金属錯体色素を含む、光及びかつ電気的に安定な二核金属錯体色素溶液に関する。 The present invention relates to an optically and electrically stable binuclear metal complex dye solution containing a binuclear metal complex dye characterized in that the gas generation temperature resulting from decomposition is 280 ° C. or higher.
また、本発明は、Ｌ１及びＬ２が窒素を含む共役系を有する環状構造を有していることを特徴とする上記の二核金属錯体を溶解した金属錯体色素溶液に関する。 The present invention also relates to a metal complex dye solution in which the above binuclear metal complex is dissolved, wherein L 1 and L 2 have a cyclic structure having a conjugated system containing nitrogen.
また、本発明は、Ｌ１及びＬ２が、ビピリジル、ピリジルキノリン、ビキノリン、またはフェナントロリンの誘導体である二座配位子であることを特徴とする上記の二核金属錯体を溶解した金属錯体色素溶液に関する。 The present invention also provides a metal complex dye having the above binuclear metal complex dissolved therein, wherein L 1 and L 2 are bidentate ligands that are bipyridyl, pyridylquinoline, biquinoline, or a derivative of phenanthroline Regarding the solution.
また、本発明は、Ｌ１が、カルボキシル基（−ＣＯＯＨ）または−ＣＯＯ−で少なくとも一つ置換された配位子であることを特徴とする上記の二核金属錯体を溶解した金属錯体色素溶液に関する。 The present invention also provides a metal complex dye solution in which the above binuclear metal complex is dissolved, wherein L 1 is a ligand substituted with at least one carboxyl group (—COOH) or —COO —. About.
また、本発明は、ＢＬが、四座配位子であることを特徴とする上記の二核金属錯体を溶解した金属錯体色素溶液に関する。 The present invention also relates to a metal complex dye solution in which the above binuclear metal complex is dissolved, wherein BL is a tetradentate ligand.
また、本発明は、Ｍ１及びＭ２が、第ＶＩＩＩ族〜第ＸＩ族の遷移金属であることを特徴とする上記の二核金属錯体を溶解した金属錯体色素溶液に関する。 The present invention also relates to a metal complex dye solution in which the above binuclear metal complex is dissolved, wherein M 1 and M 2 are Group VIII to Group XI transition metals.
また、本発明は、Ｍ１及びＭ２が、ルテニウム（Ｒｕ）、オスミウム（Ｏｓ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）または鉄（Ｆｅ）であることを特徴とする上記の二核金属錯体を溶解した金属錯体色素溶液に関する。 In the present invention, M 1 and M 2 are ruthenium (Ru), osmium (Os), cobalt (Co), nickel (Ni), copper (Cu), or iron (Fe). The present invention relates to a metal complex dye solution in which the binuclear metal complex is dissolved.
さらに、本発明は、一般式：（Ｌ１）２Ｍ１（ＢＬ）Ｍ２（Ｌ２）２（Ｘ）nで示される非対称な二核金属錯体（但し、Ｍ１及びＭ２は、遷移金属であって、同一でも異なっていてもよく、Ｌ１及びＬ２は、多座配位可能なキレート型配位子であって、Ｌ１とＬ２は異なるものであり、二つのＬ１は異なるものであってもよく、二つのＬ２も異なるものであってもよく、Ｘは対イオンであり、ｎは錯体の電荷を中和するのに必要な対イオンの数を表し、ＢＬはヘテロ原子を含む環状構造を少なくとも二つ有する架橋配位子であって、Ｍ１及びＭ２に配位する配位原子がこの環状構造に含まれるヘテロ原子であり、Ｌ１が半導体微粒子に固定され得る置換基を有し、かつ主に（Ｌ１）２Ｍ１にＬＵＭＯが分布する構造である。）からなることを特徴とする金属錯体色素を溶解した金属錯体色素溶液に関する。 Further, the present invention provides an asymmetric binuclear metal complex represented by the general formula: (L 1 ) 2 M 1 (BL) M 2 (L 2 ) 2 (X) n (where M 1 and M 2 are transitions) It is a metal and may be the same or different, L 1 and L 2 are multidentate chelate-type ligands, L 1 and L 2 are different, and two L 1 May be different, and the two L 2 may be different, X is a counter ion, n represents the number of counter ions required to neutralize the charge of the complex, and BL Is a bridging ligand having at least two cyclic structures containing heteroatoms, the coordinating atoms coordinated to M 1 and M 2 are heteroatoms contained in the cyclic structure, and L 1 is a semiconductor fine particle It has a fixed may substituent, and is mainly (L 1) LUMO in 2 M 1 are distributed structure ) Relates to a metal complex dye solution of a metal complex dye, characterized in that it consists of.
また、本発明は、上記の金属錯体色素溶液により増感された半導体微粒子を含むことを特徴とする光電変換素子に関する。 The present invention also relates to a photoelectric conversion element comprising semiconductor fine particles sensitized with the metal complex dye solution.
また、本発明は、上記の半導体微粒子が、酸化チタン、酸化亜鉛、または酸化錫であることを特徴とする光電変換素子に関する。 The present invention also relates to a photoelectric conversion element, wherein the semiconductor fine particles are titanium oxide, zinc oxide, or tin oxide.
また、本発明は、上記の光電変換素子を用いることを特徴とする光化学電池に関する。
The present invention also relates to a photochemical battery using the above-described photoelectric conversion element.
本発明により得られた耐熱性に優れた二核金属錯体色素は、既存色素を溶解させて得られた色素溶液に比べ高い吸光係数を有している。また光、電気に対する安定性が高く、安定した光化学電池を作製することに極めて優れている。また、かかる溶液により作製された光電変換素子は既存色素溶液により得られた光電変換素子に比べ光に対する安定性が極めて高く、高耐久性の光化学電池を提供するに極めて有効である。
本発明の金属錯体色素溶液を用いて作製した光化学電池は、比較色素である光電変換効率を示す色素に比べ、光電変換効率の向上が見られた。かかる二核金属錯体色素溶液から作製される光化学電池は太陽電池として極めて有効である。しかも、本発明の二核金属金属錯体色素は、現行で高い光電変換効率を示す色素とは違い、分子内に分解しやすい−ＮＣＳ基を有しておらず、本発明の二核錯体色素を溶解した溶液は光に対する安定性にも優れる。
The binuclear metal complex dye excellent in heat resistance obtained by the present invention has a higher extinction coefficient than a dye solution obtained by dissolving an existing dye. In addition, it has high stability to light and electricity, and is extremely excellent in producing a stable photochemical battery. Moreover, the photoelectric conversion element produced by such a solution has extremely high light stability compared to the photoelectric conversion element obtained from the existing dye solution, and is extremely effective for providing a highly durable photochemical battery.
In the photochemical battery produced using the metal complex dye solution of the present invention, the photoelectric conversion efficiency was improved as compared with the dye showing the photoelectric conversion efficiency as a comparative dye. A photochemical cell produced from such a binuclear metal complex dye solution is extremely effective as a solar cell. In addition, the binuclear metal complex dye of the present invention does not have a -NCS group that is easily decomposed in the molecule, unlike the dye that exhibits high photoelectric conversion efficiency at present. The dissolved solution is also excellent in light stability.
本発明の色素溶液に含まれる一般式：（Ｌ１）２Ｍ１（ＢＬ）Ｍ２（Ｌ２）２（Ｘ）ｎで示される非対称な二核金属錯体において、Ｍ１及びＭ２は、遷移金属であり、好ましくは第ＶＩＩＩ族〜第ＸＩ族の遷移金属であり、具体的には、ルテニウム（Ｒｕ）、オスミウム（Ｏｓ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）または鉄（Ｆｅ）が好ましい。中でも、ルテニウム（Ｒｕ）、オスミウム（Ｏｓ）が好ましく、ルテニウム（Ｒｕ）が特に好ましい。 In the asymmetric binuclear metal complex represented by the general formula: (L 1 ) 2 M 1 (BL) M 2 (L 2 ) 2 (X) n contained in the dye solution of the present invention, M 1 and M 2 are: A transition metal, preferably a Group VIII to XI transition metal, specifically ruthenium (Ru), osmium (Os), cobalt (Co), nickel (Ni), copper (Cu) or Iron (Fe) is preferred. Among these, ruthenium (Ru) and osmium (Os) are preferable, and ruthenium (Ru) is particularly preferable.
本発明は分解に起因するガス発生温度が280℃以上であることを特徴とした二核金属錯体を含む、光及びかつ電気的に安定な二核金属錯体色素溶液である。 The present invention is an optically and electrically stable binuclear metal complex dye solution containing a binuclear metal complex characterized in that the gas generation temperature resulting from decomposition is 280 ° C. or higher.
本発明の色素溶液において、溶液を構成する溶媒はアルコールを含むことが好ましい。さらに好ましくはアルコールの炭素数が３以上であることが望ましい。さらに好ましくはイソプロピルアルコールが望ましい。さらに、この溶液を構成する溶媒は単独または2種類以上組み合わせて使用することが出来る。 In the dye solution of the present invention, the solvent constituting the solution preferably contains an alcohol. More preferably, the alcohol has 3 or more carbon atoms. More preferably, isopropyl alcohol is desirable. Furthermore, the solvent which comprises this solution can be used individually or in combination of 2 or more types.
Ｍ１及びＭ２は、同一金属でも異なった金属であってもよい。 M 1 and M 2 may be the same metal or different metals.
Ｌ１及びＬ２は、多座配位可能なキレート型配位子であり、好ましくは二座もしくは三座もしくは四座配位可能なキレート型配位子、さらに好ましくは二座配位可能なキレート型配位子である。さらにキレート配位子が環状構造を有していることが望ましく、さらに好ましくは窒素を含む環状構造を有していることが望ましく、さらに好ましくは窒素を含む共役系を有する環状構造を有していることが望ましい。具体的には、２，２’−ビピリジン、１，１０−フェナントロリン、２−（２−ピリジニル）キノリンまたは２，２’−ビキノリンなどの誘導体などが挙げられる。Ｌ１とＬ２は、異なるものである。また、二つのＬ１は異なるものであってもよく、二つのＬ２も異なるものであってもよい。 L 1 and L 2 are chelate type ligands capable of multidentate coordination, preferably chelate type ligands capable of bidentate, tridentate or tetradentate coordination, more preferably chelate capable of bidentate coordination. Type ligand. Further, it is desirable that the chelate ligand has a cyclic structure, more preferably a nitrogen-containing cyclic structure, more preferably a nitrogen-containing conjugated system having a cyclic structure. It is desirable. Specific examples include derivatives such as 2,2′-bipyridine, 1,10-phenanthroline, 2- (2-pyridinyl) quinoline, or 2,2′-biquinoline. L 1 and L 2 are different. Further, the two L 1 may be different, and the two L 2 may be different.
本発明の二核金属錯体が光電変換素子に用いる金属錯体色素である場合、Ｌ１は、半導体微粒子に固定され得る置換基を少なくとも一つ有している。 When the binuclear metal complex of the present invention is a metal complex dye used for a photoelectric conversion element, L 1 has at least one substituent that can be fixed to semiconductor fine particles.
Ｌ１の半導体微粒子に固定され得る置換基としては、カルボキシル基（−ＣＯＯＨ）、アミノ基（−ＮＨ２）、水酸基（−ＯＨ）、硫酸基（−ＳＯ３Ｈ）、燐酸基（−ＰＯ３Ｈ２）、ニトロ基（−ＮＯ２）などが挙げられる。中でも、カルボキシル基（−ＣＯＯＨ）が好ましい。カルボキシル基の水素は、テトラブチルアンモニウムなどの４級アンモニウム、ナトリウムイオンなどのアルカリ金属イオンなどのカチオンで交換されていてもよい。また、水素は脱離していてもよい。 Examples of the substituent that can be fixed to the semiconductor fine particles of L 1 include a carboxyl group (—COOH), an amino group (—NH 2 ), a hydroxyl group (—OH), a sulfate group (—SO 3 H), and a phosphate group (—PO 3 H 2 ), nitro group (—NO 2 ) and the like. Among these, a carboxyl group (—COOH) is preferable. The hydrogen of the carboxyl group may be exchanged with a cation such as quaternary ammonium such as tetrabutylammonium or an alkali metal ion such as sodium ion. Further, hydrogen may be eliminated.
さらに、Ｌ１は、半導体微粒子に固定され得る置換基以外の置換基を有しても、有してなくてもよい。このような置換基としては、アルキル基（メチル基、エチル基など）、アルコキシ基（メトキシ基、エトキシ基など）などが挙げられる。 Further, L 1 may or may not have a substituent other than the substituent that can be fixed to the semiconductor fine particles. Examples of such a substituent include an alkyl group (such as a methyl group and an ethyl group) and an alkoxy group (such as a methoxy group and an ethoxy group).
また、本発明の二核金属錯体が光電変換素子に用いる金属錯体色素である場合、Ｌ１は、主に（Ｌ１）２Ｍ１部分にＬＵＭＯが分布するような配位子であることが好ましい。「主に（Ｌ１）２Ｍ１部分にＬＵＭＯが分布する」とは、（Ｌ２）２Ｍ２部分よりも（Ｌ１）２Ｍ１部分にＬＵＭＯが多く分布していることを意味する。主に（Ｌ１）２Ｍ１が太陽光などの光照射により電子が励起するＬＵＭＯを有する構造であることによって、この二核金属錯体を溶解した金属錯体色素溶液およびこの溶液を用いて作製した半導体微粒子を含む光電変換素子を用いて光化学電池を製造したときに、電解質から光電変換素子（負極）へのスムーズな電子移動を起こすことができ、効率のよい光化学電池を構成することができる。 When the binuclear metal complex of the present invention is a metal complex dye used for a photoelectric conversion element, L 1 may be a ligand in which LUMO is distributed mainly in the (L 1 ) 2 M 1 portion. preferable. “Mainly, LUMO is distributed in the (L 1 ) 2 M 1 portion” means that more LUMO is distributed in the (L 1 ) 2 M 1 portion than in the (L 2 ) 2 M 2 portion. . Mainly (L 1 ) 2 M 1 has a LUMO structure in which electrons are excited by light irradiation such as sunlight, so that a metal complex dye solution in which this binuclear metal complex is dissolved and a solution prepared using this solution When a photochemical battery is manufactured using a photoelectric conversion element containing semiconductor fine particles, smooth electron transfer from the electrolyte to the photoelectric conversion element (negative electrode) can occur, and an efficient photochemical battery can be configured.
ＬＵＭＯの算出は、ソフトウェアはＣｅｒｉｕｓ２あるいはＭａｔｅｒｉａｌ Ｓｔｕｄｉｏを用いた。その方法は、ＤＭｏｌ３モジュールを用いてＤＦＴ（密度汎関数法）によって金属錯体の構造最適化を行った。そのときの交換相関関数は特に限定はしないがＶＷＮ法またはＢＬＹＰ法が好適に用いられる。基底関数は特に限定はしないがＤＮＰが好適に用いられる。
エネルギー状態計算は得られた構造を用い、交換相関関数としては特に限定はしないがＢＬＹＰ，ＰＢＥが用いられ、基底関数系としては特に限定はしないがＤＮＰが好適に用いられる。
For the calculation of LUMO, the software used was Cerius 2 or Material Studio. In this method, the structure of the metal complex was optimized by DFT (density functional method) using a DMol 3 module. The exchange correlation function at that time is not particularly limited, but the VWN method or the BLYP method is preferably used. The basis function is not particularly limited, but DNP is preferably used.
The energy state calculation uses the obtained structure, and although there is no particular limitation on the exchange correlation function, BLYP and PBE are used, and the basis function system is not particularly limited, but DNP is preferably used.
Ｌ１としては、下式（Ｌ１−Ａ）で表される配位子が挙げられる。 L 1 includes a ligand represented by the following formula (L 1 -A).
式中、−ＣＯＯＨのＨは脱離していてもよく、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６は水素原子、アルコキシ基または置換もしくは無置換の炭化水素基を表すか、または、これらの二つ以上が一緒になってそれらが結合する炭素原子と共に置換もしくは無置換の芳香族炭化水素環または置換もしくは無置換の脂肪族炭化水素環を形成している。
Ｒ１〜Ｒ６は好ましくは水素原子、アルキル基、アルコキシ基であり、水素原子、アルキル基であることがより好ましい。アルキル基としては、炭素数６以下のものが好ましく、メチル基、エチル基がより好ましい。また、アルコキシ基としては、炭素数６以下のものが好ましく、メトキシ基、エトキシ基がより好ましい。
また、Ｒ２とＲ３、Ｒ４とＲ５、Ｒ１とＲ６が一緒になってそれらが結合する炭素原子と共に６員の芳香族炭化水素環（置換基を有していてもよい）を形成していることも好ましい。芳香族炭化水素環の置換基としては、アルキル基（メチル基、エチル基など）、アルコキシ基（メトキシ基、エトキシ基など）などが挙げられる。
Ｒ１〜Ｒ６は水素原子であることが特に好ましい。
In the formula, H of —COOH may be eliminated, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 represent a hydrogen atom, an alkoxy group or a substituted or unsubstituted hydrocarbon group. Or two or more of these together form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aliphatic hydrocarbon ring with the carbon atom to which they are attached.
R 1 to R 6 are preferably a hydrogen atom, an alkyl group, or an alkoxy group, and more preferably a hydrogen atom or an alkyl group. As an alkyl group, a C6 or less thing is preferable and a methyl group and an ethyl group are more preferable. Moreover, as an alkoxy group, a C6 or less thing is preferable and a methoxy group and an ethoxy group are more preferable.
In addition, R 2 and R 3 , R 4 and R 5 , R 1 and R 6 are combined together and a carbon atom to which they are bonded together with a 6-membered aromatic hydrocarbon ring (which may have a substituent) It is also preferable to form. Examples of the substituent of the aromatic hydrocarbon ring include an alkyl group (such as a methyl group and an ethyl group) and an alkoxy group (such as a methoxy group and an ethoxy group).
R 1 to R 6 are particularly preferably a hydrogen atom.
Ｌ１の具体例としては、下式（Ｌ１−１）〜（Ｌ１−４）で表される配位子が挙げられるが、本発明はこれらに限定されるものではない。 Specific examples of L 1 include ligands represented by the following formulas (L 1 -1) to (L 1 -4), but the present invention is not limited to these.
（Ｌ１−１）
２，２’−ビピリジン−４，４’−ジカルボン酸（Ｈ２ｄｃｂｐｙ）
(L 1 -1)
2,2′-bipyridine-4,4′-dicarboxylic acid (H 2 dcbpy)
（Ｌ１−２）
１，１０−フェナントロリン−４，７−ジカルボン酸（Ｈ２ｄｃｐｈｅｎ）
(L 1 -2)
1,10-phenanthroline-4,7-dicarboxylic acid (H 2 dcphen)
２−（２−（４−カルボキシピリジル））−４−カルボキシキノリン（Ｈ２ｄｃｐｑ）
2- (2- (4-carboxy-pyridyl)) - 4-
（Ｌ１−４）
２，２’−ビキノリン−４，４’−ジカルボン酸（Ｈ２ｄｃｂｉｑ）
但し、式（Ｌ１−１）〜（Ｌ１−４）中の複素環およびベンゼン環は置換基を有していてもよく、また、−ＣＯＯＨのＨは脱離していてもよい。置換基としては、メチル基、エチル基などの炭素数６以下のアルキル基、メトキシ基、エトキシ基などの炭素数６以下のアルコキシ基などが挙げられる。
(L 1 -4)
2,2′-biquinoline-4,4′-dicarboxylic acid (H 2 dcbiq)
However, the heterocyclic ring and the benzene ring in the formulas (L 1 -1) to (L 1 -4) may have a substituent, and H of —COOH may be eliminated. Examples of the substituent include an alkyl group having 6 or less carbon atoms such as a methyl group and an ethyl group, and an alkoxy group having 6 or less carbon atoms such as a methoxy group and an ethoxy group.
前述の通り、Ｌ２は、多座配位可能なキレート型配位子であり、好ましくは二座もしくは三座もしくは四座配位可能なキレート型配位子、さらに好ましくは二座配位可能なキレート型配位子である。具体的には、２，２’−ビピリジン、１，１０−フェナントロリン、２−（２−ピリジニル）キノリンまたは２，２’−ビキノリンなどの誘導体などが挙げられる。 As described above, L 2 is a chelate ligand capable of multidentate coordination, preferably a chelate ligand capable of bidentate, tridentate or tetradentate coordination, more preferably bidentate coordination. It is a chelate type ligand. Specific examples include derivatives such as 2,2′-bipyridine, 1,10-phenanthroline, 2- (2-pyridinyl) quinoline, or 2,2′-biquinoline.
Ｌ２は、置換基を有しても、有してなくてもよい。Ｌ２の置換基としては、アルキル基（メチル基、エチル基など）、アリール基（フェニル基、トリル基など）、アルコキシ基（メトキシ基、エトキシ基など）、および水酸基（−ＯＨ）などが挙げられる。特に、電子供与性を示す基が好ましい。 L 2 may or may not have a substituent. Examples of the substituent for L 2 include an alkyl group (such as a methyl group and an ethyl group), an aryl group (such as a phenyl group and a tolyl group), an alkoxy group (such as a methoxy group and an ethoxy group), and a hydroxyl group (—OH). It is done. In particular, a group showing an electron donating property is preferable.
Ｌ２としては、下式（Ｌ２−Ａ）で表される配位子が挙げられる。 L 2 includes a ligand represented by the following formula (L 2 -A).
（Ｌ２−Ａ）
式中、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６、Ｒ１７及びＲ１８は水素原子、アルコキシ基、水酸基または置換もしくは無置換の炭化水素基を表すか、または、これらの二つ以上が一緒になってそれらが結合する炭素原子と共に置換もしくは無置換の芳香族炭化水素環または置換もしくは無置換の脂肪族炭化水素環を形成している。
(L 2 -A)
In the formula, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 represent a hydrogen atom, an alkoxy group, a hydroxyl group or a substituted or unsubstituted hydrocarbon group, or these Two or more together form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aliphatic hydrocarbon ring with the carbon atom to which they are attached.
Ｒ１１〜Ｒ１８は好ましくは水素原子、アルキル基、アルコキシ基であり、水素原子、アルキル基であることがより好ましい。アルキル基としては、炭素数６以下のものが好ましく、メチル基、エチル基がより好ましい。また、アルコキシ基としては、炭素数６以下のものが好ましく、メトキシ基、エトキシ基がより好ましい。 R 11 to R 18 are preferably a hydrogen atom, an alkyl group, or an alkoxy group, and more preferably a hydrogen atom or an alkyl group. As an alkyl group, a C6 or less thing is preferable and a methyl group and an ethyl group are more preferable. Moreover, as an alkoxy group, a C6 or less thing is preferable and a methoxy group and an ethoxy group are more preferable.
また、Ｒ１１〜Ｒ１８の隣接する二つ、またはＲ１１とＲ１８が一緒になってそれらが結合する炭素原子と共に６員の芳香族炭化水素環（置換基を有していてもよい）を形成していることも好ましい。芳香族炭化水素環の置換基としては、アルキル基（メチル基、エチル基など）、アルコキシ基（メトキシ基、エトキシ基など）などが挙げられる。 Further, (which may have a substituent) two adjacent, or R 11 and R 18 together aromatic 6-membered together with the carbon atoms to which they are bonded hydrocarbon ring R 11 to R 18 It is also preferable to form. Examples of the substituent of the aromatic hydrocarbon ring include an alkyl group (such as a methyl group and an ethyl group) and an alkoxy group (such as a methoxy group and an ethoxy group).
Ｒ１１〜Ｒ１８は水素原子またはメチル基であることが特に好ましい。また、Ｒ１１とＲ１８が一緒になってそれらが結合する炭素原子と共に６員の芳香族炭化水素環（メチル基などの置換基を有していてもよい）を形成しており、Ｒ１２〜Ｒ１７は水素原子またはメチル基、より好ましくは水素原子であることも特に好ましい。 R 11 to R 18 are particularly preferably a hydrogen atom or a methyl group. R 11 and R 18 are combined to form a 6-membered aromatic hydrocarbon ring (which may have a substituent such as a methyl group) together with the carbon atom to which they are bonded, and R 12 It is particularly preferred that R 17 is a hydrogen atom or a methyl group, more preferably a hydrogen atom.
Ｌ２の具体例としては、下式（Ｌ２−１）〜（Ｌ２−４）で表される配位子が挙げられるが、本発明はこれらに限定されるものではない。 Specific examples of L 2 include ligands represented by the following formulas (L 2 -1) to (L 2 -4), but the present invention is not limited to these.
（Ｌ２−１）
２，２’−ビピリジン（ｂｐｙ）
(L 2 -1)
2,2'-bipyridine (bpy)
（Ｌ２−２）
１，１０−フェナントロリン（ｐｈｅｎ）
(L 2 -2)
1,10-phenanthroline (phen)
（Ｌ２−３）
２−（２−ピリジニル）キノリン（ｐｑ）
(L 2 -3)
2- (2-Pyridinyl) quinoline (pq)
（Ｌ２−４）
２，２’−ビキノリン（ｂｉｑ）
但し、式（Ｌ２−１）〜（Ｌ２−４）中の複素環およびベンゼン環は置換基を有していてもよい。置換基としては、炭素数６以下のアルキル基、炭素数６以下のアルコキシ基、メチル基などの置換基を有していてもよいフェニル基、水酸基などが挙げられる。
(L 2 -4)
2,2'-biquinoline (biq)
However, the heterocyclic ring and the benzene ring in the formulas (L 2 -1) to (L 2 -4) may have a substituent. Examples of the substituent include an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, a phenyl group which may have a substituent such as a methyl group, and a hydroxyl group.
ＢＬは架橋配位子であって、ヘテロ原子を含む環状構造を有するものである。そして、この環状構造（複素共役環）に含まれるヘテロ原子がＭ１及びＭ２に配位する配位原子である。ヘテロ原子としては、窒素、酸素、硫黄、燐などが挙げられる。 BL is a bridging ligand and has a cyclic structure containing a hetero atom. And the hetero atom contained in this cyclic structure (heteroconjugate ring) is a coordination atom coordinated to M 1 and M 2 . Heteroatoms include nitrogen, oxygen, sulfur, phosphorus and the like.
ＢＬは、四座配位子であることが好ましく、さらに好ましくはアニオン性である。また、ＢＬは、環状構造（複素共役環）上に置換基を有しても、有しなくてもよい。 BL is preferably a tetradentate ligand, more preferably anionic. Further, BL may or may not have a substituent on the cyclic structure (heteroconjugate ring).
ＢＬとしては、下式（ＢＬ−Ａ）で表されるものが挙げられる。 Examples of BL include those represented by the following formula (BL-A).
（ＢＬ−Ａ）
式中、Ｒ３１、Ｒ３２及びＲ３３は水素原子または置換もしくは無置換の炭化水素基を表すか、または、これらの二つ以上が一緒になってそれらが結合する炭素原子と共に置換もしくは無置換の芳香族炭化水素環または置換もしくは無置換の脂肪族炭化水素環を形成しており、Ｒ３４、Ｒ３５及びＲ３６は水素原子または置換もしくは無置換の炭化水素基を表すか、または、これらの二つ以上が一緒になってそれらが結合する炭素原子と共に置換もしくは無置換の芳香族炭化水素環または置換もしくは無置換の脂肪族炭化水素環を形成している。
(BL-A)
In the formula, R 31 , R 32 and R 33 represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group, or two or more of these together are substituted or unsubstituted with the carbon atom to which they are bonded. An aromatic hydrocarbon ring or a substituted or unsubstituted aliphatic hydrocarbon ring, and R 34 , R 35 and R 36 represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group, or Two or more together form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aliphatic hydrocarbon ring with the carbon atom to which they are attached.
Ｒ３１〜Ｒ３６は好ましくは水素原子、アルキル基、アルコキシ基であり、水素原子、アルキル基であることがより好ましい。アルキル基としては、炭素数６以下のものが好ましく、メチル基、エチル基がより好ましい。また、アルコキシ基としては、炭素数６以下のものが好ましく、メトキシ基、エトキシ基がより好ましい。 R 31 to R 36 are preferably a hydrogen atom, an alkyl group, or an alkoxy group, and more preferably a hydrogen atom or an alkyl group. As an alkyl group, a C6 or less thing is preferable and a methyl group and an ethyl group are more preferable. Moreover, as an alkoxy group, a C6 or less thing is preferable and a methoxy group and an ethoxy group are more preferable.
また、Ｒ３１〜Ｒ３６の隣接する二つが一緒になってそれらが結合する炭素原子と共に６員の芳香族炭化水素環（置換基を有していてもよい）を形成していることも好ましい。芳香族炭化水素環の置換基としては、アルキル基（メチル基、エチル基など）、アルコキシ基（メトキシ基、エトキシ基など）などが挙げられる。 It is also preferable that two adjacent R 31 to R 36 are joined together to form a 6-membered aromatic hydrocarbon ring (which may have a substituent) together with the carbon atom to which they are bonded. . Examples of the substituent of the aromatic hydrocarbon ring include an alkyl group (such as a methyl group and an ethyl group) and an alkoxy group (such as a methoxy group and an ethoxy group).
Ｒ３１〜Ｒ３６は水素原子またはメチル基であることが特に好ましく、Ｒ３１〜Ｒ３６は水素原子であることがさらに好ましい。 R 31 to R 36 are particularly preferably a hydrogen atom or a methyl group, and R 31 to R 36 are more preferably a hydrogen atom.
また、ＢＬとしては、下式（ＢＬ−Ｂ）で表されるものも挙げられる。 Moreover, as BL, what is represented by the following Formula (BL-B) is also mentioned.
式中、Ｒ４１及びＲ４２は水素原子または置換もしくは無置換の炭化水素基を表すか、または、これらが一緒になってそれらが結合する炭素原子と共に置換もしくは無置換の芳香族炭化水素環または置換もしくは無置換の脂肪族炭化水素環を形成しており、Ｒ４３及びＲ４４は水素原子または置換もしくは無置換の炭化水素基を表すか、または、これらが一緒になってそれらが結合する炭素原子と共に置換もしくは無置換の芳香族炭化水素環または置換もしくは無置換の脂肪族炭化水素環を形成している。
In the formula, R 41 and R 42 represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon ring together with a carbon atom to which they are bonded together, or Forming a substituted or unsubstituted aliphatic hydrocarbon ring, wherein R 43 and R 44 represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group, or the carbon to which they are bonded together; A substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aliphatic hydrocarbon ring is formed together with the atoms.
Ｒ４１〜Ｒ４４は好ましくは水素原子、アルキル基、アルコキシ基であり、水素原子、アルキル基であることがより好ましい。アルキル基としては、炭素数６以下のものが好ましく、メチル基、エチル基がより好ましい。また、アルコキシ基としては、炭素数６以下のものが好ましく、メトキシ基、エトキシ基がより好ましい。 R 41 to R 44 are preferably a hydrogen atom, an alkyl group, or an alkoxy group, and more preferably a hydrogen atom or an alkyl group. As an alkyl group, a C6 or less thing is preferable and a methyl group and an ethyl group are more preferable. Moreover, as an alkoxy group, a C6 or less thing is preferable and a methoxy group and an ethoxy group are more preferable.
また、Ｒ４１とＲ４２、Ｒ４３とＲ４４が一緒になってそれらが結合する炭素原子と共に６員の芳香族炭化水素環（置換基を有していてもよい）を形成していることも好ましい。芳香族炭化水素環の置換基としては、アルキル基（メチル基、エチル基など）、アルコキシ基（メトキシ基、エトキシ基など）などが挙げられる。 R 41 and R 42 , R 43 and R 44 together form a 6-membered aromatic hydrocarbon ring (which may have a substituent) together with the carbon atom to which they are bonded. Is also preferable. Examples of the substituent of the aromatic hydrocarbon ring include an alkyl group (such as a methyl group and an ethyl group) and an alkoxy group (such as a methoxy group and an ethoxy group).
Ｒ４１〜Ｒ４４は水素原子またはメチル基であることが特に好ましく、Ｒ４１〜Ｒ４４は水素原子であることがさらに好ましい。また、Ｒ４１とＲ４２、Ｒ４３とＲ４４が一緒になってそれらが結合する炭素原子と共に６員の芳香族炭化水素環（メチル基などの置換基を有していてもよい）を形成していることも特に好ましい。 R 41 to R 44 are particularly preferably a hydrogen atom or a methyl group, and R 41 to R 44 are more preferably a hydrogen atom. R 41 and R 42 , R 43 and R 44 together form a 6-membered aromatic hydrocarbon ring (which may have a substituent such as a methyl group) together with the carbon atom to which they are bonded. It is also particularly preferable.
上式（ＢＬ−Ｂ）で表されるもの中では、下式（ＢＬ−Ｃ）で表されるものが好ましい。 Among those represented by the above formula (BL-B), those represented by the following formula (BL-C) are preferred.
式中、Ｒ５１、Ｒ５２、Ｒ５３及びＲ５４は水素原子または置換もしくは無置換の炭化水素基を表すか、または、これらの二つ以上が一緒になってそれらが結合する炭素原子と共に置換もしくは無置換の芳香族炭化水素環または置換もしくは無置換の脂肪族炭化水素環を形成しており、Ｒ５５、Ｒ５６、Ｒ５７及びＲ５８は水素原子または置換もしくは無置換の炭化水素基を表すか、または、これらの二つ以上が一緒になってそれらが結合する炭素原子と共に置換もしくは無置換の芳香族炭化水素環または置換もしくは無置換の脂肪族炭化水素環を形成している。
In the formula, R 51 , R 52 , R 53 and R 54 represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group, or two or more of these together are substituted with a carbon atom to which they are bonded. Or an unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aliphatic hydrocarbon ring, and R 55 , R 56 , R 57 and R 58 are each a hydrogen atom or a substituted or unsubstituted hydrocarbon group. Or two or more of these together form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aliphatic hydrocarbon ring with the carbon atom to which they are attached.
Ｒ５１〜Ｒ５８は好ましくは水素原子、アルキル基、アルコキシ基であり、水素原子、アルキル基であることがより好ましい。アルキル基としては、炭素数６以下のものが好ましく、メチル基、エチル基がより好ましい。また、アルコキシ基としては、炭素数６以下のものが好ましく、メトキシ基、エトキシ基がより好ましい。 R 51 to R 58 are preferably a hydrogen atom, an alkyl group, or an alkoxy group, and more preferably a hydrogen atom or an alkyl group. As an alkyl group, a C6 or less thing is preferable and a methyl group and an ethyl group are more preferable. Moreover, as an alkoxy group, a C6 or less thing is preferable and a methoxy group and an ethoxy group are more preferable.
また、Ｒ５１〜Ｒ５８の隣接する二つが一緒になってそれらが結合する炭素原子と共に６員の芳香族炭化水素環（置換基を有していてもよい）を形成していることも好ましい。芳香族炭化水素環の置換基としては、アルキル基（メチル基、エチル基など）、アルコキシ基（メトキシ基、エトキシ基など）などが挙げられる。 It is also preferable that two adjacent R 51 to R 58 are joined together to form a 6-membered aromatic hydrocarbon ring (which may have a substituent) together with the carbon atom to which they are bonded. . Examples of the substituent of the aromatic hydrocarbon ring include an alkyl group (such as a methyl group and an ethyl group) and an alkoxy group (such as a methoxy group and an ethoxy group).
Ｒ５１〜Ｒ５８は水素原子またはメチル基であることが特に好ましく、Ｒ５１〜Ｒ５８は水素原子であることがさらに好ましい。 R 51 to R 58 are particularly preferably a hydrogen atom or a methyl group, and R 51 to R 58 are more preferably a hydrogen atom.
ＢＬの具体例としては、下式（ＢＬ−１）〜（ＢＬ−４）で表されるものが挙げられるが、本発明はこれらに限定されるものではない。 Specific examples of BL include those represented by the following formulas (BL-1) to (BL-4), but the present invention is not limited to these.
（ＢＬ−１）
２，２’−ビピリミジン（ｂｐｍ）
(BL-1)
2,2'-bipyrimidine (bpm)
（ＢＬ−２）
テトラチアフルバレン（ＴＴＦ）
(BL-2)
Tetrathiafulvalene (TTF)
（ＢＬ−３）
２，２’−ビイミダゾラト（ＢｉＩｍ）
(BL-3)
2,2'-biimidazolate (BiIm)
（ＢＬ−４）
２，２’−ビベンズイミダゾラト（ＢｉＢｚＩｍ）
但し、式（ＢＬ−１）〜（ＢＬ−４）中の複素環およびベンゼン環は置換基を有していてもよい。置換基としては、炭素数６以下のアルキル基、炭素数６以下のアルコキシ基などが挙げられ、また、式（ＢＬ−４）中のベンゼン環上の隣接する二つの炭素原子が一緒になって新たなベンゼン環（置換基を有していてもよい）を形成していてもよい。
(BL-4)
2,2'-bibenzimidazolate (BiBzIm)
However, the heterocyclic ring and the benzene ring in formulas (BL-1) to (BL-4) may have a substituent. Examples of the substituent include an alkyl group having 6 or less carbon atoms and an alkoxy group having 6 or less carbon atoms, and two adjacent carbon atoms on the benzene ring in the formula (BL-4) are joined together. A new benzene ring (which may have a substituent) may be formed.
光電変換素子に用いる金属錯体色素である場合、ＢＬが上式（ＢＬ−３）、または（ＢＬ−４）で表される配位子であることが好ましい。 In the case of a metal complex dye used for a photoelectric conversion element, BL is preferably a ligand represented by the above formula (BL-3) or (BL-4).
また、（Ｌ１）２Ｍ１（ＢＬ）Ｍ２（Ｌ２）２（Ｘ）ｎは、水または有機溶媒を結晶溶媒として含んでいてもよい。有機溶媒としては、ＤＭＳＯ、アセトニトリル、ＤＭＦ、ＤＭＡＣ、メタノールなどが挙げられる。尚、結晶溶媒の数は特に規定されない。 Further, (L 1 ) 2 M 1 (BL) M 2 (L 2 ) 2 (X) n may contain water or an organic solvent as a crystal solvent. Examples of the organic solvent include DMSO, acetonitrile, DMF, DMAC, methanol and the like. The number of crystal solvents is not particularly specified.
Ｘは対イオンであり、錯体［（Ｌ１）２Ｍ１（ＢＬ）Ｍ２（Ｌ２）２］がカチオンであれば対イオンはアニオン、錯体［（Ｌ１）２Ｍ１（ＢＬ）Ｍ２（Ｌ２）２］がアニオンであれば対イオンはカチオンである。ここにｎは、錯体の電荷を中和するのに必要な対イオンの数を表す。 X is a counter ion, and if the complex [(L 1 ) 2 M 1 (BL) M 2 (L 2 ) 2 ] is a cation, the counter ion is an anion, and the complex [(L 1 ) 2 M 1 (BL) M If 2 (L 2 ) 2 ] is an anion, the counter ion is a cation. Here, n represents the number of counter ions necessary to neutralize the charge of the complex.
Ｘの具体例として、対イオンがアニオンの場合、ヘキサフルオロリン酸イオン、過塩素酸イオン、テトラフェニルホウ酸イオン、テトラフルオロホウ酸イオン、トリフルオロメタンスルホン酸イオン、チオシアン酸イオン、硫酸イオン、硝酸イオン、および塩化物イオン、ヨウ化物イオンなどのハロゲン化物イオンなどが挙げられる。 As specific examples of X, when the counter ion is an anion, hexafluorophosphate ion, perchlorate ion, tetraphenylborate ion, tetrafluoroborate ion, trifluoromethanesulfonate ion, thiocyanate ion, sulfate ion, nitric acid Ions, and halide ions such as chloride ions and iodide ions.
Ｘの具体例として、対イオンがカチオンの場合、アンモニウムイオン、テトラブチルアンモニウムイオン、ナトリウムイオンなどのアルカリ金属イオン、およびプロトンなどが挙げられる。 Specific examples of X include, when the counter ion is a cation, ammonium metal, tetrabutylammonium ion, alkali metal ions such as sodium ion, and proton.
金属錯体色素としては、特に、Ｌ１が上式（Ｌ１−１）で表される配位子（−ＣＯＯＨのＨが脱離しているもの、複素環およびベンゼン環がさらに置換基を有しているものも含む）であり、Ｌ２が上式（Ｌ２−１）または（Ｌ２−２）で表される配位子（複素環およびベンゼン環が置換基を有しているものも含む）であり、ＢＬが上式（ＢＬ−３）または（ＢＬ−４）で表される配位子（複素環およびベンゼン環が置換基を有しているものも含む）であり、Ｍ１及びＭ２がルテニウム（Ｒｕ）、オスミウム（Ｏｓ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）または鉄（Ｆｅ）であるものが好ましい。 As the metal complex dye, in particular, L 1 is a ligand represented by the above formula (L 1 -1) ( one from which H of —COOH is eliminated, a heterocyclic ring and a benzene ring further having a substituent. And L 2 is a ligand represented by the above formula (L 2 -1) or (L 2 -2) (a heterocycle and a benzene ring having a substituent) BL is a ligand represented by the above formula (BL-3) or (BL-4) (including those having a heterocyclic ring and a benzene ring having a substituent), and M 1 And M 2 is preferably ruthenium (Ru), osmium (Os), cobalt (Co), nickel (Ni), copper (Cu) or iron (Fe).
本発明の（Ｌ１）２Ｍ１（ＢＬ）Ｍ２（Ｌ２）２（Ｘ）ｎで示される非対称な二核金属錯体の具体例としては、下式（Ｄ−１）〜（Ｄ−１６）で表されるものが挙げられるが、本発明はこれらに限定されるものではない。 Specific examples of the asymmetric binuclear metal complex represented by (L 1 ) 2 M 1 (BL) M 2 (L 2 ) 2 (X) n of the present invention include the following formulas (D-1) to (D- Although what is represented by 16) is mentioned, this invention is not limited to these.
［（Ｈ２ｄｃｂｐｙ）２Ｒｕ（ＢｉＩｍ）Ｒｕ（ｂｐｙ）２］（ＣｌＯ４）２
[(H 2 dcbpy) 2 Ru (BiIm) Ru (bpy) 2 ] (ClO 4 ) 2
［（Ｈ２ｄｃｂｐｙ）（Ｈｄｃｂｐｙ）Ｒｕ（ＢｉＩｍ）Ｒｕ（ｂｐｙ）２］（ＰＦ６）
[(H 2 dcbpy) (Hdcbpy) Ru (BiIm) Ru (bpy) 2 ] (PF 6 )
［（Ｈ２ｄｃｂｉｑ）（Ｈｄｃｂｉｑ）Ｒｕ（ＢｉＩｍ）Ｒｕ（ｂｐｙ）２］（ＰＦ６）
[(H 2 dcbiq) (Hdcbiq) Ru (BiIm) Ru (bpy) 2 ] (PF 6 )
（Ｄ−４）
［（Ｈ２ｄｃｂｐｙ）（Ｈｄｃｂｐｙ）Ｒｕ（ＢｉＢｚＩｍ）Ｒｕ（ｂｐｙ）２］（ＰＦ６）
(D-4)
[(H 2 dcbpy) (Hdcbpy) Ru (BiBzIm) Ru (bpy) 2 ] (PF 6 )
（Ｄ−５）
［（Ｈ２ｄｃｂｐｙ）（Ｈｄｃｂｐｙ）Ｒｕ（ＢｉＢｚＩｍ）Ｒｕ（ｂｐｙ）２］（ＢＦ４）
(D-5)
[(H 2 dcbpy) (Hdcbpy) Ru (BiBzIm) Ru (bpy) 2 ] (BF 4 )
（Ｄ−６）
［（Ｈ２ｄｃｂｐｙ）（Ｈｄｃｂｐｙ）Ｒｕ（ＢｉＢｚＩｍ）Ｒｕ（ｂｐｙ）２］（ＢＰｈ４）
(D-6)
[(H 2 dcbpy) (Hdcbpy) Ru (BiBzIm) Ru (bpy) 2 ] (BPh 4 )
（Ｄ−７）
［（Ｈ２ｄｃｂｐｙ）（Ｈｄｃｂｐｙ）Ｒｕ（ＢｉＢｚＩｍ）Ｒｕ（ｂｐｙ）２］（ＯＳＯ２ＣＦ３）
(D-7)
[(H 2 dcbpy) (Hdcbpy) Ru (BiBzIm) Ru (bpy) 2 ] (OSO 2 CF 3 )
（Ｄ−８）
［（Ｈ２ｄｃｂｐｙ）（Ｈｄｃｂｐｙ）Ｒｕ（ＢｉＢｚＩｍ）Ｒｕ（ｂｐｙ）２］（ＣｌＯ４）
(D-8)
[(H 2 dcbpy) (Hdcbpy) Ru (BiBzIm) Ru (bpy) 2 ] (ClO 4 )
（Ｄ−９）
［（Ｈ２ｄｃｂｐｙ）（Ｈｄｃｂｐｙ）Ｒｕ（ＢｉＢｚＩｍ）Ｒｕ（ｂｐｙ）２］（ＮＯ３）
(D-9)
[(H 2 dcbpy) (Hdcbpy) Ru (BiBzIm) Ru (bpy) 2 ] (NO 3 )
（Ｄ−１０）
［（Ｈ２ｄｃｂｐｙ）（Ｈｄｃｂｐｙ）Ｒｕ（ＢｉＢｚＩｍ）Ｒｕ（ｂｐｙ）２］（Ｉ）
(D-10)
[(H 2 dcbpy) (Hdcbpy) Ru (BiBzIm) Ru (bpy) 2 ] (I)
（Ｄ−１１）
［（Ｈ２ｄｃｂｐｙ）（Ｈｄｃｂｐｙ）Ｒｕ（ＢｉＢｚＩｍ）Ｒｕ（ｐｈｅｎ）２］（ＰＦ６）
(D-11)
[(H 2 dcbpy) (Hdcbpy) Ru (BiBzIm) Ru (phen) 2 ] (PF 6 )
（Ｄ−１２）
［（Ｈ２ｄｃｂｐｙ）（Ｈｄｃｂｐｙ）Ｒｕ（ＢｉＢｚＩｍ）Ｒｕ（ｂｉｑ）２］（ＰＦ６）
(D-12)
[(H 2 dcbpy) (Hdcbpy) Ru (BiBzIm) Ru (biq) 2 ] (PF 6 )
（Ｄ−１３）
［（Ｈ２ｄｃｂｐｙ）（Ｈｄｃｂｐｙ）Ｒｕ（ＢｉＢｚＩｍ）Ｒｕ（ｄｍｂｐｙ）２］（ＰＦ６）
(D-13)
[(H 2 dcbpy) (Hdcbpy) Ru (BiBzIm) Ru (dmbpy) 2 ] (PF 6 )
（Ｄ−１４）
［（Ｈ２ｄｃｂｐｙ）（Ｈｄｃｂｐｙ）Ｒｕ（ＴＭＢｉＢｚＩｍ）Ｒｕ（ｂｐｙ）２］（ＰＦ６）
(D-14)
[(H 2 dcbpy) (Hdcbpy) Ru (TMBiBzIm) Ru (bpy) 2 ] (PF 6 )
（Ｄ−１５）
［（Ｈ２ｄｃｂｐｙ）（Ｈｄｃｂｐｙ）Ｒｕ（ＢｉＢｚＩｍ）Ｏｓ（ｂｐｙ）２］（ＰＦ６）
(D-15)
[(H 2 dcbpy) (Hdcbpy) Ru (BiBzIm) Os (bpy) 2 ] (PF 6 )
（Ｄ−１６）
［（Ｈｄｃｂｐｙ）２Ｒｕ（ｂｐｍ）Ｒｕ（ｂｐｙ）２］（ＰＦ6）２
(D-16)
[(Hdcbpy) 2 Ru (bpm) Ru (bpy) 2 ] (PF 6 ) 2
本発明の溶液に溶解している金属錯体は、Ｉｎｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ、第１７巻、第９号、第２６６０〜２６６６頁、１９７８年、Ｊｏｕｒｎａｌ ｏｆ ｔｈｅ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ、第１１５巻、第６３８２〜６３９０頁、１９９３年等の文献中に引用された方法を参考にして製造することができる。 The metal complex dissolved in the solution of the present invention includes Inorganic Chemistry, Vol. 17, No. 9, 2660-2666, 1978, Journal of the American Chemical Society, 115, 6382-6390, It can be produced by referring to a method cited in a literature such as 1993.
本発明の金属錯体（Ｌ１）２Ｍ１（ＢＬ）Ｍ２（Ｌ２）２（Ｘ）ｎは、例えば、次のようにして二つの単核金属錯体（Ｌ１）２Ｍ１Ｃｌ２と（ＢＬ）Ｍ２（Ｌ２）２を合成し、これらを反応させることにより合成することができる。 The metal complex (L 1 ) 2 M 1 (BL) M 2 (L 2 ) 2 (X) n of the present invention is, for example, two mononuclear metal complexes (L 1 ) 2 M 1 Cl 2 as follows. And (BL) M 2 (L 2 ) 2 can be synthesized and reacted.
Ｌ１が上式（Ｌ１−１）であり、Ｍ１がＲｕである単核金属錯体（Ｌ１）２Ｍ１Ｃｌ２（Ｍ１Ｃ−１）は次の合成スキームに従って合成することができる。 A mononuclear metal complex (L 1 ) 2 M 1 Cl 2 (M 1 C-1) in which L 1 is the above formula (L 1 -1) and M 1 is Ru can be synthesized according to the following synthesis scheme. it can.
上式において、Ｌ１がカルボキシル基以外の置換基を有するもの、Ｍ１がＲｕ以外の遷移金属であるものも同様にして合成することができる。
In the above formula, those in which L 1 has a substituent other than a carboxyl group and those in which M 1 is a transition metal other than Ru can be synthesized in the same manner.
また、Ｌ１が上式（Ｌ１−４）であり、Ｍ１がＲｕである単核金属錯体（Ｌ１）２Ｍ１Ｃｌ２（Ｍ１Ｃ−２）は次の合成スキームに従って合成することができる。 A mononuclear metal complex (L 1 ) 2 M 1 Cl 2 (M 1 C-2) in which L 1 is the above formula (L 1 -4) and M 1 is Ru is synthesized according to the following synthesis scheme. be able to.
上式において、Ｌ１がカルボキシル基以外の置換基を有するもの、Ｍ１がＲｕ以外の遷移金属であるものも同様にして合成することができる。
In the above formula, those in which L 1 has a substituent other than a carboxyl group and those in which M 1 is a transition metal other than Ru can be synthesized in the same manner.
一方、単核金属錯体（ＢＬ）Ｍ２（Ｌ２）２は次の合成スキームに従って合成することができる。 On the other hand, the mononuclear metal complex (BL) M 2 (L 2 ) 2 can be synthesized according to the following synthesis scheme.
スキーム中のＨ２ＢＬはＢＬ中の二つのヘテロ原子（窒素原子など）がプロトン化された状態を示す。
H 2 BL in the scheme indicates a state in which two heteroatoms (such as a nitrogen atom) in BL are protonated.
尚、ＢＬが上式（ＢＬ−１）〜（ＢＬ−４）で表されるもの（置換基を有しているものも含む）、Ｌ２が上式（Ｌ２−１）〜（Ｌ２−４）で表されるもの（置換基を有しているものも含む）は何れも、この合成スキームに従って合成することができる。但し、ＢＬが上式（ＢＬ−１）で表されるもの（置換基を有しているものも含む）については、後段のＮａＯＭｅによる反応工程は不要で、Ｍ２（Ｌ２）２Ｃｌ２とＨ２ＢＬを反応させると（ＢＬ）Ｍ２（Ｌ２）２が得られる。
Incidentally, BL (also including those having a substituent) represented by those in the above formula (BL-1) ~ (BL -4),
このようにして合成した（Ｌ１）２Ｍ１Ｃｌ２（Ｍ１Ｃ）と（ＢＬ）Ｍ２（Ｌ２）２（Ｍ２Ｃ）を次の合成スキームに従って反応させ、（Ｌ１）２Ｍ１（ＢＬ）Ｍ２（Ｌ２）２（Ｘ）ｎを合成することができる。 The (L 1 ) 2 M 1 Cl 2 (M 1 C) synthesized in this way and (BL) M 2 (L 2 ) 2 (M 2 C) are reacted according to the following synthetic scheme, and (L 1 ) 2 M 1 (BL) M 2 (L 2 ) 2 (X) n can be synthesized.
上記の金属錯体は、金属錯体色素として用いることができ、金属錯体色素により増感された半導体微粒子を用いて、光化学電池を製造することができる。
The above metal complex can be used as a metal complex dye, and a photochemical battery can be produced using semiconductor fine particles sensitized with the metal complex dye.
本発明の光電変換素子は、上記の金属錯体色素により増感された半導体微粒子を含むものである。より具体的には、上記の金属錯体色素により増感された半導体微粒子を電極上に固定したものである。 The photoelectric conversion element of this invention contains the semiconductor fine particle sensitized with said metal complex pigment | dye. More specifically, the semiconductor fine particles sensitized with the metal complex dye are fixed on the electrode.
導電性電極は、透明基板上に形成された透明電極であることが好ましい。導電剤としては、金、銀、銅、白金、パラジウムなどの金属、錫をドープした酸化インジウム（ＩＴＯ）に代表される酸化インジウム系化合物、フッ素をドープした酸化錫（ＦＴＯ）に代表される酸化錫系化合物、酸化亜鉛系化合物などが挙げられる。 The conductive electrode is preferably a transparent electrode formed on a transparent substrate. Examples of the conductive agent include metals such as gold, silver, copper, platinum, and palladium, indium oxide compounds typified by tin-doped indium oxide (ITO), and oxidation typified by fluorine-doped tin oxide (FTO). Examples thereof include tin compounds and zinc oxide compounds.
半導体微粒子としては、酸化チタン、酸化亜鉛、または酸化錫などが挙げられる。また、酸化インジウム、酸化ニオブ、酸化タングステン、酸化バナジウムや、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸バリウム、ニオブ酸カリウムなどの複合酸化物半導体、カドミウムまたはビスマスの硫化物、カドミウムのセレン化物またはテルル化物、ガリウムのリン化物またはヒ素化物なども挙げられる。半導体微粒子としては、酸化物が好ましく、酸化チタン、酸化亜鉛、または酸化錫、およびこれらのいずれか１種以上を含む混合物が特に好ましい。 Examples of the semiconductor fine particles include titanium oxide, zinc oxide, and tin oxide. Also, indium oxide, niobium oxide, tungsten oxide, vanadium oxide, composite oxide semiconductors such as strontium titanate, calcium titanate, barium titanate, potassium niobate, cadmium or bismuth sulfide, cadmium selenide or tellurium And gallium phosphide or arsenide. As the semiconductor fine particles, oxides are preferable, and titanium oxide, zinc oxide, or tin oxide, and a mixture containing any one or more of these are particularly preferable.
半導体微粒子の一次粒子径は特に限定されないが、通常、１〜５０００ｎｍ、好ましくは２〜５００ｎｍ、特に好ましくは５〜３００ｎｍである。 The primary particle diameter of the semiconductor fine particles is not particularly limited, but is usually 1 to 5000 nm, preferably 2 to 500 nm, and particularly preferably 5 to 300 nm.
本発明の光化学電池は、上記の光電変換素子を用いたものである。より具体的には、電極として上記の本発明の光電変換素子と対極とを有し、その間に電解質層を有するものである。本発明の光電変換素子に用いた電極と対極の少なくとも片方は透明電極である。 The photochemical cell of the present invention uses the above photoelectric conversion element. More specifically, the photoelectric conversion element of the present invention and a counter electrode are provided as electrodes, and an electrolyte layer is provided therebetween. At least one of the electrode and the counter electrode used in the photoelectric conversion element of the present invention is a transparent electrode.
対極は光電変換素子と組み合わせて光化学電池としたときに正極として作用するものである。対極としては、上記導電性電極と同様に導電層を有する基板を用いることもできるが、金属板そのものを使用すれば、基板は必ずしも必要ではない。対極に用いる導電剤としては、白金や炭素などの金属、フッ素をドープした酸化錫などの導電性金属酸化物が挙げられる。 The counter electrode functions as a positive electrode when combined with a photoelectric conversion element to form a photochemical battery. As the counter electrode, a substrate having a conductive layer can be used as in the case of the conductive electrode. However, if the metal plate itself is used, the substrate is not necessarily required. Examples of the conductive agent used for the counter electrode include metals such as platinum and carbon, and conductive metal oxides such as tin oxide doped with fluorine.
電解質（酸化還元対）としては特に限定されず、公知のものをいずれも用いることができる。例えば、ヨウ素とヨウ化物（例えば、ヨウ化リチウム、ヨウ化カリウム等の金属ヨウ化物、またはヨウ化テトラブチルアンモニウム、ヨウ化テトラプロピルアンモニウム、ヨウ化ピリジニウム、ヨウ化イミダゾリウム等の４級アンモニウム化合物のヨウ化物）の組み合わせ、臭素と臭化物の組み合わせ、塩素と塩化物の組み合わせ、アルキルビオローゲンとその還元体の組み合わせ、キノン／ハイドロキノン、鉄（ＩＩ）イオン／鉄（ＩＩＩ）イオン、銅（Ｉ）イオン／銅（ＩＩ）イオン、マンガン（ＩＩ）イオン／マンガン（ＩＩＩ）イオン、コバルトイオン（ＩＩ）／コバルトイオン（ＩＩＩ）等の遷移金属イオン対、フェロシアン／フェリシアン、四塩化コバルト（ＩＩ）／四塩化コバルト（ＩＩＩ）、四臭化コバルト（ＩＩ）／四臭化コバルト（ＩＩＩ）、六塩化イリジウム（ＩＩ）／六塩化イリジウム（ＩＩＩ）、六シアノ化ルテニウム（ＩＩ）／六シアノ化ルテニウム（ＩＩＩ）、六塩化ロジウム（ＩＩ）／六塩化ロジウム（ＩＩＩ）、六塩化レニウム（ＩＩＩ）／六塩化レニウム（ＩＶ）、六塩化レニウム（ＩＶ）／六塩化レニウム（Ｖ）、六塩化オスミウム（ＩＩＩ）／六塩化オスミウム（ＩＶ）、六塩化オスミウム（ＩＶ）／六塩化オスミウム（Ｖ）等の錯イオンの組み合わせ、コバルト、鉄、ルテニウム、マンガン、ニッケル、レニウムといった遷移金属とビピリジンやその誘導体、ターピリジンやその誘導体、フェナントロリンやその誘導体といった複素共役環及びその誘導体で形成されているような錯体類、フェロセン／フェロセニウムイオン、コバルトセン／コバルトセニウムイオン、ルテノセン／ルテノセウムイオンといったシクロペンタジエン及びその誘導体と金属の錯体類、ポルフィリン系化合物類等が使用できる。好ましい電解質は、ヨウ素とヨウ化リチウムや４級アンモニウム化合物のヨウ化物とを組み合わせた電解質である。電解質の状態は、有機溶媒に溶解した液体であっても、溶融塩、ポリマーマトリックスに含浸漬したいわゆるゲル電解質や、固体電解質であってもよい。 The electrolyte (redox couple) is not particularly limited, and any known one can be used. For example, iodine and iodide (for example, metal iodides such as lithium iodide and potassium iodide, or quaternary ammonium compounds such as tetrabutylammonium iodide, tetrapropylammonium iodide, pyridinium iodide, imidazolium iodide) Iodide), bromine and bromide, chlorine and chloride, alkyl viologen and its reduced form, quinone / hydroquinone, iron (II) ion / iron (III) ion, copper (I) ion / Transition metal ion pairs such as copper (II) ion, manganese (II) ion / manganese (III) ion, cobalt ion (II) / cobalt ion (III), ferrocyan / ferricyan, cobalt tetrachloride (II) / four Cobalt (III) chloride, cobalt (II) tetrabromide / four odors Cobalt (III), iridium hexachloride (II) / iridium hexachloride (III), ruthenium hexacyanide (II) / ruthenium hexacyanide (III), rhodium hexachloride (II) / rhodium hexachloride (III), six Rhenium chloride (III) / rhenium chloride (IV), rhenium hexachloride (IV) / rhenium hexachloride (V), osmium hexachloride (III) / osmium hexachloride (IV), osmium hexachloride (IV) / hexachloride It is composed of a combination of complex ions such as osmium (V), transition metals such as cobalt, iron, ruthenium, manganese, nickel, rhenium and biconjugated and derivatives thereof, terpyridine and derivatives thereof, heteroconjugated rings such as phenanthroline and derivatives thereof, and derivatives thereof. Complexes, ferrocene / ferrocenium ions, cobalt On / cobalt-ion-, ruthenocene / lutein placed um cyclopentadiene and its derivatives and metal complexes such as an ion, porphyrin compounds and the like can be used. A preferable electrolyte is an electrolyte in which iodine and lithium iodide or iodide of a quaternary ammonium compound are combined. The state of the electrolyte may be a liquid dissolved in an organic solvent, a molten salt, a so-called gel electrolyte immersed in a polymer matrix, or a solid electrolyte.
本発明の光化学電池は、従来から適用されている方法によって製造することができる。
例えば、透明電極上に酸化物等の半導体微粒子のペーストを塗布し、加熱焼成し半導体微粒子の薄膜を作製する。半導体微粒子の薄膜がチタニアの場合、温度４５０℃、反応時間３０分で焼成する。この薄膜の付いた透明電極を色素溶液に浸漬し、色素を担持して光電変換素子を作製する。さらにこの光電変換素子と対極として白金あるいは炭素を蒸着した透明電極を合わせ、その間に電解質溶液を入れることにより本発明の光化学電池を製造することが出来る。
The photochemical cell of the present invention can be produced by a conventionally applied method.
For example, a semiconductor fine particle paste such as an oxide is applied on a transparent electrode and heated and fired to produce a thin film of semiconductor fine particles. When the thin film of semiconductor fine particles is titania, it is fired at a temperature of 450 ° C. and a reaction time of 30 minutes. The transparent electrode with the thin film is immersed in a dye solution, and the photoelectric conversion element is manufactured by supporting the dye. Furthermore, the photochemical cell of the present invention can be manufactured by combining this photoelectric conversion element with a transparent electrode on which platinum or carbon is deposited as a counter electrode, and inserting an electrolyte solution therebetween.
本発明を以下の実施例によりさらに詳細に説明するが、本発明はそれらに限定されるものではない。
）。
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
).
（実施例１）色素の熱安定性評価
Ｄ−４，Ｄ−１１，Ｄ−１３および比較色素Ａ、Bについて、ＴＧ−ＭＳ測定により擬似Ａｉｒ（Ｈｅ：８０％＋Ｏ２：２０％）下における各色素の熱安定性を分解ガス成分の発生温度によって評価した。尚、ＴＧは、株式会社リガク製のＴｈｅｒｍｏ ｐｌｕｓ ＴＧ８１２０を用い、昇温速度１０℃／ｍｉｎ、擬似Ａｉｒ流量１００ｍｌ／ｍｉｎの条件で測定し、トランスファーライン温度２００℃でＭＳ装置に導入した。ＭＳは、株式会社島津製作所製の質量分析装置ＱＰ−５０００複合システムを用い、注入口温度２５０℃、インターフェイス温度３００℃、イオン化法ＥＩ（７０ｅＶ）、走査質量範囲１０〜３００の条件で測定した。
(Example 1) The thermal stability of dye Evaluation D-4, D-11, D-13 and Comparative Dye A, the B, pseudo Air by TG-MS measurement (He: 80% + O 2 : 20%) under The thermal stability of each dye was evaluated by the generation temperature of the decomposition gas component. The TG was measured using a Thermo plus TG8120 manufactured by Rigaku Corporation under the conditions of a temperature rising rate of 10 ° C./min and a pseudo Air flow rate of 100 ml / min, and introduced into the MS apparatus at a transfer line temperature of 200 ° C. MS was measured using a mass spectrometer QP-5000 combined system manufactured by Shimadzu Corporation under conditions of an inlet temperature of 250 ° C., an interface temperature of 300 ° C., an ionization method EI (70 eV), and a scanning mass range of 10 to 300.
表１にそれぞれの色素を熱分解した際に発生する配位子由来のガス成分の発生開始温度を示す。
Table 1 shows the generation start temperatures of the ligand-derived gas components generated when each dye is thermally decomposed.
表１より、本発明の二核金属錯体はいずれもカルボキシル基（−ＣＯＯＨ）由来のガス成分と考えられるＣＯ２の発生開始温度が比較色素Ａよりも３０℃以上高いことがわかる。さらに、比較色素Ａの場合はカルボキシル基の分解温度よりも低温でイソチオシアナート基（−ＮＣＳ）由来のガス成分であると考えられるＳＯ２の発生が観測されたが、本発明の二核金属錯体では、カルボキシル基の分解温度よりも低温側では他のガス成分は観測されなかった。したがって、本発明の二核金属錯体は、分解部位が少ないことからも熱安定性に優れているため、大変好ましい。
From Table 1, it can be seen that the binuclear metal complex of the present invention has a CO 2 generation start temperature that is considered to be a gas component derived from a carboxyl group (—COOH) higher by 30 ° C. or more than that of the comparative dye A. Further, in the case of the comparative dye A, generation of SO 2 considered to be a gas component derived from an isothiocyanate group (—NCS) was observed at a temperature lower than the decomposition temperature of the carboxyl group, but the binuclear metal of the present invention was observed. In the complex, no other gas component was observed at a temperature lower than the decomposition temperature of the carboxyl group. Therefore, the binuclear metal complex of the present invention is very preferable because it has excellent thermal stability because it has few decomposition sites.
（実施例２）
１．多孔質チタニア電極の作製
（多孔質チタニア電極の作製）
チタニア微粒子３．０ｇをｐＨ０．７の硝酸７ｇに分散させた。このペーストにアセチルアセトン０．２ｍｌと界面活性剤である１０％トリトンＸを０．２ｍｌ添加した。次に分子量２００００のポリエチレングリコール１．２ｇを添加し、最後にこのペーストにエタノール１ｍｌを添加、そしてこのペーストに超音波を照射しながら、１５分間攪拌、分散化させた。この超音波攪拌作業を４回繰り返しペーストを得た。得られたペーストを旭硝子株式会社製透明導電性ガラス電極上に、電極の一部をマスクして、１００μｍのドクターブレードで塗布した。得られた膜を２５℃、６０％の雰囲気下で１０分間エージングし、このエージングした膜を４５０℃で３０分間焼成した。冷却した膜に対し、同じ作業を再度行い二層化し、１ｃｍ２の多孔質チタニア電極を作製した。
(Example 2)
1. Production of porous titania electrode (Production of porous titania electrode)
3.0 g of titania fine particles were dispersed in 7 g of nitric acid having a pH of 0.7. To this paste, 0.2 ml of acetylacetone and 0.2 ml of 10% Triton X as a surfactant were added. Next, 1.2 g of polyethylene glycol having a molecular weight of 20000 was added. Finally, 1 ml of ethanol was added to the paste, and the paste was stirred and dispersed for 15 minutes while being irradiated with ultrasonic waves. This ultrasonic stirring operation was repeated 4 times to obtain a paste. The obtained paste was applied on a transparent conductive glass electrode manufactured by Asahi Glass Co., Ltd. with a part of the electrode masked, and a 100 μm doctor blade. The obtained film was aged for 10 minutes in an atmosphere of 25 ° C. and 60%, and the aged film was baked at 450 ° C. for 30 minutes. The same operation was again performed on the cooled membrane to form a double layer, and a 1 cm 2 porous titania electrode was produced.
２．色素を吸着した多孔質チタニア電極の作製
Ｄ−４のIPAを用いた飽和色素溶液に多孔質チタニア電極を３０℃で２０時間浸漬した。次に、エタノールで洗浄し乾燥後、色素吸着多孔質チタニア電極を得た。各溶液の飽和溶液濃度を表２〜４に示す。
2. Production of Porous Titania Electrode Adsorbed with Dye A porous titania electrode was immersed in a saturated dye solution using IPA of D-4 at 30 ° C. for 20 hours. Next, after washing with ethanol and drying, a dye-adsorbing porous titania electrode was obtained. The saturated solution concentration of each solution is shown in Tables 2-4.
３．光化学電池の作製
以上のようにして得られた色素吸着多孔質チタニア電極と白金板（対極）を重ね合わせた。次に、電解質溶液として３−メトキシプロピオニトリルにヨウ化リチウム、ヨウ素、４−ｔ−ブチルピリジン、および１，２−ジメチル−３−プロピルイミダゾリウムアイオダイドをそれぞれ０．１、０．０５、０．５、および０．６ｍｏｌ／ｌとなるように溶解、調整したものを用い、両電極の隙間に毛細管現象を利用して染み込ませることにより光化学電池を作製した。
3. Production of Photochemical Battery The dye-adsorbed porous titania electrode obtained as described above and a platinum plate (counter electrode) were superposed. Next, as an electrolyte solution, 3-iodopropionitrile was mixed with lithium iodide, iodine, 4-t-butylpyridine, and 1,2-dimethyl-3-propylimidazolium iodide at 0.1, 0.05, respectively. A photochemical battery was prepared by using a solution that was dissolved and adjusted to 0.5 and 0.6 mol / l, and soaking the gap between both electrodes by utilizing capillary action.
４．光電変換効率の測定
得られた光化学電池の光電変換効率を英弘精機株式会社製のソーラーシュミレーターを用い、１００ｍＷ／ｃｍ２の擬似太陽光を照射し測定した。表２に光電変換効率を示す。
4). Measurement of photoelectric conversion efficiency The photoelectric conversion efficiency of the obtained photochemical battery was measured by irradiating 100 mW / cm 2 of pseudo-sunlight using a solar simulator manufactured by Eihiro Seiki Co., Ltd. Table 2 shows the photoelectric conversion efficiency.
（実施例３）
色素溶液を作製する溶媒を混合溶媒を用いた以外は実施例１記載の手法により光化学電池を作製し、光電変換効率の測定を行った。各色素溶液の飽和溶液濃度と光電変換効率の結果を表３に示す。
(Example 3)
A photochemical battery was prepared by the method described in Example 1 except that a mixed solvent was used as the solvent for preparing the dye solution, and the photoelectric conversion efficiency was measured. Table 3 shows the results of the saturated solution concentration and photoelectric conversion efficiency of each dye solution.
（比較例１）
色素作製用の溶媒を非アルコール溶媒を用いた以外は実施例１記載の手法を用い、光化学電池を作製し、光電変換効率の測定を行った。各色素溶液の飽和溶液濃度と光電変換効率の結果を表４に示す。
(Comparative Example 1)
A photochemical battery was prepared using the method described in Example 1 except that a non-alcohol solvent was used as the solvent for preparing the dye, and the photoelectric conversion efficiency was measured. Table 4 shows the results of the saturated solution concentration and photoelectric conversion efficiency of each dye solution.
比較色素Ａ
Comparative dye A
（比較例２）
比較色素Ａを用い非特許文献３の手法により溶液を調整した以外は実施例１記載の手法を用い、光化学電池を作製し、光電変換効率の測定を行った。光電変換効率の結果を表５に示す。
(Comparative Example 2)
A photochemical battery was prepared and the photoelectric conversion efficiency was measured using the method described in Example 1 except that the solution was prepared by the method of
表２および表３と表４、５の比較より、本発明のアルコールを含む金属錯体色素色素は飽和溶液濃度の高い非アルコール溶液に比べ高い光電変換効率が得られた。
From the comparison between Table 2 and Table 3, and Tables 4 and 5, the metal complex dye containing the alcohol of the present invention has a higher photoelectric conversion efficiency than a non-alcohol solution having a high saturated solution concentration.
（実施例４）
D-4をエタノールに溶解し、５×１０−５ｍｏｌ／ｌの溶液を調整した。この溶液を石英製の紫外可視吸収スペクトル測定用セルに入れ屋外放置し、吸収スペクトルの変化の測定を行った。測定条件は波長が２５０ｎｍから８００ｎｍで紫外可視吸収スペクトル（日本分光株式会社製Ｖ−５７０）を用いて測定した。
測定回数は調整直後、１、５、７、１２日後の５回行った。この結果を図１に示す。また、吸光度の変化を図４に示す。
また照射前後写真を図５に示す。
Example 4
D-4 was dissolved in ethanol to prepare a 5 × 10 −5 mol / l solution. This solution was placed in a quartz ultraviolet-visible absorption spectrum measurement cell and allowed to stand outdoors, and the change in absorption spectrum was measured. The measurement conditions were a wavelength of 250 nm to 800 nm and an ultraviolet-visible absorption spectrum (V-570 manufactured by JASCO Corporation).
The measurement was performed five times immediately after adjustment, 1, 5, 7, and 12 days later. The result is shown in FIG. Further, the change in absorbance is shown in FIG.
Moreover, the photographs before and after irradiation are shown in FIG.
（比較例３）
色素を既存色素Ａ（Ｎ３ｄｙｅ，小島化学薬品社製ルテニウム有機錯体）に変えた以外は実施例３と同様の方法で紫外可視吸収巣ペクトトルの測定を行った。この結果を図２に示す。また、吸光度の変化を図４に示す。また照射前後写真を図５に示す。
(Comparative Example 3)
The UV-visible absorption spectrum was measured in the same manner as in Example 3 except that the dye was changed to the existing dye A (N3dye, a ruthenium organic complex manufactured by Kojima Chemical Co., Ltd.). The result is shown in FIG. Further, the change in absorbance is shown in FIG. Moreover, the photographs before and after irradiation are shown in FIG.
（比較例４）
色素を既存色素Ｂ（Ｎ７１９ｄｙｅ，小島化学薬品社製ルテニウム有機錯体）に変えた以外は実施例３と同様の方法で紫外可視吸収巣ペクトトルの測定を行った。この結果を図３に示す。また、吸光度の変化を図４に示す。また照射前後写真を図５に示す。
図１〜５の結果から、二核金属錯体色素溶液は既存色素溶液に比べ光に対する耐久能力が高いことが明らかとなった。
(Comparative Example 4)
The UV-visible absorption spectrum was measured in the same manner as in Example 3 except that the dye was changed to the existing dye B (N719dye, a ruthenium organic complex manufactured by Kojima Chemical Co., Ltd.). The result is shown in FIG. Further, the change in absorbance is shown in FIG. Moreover, the photographs before and after irradiation are shown in FIG.
From the results of FIGS. 1 to 5, it became clear that the binuclear metal complex dye solution has higher durability against light than the existing dye solution.
（実施例５）
D-4をＤＭＦに溶解し、０．２ｍｏｌ／ｌの溶液を調整した。この溶液に０．１ｍｏｌの過塩素酸テトラ−ｎ−ブチルアンモニウムを加え、２０ｍＶ／ｓｅｃで電位送引を１００サイクル行い、１サイクル目と１００サイクル目のサイクリックボルタンメトリーのデータから電気化学的安定性の測定を行った。この結果を図６に示す。
(Example 5)
D-4 was dissolved in DMF to prepare a 0.2 mol / l solution. To this solution, 0.1 mol of tetra-n-butylammonium perchlorate was added, and potential feeding was performed for 100 cycles at 20 mV / sec, and electrochemical stability was determined from cyclic voltammetry data at the first and 100th cycles. Was measured. The result is shown in FIG.
（比較例５）
色素を既存色素Ｂ（Ｎ７１９ｄｙｅ，小島化学薬品社製ルテニウム有機錯体）に変えた以外は実施例４と同様の方法で電気化学的安定性の測定を行った。この結果を図７に示す。
図６，７の結果から既存色素溶液に比べ二核金属錯体色素溶液は電気的に安定であることが明らかとなった。
(Comparative Example 5)
Electrochemical stability was measured in the same manner as in Example 4 except that the dye was changed to the existing dye B (N719dye, a ruthenium organic complex manufactured by Kojima Chemical Co., Ltd.). The result is shown in FIG.
From the results of FIGS. 6 and 7, it was revealed that the binuclear metal complex dye solution is electrically stable compared to the existing dye solution.
（実施例６）
実施例１記載の方法で得られた光電変換素子３５６ｎｍの光を２４時間照射し退色の様子を観察した。結果を図８に示す。
(Example 6)
The light of 356 nm photoelectric conversion element obtained by the method described in Example 1 was irradiated for 24 hours, and the state of fading was observed. The results are shown in FIG.
（比較例６）
比較色素Ａ、Ｂを用い非特許文献３の手法により溶液を調整した以外は実施例１記載の手法を用いて得られた光電変換素子３５６ｎｍの光を２４時間照射し退色の様子を観察した。結果を図８に示す。
図８の結果から、比較色素溶液から得られた光電変換素子に比べ、二核金属錯体色素溶液から得られた光電変換素子は光に対し安定であることが明らかとなった。
(Comparative Example 6)
Except that the solution was prepared by the method described in
From the results in FIG. 8, it was revealed that the photoelectric conversion element obtained from the binuclear metal complex dye solution was more stable to light than the photoelectric conversion element obtained from the comparative dye solution.
（実施例７）吸収スペクトルの測定
Ｄ−４，Ｄ−１１，Ｄ−１２，Ｄ−１３および既存の単核金属錯体色素である下記の比較色素Ａ（Ｎ３ｄｙｅ，小島化学薬品社製ルテニウム有機錯体）について、濃度３×１０−５ｍｏｌ／ｌのエタノール溶液を調製し、波長が２５０ｎｍから８００ｎｍの紫外可視吸収スペクトル（日本分光株式会社製Ｖ−５７０）を用いて測定した。結果を図９，図１０，図１１および図１２に示す。
(Example 7) Measurement of absorption spectrum D-4, D-11, D-12, D-13 and the following comparative dye A which is an existing mononuclear metal complex dye (N3dye, a ruthenium organic complex manufactured by Kojima Chemical Co., Ltd.) ), An ethanol solution having a concentration of 3 × 10 −5 mol / l was prepared and measured using an ultraviolet-visible absorption spectrum (V-570 manufactured by JASCO Corporation) having a wavelength of 250 nm to 800 nm. The results are shown in FIGS. 9, 10, 11 and 12.
（実施例８）
１．多孔質チタニア電極の作製
（多孔質チタニア電極の作製）
触媒化成製のチタニアペーストＰＳＴ−１８ＮＲとＰＳＴ−４００Ｃを用い、旭硝子株式会社製透明導電性ガラス電極上に、スクリーン印刷機を用いて塗布した。得られた膜を２５℃、６０％の雰囲気下で５分間エージングし、このエージングした膜を４５０℃で３０分間焼成した。冷却した膜に対し、同じ作業を所定の厚みになるまで繰り返し、16mm２の多孔質チタニア電極を作製した。
(Example 8)
1. Production of porous titania electrode (Production of porous titania electrode)
A catalytic printing titania paste PST-18NR and PST-400C were used and applied on a transparent conductive glass electrode manufactured by Asahi Glass Co., Ltd. using a screen printer. The obtained film was aged at 25 ° C. in an atmosphere of 60% for 5 minutes, and the aged film was baked at 450 ° C. for 30 minutes. The same operation was repeated on the cooled membrane until a predetermined thickness was obtained, and a 16 mm 2 porous titania electrode was produced.
２．色素を吸着した多孔質チタニア電極の作製
Ｄ−４のIPAを用いた飽和色素溶液に多孔質チタニア電極を３０℃で所定の時間浸漬し、色素吸着多孔質チタニア電極を得た。
2. Production of Porous Titania Electrode Adsorbing Dye A porous titania electrode was immersed in a saturated dye solution using IPA of D-4 at 30 ° C. for a predetermined time to obtain a dye adsorbing porous titania electrode.
３．光化学電池の作製
以上のようにして得られた色素吸着多孔質チタニア電極と白金板（対極）を重ね合わせた。次に、電解質溶液として３−メトキシプロピオニトリルにヨウ化リチウム、ヨウ素、４−ｔ−ブチルピリジン、および１，２−ジメチル−３−プロピルイミダゾリウムアイオダイドをそれぞれ０．１、０．０５、０．５、および０．６ｍｏｌ／ｌとなるように溶解、調整したものを用い、両電極の隙間に毛細管現象を利用して染み込ませることにより光化学電池を作製した。
3. Production of Photochemical Battery The dye-adsorbed porous titania electrode obtained as described above and a platinum plate (counter electrode) were superposed. Next, as an electrolyte solution, 3-iodopropionitrile was mixed with lithium iodide, iodine, 4-t-butylpyridine, and 1,2-dimethyl-3-propylimidazolium iodide at 0.1, 0.05, respectively. A photochemical battery was prepared by using a solution that was dissolved and adjusted to 0.5 and 0.6 mol / l, and soaking the gap between both electrodes by utilizing capillary action.
４．光電変換効率の測定
得られた光化学電池の光電変換効率を英弘精機株式会社製のソーラーシュミレーターを用い、１００ｍＷ／ｃｍ２の擬似太陽光を照射し測定した。表６に膜厚、浸漬時間と光電変換効率を示す。
4). Measurement of photoelectric conversion efficiency The photoelectric conversion efficiency of the obtained photochemical battery was measured by irradiating 100 mW / cm 2 of pseudo-sunlight using a solar simulator manufactured by Eihiro Seiki Co., Ltd. Table 6 shows the film thickness, immersion time and photoelectric conversion efficiency.
Claims (13)
General formula: (L 1 ) 2 M 1 (BL) M 2 (L 2 ) 2 (X) A dye solution in which an asymmetric binuclear metal complex represented by n is dissolved. (However, M 1 and M 2 are transition metals and may be the same or different, and L 1 and L 2 are multidentate chelate-type ligands, and L 1 and L 2 2 is different, two L 1 may be different, two L 2 may be different, and BL is a bridging ligand having at least two cyclic structures containing heteroatoms Wherein the coordinating atoms coordinated to M 1 and M 2 are heteroatoms contained in this cyclic structure, X is a counter ion, and n is a counter ion necessary to neutralize the charge of the complex. Represents the number of
The dye solution having a binuclear metal complex dissolved therein according to claim 1, wherein L 1 and L 2 are chelate type ligands capable of bidentate, tridentate or tetradentate coordination.
3. A light and electrically stable binuclear metal complex dye solution comprising the binuclear metal complex according to claim 2, wherein a gas generation temperature resulting from decomposition is 280 ° C. or higher.
配位子であることを特徴とする請求項３記載の色素溶液。
L 1 is substituted with at least one carboxyl group (—COOH) or —COO — .
The dye solution according to claim 3, wherein the dye solution is a ligand.
（Ｌ２−Ａ）
（式中、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６、Ｒ１７及びＲ１８は水素原子、アルコキシ基、水酸基または置換もしくは無置換の炭化水素基を表すか、または、これらの二つ以上が一緒になってそれらが結合する炭素原子と共に置換もしくは無置換の芳香族炭化水素環または置換もしくは無置換の脂肪族炭化水素環を形成している。） L 2 is a dye solution according to claim 3, characterized in that the ligand represented by the following formula (L 2 -A).
(L 2 -A)
(Wherein R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 represent a hydrogen atom, an alkoxy group, a hydroxyl group or a substituted or unsubstituted hydrocarbon group, or Two or more of these together form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aliphatic hydrocarbon ring with the carbon atom to which they are attached.)
（式中、Ｒ５１、Ｒ５２、Ｒ５３及びＲ５４は水素原子または置換もしくは無置換の炭化水素基を表すか、または、これらの二つ以上が一緒になってそれらが結合する炭素原子と共に置換もしくは無置換の芳香族炭化水素環または置換もしくは無置換の脂肪族炭化水素環を形成しており、Ｒ５５、Ｒ５６、Ｒ５７及びＲ５８は水素原子または置換もしくは無置換の炭化水素基を表すか、または、これらの二つ以上が一緒になってそれらが結合する炭素原子と共に置換もしくは無置換の芳香族炭化水素環または置換もしくは無置換の脂肪族炭化水素環を形成している。） The dye solution according to claim 3, wherein BL is a ligand represented by the following formula (BL-C).
(Wherein R 51 , R 52 , R 53 and R 54 represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group, or two or more of these together together with a carbon atom to which they are bonded) A substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aliphatic hydrocarbon ring is formed, and R 55 , R 56 , R 57 and R 58 are a hydrogen atom or a substituted or unsubstituted hydrocarbon group Or two or more of these together form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aliphatic hydrocarbon ring with the carbon atom to which they are attached. )
4. The dye solution in which the binuclear metal complex is dissolved according to claim 3, wherein M 1 and M 2 are Group VIII to Group XI transition metals.
Ｌ２が、式（Ｌ２−１）、（Ｌ２−２）、または（Ｌ２−４）のいずれかで表される配位子であり、
ＢＬが、式（ＢＬ−１）、（ＢＬ−３）、または（ＢＬ−４）で表される配位子であり、
Ｍ１及びＭ２が、ルテニウム（Ｒｕ）、オスミウム（Ｏｓ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）または鉄（Ｆｅ）であることを特徴とする請求項３記載の色素溶液。
（Ｌ１−１）
（Ｌ１−４）
（Ｌ２−１）
（Ｌ２−２）
（Ｌ２−４）
（ＢＬ−１）
（ＢＬ−３）
（ＢＬ−４）
L 1 is a ligand represented by the formula (L 1 -1) or (L 1 -4);
L 2 is a ligand represented by any of the formulas (L 2 -1), (L 2 -2), or (L 2 -4),
BL is a ligand represented by the formula (BL-1), (BL-3), or (BL-4);
4. The dye solution according to claim 3, wherein M 1 and M 2 are ruthenium (Ru), osmium (Os), cobalt (Co), nickel (Ni), copper (Cu) or iron (Fe). .
(L 1 -1)
(L 1 -4)
(L 2 -1)
(L 2 -2)
(L 2 -4)
(BL-1)
(BL-3)
(BL-4)
General formula: (L 1 ) 2 M 1 (BL) M 2 (L 2 ) 2 (X) An asymmetric binuclear metal complex represented by n (provided that M 1 and M 2 are transition metals and are the same But may be different, L 1 and L 2 is a capable of multidentate coordination chelate ligand, L 1 and L 2 are different, the two L 1 is be different And two L 2 may be different, X is a counter ion, n represents the number of counter ions necessary to neutralize the charge of the complex, and BL represents a ring containing a hetero atom. A bridging ligand having at least two structures, wherein the coordinating atoms coordinated to M 1 and M 2 are heteroatoms contained in the cyclic structure, and L 1 is a substituent capable of being fixed to the semiconductor fine particles a, and a structure mainly (L 1) LUMO in 2 M 1 are distributed.) made possible the Dye solution obtained by dissolving a metal complex dye, characterized.
A photoelectric conversion element comprising semiconductor fine particles sensitized by using a dye solution in which the metal complex dye according to claim 3 is dissolved.
A photochemical cell using the photoelectric conversion device according to claim 12.
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| JP2009067838A (en) * | 2007-09-11 | 2009-04-02 | Ube Ind Ltd | Binuclear ruthenium complex pigment and manufacturing method for the same |
| WO2009102068A1 (en) * | 2008-02-14 | 2009-08-20 | Ube Industries, Ltd. | Binuclear ruthenium complex dye solution, photoelectric conversion device using photosensitized semiconductor particle obtained by using the complex dye solution, and photochemical cell using the photoelectric conversion device |
| WO2009130562A1 (en) * | 2008-04-21 | 2009-10-29 | Universite De Strasbourg | Method and device for producing and storing energy |
| JP2010097896A (en) * | 2008-10-20 | 2010-04-30 | Ube Ind Ltd | Photoelectric conversion element and photochemical battery |
| WO2010055856A1 (en) * | 2008-11-12 | 2010-05-20 | 宇部興産株式会社 | Photochemical cell comprising semiconductor microparticles sensitized with binuclear metal complex dye and electrolysis solution mainly composed of ionic liquid |
| JP2011060589A (en) * | 2009-09-10 | 2011-03-24 | Ube Industries Ltd | Photochemical battery including semiconductor fine particle sensitized by binuclear ruthenium complex dye and electrolyte solution containing arylamine compound |
| EP2311916A1 (en) * | 2008-06-19 | 2011-04-20 | Ube Industries, Ltd. | Binuclear ruthenium complex dye, ruthenium-osmium complex dye, photoelectric conversion element using any one of the complex dyes, and photochemical cell |
| CN102884137A (en) * | 2010-03-16 | 2013-01-16 | 宇部兴产株式会社 | Photoelectric conversion element that contains dye consisting of binuclear ruthenium complex having substituted bipyridyl groups, and photochemical cell |
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| JP2000323191A (en) * | 1999-05-14 | 2000-11-24 | Fuji Photo Film Co Ltd | Photoelectric transfer element, photoelectrochemical battery and metal complex pigment |
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| JP2000323191A (en) * | 1999-05-14 | 2000-11-24 | Fuji Photo Film Co Ltd | Photoelectric transfer element, photoelectrochemical battery and metal complex pigment |
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| JP2009067838A (en) * | 2007-09-11 | 2009-04-02 | Ube Ind Ltd | Binuclear ruthenium complex pigment and manufacturing method for the same |
| JPWO2009102068A1 (en) * | 2008-02-14 | 2011-06-16 | 宇部興産株式会社 | Binuclear ruthenium complex dye solution, photoelectric conversion element using photosensitized semiconductor fine particles obtained using the complex dye solution, and photochemical battery using the same |
| WO2009102068A1 (en) * | 2008-02-14 | 2009-08-20 | Ube Industries, Ltd. | Binuclear ruthenium complex dye solution, photoelectric conversion device using photosensitized semiconductor particle obtained by using the complex dye solution, and photochemical cell using the photoelectric conversion device |
| WO2009130562A1 (en) * | 2008-04-21 | 2009-10-29 | Universite De Strasbourg | Method and device for producing and storing energy |
| US8496788B2 (en) | 2008-04-21 | 2013-07-30 | Is2 S.A.S. | Method and device for producing and storing energy |
| CN102124060A (en) * | 2008-06-19 | 2011-07-13 | 宇部兴产株式会社 | Dinuclear ruthenium complex dye, ruthenium-osmium complex dye, photoelectric conversion element using any one of the complex dyes, and photochemical cell |
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| EP2311916A4 (en) * | 2008-06-19 | 2012-06-06 | Ube Industries | Binuclear ruthenium complex dye, ruthenium-osmium complex dye, photoelectric conversion element using any one of the complex dyes, and photochemical cell |
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| JP2010097896A (en) * | 2008-10-20 | 2010-04-30 | Ube Ind Ltd | Photoelectric conversion element and photochemical battery |
| WO2010055856A1 (en) * | 2008-11-12 | 2010-05-20 | 宇部興産株式会社 | Photochemical cell comprising semiconductor microparticles sensitized with binuclear metal complex dye and electrolysis solution mainly composed of ionic liquid |
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| CN102884137A (en) * | 2010-03-16 | 2013-01-16 | 宇部兴产株式会社 | Photoelectric conversion element that contains dye consisting of binuclear ruthenium complex having substituted bipyridyl groups, and photochemical cell |
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