US20100326529A1 - Photosensitizing transition metal complex and its use for photovoltaic cell - Google Patents
Photosensitizing transition metal complex and its use for photovoltaic cell Download PDFInfo
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- US20100326529A1 US20100326529A1 US12/872,499 US87249910A US2010326529A1 US 20100326529 A1 US20100326529 A1 US 20100326529A1 US 87249910 A US87249910 A US 87249910A US 2010326529 A1 US2010326529 A1 US 2010326529A1
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- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 20
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 20
- 230000002165 photosensitisation Effects 0.000 title claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 41
- 239000004065 semiconductor Substances 0.000 claims abstract description 23
- 239000003446 ligand Substances 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 6
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 140
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 5
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 5
- 238000004873 anchoring Methods 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- -1 trifluoro group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 125000005110 aryl thio group Chemical group 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 2
- 125000001302 tertiary amino group Chemical group 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 2
- 229910052762 osmium Inorganic materials 0.000 abstract 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 abstract 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 150000003141 primary amines Chemical class 0.000 abstract 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052702 rhenium Inorganic materials 0.000 abstract 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 abstract 1
- 150000003335 secondary amines Chemical class 0.000 abstract 1
- 229910052713 technetium Inorganic materials 0.000 abstract 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 abstract 1
- 150000003512 tertiary amines Chemical class 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 95
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
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- LNQRTGFXLPJUKT-UHFFFAOYSA-N 4-hexadecyl-2-hydroxy-6-oxo-1h-pyridine-3-carbonitrile Chemical compound CCCCCCCCCCCCCCCCC1=CC(O)=NC(O)=C1C#N LNQRTGFXLPJUKT-UHFFFAOYSA-N 0.000 description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 27
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- 239000010410 layer Substances 0.000 description 24
- JWWGPSIXULKWJT-UHFFFAOYSA-N ethyl 2-bromo-6-(4-ethoxycarbonylpyridin-2-yl)pyridine-4-carboxylate Chemical compound CCOC(=O)C1=CC=NC(C=2N=C(Br)C=C(C=2)C(=O)OCC)=C1 JWWGPSIXULKWJT-UHFFFAOYSA-N 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
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- RKHUINAZLMTDLC-UHFFFAOYSA-N ethyl 2-(4-ethoxycarbonylpyridin-2-yl)-6-(4-nonadecylpyridin-2-yl)pyridine-4-carboxylate Chemical compound CCCCCCCCCCCCCCCCCCCC1=CC=NC(C=2N=C(C=C(C=2)C(=O)OCC)C=2N=CC=C(C=2)C(=O)OCC)=C1 RKHUINAZLMTDLC-UHFFFAOYSA-N 0.000 description 15
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- ORBQEFJMHGVQEP-UHFFFAOYSA-N ethyl 3-oxononadecanoate Chemical compound CCCCCCCCCCCCCCCCC(=O)CC(=O)OCC ORBQEFJMHGVQEP-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 13
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- VNYKJZGMVARMFN-UHFFFAOYSA-N 4-hexadecyl-6-hydroxy-1h-pyridin-2-one Chemical compound CCCCCCCCCCCCCCCCC1=CC(O)=NC(O)=C1 VNYKJZGMVARMFN-UHFFFAOYSA-N 0.000 description 11
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- 239000000463 material Substances 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- FRCVPOCFOUYRLS-UHFFFAOYSA-N 2,6-dibromo-4-hexadecylpyridine Chemical compound CCCCCCCCCCCCCCCCC1=CC(Br)=NC(Br)=C1 FRCVPOCFOUYRLS-UHFFFAOYSA-N 0.000 description 10
- UEJJXCRFGURPDR-UHFFFAOYSA-N 2-bromo-4-methyl-6-(4-methylpyridin-2-yl)pyridine Chemical compound CC1=CC=NC(C=2N=C(Br)C=C(C)C=2)=C1 UEJJXCRFGURPDR-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
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- 0 COC(=O)C1=CC=CC(C(=O)OC)=C1OC.COCC1=CC=CC(COC)=N1.NCC1=CC=CC(CN)=N1.NCCNCCN.[3*]C.[3*]C.[3*]C Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1OC.COCC1=CC=CC(COC)=N1.NCC1=CC=CC(CN)=N1.NCCNCCN.[3*]C.[3*]C.[3*]C 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
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- 239000008346 aqueous phase Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 6
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 6
- 229910000080 stannane Inorganic materials 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 229910001887 tin oxide Inorganic materials 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- SBKQQGZXSADORS-UHFFFAOYSA-N tributyl-[4-hexadecyl-6-(4-nonadecylpyridin-2-yl)pyridin-2-yl]stannane Chemical compound CCCCCCCCCCCCCCCCCCCC1=CC=NC(C=2N=C(C=C(CCCCCCCCCCCCCCCC)C=2)[Sn](CCCC)(CCCC)CCCC)=C1 SBKQQGZXSADORS-UHFFFAOYSA-N 0.000 description 6
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- 230000004048 modification Effects 0.000 description 2
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
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- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
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- YFBUDXNMBTUSOC-UHFFFAOYSA-L quinoxaline-2,3-dithiolate Chemical compound C1=CC=C2N=C([S-])C([S-])=NC2=C1 YFBUDXNMBTUSOC-UHFFFAOYSA-L 0.000 description 1
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- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
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- 235000011152 sodium sulphate Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/331—Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/348—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising osmium
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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
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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
- Y02E10/549—Organic PV cells
Definitions
- the invention relates to new photosensitizing transition metal complex and its use for photovoltaic cell such as solar cell.
- Photosensitive dyes are coated on metal oxide films rendering a device as solar cell effective in the conversion of visible light to electric energy.
- a monolayer of dye is attached to the surface of nanocrystalline metal dioxide film.
- Photoexcitation of the dye results in the injection of an electron into the conduction band of the metal oxide.
- the original state of the dye is subsequently restored by electron donation from a redox system, such as iodide/triiodide couple.
- a redox system such as iodide/triiodide couple.
- Molecular design of ruthenium polypyridyl photosensitizers for nanocrystalline TiO 2 film in solar cell that can absorb visible lights of all colors presents a challenging task.
- the dyes should have suitable ground—and excited state redox properties so that the two key electron transfer steps (charge injection and regeneration of the dye) occur efficiently.
- the most efficient transition metal complexes employed so far in the solar cell are Ru(II) polypyridyl complexes because of their intense charge-transfer (CT) absorption in the whole visible range, moderately intense emission with fairly long lifetime in fluid solution at ambient temperature, high quantum yield for the formation of the lowest CT excited state, and redox reactivity and ease of tunability of redox properties.
- the most successful photosensitizers employed in solar cell are Ru(4,4′-dicarboxy-2,2′-bipyridine) 2 (NCS) 2 and Ru(4,4′,4′′-tricarboxy-2,2′:6′,2′′-terpyridine)(NCS) 3 .
- the role of the monodentate thiocyanato ligands is to tune the spectral and redox properties of the photosensitizers by destabilization of the metal t 2g orbital.
- NCS— monodentate donor ligands
- the present invention aims to provide a new series of ptotochemically stable amphiphilic transition metal complexes to improve the efficiency, durability and stability of dye sensitized nanocrystalline solar cell.
- M is a transition metal selected from Ru(II), Os(II), Fe(II), Re(I) and Tc(I);
- L is a polypyridine ligand having the general formula (II):
- a 1 , A 2 and A 3 is an anchoring group selected from —COOH, —COON(C 4 H 9 ) 4 , —PO(OH) 2 , —PO(OR 1 ) 2 (where R 1 is an alkyl group having 1 to 30 carbon atoms), —CO(NHOH), and when there is the remaining A 1 , A 2 and A 3 being not said anchoring group, it may be a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, an alkylamide group having 2 to 50 carbon atoms or an aralkyl group having 7 to 50 carbon atoms.
- a 1 , A 2 and A 3 contain at least one anchoring group as mentioned above and at least one group selected from the alkyl, alkylamide and aralkyl groups.
- X is a ligand selected from NCS—, Cl—, Br—, I—, CN—, NCO—, H 2 O or pyridine group which may be substituted by vinyl, primary, secondary or tertiary amino, alkylthio or arylthio, hydroxyl or C 1-30 alkyl.
- Y 1 is a group selected from the formulae (IIIa) to (IIId):
- R 3 is an alkyl group having 1 to 50 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, an aminoalkyl group having 1 to 30 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylamide group having 2 to 30 carbon atoms, a cyano group or a hydrogen atom.
- Y 2 is a group having the general formula (IVa-1):
- R 4 , R 5 and R 6 are independently an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkylamide group having 2 to 30 carbon atoms, a perfluoroalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, cyano group, hydroxyl group, nitro group, amino group, trifluoro group, halogen atom or hydrogen atom.
- Y 3 is a group having the formula (IVa-2):
- R 7 is a trifluoro or perfluoroalkyl group having 1 to 12 carbon atoms
- R 8 and R 9 are independently the same meanings as R 5 and R 6 of the formula (IVa-1).
- Y 4 is a group selected from the formulae (IVb-1 to 3), (IVc-1 to 4), (IVd-1 to 8) and (IVe-1 or 2):
- R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are the same or different an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an perfluoroalkyl group having 2 to 12 carbon atoms, an alkylamide group having 2 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, cyano group, hydroxyl group, nitro group, amino group, trifluoro group, halogen atom or hydrogen atom.
- the present invention further provides a photovoltaic cell comprising a support, a conductive layer formed on the support, and a porous semiconductor layer formed on the conductive layer, wherein the porous semiconductor layer carries a photosensitizing transition metal complex as defined above.
- FIG. 1 is a diagrammatic sectional view showing the structure of a solar cell constructed in the present invention.
- the transition metal for M is preferred to be Ru(II) and Os(II).
- the ligand for X is preferred to be NCS— and CN—.
- polytpyridine ligand for the general formula (II) is preferred to be those of the subformula (IIa):
- B 1 , B 2 and B 3 are H, —COOH, —COON(C 4 H 9 ) 4 or —PO(OH) 2 provided that at least one of B 1 , B 2 and B 3 is different from hydrogen atom; and subformula (IIb):
- B 1 and B 2 are, the same or different, a hydrogen atom, —COOH, —COON(C 4 H 9 ) 4 , —PO(OH) 2 , provided that any one of B 1 and B 2 is different from a hydrogen atom, and C is an alkyl group having 6 to 30 carbon atoms.
- the alkyl moiety used in the alkyl group, the alkylamide group, the aralkyl group, the alkoxyalkyl group, the aminoalkyl group, the alkoxycarbonyl group, the alkylthio group, the tri or perfluoro alkyl may be either straight chain or branched chain and further may be optionally substituted by any group(s) which does not interfere the property for photosensitizer.
- the aryl moiety used in the aralkyl group may be optionally substituted by any group(s) which does not interfere the property for photosensitizer.
- Preferred polypyridine ligands for L which can contribute for the best to increase the efficiency and stability of photovoltaic cell are those having at least one anchoring group of —COOH and —PO(OH) 2 , specifically as mentioned below.
- photosensitizing transition metal complexes of the general formula (Ia) are ruthenium complexes as shown by Complex types 1 to 4 in Table 1 to 4.
- photosensitizing transition metal complex of the general formula (Ib) are ruthenium complexes as shown by Complex type 5 in Table 5.
- photosensitizing transition metal complex of the general formula (Ic) are ruthenium complexes as shown by Complex type 6 in Table 6 and 7.
- R 4 No CH 3 H CH 3 1 CH 3 CH3 CH 3 2 t-Bu H t-Bu 3 Ph H CH 3 4 Ph H Ph 5 CH 3 H R 1 6 CF 3 H CH 3 7 CF 3 H CH 2 CN 8 CF 3 H CF 3 9 CF 3 H R 1 10 CF 3 H CF 3 —CF 2 11 CF 3 H Ph 12 R 1 being selected from C 1-30 alkyl
- photosensitizing transition metal complex of the general formula (Id) are ruthenium complexes as shown by Complex type 7 in Table 8 and 9.
- photosensitizing transition metal complexes of the general formula (Ie) are ruthenium complexes as shown by Complex types 8 to 11 in Table 10 to 13.
- a dye-sensitized solar cell shown in FIG. 1 has such a structure containing an electroconductive support 8 , a porous photovoltaic layer 3 having a photosensitizing dye adsorbed thereon and/or therein formed on the electroconductive support 8 , a counter electrode side 9 , a hole transporting layer 4 filled between the porous photovoltaic layer 3 and the counter electrode side 9 , and a sealant 7 sealing the side surfaces.
- the electroconductive support 8 is constituted with a substrate 1 and a transparent electroconductive film 2 .
- the material used in the substrate 1 is not particularly limited and can be various kinds of transparent materials, and glass is preferably used.
- the material used in the transparent electroconductive film 2 is also not particularly limited, and it is preferred to use a transparent electroconductive metallic oxide electrode such as fluorine-doped tin oxide (SnO 2 :F), antimony doped tin oxide (SnO 2 :Sb), indium-doped tin oxide (In 2 O 3 :Sn), aluminium-doped zinc oxide (ZnO:Al) and gallium-doped zinc oxide (ZnO:Ga).
- a transparent electroconductive metallic oxide electrode such as fluorine-doped tin oxide (SnO 2 :F), antimony doped tin oxide (SnO 2 :Sb), indium-doped tin oxide (In 2 O 3 :Sn), aluminium-doped zinc oxide (ZnO:Al) and gallium-doped zinc oxide (ZnO:Ga).
- Examples of the method for forming the transparent electroconductive film 2 on the substrate 1 include a vacuum vapor deposition method, a sputtering method, a CVD (chemical vapor deposition) method and a PVD (physical vapor deposition) method using a component of the material, and a coating method by a sol-gel method.
- the material of the porous semiconductor layer used in the porous photovoltaic layer 3 is not particularly limited as far as it is an n-type semiconductor. It is preferred to use an oxide semiconductor such as titanium oxide (TiO 2 ), zinc oxide (ZnO), tin oxide (SnO 2 ), indium oxide (In 2 O 3 ) and niobium oxide (Nb 2 O 3 ). It is preferred that the oxide semiconductor have a large surface area for reasons of obtaining high performance of a solar cell.
- the oxide semiconductor preferably has a particle diameter of 1 to 200 nm, more preferably 50 nm or less.
- the oxide semiconductor preferably has a specific surface area of 5 to 100 m2/g.
- the oxide semiconductor is immobilized on the conductive surface to form a generally porous film having a thickness of at least 200 nm, preferably 1000 to 20000 nm.
- a dye sensitized semiconductor electrode according to the present invention may be obtained by fixing the above described metal complex of the present invention to a film or layer of oxide semiconductor particles formed on an electrically conductive surface of a substrate in any suitable conventional manner.
- Fixation of the oxide semiconductor on the conductive surface may be effected by dipping or coating in or with a suspension or slurry containing the oxide semiconductor, followed by drying and calcination.
- a water medium which may contain a surfactant, a thickening agent such as polyethylene glycol and any suitable additive, is generally used for forming the suspension or slurry.
- the calcination is generally carried out at 300 to 900° C., preferably 400 to 600° C.
- the metal complex is fixed to the semiconductor layer.
- the metal complex is dissolved in a suitable solvent such as methanol, ethanol, acetonitrile, n-butanol, tert-butanol or dimethylformamide.
- a suitable solvent such as methanol, ethanol, acetonitrile, n-butanol, tert-butanol or dimethylformamide.
- the above described semiconductor electrode is then impregnated with this solution by immersion, coating or any other suitable method. It is preferred that the solution penetrates deep into the porous layer of the oxide semiconductor.
- the semiconductor electrode is preferably evacuated at an elevated temperature to remove gases trapped therein.
- the metal complex preferably forms a monolayer on surfaces of the oxide semiconductor.
- the support on a counter electrode side 9 is constituted by a substrate 5 and a counter electrode layer 6 .
- the material used for the substrate 5 is not particularly limited as similar to the substrate 1 , and it can be various kinds of transparent materials, with glass being preferably used.
- the material used for the counter electrode layer 6 is also not particularly limited, and one of a platinum thin film, a carbon thin film, fluorine-doped tin oxide (SnO 2 :F), antimony doped tin oxide (SnO 2 :Sb), tin-doped indium oxide (In 2 O 3 :Sn), aluminium-doped zinc oxide (ZnO:Al) and gallium-doped zinc oxide (ZnO:Ga), an accumulated layer of plurality thereof, and a composite film of plurality thereof are preferably used.
- the role of the counter electrode layer 6 is to facilitate the transfer of electrons from the counter electrode to the electrolyte.
- Examples of the method for forming the counter electrode film 6 on the substrate 5 include a vacuum vapor deposition method, a sputtering method, a CVD (chemical vapor deposition) method and a PVD (physical vapor deposition) method using a component of the material, and a coating method by a sol-gel method.
- a further possible modification of the counterelectrode is to make it reflective to light that has passed through the electrolyte and the first plate.
- the outside of the substrates may be coated with plastics like PS, PMMA, or preferably PC to protect the TiO2 layer, the dyestuff and the electrolyte against UV-light to give long term stability.
- the hole transporting layer 4 filled between the porous semiconductor layer 3 having the photosensitizing dye adsorbed thereon formed on the electroconductive support 8 and the support on a counter electrode side 9 materials that can transport an electron, a hole or an ion can be used.
- a hole transporting material such as polyvinyl carbazole, an electron transporting material such as tetranitrofluorenone, an electroconductive polymer such as polypyrrol, a liquid electrolyte, and an ionic electroconductive material such as a polymer solid electrolyte, can be used.
- Illustrative of the redox pairs for a liquid electrolyte are I—/I 3 —, Br—/Br 3 — and quinone/hydroquinone pairs.
- I—/I 3 — for example, lithium iodide and iodine may be used.
- an electrochemically inert solvent capable of dissolving the electrolyte in a large amount, such as acetonitrile or propylene carbonate.
- 6-Bromo-4,4′-diethoxycarbonyl-2,2′-bipyridine (10) (1 mmol), 2-tributyl(4-nonadecylpyridine-2-yl)stannane (4) (1 mmol) and (Ph 3 P)4Pd (0.01 equiv) were heated under N 2 in toluene (50 mL) for 16 h. Upon cooling to room temperature aqueous saturated NH4Cl solution (20 mL) was added. The mixture was stirred for further 30 min and then filtered over celite. The precipitate was washed with CH 2 Cl 2 (50 mL) and the organic phase was separated. The aqueous phase was extracted with toluene.
- 4,4′-Bis(hydroxymethyl)-4′′-nonadecyl-2,2′:6′,2′′-terpyridine (2.35 g, 4.2 mmol) was dissolved in a mixture of 48% HBr (20 mL) and concentrated sulfuric acid (6.7 mL). The resulting solution was refluxed for 6 h and then allowed to cool to room temperature, and 40 mL of water was added. The pH was adjusted to neutral with NaOH solution and the resulting precipitate was filtered, washed with water (pH)) 7), and air-dried. The product was dissolved in chloroform (40 mL) and filtered.
- This compound was prepared by an analogous procedure to that described in Example 2 (step d).
- This compound was prepared by an analogous procedure to that described in Example 2 (steps a-d).
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- Powder Ru(4,4′4′′-tricarboxy-2,2′:6′,2′′-terpyridine)(pdm) was dissolved in 0.1 M aqueous tetrabutylammonium hydroxide (TBAOH) and the mixture heated to 110° C., for 4 h (the pH of the solution was about 11).
- TSAOH aqueous tetrabutylammonium hydroxide
- the resulting purple solution was filtered to remove a small amount of insoluble material and the pH was adjusted to 5.0 with dilute hydrochloric acid.
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- the complex Ru(4,4′-diethoxycarbonyl-4′′-nonadecyl-2,2′:6′,2′′-terpyridine)(NCS) 3 was synthesized in dark under an argon atmosphere by refluxing at 130° C., a solution of NH 4 NCS (2 g, in 10 mL of H 2 O) and Ru(4,4′-diethoxycarbonyl-4′′-nonadecyl-2,2′:6′,2′′-terpyridine)Cl 3 complex (0.5 g, in 50 mL of DMF) for 4 h.
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 10 (step c).
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 17 (step b).
- This compound was prepared by an analogous procedure to that described in Example 10 (step c).
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 17 (step b).
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 17 (step b).
- This compound was prepared by an analogous procedure to that described in Example 10 (step c).
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 17 (step b).
- This compound was prepared by an analogous procedure to that described in Example 10 (step c).
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 17 (step b).
- Nanocrystalline TiO 2 films of about 20 ⁇ m were prepared by spreading a viscous dispersion of colloidal TiO 2 particles (Sloaronix) on a conducting glass support (Asahi TCO glass, fluorine-doped SnO 2 overlayer, transmission >85% in the visible, sheet registance 7-8 ohms/square) with heating under air for 30 min at 500° C.
- the performance of the film as a sensitized photoanode was improved by further deposition of TiO 2 from aqueous TiCl 4 solution.
- a freshly prepared aqueous 0.2 M TiCl 4 solution applied onto the electrode. After being left for 20 min at 70° C. in a closed chamber, the electrode was washed with distilled water.
- a solar cell (size: 0.25 cm 2 ) was fabricated using the above electrode and a counter electrode, which was a platinum electrode, obtained by vacuum-deposition of platinum on a conductive glass.
- the platinum layer had a thickness of 20 nm.
- An electrolyte solution to be placed between the two electrodes was a redox pair of I—/I 3 — obtained using 0.5 M 4-tert-butylpyridine, 0.1 M LiI, 0.6M 1,2-dimethyl-3-propyl imidazolium iodide and 0.1 M I 2 as solutes and a liquid of acetonitrile.
- a potentiostat was used for measuring short-circuit electric current, open circuit voltage and fill factor. Experiments are carried out with a high pressure Xenon lamp equipped with appropriate filters to simulate AM 1.5 solar radiation. The intensity of the light is 100 mW/cm 2 .
- the fill factor defined as the maximum electric power output of the cell divided by the product of open circuit voltage and short circuit current.
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Abstract
A photosensitizing transition metal complex of the formula (Ia) MLY1, (Ib) MLX3 (Ic) MLY2X, (Id) MLY3X or (Ie) MLY4X in which M is a transition metal selected from ruthenium, osmium, iron, rhenium and technetium, preferably ruthenium or osmium. X is a co-ligand independently selected from NCS—, Cl—, Br—, I—, CN—, H2O; pyridine unsubstituted or substituted by at least one group selected from vinyl, primary, secondary or tertiary amine, OH and C1-30 alkyl, preferably NSC and CN—; L is a tridentate polypyridine ligand, carrying at least one carboxylic, phosphoric acid or a chelating group and one substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted alkylamide group having 2 to 30 carbon atoms or substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms. A dye-sensitized electrode includes a substrate having an electrically conductive surface, an oxide semiconductor film formed on the conductive surface, and the above sensitizer of formula (Ia), (Ib), (Ic), (Id) or (Ie) as specified above; supported on the film. A solar cell includes the above electrode, a counter electrode, and an electrolyte deposited there between.
Description
- The present application is a divisional of U.S. application Ser. No. 10/964,745 (allowed), which was filed Oct. 15, 2004 (published as US 2005-0081911 A1 on Apr. 21, 2005), which claims benefit of Japanese Patent Application Nos. 2003-358266, filed Oct. 17, 2003 and 2003-407877, filed Dec. 5, 2003, the entire contents of each of which is incorporated herein by reference.
- 1. Field of the Invention
- The invention relates to new photosensitizing transition metal complex and its use for photovoltaic cell such as solar cell.
- 2. Description of the Related Art
- Photosensitive dyes are coated on metal oxide films rendering a device as solar cell effective in the conversion of visible light to electric energy. In this solar cell, a monolayer of dye is attached to the surface of nanocrystalline metal dioxide film. Photoexcitation of the dye results in the injection of an electron into the conduction band of the metal oxide. The original state of the dye is subsequently restored by electron donation from a redox system, such as iodide/triiodide couple. Molecular design of ruthenium polypyridyl photosensitizers for nanocrystalline TiO2 film in solar cell that can absorb visible lights of all colors presents a challenging task. The dyes should have suitable ground—and excited state redox properties so that the two key electron transfer steps (charge injection and regeneration of the dye) occur efficiently.
- The most efficient transition metal complexes employed so far in the solar cell are Ru(II) polypyridyl complexes because of their intense charge-transfer (CT) absorption in the whole visible range, moderately intense emission with fairly long lifetime in fluid solution at ambient temperature, high quantum yield for the formation of the lowest CT excited state, and redox reactivity and ease of tunability of redox properties. So far, the most successful photosensitizers employed in solar cell are Ru(4,4′-dicarboxy-2,2′-bipyridine)2(NCS)2 and Ru(4,4′,4″-tricarboxy-2,2′:6′,2″-terpyridine)(NCS)3. The role of the monodentate thiocyanato ligands is to tune the spectral and redox properties of the photosensitizers by destabilization of the metal t2g orbital.
- The presence of monodentate donor ligands (NCS—) can undergo ligand photosubstitution or photodegradation reaction via population of an upper lying ligand field excited state and these processes can be reduced by multidentate ligands.
- As relevant prior arts are mentioned U.S. Pat. No. 6,245,988, U.S. Pat. No. 5,789,592, Japanese Patent Kokai No. 2003-212851 and New J. Chem. 26 (2002) 966-968.
- The present invention aims to provide a new series of ptotochemically stable amphiphilic transition metal complexes to improve the efficiency, durability and stability of dye sensitized nanocrystalline solar cell.
- According to the invention, there is provided photosensitizing transition metal complexes represented by the formulae (Ia), (Ib), (Ic), (Id) and (Ie)
-
MLY1 (Ia) -
MLX3 (Ib) -
MLY2X (Ic) -
MLY3X (Id) and -
MLY4X (Ie) - In the formulae, M is a transition metal selected from Ru(II), Os(II), Fe(II), Re(I) and Tc(I);
- L is a polypyridine ligand having the general formula (II):
- wherein at least one of A1, A2 and A3 is an anchoring group selected from —COOH, —COON(C4H9)4, —PO(OH)2, —PO(OR1)2 (where R1 is an alkyl group having 1 to 30 carbon atoms), —CO(NHOH), and when there is the remaining A1, A2 and A3 being not said anchoring group, it may be a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, an alkylamide group having 2 to 50 carbon atoms or an aralkyl group having 7 to 50 carbon atoms.
- Preferably, A1, A2 and A3 contain at least one anchoring group as mentioned above and at least one group selected from the alkyl, alkylamide and aralkyl groups.
- X is a ligand selected from NCS—, Cl—, Br—, I—, CN—, NCO—, H2O or pyridine group which may be substituted by vinyl, primary, secondary or tertiary amino, alkylthio or arylthio, hydroxyl or C1-30 alkyl.
- Y1 is a group selected from the formulae (IIIa) to (IIId):
- where R3 is an alkyl group having 1 to 50 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, an aminoalkyl group having 1 to 30 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylamide group having 2 to 30 carbon atoms, a cyano group or a hydrogen atom.
- Y2 is a group having the general formula (IVa-1):
- where R4, R5 and R6 are independently an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkylamide group having 2 to 30 carbon atoms, a perfluoroalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, cyano group, hydroxyl group, nitro group, amino group, trifluoro group, halogen atom or hydrogen atom.
- Y3 is a group having the formula (IVa-2):
- where R7 is a trifluoro or perfluoroalkyl group having 1 to 12 carbon atoms, R8 and R9 are independently the same meanings as R5 and R6 of the formula (IVa-1).
- Y4 is a group selected from the formulae (IVb-1 to 3), (IVc-1 to 4), (IVd-1 to 8) and (IVe-1 or 2):
- where R10, R11, R12, R13, R14, R15, R16 and R17 are the same or different an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an perfluoroalkyl group having 2 to 12 carbon atoms, an alkylamide group having 2 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, cyano group, hydroxyl group, nitro group, amino group, trifluoro group, halogen atom or hydrogen atom.
- The present invention further provides a photovoltaic cell comprising a support, a conductive layer formed on the support, and a porous semiconductor layer formed on the conductive layer, wherein the porous semiconductor layer carries a photosensitizing transition metal complex as defined above.
- These and other objects of the present application will become more readily apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
-
FIG. 1 is a diagrammatic sectional view showing the structure of a solar cell constructed in the present invention. - In the formulae (Ia) to (Ie), the symbols or groups will be explained in detail.
- The transition metal for M is preferred to be Ru(II) and Os(II).
- The ligand for X is preferred to be NCS— and CN—.
- The polytpyridine ligand for the general formula (II) is preferred to be those of the subformula (IIa):
- where B1, B2 and B3 are H, —COOH, —COON(C4H9)4 or —PO(OH)2 provided that at least one of B1, B2 and B3 is different from hydrogen atom; and
subformula (IIb): - where B1 and B2 are, the same or different, a hydrogen atom, —COOH, —COON(C4H9)4, —PO(OH)2, provided that any one of B1 and B2 is different from a hydrogen atom, and C is an alkyl group having 6 to 30 carbon atoms.
- The alkyl moiety used in the alkyl group, the alkylamide group, the aralkyl group, the alkoxyalkyl group, the aminoalkyl group, the alkoxycarbonyl group, the alkylthio group, the tri or perfluoro alkyl may be either straight chain or branched chain and further may be optionally substituted by any group(s) which does not interfere the property for photosensitizer.
- The aryl moiety used in the aralkyl group may be optionally substituted by any group(s) which does not interfere the property for photosensitizer.
- Preferred polypyridine ligands for L which can contribute for the best to increase the efficiency and stability of photovoltaic cell are those having at least one anchoring group of —COOH and —PO(OH)2, specifically as mentioned below.
- Specifically, preferred illustrative examples of the photosensitizing transition metal complexes of the general formula (Ia) are ruthenium complexes as shown by
Complex types 1 to 4 in Table 1 to 4. -
-
TABLE 1 Complex type No A1 A2 A3 1a COOH COOH COOH 1b COOH COOH nC19H39 1c COOH COOH nCH(C12H25)2 1d nC19H39 COOH nC19H39 1e COOH nC16H33 nC19H39 1f COOH COOH nC17H35 1g COOH COOH nCH(C8H17)2 1h nC17H35 COOH nC17H35 1i COOH nC8H17 nC9H19 -
-
TABLE 2 Complex type No A1 A2 A3 2a COOH COOH COOH 2b COOH COOH nC19H39 2c COOH COOH nCH(C12H25)2 2d nC19H39 COOH nC19H39 2e COOH nC16H33 nC19H39 -
-
TABLE 3 Complex type No A1 A2 A3 R3 3a COOH COOH COOH H 3b COOH COOH COOH nC16H33 3c COOH COOH nC19H39 H 3d COOH COOH nC19H39 nC16H33 3e COOH COOH nCH(C12H25)2 H 3f nC19H39 COOH nC19H39 H 3g COOH nC16H33 nC19H39 H 3h COOH COOH nC17H35 H 3i COOH COOH nCH(C8H17)2 H 3j nC17H35 COOH nC17H35 H 3k COOH NC8H17 NC9H19 H -
-
TABLE 4 Complex type No A1 A2 A3 4a COOH COOH COOH 4b COOH COOH NC19H39 4c COOH COOH nCH(C12H25)2 4d nC19H39 COOH NC19H39 4e COOH nC16H33 NC19H39 - Specifically, preferred illustrative examples of the photosensitizing transition metal complex of the general formula (Ib) are ruthenium complexes as shown by
Complex type 5 in Table 5. -
-
TABLE 5 Complex type No A1 A2 A3 X 5a COOH COOH nC19H39 NSC- 5b COOH COOH nCH(C12H25)2 NSC- 5c nC19H39 COOH nC19H39 NSC- 5d COOH nC16H33 nC19H39 NSC- - Specifically, preferred illustrative examples of the photosensitizing transition metal complex of the general formula (Ic) are ruthenium complexes as shown by Complex type 6 in Table 6 and 7.
-
-
TABLE 6 R4 R5 R6 No CH3 H CH3 1 CH3 CH3 CH3 2 t-Bu H t-Bu 3 Ph H CH 3 4 Ph H Ph 5 CH3 H R1 6 CF3 H CH3 7 CF3 H CH2CN 8 CF3 H CF3 9 CF3 H R1 10 CF3 H CF3—CF2 11 CF3 H Ph 12 R1 being selected from C1-30 alkyl -
TABLE 7 Complex type No A1 A2 A3 R4 R6 X 6a COOH COOH nC19H39 CF3 CH3 NSC- 6b COOH COOH nCH(C12H25)2 CF3 CH3 NSC- 6c nC19H39 COOH nC19H39 CF3 CH3 NSC- 6d COOH nC16H33 nC19H39 CF3 CH3 NSC- 6e COOH COOH NC17H35 CF3 CH3 NSC- 6f COOH COOH nCH(C8H17)2 CF3 CH3 NSC- 6g nC17H35 COOH nC17H35 CF3 CH3 NSC- 6h COOH NC8H17 NC9H19 CF3 CH3 NSC- - Specifically, preferred illustrative examples of the photosensitizing transition metal complex of the general formula (Id) are ruthenium complexes as shown by
Complex type 7 in Table 8 and 9. -
-
TABLE 8 R7 R8 R9 No CF3 H 4- F 1 CF3 H 4- Cl 2 CF3 H 4 -CN 3 CF3 H 4- CF 34 CF3 H 4- CH 35 CF3 H 4-NO2 6 CF3—CF2 H 4- F 7 CF3—CF2 H 4- Cl 8 CF3—CF2 H 4-CN 9 CF3 F 4-F 10 CF3 F 4-Cl 11 CF3 F 4-CN 12 CF3 F 4-CF3 13 CF3 F 4-CH3 14 CF3 H H 15 CF3—CF2 H 4-CF3 16 CF3—CF2 H 4-CH3 17 CF3—CF2 H H 18 -
TABLE 9 Complex type No A1 A2 A3 R7 R9 X 7a COOH COOH COOH CF3 H NSC- 7b COOH COOH COOH CF3 F NSC- 7c COOH COOH COOH CF3 Cl NSC- 7d COOH COOH COOH CF3 CH3 NSC- 7e COOH COOH nC19H39 CF3 CH3 NSC- 7f COOH COOH nCH(C12H25)2 CF3 CH3 NSC- 7g nC19H39 COOH nC19H39 CF3 CH3 NSC- 7h COOH nC16H33 nC19H39 CF3 CH3 NSC- 7i COOH COOH NC17H35 CF3 CH3 NSC- 7j COOH COOH nCH(C8H17)2 CF3 CH3 NSC- 7k nC17H35 COOH nC17H35 CF3 CH3 NSC- 7l COOH NC8H17 NC9H19 CF3 CH3 NSC- 7m COOH COOH nC19H39 CF3 F NSC- 7n COOH COOH nCH(C12H25)2 CF3 F NSC- 7o nC19H39 COOH nC19H39 CF3 F NSC- 7p COOH nC16H33 nC19H39 CF3 F NSC- 7q COOH COOH NC17H35 CF3 F NSC- 7r COOH COOH nCH(C8H17)2 CF3 F NSC- 7s nC17H35 COOH nC17H35 CF3 F NSC- 7t COOH NC8H17 NC9H19 CF3 F NSC- 7u COOH COOH COOH CF3 CF3 NSC- - Specifically, preferred illustrative examples of the photosensitizing transition metal complexes of the general formula (Ie) are ruthenium complexes as shown by
Complex types 8 to 11 in Table 10 to 13. -
-
TABLE 10 Complex type No A1 A2 A3 X 8a COOH COOH nC19H39 NSC- 8b COOH COOH nCH(C12H25)2 NSC- 8c nC19H39 COOH nC19H39 NSC- 8d COOH nC16H33 nC19H39 NSC- -
-
TABLE 11 Complex type No A1 A2 A3 X 9a COOH COOH nC19H39 NSC- 9b COOH COOH nCH(C12H25)2 NSC- 9c nC19H39 COOH nC19H39 NSC- 9d COOH nC16H33 nC19H39 NSC- -
-
TABLE 12 Complex type No A1 A2 A3 X 10a COOH COOH nC19H39 NSC- 10b COOH COOH nCH(C12H25)2 NSC- 10c nC19H39 COOH nC19H39 NSC- 10d COOH nC16H33 nC19H39 NSC- -
-
TABLE 13 Complex type No A1 A2 A3 X 11a COOH COOH nC19H39 NSC- 11b COOH COOH nCH(C12H25)2 NSC- 11c nC19H39 COOH nC19H39 NSC- 11d COOH nC16H33 nC19H39 NSC- - An embodiment of the present invention will be described with reference to
FIG. 1 . A dye-sensitized solar cell shown inFIG. 1 has such a structure containing anelectroconductive support 8, a porous photovoltaic layer 3 having a photosensitizing dye adsorbed thereon and/or therein formed on theelectroconductive support 8, a counter electrode side 9, ahole transporting layer 4 filled between the porous photovoltaic layer 3 and the counter electrode side 9, and asealant 7 sealing the side surfaces. Theelectroconductive support 8 is constituted with asubstrate 1 and atransparent electroconductive film 2. The material used in thesubstrate 1 is not particularly limited and can be various kinds of transparent materials, and glass is preferably used. The material used in thetransparent electroconductive film 2 is also not particularly limited, and it is preferred to use a transparent electroconductive metallic oxide electrode such as fluorine-doped tin oxide (SnO2:F), antimony doped tin oxide (SnO2:Sb), indium-doped tin oxide (In2O3:Sn), aluminium-doped zinc oxide (ZnO:Al) and gallium-doped zinc oxide (ZnO:Ga). Examples of the method for forming thetransparent electroconductive film 2 on thesubstrate 1 include a vacuum vapor deposition method, a sputtering method, a CVD (chemical vapor deposition) method and a PVD (physical vapor deposition) method using a component of the material, and a coating method by a sol-gel method. - The material of the porous semiconductor layer used in the porous photovoltaic layer 3 is not particularly limited as far as it is an n-type semiconductor. It is preferred to use an oxide semiconductor such as titanium oxide (TiO2), zinc oxide (ZnO), tin oxide (SnO2), indium oxide (In2O3) and niobium oxide (Nb2O3). It is preferred that the oxide semiconductor have a large surface area for reasons of obtaining high performance of a solar cell. Thus, the oxide semiconductor preferably has a particle diameter of 1 to 200 nm, more preferably 50 nm or less. The oxide semiconductor preferably has a specific surface area of 5 to 100 m2/g. The oxide semiconductor is immobilized on the conductive surface to form a generally porous film having a thickness of at least 200 nm, preferably 1000 to 20000 nm.
- A dye sensitized semiconductor electrode according to the present invention may be obtained by fixing the above described metal complex of the present invention to a film or layer of oxide semiconductor particles formed on an electrically conductive surface of a substrate in any suitable conventional manner.
- Fixation of the oxide semiconductor on the conductive surface may be effected by dipping or coating in or with a suspension or slurry containing the oxide semiconductor, followed by drying and calcination. A water medium, which may contain a surfactant, a thickening agent such as polyethylene glycol and any suitable additive, is generally used for forming the suspension or slurry. The calcination is generally carried out at 300 to 900° C., preferably 400 to 600° C.
- The metal complex is fixed to the semiconductor layer. The metal complex is dissolved in a suitable solvent such as methanol, ethanol, acetonitrile, n-butanol, tert-butanol or dimethylformamide. The above described semiconductor electrode is then impregnated with this solution by immersion, coating or any other suitable method. It is preferred that the solution penetrates deep into the porous layer of the oxide semiconductor. Thus, the semiconductor electrode is preferably evacuated at an elevated temperature to remove gases trapped therein. The metal complex preferably forms a monolayer on surfaces of the oxide semiconductor.
- The support on a counter electrode side 9 is constituted by a
substrate 5 and a counter electrode layer 6. The material used for thesubstrate 5 is not particularly limited as similar to thesubstrate 1, and it can be various kinds of transparent materials, with glass being preferably used. The material used for the counter electrode layer 6 is also not particularly limited, and one of a platinum thin film, a carbon thin film, fluorine-doped tin oxide (SnO2:F), antimony doped tin oxide (SnO2:Sb), tin-doped indium oxide (In2O3:Sn), aluminium-doped zinc oxide (ZnO:Al) and gallium-doped zinc oxide (ZnO:Ga), an accumulated layer of plurality thereof, and a composite film of plurality thereof are preferably used. The role of the counter electrode layer 6 is to facilitate the transfer of electrons from the counter electrode to the electrolyte. Examples of the method for forming the counter electrode film 6 on thesubstrate 5 include a vacuum vapor deposition method, a sputtering method, a CVD (chemical vapor deposition) method and a PVD (physical vapor deposition) method using a component of the material, and a coating method by a sol-gel method. A further possible modification of the counterelectrode is to make it reflective to light that has passed through the electrolyte and the first plate. Further the outside of the substrates may be coated with plastics like PS, PMMA, or preferably PC to protect the TiO2 layer, the dyestuff and the electrolyte against UV-light to give long term stability. - In the present invention, as the
hole transporting layer 4 filled between the porous semiconductor layer 3 having the photosensitizing dye adsorbed thereon formed on theelectroconductive support 8 and the support on a counter electrode side 9, materials that can transport an electron, a hole or an ion can be used. For example, a hole transporting material such as polyvinyl carbazole, an electron transporting material such as tetranitrofluorenone, an electroconductive polymer such as polypyrrol, a liquid electrolyte, and an ionic electroconductive material such as a polymer solid electrolyte, can be used. - Illustrative of the redox pairs for a liquid electrolyte are I—/I3—, Br—/Br3— and quinone/hydroquinone pairs. In the case of I—/I3—, for example, lithium iodide and iodine may be used. As a solvent for the electrolyte, there may be used an electrochemically inert solvent capable of dissolving the electrolyte in a large amount, such as acetonitrile or propylene carbonate.
- The following examples of the present invention will further illustrate.
- This compound was prepared by an analogous procedure to that described in J. Am. Chem. Soc. 123 (2001) 1613.
-
- Into a 300-mL flask equipped with a mechanical stirrer, N2 inlet, pressure-equalizing addition funnel which is thermostated in oil bath, were added 14.8 g of sodium amide (0.38 mol) and 64.0 mL of 4-methylpyridine (61.1 g, 0.656 mol). The mixture was stirred under N2 for 1 h while a color change to deep red was observed. A 110-mL sample of n-octadecyl chloride (95.0 g; 0.33 mol) was added to the rapidly stirred reaction mixture over a period of 1.5 h. Shortly after addition was begun, the reaction mixture was warmed to 60° C. to prevent solidification and was subsequently stirred overnight at 100° C. The reaction mixture was cooled to room temperature, diluted with 200 mL of chloroform, washed three times with 200 mL of H2O, and reduced to dryness with the rotary evaporator. The resultant dark brown product was vacuum distilled three times at 0.07 mmHg to finally afford 48.8 g of constant-boiling (180° C. (0.07 mmHg)), white, waxy solid (0.141 mol, 43% yield based on n-octadecyl chloride). Anal. Calcd for C24H43N: C, 83.41; H, 12.54; N, 4.05. Found: C, 83.6; H, 12.7; N, 4.0. MS (ESIMS): m/z: 345.3.
- A mixture of 0.5 molar portion of 4-nonadecylpyridine, 0.59 mole of sodium amide and 1.18 moles of N,N-dimethylaniline was heated at 150° C. for six hours. The reaction mixture, after cooling, was poured into water, and the dimethylaniline layer was separated and dried over anhydrous potassium carbonate. After removal of the solvent in vacuo the residue was stirred in petroleum ether and crystallized from ethyl acetate/ligroin. Yield 45%. Anal. Calcd for C24H44N2: C, 79.93; H, 12.30; N, 7.77. Found: C, 79.63; H, 12.40; N, 7.60. MS (ESIMS): m/z: 360.4.
- Powdered 2-amino-4-nonadecylpyridine (110.6 g, 0.31 mol) was added under vigorous stirring in portions to 48% hydrobromic acid (500 mL) at 20 to 30° C. in a 4-L glass reactor. After all of the compound was dissolved, the mixture was cooled at −20° C. To this suspension was added cooled bromine (44.3 mL, 0.86 mol) dropwise over 30 min, maintaining the temperature at −20° C. The resulting paste was stirred for 90 min at this temperature. Then sodium nitrite (56.6 g, 0.82 mol) in water (250 mL) was added dropwise. After that the reaction mixture was allowed to warm to 15° C. over 1 h and was stirred for an additional 45 min. The mixture was cooled to −20° C. and treated with cooled aqueous NaOH (222 g, 330 mL H2O). During the addition the temperature was kept at −10° C. maximum. The mixture was allowed to warm to room temperature and stirred for 1 h. The mixture was extracted with ethyl acetate, the organic phase was dried with Na2SO4, and the solvent was removed in vacuo. The residue was subjected to distillation in vacuo to yield the desired. Yield 50%. Anal. Calcd for C24H42BrN: C, 67.90; H, 9.97; N, 3.30. Found: C, 67.50; H, 9.87; N, 3.40. MS (ESIMS): m/z: 423.3.
- To 2-bromo-4-nonadecylpyridine (70.0 g, 165 mmol) in absolute THF (400 mL) at −78° C. was added dropwise n-butyllithium (110 mL, 178 mmol, 1.6 M in hexane). After the solution was stirred at −78° C. for 90 min, tributyltinchloride (53.6 mL, 198 mmol) was added, and the mixture was allowed to warm to room temperature. Water (90 mL) was poured into the reaction mixture, and the phases were separated. The aqueous layer was extracted with diethyl ether (4×200 mL). The combined organic phases were dried over Na2SO4, and the solvent was removed in vacuo. The resulting oil was purified by fractionated Kugelrohr distillation. Selected analytical data follows. Yield: 55%. Anal. C36H69NSn: Calcd: C, 68.13; H, 10.96; N, 2.21; Found: C, 68.65; H, 10.76; N, 2.27;. MS (ESIMS): m/z: 635.4.
- To 2-bromo-picoline (28.4 g, 165 mmol) in absolute THF (250 mL) at −78° C. was added dropwise n-butyllithium (110 mL, 178 mmol, 1.6 M in hexane). After the solution was stirred at −78° C. for 90 min, tributyltinchloride (53.6 mL, 198 mmol) was added, and the mixture was allowed to warm to room temperature. Water (90 mL) was poured into the reaction mixture, and the phases were separated. The aqueous layer was extracted with diethyl ether (4×200 mL). The combined organic phases were dried over Na2SO4, and the solvent was removed in vacuo. The resulting oil was purified by fractionated Kugelrohr distillation. Colorless liquid, by 120° C. (2.5×10−5 mbar), Yield 60%; Anal. C18H33NSn: Calcd: C, 56.56; H, 8.64; N, 3.67; Found: C, 56.22; H, 8.70; N, 3.21. MS (ESIMS): m/z: 383.2.
- A mixture of 2,6-dihydroxy-3-cyano-4-methylpyridine (4.32 g, 28.8 mmol), concentrated H2SO4(12 mL) and water (10 mL) was heated under reflux for 5 h. The mixture was cooled with ice and neutralized with solid NaHCO3. The precipitate was filtered, washed with water and Et2O and dried in vacuo to give a mixture of 2,6-dihydroxy-4-methylpyridine and of the free acid, which was not decarboxylated. The mixture was used without further purification for the next reaction step. Yield: 72%. Anal. C6H7NO2: Calcd: C, 57.59; H, 5.64; N, 11.19; O, 25.57; Found: C, 57.74; H, 5.55; N, 11.19; O, 25.66. MS (ESIMS): m/z: 125.0.
- Compound 6 (1.0 g, 7.93 mmol) and POBr3 (7.26 g, 25.33 mmol) were ground and melted together at 140-150 C for 1 h. After cooling, the mixture was quenched with water, neutralized with solid NaHCO3 and extracted with CHCl3 (3×100 mL). The combined organic phases were washed with water and purified by column chromatography on silica with hexane/EOAc (9/1, v/v) to give 2,6-dibromo-4-methylpyridine as a colorless oil. Yield: 58%. Anal. C6H5Br2N: Calcd: C, 28.72; H, 2.01; N, 5.58; Found: C, 28.58; H, 2.07; N, 5.46. MS (ESIMS): m/z: 250.9.
-
Dibromocompound 2,6-dibromo-4-methylpyridine (1 mmol), 2-tributylstannyl-picolines (1 mol) and (Ph3Ph)4Pd (0.01 equiv) were heated under N2 in toluene (50 mL) for 16 h. Upon cooling to room temperature aqueous saturated NH4Cl solution (20 mL) was added. The mixture was stirred for further 30 min and then filtered over Celite. The precipitate was washed with CH2Cl2 (50 mL) and the organic phase was separated. The aqueous phase was extracted with toluene. The combined organic phases were dried (MgSO4) and the solvent was removed. Concentrated HCl (30 mL) was added to the residue followed by extracting with CH2Cl2. The aqueous phase was cautiously neutralized by solid NaOH. The product was then extracted with CH2Cl2 and dried. The solvent was removed and the product purified by chromatography on silica gel with CH2Cl2/hexane (1:2) as eluent. Yield: 25%. Anal. C12H11BrN2: Calcd: C, 54.77; H, 4.21; N, 10.65; Found: C, 54.54; H, 4.30; N, 10.45. MS (ESIMS): m/z: 262.0. - To a stirring solution of sulfuric acid (98%, 125 mL), 5.37 g (20.5 mmoles) of 6-bromo-4,4′-dimethyl-2,2′-bipyridine was added. With efficient stirring, 24 g (81.5 mmoles) of potassium dichromate was then added in small portions, such that the temperature remained between 70 and 80° C. Occasional cooling in a water bath was usually necessary during the addition of potassium dichromate. After all the potassium dichromate was added, the reaction stirred at room temperature until the temperature fell below 40° C. The deep green reaction mixture was poured into 800 mL of ice water and filtered. The solid was washed with water until the filtrate was colorless and allowed to dry. The resulting light yellow solid was then further purified by refluxing it in 170 mL of 50% nitric acid for 4 hours. This solution was poured over ice, diluted with 1 L of water and cooled to 5° C. The precipitate was filtered, washed with water (5×50 mL), then acetone (2×20 mL) and allowed to dry giving 6.2 g (94%) of 6-bromo-4,4′-dicarboxy-2,2′-bipyridine as a fine white solid. Anal. C12H7BrN2O4: Calcd: C, 44.61; H, 2.18; N, 8.67; Found: C, 44.23; H, 2.14; N, 8.56. MS (ESIMS): m/z: 322.0.
- To a suspension of 6-bromo-4,4′-dicarboxy-2,2′bipyridine (6.6 g, 20.5 mmol) in 400 mL of absolute ethanol was added 5 mL of concentrated sulfuric acid. The mixture was refluxed for 80 h to obtain a clear solution and then cooled to room temperature. Water (400 mL) was added and the excess ethanol removed under vacuum. The pH was adjusted to neutral with NaOH solution, and the resulting precipitate was filtered and washed with water (pH=7). The solid was dried to obtain 7.0 g (90%) of 6-bromo-4,4′-diethoxycarbonyl-2,2′-bipyridine. Anal. C16H15BrN2O4: Calcd: C, 50.68; H, 3.99; N, 7.39; Found: C, 50.45; H, 3.92; N, 7.33. MS (ESIMS): m/z: 378.0.
- 6-Bromo-4,4′-diethoxycarbonyl-2,2′-bipyridine (10) (1 mmol), 2-tributyl(4-nonadecylpyridine-2-yl)stannane (4) (1 mmol) and (Ph3P)4Pd (0.01 equiv) were heated under N2 in toluene (50 mL) for 16 h. Upon cooling to room temperature aqueous saturated NH4Cl solution (20 mL) was added. The mixture was stirred for further 30 min and then filtered over celite. The precipitate was washed with CH2Cl2 (50 mL) and the organic phase was separated. The aqueous phase was extracted with toluene. The combined organic phase were dried (MgSO4) and the solvent was removed. Concentrated HCl (30 mL) was added to the residue and extracted with CH2Cl2. The aqueous phase was cautiously neutralized by solid NaOH. The product was then extracted with CH2Cl2 and dried. The solvent was removed and the product purified by chromatography on silica gel with CH2Cl2/hexane (1:2) as eluent. Yield: 25%. Anal. C40H57N3O4: Calcd: C, 74.61; H, 8.92; N, 6.53; Found: C, 74.22; H, 8.72; N, 6.49. MS (ESIMS): m/z: 643.4.
-
- A solution of butyllithium (1.6 M in hexane; 2.05 equiv.) was added to a solution of diisopropylamine (0.2 M; 2.1 equiv.) in dry ether at −15° C. After stirring for 30 min, freshly distilled 4-methylpyridine (1 eqiv.) was added dropwise. The resulting red solution was stirred for 15 min at −15° C. and then a solution of alkyl halide (1 M; 2.05 equiv.) in dry ether was added in one portion. The mixture was stirred overnight at room temperature. Ether was added and the reaction mixture was washed twice with 1 M NH4Cl solution, dried with Na2SO4 and evaporated to dryness. The product was purified by chromatography on Al2O3 (neutral), gradient-eluting with hexane and finally hexane/ether (5:1) to give the product in yield 70%. Anal. C30H55N: Calcd: C, 83.84; H, 12.90; N, 3.26; Found: C, 83.55; H, 12.84; N, 3.21. MS (ESIMS): m/z: 429.4.
- This compound was prepared by an analogous procedure to that described in Example 2 (step b). Anal. C30H56N2: Calcd: C, 81.01; H, 12.69; N, 6.30; Found: C, 81.11; H, 12.77; N, 6.25. MS (ESIMS): m/z: 444.8.
- This compound was prepared by an analogous procedure to that described in Example 2 (step c). Anal. C30H54BrN: Calcd: C, 70.84; H, 10.70; N, 2.75; Found: C, 70.45; H, 10.67; N, 2.69. MS (ESIMS): m/z: 507.3.
- This compound was prepared by an analogous procedure to that described in Example 2 (step d). Anal. C42H81NSn: Calcd: C, 70.18; H, 11.36; N, 1.95; Found: C, 70.0; H, 11.31; N, 1.97. MS (ESIMS): m/z: 719.5.
- This compound was prepared by an analogous procedure to that described in Example 2 (step e-j). Anal. C16H15BrN2O4: Calcd: C, 50.68; H, 3.99; N, 7.39; Found: C, 50.35; H, 3.78; N, 7.34. MS (ESIMS): m/z: 379.02
- This compound was prepared by an analogous procedure to that described in Example 2 (step k). Anal. C46H69N3O4: Calcd: C, 75.89; H, 9.55; N, 5.77; O, 8.79; Found: C, 75.89; H, 9.55; N, 5.77; O, 8.79. MS (ESIMS): m/z: 728.0.
-
- This compound was prepared by an analogous procedure to that described in Example 2.
- 8.2 g of sodium borohydride was added to a suspension of 4,4′-diethoxycarbonyl-4″-nonadecyl-2,2′:6′,2″-terpyridine (6.4 g, 10.0 mmol) in 200 mL of absolute ethanol. The mixture was refluxed for 3 h and cooled to room temperature, and then 200 mL of an ammonium chloride saturated water solution was added to decompose the excess borohydride. The ethanol was removed under vacuum and the precipitated solid was dissolved in a minimal amount of water. The resulting solution was extracted with ethyl acetate (5×200 mL) and dried over sodium sulfate, and the solvent was removed under vacuum. The desired solid was obtained in 79% yield and was used without further purification. Anal. C36H53N3O2: Calcd: C, 77.24; H, 9.54; N, 7.51; Found: C, 77.10; H, 9.47; N, 7.49. MS (ESIMS): m/z: 559.4.
- 4,4′-Bis(hydroxymethyl)-4″-nonadecyl-2,2′:6′,2″-terpyridine (2.35 g, 4.2 mmol) was dissolved in a mixture of 48% HBr (20 mL) and concentrated sulfuric acid (6.7 mL). The resulting solution was refluxed for 6 h and then allowed to cool to room temperature, and 40 mL of water was added. The pH was adjusted to neutral with NaOH solution and the resulting precipitate was filtered, washed with water (pH)) 7), and air-dried. The product was dissolved in chloroform (40 mL) and filtered. The solution was dried over magnesium sulfate and evaporated to dryness, yielding 2.45 g of 4,4′-bis(bromomethyl)-4″-nonadecyl-2,2′:6′,2″-terpyridine (85% yield) as a white powder. Anal. C36H51Br2N3: calcd C, 63.07; H, 7.50; N, 6.13; found C, 62.88; H, 7.45; N, 6.19. MS (ESIMS): m/z: 685.2.
- A chloroform (10 mL) solution of 4,4′-Bis(bromomethyl)-4″-nonadecyl-2,2′:6′,2″-terpyridine (3.02 g, 4.4 mmol) and 15 mL of triethyl phosphite was refluxed for 3 h under nitrogen. The excess phosphite was removed under high vacuum, and then the crude product was purified by column chromatography on silica gel (eluent ethyl acetate/methanol 80/20) yielding 2.82 g (80%) of 4,4′-bis(diethylmethylphosphonate)-4″-nonadecyl-2,2′:6′,2″-terpyridine. Anal. C44H71N3O6P2: calcd C, 66.06; H, 8.95; N, 5.25; found C, 65.67; H, 8.88; N, 5.45;. MS (ESIMS): m/z: 799.5.
-
- This compound was prepared by an analogous procedure to that described in Example 2 (step g). Anal. C6H3Br2NO2: Calcd: C, 25.65; H, 1.08; Br, 56.89; N, 4.99; O, 11.39. Found: C, 25.52; H, 1.14; Br, 56.77; N, 5.04; O, 11.25. (ESIMS): m/z: 280.9.
- This compound was prepared by an analogous procedure to that described in Example 2 (step j). Anal. C8H7Br2NO2: Calcd: C, 31.10; H, 2.28; Br, 51.73; N, 4.53; O, 10.36. Found: C, 31.22.H, 2.15Br, 51.81; N, 4.45 O, 10.31. (ESIMS): m/z: 308.9.
- This compound was prepared by an analogous procedure to that described in Example 2 (step d).
- 2,6-Dibromo-4-ethoxycarbonyl-pyridine(2) (1 mol), 2-tributyl(4-nonadecylpyridine-2-yl)stannane (2 mol) and (Ph3P)4Pd (0.01 equiv) were heated under N2 in toluene (50 mL) for 16 h. Upon cooling to room temperature aqueous saturated NH4Cl solution (20 mL) was added. The mixture was stirred for further 30 min and then filtered over Celite. The precipitate was washed with CH2Cl2 (50 mL) and the organic phase was separated. The aqueous phases was extracted with toluene. The combined organic phases were dried (MgSO4) and the solvent was removed. Concentrated HCl (30 mL) was added to the residue, followed by extracting with CH2Cl2. The aqueous phase was cautiously neutralized by solid NaOH. The product was then extracted with CH2Cl2 and dried. The solvent was removed and the product was purified by chromatography on silica gel with CH2Cl2/hexane (1:2) as eluent. Yield: (25%). Anal. C56H91N3O2: Calcd: C, 80.23; H, 10.94; N, 5.01; O, 3.82. Found: C, 80.05, 10.99 N, 5.23; O, 3.71, MS (ESIMS): m/z: 837.7.
-
- To a solution of sodium hydride (1.2 g, 50 mmol) in THF, distilled ethyl acetoacetate (4.16 g, 32 mmol) was added dropwise. The resulting mixture was stirred for 30 min at room temperature and then cooled at −78° C. A solution of n-butyllithium in hexane (16.1 mL, 35.2 mmol) was added dropwise. After stirring for an additional 1 h at 0° C., 1-bromohexadecane (19.1 mmol) in THF was added and the mixture was stirred for 12 h. Ethanol (15 mL) was added slowly at room temperature. The resulting solution was filtered through a Celite pad, concentrated in vacuum and purified by chromatography on silica gel to give the 3-oxo-nonadecanoic acid ethyl ester as a solid. Anal. C21H40O3: Calcd: C, 74.07; H, 11.84; O, 14.09. Found: C, 73.98; H, 11.59; O, 14.25. MS (ESIMS): m/z: 340.3.
- 3-Oxo-nonadecanoic acid ethyl ester (11.3 mmol), cyanoacetamide (0.95 g, 11.3 mmol) and piperidine (0.95 g, 11.3 mmol) in MeOH (3 mL) were heated under reflux for 24 h. The solvent was evaporated, and the residue was dissolved in hot water. The product was precipitated by addition of concentrated HCl, filtered, washed with ice water and CHCl3 and dried in vacuum to give 3-cyano-2,6-dihydroxy-4-hexadecyl-pyridine as a white powder. Yield: 40%. Anal. C22H36N2O2: Calcd: C, 73.29; H, 10.06; N, 7.77; O, 8.88. Found: C, 73.35; H, 10.12; N, 7.85; O, 8.97. MS (ESIMS): m/z: 360.3.
- This compound was prepared by an analogous procedure to that described in Example 2 (step f). Anal. C21H37NO2: Calcd: C, 75.17; H, 11.12; N, 4.17; O, 9.54. Found: C, 75.03; H, 11.09; N, 4.25; O, 9.38. MS (ESIMS): m/z: 335.3.
- This compound was prepared by an analogous procedure to that described in Example 2 (step g). Anal. C21H35Br2N: Calcd: C, 54.67; H, 7.65; Br, 34.64; N, 3.04. Found: C, 54.84; H, 7.61; Br, 34.52; N, 3.11. MS (ESIMS): m/z: 461.1.
- This compound was prepared by an analogous procedure to that described in Example 2 (steps a-d).
- This compound was prepared by an analogous procedure to that described in Example 2 (step h). Anal. C45H77BrN2: Calcd: C, 74.45; H, 10.69; Br, 11.01; N, 3.86. Found: C, 74.59; H, 10.84; Br, 11.13; N, 3.82. MS (ESIMS): m/z: 724.5.
- This compound was prepared by an analogo us procedure to that described in Example 2 (step e). Anal. C57H104N2Sn: Calcd: C, 73.13; H, 11.20; N, 2.99; Sn, 12.68. Found: C, 73.22; H, 11.28; N, 3.01; Sn, 12.59. MS (ESIMS): m/z: 936.7.
- This compound was prepared by an analogous procedure to that described in Example 2 (step i). Anal. C6H4BrNO2: Calcd: C, 35.67; H, 2.00; Br, 39.56; N, 6.93; O, 15.84. Found: C, 35.75; H, 2.03; Br, 39.61; N, 6.90; O, 15.77. MS (ESIMS): m/z: 200.9.
- This compound was prepared by an analogous procedure to that described in Example 2 (step j). Anal. C8H8BrNO2: Calcd: C, 41.77; H, 3.50; Br, 34.73; N, 6.09; O, 13.91. Found: C, 41.87; H, 3.45; Br, 34.82; N, 6.03; O, 14.01. MS (ESIMS): m/z: 229.0.
- This compound was prepared by an analogous procedure to that described in Example 2 (step k). Anal. C53H85N3O2: Calcd: C, 79.94; H, 10.76; N, 5.28; O, 4.02. Found: C, 79.89; H, 10.70; N, 5.31; O, 3.98. MS (ESIMS): m/z: 795.7.
- To a solution of hexamethylenetriamine (10.4 mmol) in CHCl3 (50 mL) heated at reflux, a solution of 2,6-bis-(bromomethyl)-pyridine (4.97 mmol) in CHCl3 (50 mL) was added dropwise, and the mixture was refluxed for further 3 h. The mixture was allowed to cool to room temperature and to stand. The solid deposited was filtered off, dried, and suspended in H2O/EtOH/conc. HCl. The mixture was stirred at 70° C. until the solid had completely dissolved. The salt (2,6-bis-(aminomethyl)-pyridine). HCl which was crystallized from solution on standing overnight at room temperature was filtered off and dried. Yield 70%. Anal. C7H11N3: Calcd: C, 61.29; H, 8.08; N, 30.63. Found: C, 61.45; H, 8.00; N, 30.44. MS (ESIMS): m/z: 137.1.
- This compound was prepared from 2-methoxyisophthalic acid by an analogous procedure to that described in reference Chem. Bar 1889, 12, 816. Anal. C8H6O5: Calcd: C, 52.76; H, 3.32; O, 43.92. Found: C, 52.45; H, 3.30; O, 43.52. MS (ESIMS): m/z: 182.0.
- Ethyl alcohol (50 ml) and RuCl3 (0.26 g) were reacted under argon. After the mixture was stirred for 2 min, a solution of the
ligand - To a solution of the complex Ru(4,4′4″-trimethoxycarbonyl-2,2′:6′,2″-terpyridine)Cl3 (300 mg, 0.5 mmol) in DMF (100 mL) was added diethylenetriamine (2.0 mmol) and Et3N (0.5 mL). The reaction mixture was refluxed for 8 h. Then, 10 mL of Et3N was added, and the solution was refluxed for further 24 h to hydrolyze the ester groups on the terpyridine ligand. The reaction mixture was allowed to cool, and the solvent was removed on a rotary evaporator. The resulting solid was dissolved in 0.1 M aqueous NaOH and Ru(4,4′4″-tricarboxy-2,2′:6′,2″-terpyridine)(deta) was precipitated by the addition of 0.1 M HNO3. The resulting precipitate was filtered and dried. The isolated solid was recrystallized from methanol-diethyl ether, after which it was further purified on a Sephadex LH20 column, using methanol as eluent (yield 75%). Anal. C22H24Cl2N6O6Ru: Calcd: C, 41.26; H, 3.78; N, 13.12. Found: C, 41.04; H, 3.73; N, 13.03. MS (ESIMS): m/z: 640.02.
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 9 (step b). Anal. C25H18N4O8Ru: Calcd: C, 49.75; H, 3.01; N, 9.28. Found: C, 49.75; H, 3.01; N, 9.28. MS (ESIMS): m/z: 604.02.
- Powder Ru(4,4′4″-tricarboxy-2,2′:6′,2″-terpyridine)(pdm) was dissolved in 0.1 M aqueous tetrabutylammonium hydroxide (TBAOH) and the mixture heated to 110° C., for 4 h (the pH of the solution was about 11). The resulting purple solution was filtered to remove a small amount of insoluble material and the pH was adjusted to 5.0 with dilute hydrochloric acid. A dense precipitate formed immediately but the suspension was nevertheless refrigerated overnight prior to filtration to collect the product. After allowing to cool to (25° C.) room temperature, it was filtered through a sintered glass crucible and dried under vacuum. Anal. C57H88N6O8Ru: Calcd: C, 63.02; H, 8.16; N, 7.7. Found: C, 63.02; H, 8.16; N, 7.7. MS (ESIMS): m/z: 1086.57.
- This compound was prepared by an analogous procedure to that described in Example 9 (step a). Anal. C39H53Cl3N3O6Ru: Calcd: C, 54.01; H, 6.16; N, 4.85. Found: C, 53.80; H, 6.13; N, 4.77. MS (ESIMS): m/z: 866.20.
- This compound was prepared by an analogous procedure to that described in Example 9 (step b). Anal. C41H62N6O6Ru: Calcd: C, 58.90; H, 7.47; N, 10.05. Found: C, 58.90; H, 7.47; N, 10.05. MS (ESIMS): m/z: 836.38.
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 9 (step b). Anal. C44H56N4O8Ru: Calcd: C, 58.90; H, 7.47; N, 10.05. Found: C, 58.90; H, 7.47; N, 10.05. MS (ESIMS): m/z: 870.31.
- This compound was prepared by an analogous procedure to that described in Example 10 (step c). Anal. C60H91N5O8Ru: Calcd: C, 64.84; H, 8.25; N, 6.30. Found: C, 64.84; H, 8.25; N, 6.30. MS (ESIMS): m/z: 1111.59.
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 9 (step b). Anal. C25H22N6O6Ru: Calcd: C, 49.75; H, 3.67; N, 13.92. Found: C, 49.23; H, 3.61; N, 13.88. MS (ESIMS): m/z: 604.06.
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 9 (step b). Anal. C44H60N6O6Ru: Calcd: C, 60.74; H, 6.95; N, 9.66. Found: C, 60.74; H, 6.95; N, 9.66. MS (ESIMS): m/z: 870.36.
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 9 (step b). Anal. C26H14N3O11Ru: Calcd: C, 48.38; H, 2.19; N, 6.51; Found: C, 48.05; H, 2.11; N, 6.61. MS (ESIMS): m/z: 645.97.
- This compound was prepared by an analogous procedure to that described in Example 10 (step c). Anal. C75H124N6O11Ru: Calcd: C, 64.95; H, 9.01; N, 6.06. Found: C, 64.34; H, 9.12; N, 6.00. MS (ESIMS): m/z: 1386.84.
- This compound was prepared by an analogous procedure to that described in Example 9 (step a). Anal. C40H57Cl3N3O4Ru: Calcd: C, 56.43; H, 6.75; N, 4.94. Found: C, 56.12; H, 6.65; N, 4.87. MS (ESIMS): m/z: 850.25.
- The complex Ru(4,4′-diethoxycarbonyl-4″-nonadecyl-2,2′:6′,2″-terpyridine)(NCS)3 was synthesized in dark under an argon atmosphere by refluxing at 130° C., a solution of NH4NCS (2 g, in 10 mL of H2O) and Ru(4,4′-diethoxycarbonyl-4″-nonadecyl-2,2′:6′,2″-terpyridine)Cl3 complex (0.5 g, in 50 mL of DMF) for 4 h. Then, 20 mL of triethylamine and 10 mL of H2O were added, and the solution was refluxed for a further 24 h to hydrolyze the ester groups on the terpyridine ligand. The solvent volume was reduced on a rotary evaporator to about 10 mL, and than the solution was added to 70 mL of H2O. The resulting precipitate was filtered and dried. The isolated solid was recrystallized from methanol-diethyl ether, after which it was further purified on a Sephadex LH20 column, using methanol as eluent (yield 75%). Anal. C39H49N6O4RuS3: Calcd: C, 54.27; H, 5.72; N, 9.74. Found: C, 53.78; H, 5.52; N, 9.64. MS (ESIMS): m/z: 863.20.
- This compound was prepared by an analogous procedure to that described in Example 10 (step c). Anal. C71H120N8O4RuS3: Calcd: C, 63.31; H, 8.98; N, 8.32. Found: C, 63.31; H, 8.98; N, 8.32. MS (ESIMS): m/z: 1346.76.
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- To a solution of the complex Ru(4,4′-diethoxycarbonyl-4″-nonadecyl-2,2′:6′,2″-terpyridine)Cl3 (300 mg, 0.5 mmol) in methanol (100 mL) was added tfac (236 μL, 2.0 mmol) and Et3N (0.5 mL). The reaction mixture was refluxed for 8 h and the solvent was then allowed to evaporate on a rotary evaporator. The solid mass thus obtained was dissolved in 30 mL of DMF under nitrogen. To this solution was added 5 mL of an aqueous solution of NaSCN (300 mg, 3.7 mmol). After being refluxed for 8 h, 10 mL of Et3N was added, and the solution was refluxed for further 24 h to hydrolyze the ester groups on the terpyridine ligand. The reaction mixture was allowed to cool, and the solvent was removed on a rotary evaporator. The resulting solid was dissolved in 0.1 M aqueous NaOH and Ru(4,4′-dicarboxy-4″-nonadecyl-2,2′:6′,2″-terpyridine)(tfac)(NCS) was precipitated by the addition of 0.1 M HNO3. The resulting precipitate was filtered and dried. The isolated solid was recrystallized from methanol-diethyl ether, after which it was further purified on a Sephadex LH20 column, using methanol as eluent (yield 75%).
- This compound was prepared by an analogous procedure to that described in Example 10 (step c).
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 17 (step b).
- This compound was prepared by an analogous procedure to that described in Example 10 (step c).
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 17 (step b).
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 17 (step b).
- This compound was prepared by an analogous procedure to that described in Example 10 (step c).
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 17 (step b).
- This compound was prepared by an analogous procedure to that described in Example 10 (step c).
- This compound was prepared by an analogous procedure to that described in Example 9 (step a).
- This compound was prepared by an analogous procedure to that described in Example 17 (step b).
- Nanocrystalline TiO2 films of about 20 μm were prepared by spreading a viscous dispersion of colloidal TiO2 particles (Sloaronix) on a conducting glass support (Asahi TCO glass, fluorine-doped SnO2 overlayer, transmission >85% in the visible, sheet registance 7-8 ohms/square) with heating under air for 30 min at 500° C. The performance of the film as a sensitized photoanode was improved by further deposition of TiO2 from aqueous TiCl4 solution. A freshly prepared aqueous 0.2 M TiCl4 solution applied onto the electrode. After being left for 20 min at 70° C. in a closed chamber, the electrode was washed with distilled water. Immediately before being dipped into the dye solution, it was fired again for 30 min at 500° C. in air. After cooling under a continuous argon flow the glass sheet is immediately transferred to a 2×10−4 M solution in 1:1 acetonitrile:n-butanol of the tetrabutylammonium salt of ruthenium complex of 7b (example 18), this solution further containing 40 mM of deoxycholic acid as a co-adsorbent. The adsorption of photosensitizer from the dye solution is allowed to continue for 15 hours after that the glass sheet is withdrawn and washed briefly with absolute ethanol. The TiO2 layer on the sheet assumed a black color owing to the photosensitive coating.
- A solar cell (size: 0.25 cm2) was fabricated using the above electrode and a counter electrode, which was a platinum electrode, obtained by vacuum-deposition of platinum on a conductive glass. The platinum layer had a thickness of 20 nm. An electrolyte solution to be placed between the two electrodes was a redox pair of I—/I3— obtained using 0.5 M 4-tert-butylpyridine, 0.1 M LiI, 0.6
M 1,2-dimethyl-3-propyl imidazolium iodide and 0.1 M I2 as solutes and a liquid of acetonitrile. - A potentiostat was used for measuring short-circuit electric current, open circuit voltage and fill factor. Experiments are carried out with a high pressure Xenon lamp equipped with appropriate filters to simulate AM 1.5 solar radiation. The intensity of the light is 100 mW/cm2. The fill factor defined as the maximum electric power output of the cell divided by the product of open circuit voltage and short circuit current.
- It was found that the thus constructed solar cell using sensitizer 7b gave a short-circuit electric current of 20 mA/cm2, an open circuit voltage of 0.70 V and a fill factor FF of 0.73 under irradiation of AM 1.5 using solar simulator light (100 mW/cm2).
Claims (4)
1. A photosensitizing transition metal complex having the general formula (Ie):
MLY4X (Ie)
MLY4X (Ie)
in which M is a transition metal selected from Ru(II), Os(II), Fe(II), Re(I) and Tc(I);
L is a polypyridine ligand having the general formula (II),
wherein A1, A2 and A3 contain at least one anchoring group selected from —COOH, —COON(C4H9)4, —PO(OH)2, —PO(OR1)2 (where R1 is an alkyl group having 1 to 30 carbon atoms), —CO(NHOH), and at least one group selected from an alkyl group having 1 to 50 carbon atoms, an alkylamide group having 2 to 50 carbon atoms or an aralkyl group having 7 to 50 carbon atoms; and
X is a ligand selected from NCS—, Cl—, Br—, I—, CN—, NCO—, H20 or pyridine group which may be substituted by vinyl, primary, secondary or tertiary amino, alkylthio, arylthio, hydroxyl or C1-30 alkyl; and
Y4 is a group selected from the formulae (IVb-1 to 3), (IVc-1 to 4), (IVd-1 to 8) and (IVe-1 to 2):
where R10, R11, R12, R13, R14, R15, R16 and R17 are the same or different an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an perfluoroalkyl group having 2 to 12 carbon atoms, an alkylamide group having 2 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, trifluoro group, halogen atom or hydrogen atom.
2. A photosensitizing transition metal complex of claim 1 , which is a complex of the formula (Ie) where M is Ru(II) or Os(II), X is NCS— or CN—, and Y4 is a group of the formula (IVb-1), (IVb-2) or (IVb-3).
3. A photosensitizing transition metal complex of claim 1 , which is a complex of the formula (Ie) where M is Ru(II) or Os(II), L is a polypyrigine ligand of the formula (IIb)
4. A photovoltaic cell comprising a support, a conductive layer formed on the support, and a porous semiconductor layer formed on the conductive layer, a counter electrode, and an electrolyte deposited there between wherein the porous semiconductor layer carries a photosensitizing transition metal complex as claimed in claim 1 .
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Also Published As
Publication number | Publication date |
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US7812251B2 (en) | 2010-10-12 |
US20100326528A1 (en) | 2010-12-30 |
US20050081911A1 (en) | 2005-04-21 |
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