WO2014077357A1 - Complexe métallique, colorant pour complexe métallique, élément de conversion photoélectrique, cellule solaire à colorant, solution de colorant, électrode à adsorption de colorant, et procédé de fabrication d'une cellule solaire à colorant - Google Patents

Complexe métallique, colorant pour complexe métallique, élément de conversion photoélectrique, cellule solaire à colorant, solution de colorant, électrode à adsorption de colorant, et procédé de fabrication d'une cellule solaire à colorant Download PDF

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WO2014077357A1
WO2014077357A1 PCT/JP2013/080884 JP2013080884W WO2014077357A1 WO 2014077357 A1 WO2014077357 A1 WO 2014077357A1 JP 2013080884 W JP2013080884 W JP 2013080884W WO 2014077357 A1 WO2014077357 A1 WO 2014077357A1
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ring
group
dye
atom
integer
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Japanese (ja)
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渡辺　康介
征夫 谷
晃逸 佐々木
小林　克
寛敬 佐藤
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/55—Acids; Esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/57—Nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/107—The polymethine chain containing an even number of >CH- groups four >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/007—Squaraine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/008—Triarylamine dyes containing no other chromophores
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
    • 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
    • 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
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a metal complex, a metal complex dye, a photoelectric conversion element, a dye-sensitized solar cell, a dye solution, a dye-adsorbing electrode, and a method for producing a dye-sensitized solar cell.
  • Photoelectric conversion elements are used in various optical sensors, copiers, solar cells and the like.
  • Various types of photoelectric conversion elements have been put to practical use, such as those using metals, semiconductors, organic pigments and dyes, or combinations thereof.
  • a solar cell using non-depleting solar energy does not require fuel, and its full-scale practical use is expected as an inexhaustible clean energy.
  • silicon-based solar cells have been researched and developed for a long time, and are spreading due to the policy considerations of each country.
  • silicon is an inorganic material, there is a limit to improving throughput and cost.
  • N3, N719, Z907, J2 and the like have been developed as metal complex dyes used for photoelectric conversion elements.
  • conventional dye-sensitized solar cells generally have low photoelectric conversion efficiency and often have poor durability.
  • the dye proposed in Patent Document 1 exhibits absorption in the long wavelength region of the sunlight spectrum, and when employed in a photoelectric conversion element, the photoelectric conversion efficiency ( ⁇ ) can be improved over conventional dyes. Presumed to be possible.
  • the required performance level for dye-sensitized solar cells is increasing year by year, and further improvement is demanded particularly in terms of improvement of photoelectric conversion efficiency ( ⁇ ).
  • the object of the present invention is to provide a metal complex dye exhibiting excellent performance in photoelectric conversion efficiency ( ⁇ ), a metal complex that is a synthetic intermediate of this metal complex dye, and an excellent performance by using this metal complex dye.
  • the object is to provide a photoelectric conversion element, a dye adsorption electrode, a dye-sensitized solar cell, a method for producing the same, and a dye solution containing a metal complex dye.
  • a photoelectric conversion element having semiconductor fine particles carrying a dye was achieved by the following means.
  • Ring A, ring B and ring C each independently represent a nitrogen-containing aromatic heterocycle.
  • Z 1 and Z 2 each independently represent a carbon atom or a nitrogen atom.
  • the bond between Z 1 and the N atom and the bond between Z 2 and the N atom may be a single bond or a double bond.
  • R 1 to R 3 each independently represent a substituent having no Anc1 to Anc3.
  • n1 and n3 each independently represents an integer of 0 to 4, and n2 represents an integer of 0 to 3.
  • X 1 represents a linking group.
  • X 2 represents —O—, —S—, —NR ′ (R ′ represents a hydrogen atom or a substituent) —, a saturated aliphatic group, or an unsaturated aliphatic group having an unsaturated group that is not ⁇ -conjugated with the ring B.
  • R ′ represents a hydrogen atom or a substituent
  • X 3 represents a single bond or a linking group.
  • Anc1 to Anc3 each independently represents an acidic group.
  • l1 and l3 each independently represents an integer of 1 to 4, and l2 represents an integer of 1 to 5, respectively.
  • L 1 to L 3 each represents a ligand and is a bidentate ligand in which L 1 and L 2 are bonded to each other, or a tridentate ligand in which L 1 , L 2 and L 3 are bonded to each other is there.
  • one or two of L 1 to L 3 represent a ligand having an anionic coordination atom.
  • Y represents a counter ion necessary for neutralizing the charge, and n represents an integer of 0 to 2.
  • ring A and ring C are each independently a pyridine ring, pyrimidine ring, triazine ring, imidazole ring, oxazole ring, thiazole ring, oxadiazole ring, thiadiazole ring, isoxazole ring,
  • ring B is a pyridine ring or a pyrimidine ring.
  • Anc1 to Anc3 are each independently —COOH, —SO 3 H, —PO 3 H 2 , —OH or —SH.
  • the photoelectric conversion element as described.
  • At least one of X 1 and X 3 is each independently represented by any one of the following formulas (3) to (10) or a combination thereof: ).
  • R 31 to R 102 represent a hydrogen atom or a substituent, and a plurality of substituents may be bonded directly or via a linking group to form a ring.
  • Ring D represents an aromatic ring.
  • a 111 to A 141 each represents an anionic nitrogen atom or carbon atom, and A 151 represents any one of an anionic nitrogen atom, oxygen atom or sulfur atom.
  • R 111 to R 154 each represent a hydrogen atom or a substituent having no Anc1, Anc2 and Anc3.
  • a tridentate ligand in which L 1 , L 2 and L 3 are bonded to each other is represented by any of the following formulas (3L-1) to (3L-5)
  • Ring D represents an aromatic ring.
  • a 211 to A 242 represent a nitrogen atom or a carbon atom, and A 251 and A 252 represent any of a nitrogen atom, an oxygen atom, or a sulfur atom. However, at least one of A 211 and A 212 , A 221 and A 222 , A 231 and A 232 , A 241 and A 242 , and A 251 and A 252 is anionic.
  • R 211 to R 253 each represent a hydrogen atom or a substituent having no Anc1, Anc2 and Anc3.
  • a dye-sensitized solar cell comprising the photoelectric conversion device according to any one of (1) to (9).
  • a dye-adsorbing electrode for a dye-sensitized solar cell in which the dye solution described in (12) or (13) is applied to a conductive support provided with a semiconductor, and then cured by reaction to form a photoreceptor layer.
  • Ring A, ring B and ring C each independently represent a nitrogen-containing aromatic heterocycle.
  • Z 1 and Z 2 each independently represent a carbon atom or a nitrogen atom.
  • the bond between Z 1 and the N atom and the bond between Z 2 and the N atom may be a single bond or a double bond.
  • R 1 to R 3 each independently represents a substituent.
  • n1 and n3 each independently represents an integer of 0 to 4, and n2 represents an integer of 0 to 3.
  • X 10 and X 30 each independently represent a single bond or a linking group.
  • X 20 is a single bond or —O—, —S—, —NR ′ (R ′ represents a hydrogen atom or a substituent) —, a saturated aliphatic group, or an unsaturated group that does not have a ⁇ -conjugated unsaturated group with the ring B.
  • R ′ represents a hydrogen atom or a substituent
  • a saturated aliphatic group, a non-aromatic hydrocarbon ring group, a non-aromatic heterocyclic group, or a combination thereof is represented.
  • G represents an aldehyde group or an acetal group which is represented by any one of the following structures and may have a substituent.
  • p1 represents an integer of 1 to 4
  • p2 represents an integer of 0 to 3
  • p3 represents an integer of 0 to 4, respectively.
  • L 1 to L 3 each represents a ligand, both of which are monodentate ligands, bidentate ligands in which L 1 and L 2 are bonded to each other, or L 1 , L 2 and L 3 are bonded to each other Tridentate ligand.
  • one or two of L 1 to L 3 represent a ligand having an anionic coordination atom.
  • Y represents a counter ion necessary for neutralizing the charge, and n represents an integer of 0 to 2.
  • each R G independently represents an alkyl group. * Represents a bonding position with X 10 , X 20 or X 30. )
  • the carbon-carbon double bond may be any of E-type and Z-type in the molecule, or a mixture thereof.
  • substituents, etc. linking groups, ligands, etc.
  • substituents etc.
  • a special notice is given.
  • each substituent etc. may mutually be same or different. The same applies to the definition of the number of substituents and the like.
  • substituents and the like when a plurality of substituents and the like are close to each other (especially when they are adjacent to each other), they may be connected to each other to form a ring unless otherwise specified.
  • a ring such as an alicyclic ring, an aromatic ring, or a heterocyclic ring may be further condensed to form a condensed ring.
  • a metal complex dye exhibiting excellent performance capable of improving photoelectric conversion efficiency ( ⁇ ), a metal complex which is a synthetic intermediate of this metal complex dye, and an excellent use of this metal complex dye
  • a photoelectric conversion element and a dye adsorption electrode, a dye-sensitized solar cell and a method for producing the same, and a dye solution containing a metal complex dye can be provided.
  • FIG. 1 is a cross-sectional view schematically showing an embodiment of the photoelectric conversion element of the present invention, including an enlarged view of a circular portion in a layer.
  • FIG. 2 is a cross-sectional view schematically showing the dye-sensitized solar cell produced in Example 2.
  • FIG. 3 is a chart of 1 H-NMR spectrum of Compound (6), which is a synthetic intermediate of metal complex dye Dye-1 synthesized in Example 1.
  • FIG. 4 is a chart of 1 H-NMR spectrum of compound (7), which is a synthetic intermediate of metal complex dye Dye-1 synthesized in Example 1.
  • FIG. 5 is a chart of the 1 H-NMR spectrum of the metal complex dye Dye-1 synthesized in Example 1.
  • FIG. 1 is a cross-sectional view schematically showing an embodiment of the photoelectric conversion element of the present invention, including an enlarged view of a circular portion in a layer.
  • FIG. 2 is a cross-sectional view schematically showing the dye-sensitized solar cell
  • FIG. 6 is a chart of the 1 H-NMR spectrum of compound (11), which is a synthetic intermediate of metal complex dye Dye-2 synthesized in Example 1.
  • FIG. 7 is a chart of 1 H-NMR spectrum of Compound (12), which is a synthetic intermediate of metal complex dye Dye-2 synthesized in Example 1.
  • FIG. 8 is a chart of 1 H-NMR spectrum of the metal complex dye Dye-2 synthesized in Example 1.
  • FIG. 9 is a chart of 1 H-NMR spectrum of the metal complex dye Dye-4 synthesized in Example 1.
  • FIG. 10 is a chart of an ultraviolet-visible spectrum of the metal complex dye Dye-1 synthesized in Example 1.
  • FIG. 11 is an ultraviolet-visible spectrum chart of the metal complex dye Dye-2 synthesized in Example 1.
  • FIG. 10 is a chart of an ultraviolet-visible spectrum of the metal complex dye Dye-1 synthesized in Example 1.
  • FIG. 11 is an ultraviolet-visible spectrum chart of the metal complex dye Dye-2 synthesized in Example 1.
  • FIG. 12 is a chart of an ultraviolet-visible spectrum of the metal complex dye Dye-4 synthesized in Example 1.
  • FIG. 13 is a chart of an ultraviolet-visible spectrum of the metal complex dye Dye-5 synthesized in Example 1.
  • FIG. 14 is an ultraviolet-visible spectrum chart of the metal complex dye Dye-6 synthesized in Example 1.
  • FIG. 15 is a visible absorption spectrum diagram of a titanium oxide film in which the metal complex dye Dye-1 synthesized in Example 1 is adsorbed on titanium oxide.
  • FIG. 16 is a visible absorption spectrum diagram of a titanium oxide film in which the metal complex dye Dye-5 synthesized in Example 1 is adsorbed on titanium oxide.
  • FIG. 17 is a visible absorption spectrum diagram of a titanium oxide film obtained by adsorbing the metal complex dye Dye-6 synthesized in Example 1 on titanium oxide.
  • the photoelectric conversion element 10 of the present invention has a photoelectric conversion element 10 including a conductive support 1, a photoreceptor layer 2 including semiconductor fine particles sensitized by a dye (metal complex dye) 21, It consists of a charge transfer layer 3 and a counter electrode 4 which are hole transport layers.
  • the conductive support 1 provided with the photoreceptor layer 2 functions as a working electrode in the photoelectric conversion element 10.
  • the photoelectric conversion element 10 is shown as a system 100 using a dye-sensitized solar cell that can be used for a battery for causing the operating means M to work with the external circuit 6.
  • the light-receiving electrode 5 includes a conductive support 1 and a photoreceptor layer 2 containing semiconductor fine particles adsorbed with a dye (metal complex dye) 21.
  • the photoreceptor layer 2 is designed according to the purpose, and may be a single layer structure or a multilayer structure.
  • the dye (metal complex dye) 21 in one photosensitive layer may be one kind or a mixture of various kinds, but at least one of them uses the metal complex dye of the present invention described above.
  • the light incident on the photoreceptor layer 2 excites the dye (metal complex dye) 21.
  • the excited dye has high energy electrons, and the electrons are transferred from the dye (metal complex dye) 21 to the conduction band of the semiconductor fine particles 22 and reach the conductive support 1 by diffusion.
  • the dye (metal complex dye) 21 is an oxidant, but the electrons on the electrode work in the external circuit 6 and pass through the counter electrode 4 so that the oxidant of the dye (metal complex dye) 21 and By returning to the photoreceptor layer 2 where the electrolyte is present, it functions as a solar cell.
  • the materials used for the photoelectric conversion element or the dye-sensitized solar cell and the method for producing each member may be the usual ones of this type, for example, US Pat. No. 4,927,721.
  • an outline of the main members will be described.
  • the photoreceptor layer is a layer containing semiconductor fine particles containing an electrolyte described later and carrying a sensitizing dye containing the metal complex dye of the present invention described below.
  • the metal complex dye of the present invention is represented by the following formula (I).
  • M represents a metal ion.
  • Ring A, ring B and ring C each independently represent a nitrogen-containing aromatic heterocycle.
  • Z 1 and Z 2 each independently represent a carbon atom or a nitrogen atom.
  • the bond between Z 1 and the N atom and the bond between Z 2 and the N atom may be a single bond or a double bond.
  • R 1 to R 3 each independently represent a substituent having no Anc1 to Anc3.
  • n1 and n3 each independently represents an integer of 0 to 4, and n2 represents an integer of 0 to 3.
  • X 1 represents a linking group.
  • X 2 represents —O—, —S—, —NR ′ (R ′ represents a hydrogen atom or a substituent) —, a saturated aliphatic group, or an unsaturated aliphatic group having an unsaturated group that is not ⁇ -conjugated with the ring B.
  • R ′ represents a hydrogen atom or a substituent
  • X 3 represents a single bond or a linking group.
  • Anc1 to Anc3 each independently represents an acidic group.
  • l1 and l3 each independently represents an integer of 1 to 4, and l2 represents an integer of 1 to 5, respectively.
  • L 1 to L 3 each represents a ligand and is a bidentate ligand in which L 1 and L 2 are bonded to each other, or a tridentate ligand in which L 1 , L 2 and L 3 are bonded to each other is there.
  • one or two of L 1 to L 3 represent a ligand having an anionic coordination atom.
  • Y represents a counter ion necessary for neutralizing the charge, and n represents an integer of 0 to 2.
  • Metal complex dye of the formula (I), the linking groups X 1 and an acid group Anc1 has at least one linked ring A, a tridentate ligand consisting of ring A, ring B and ring C, distribution
  • the ligand atom has a ligand L 1 to L 3 containing one or two anionic ligands.
  • the metal complex dye having such a structure greatly increases the photoelectric conversion efficiency ( ⁇ ) and is excellent in reducing adsorption stability and performance.
  • the metal complex dye represented by the formula (I) is represented by the following formula (I-1) when m3 is an integer of 1 to 4, and is represented by the following formula (I-2) when m3 is 0.
  • the metal complex dye represented by the formula (I) is represented by the following formula (I-1) when m3 is an integer of 1 to 4, and is represented by the following formula (I-2) when m3 is 0.
  • M ring A to ring C, Z 1 , Z 2 , R 1 to R 3 , n1 to n3, X 1 to X 3 , Anc1 to Anc3, l1 to l3, m1 and m2, L 1 to L 3 , Y and n have the same meanings as in formula (I), and preferred ranges are also the same.
  • m31 is an integer of 1 to 4.
  • Metal complex dye of the formula (I-1) has only to have a Anc3 and linking groups X 3 in at least one ring C a Anc1 and linking groups X 1 to the ring A, ring B is linked it may or may not have a group X 2 and Anc2. Since the metal complex dye represented by the formula (I-1) has at least one Anc1 and at least one Anc3 as acidic groups, it is strongly adsorbed by the semiconductor fine particles. Therefore, this metal complex dye exhibits a still higher photoelectric conversion efficiency ( ⁇ ) and is excellent in durability and reduction in variation in performance. Metal complex dye represented by formula (I-2) may have at least one of Anc1 and linking groups X 1 to the ring A, ring B, which may have a linking group X 2 and Anc2 It does not have to be.
  • M-M is a central metal of the metal complex dye, and examples thereof include elements of groups 6 to 12 on the long periodic table. Examples of such elements include Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn, and Zn.
  • M is preferably Os 2+ , Ru 2+ , Fe 2+ or Cu 2+, more preferably Os 2+ , Ru 2+ and Fe 2+ , more preferably Os 2+ and Ru 2+ , and particularly preferably Ru 2+ .
  • the valence of M may be changed by an oxidation-reduction reaction with surrounding materials.
  • the tridentate ligand formed by connecting the ring A, the ring B, and the ring C to each other has an adsorbing group (also referred to as an acidic group) that is adsorbed on the surface of the semiconductor fine particles.
  • This ligand is sometimes referred to as an “acceptor ligand”.
  • this acceptor ligand will be described.
  • Ring A, Ring B, and Ring C are each a nitrogen-containing aromatic heterocycle, and each ring-constituting atom is connected to each other without using a linking group to form a tridentate as an acceptor ligand.
  • Ligand is formed.
  • the nitrogen atom constituting ring A and ring C and bonded to metal ion M may be an anion, but preferably has a lone pair of electrons.
  • Z 1 and Z 2 represent a carbon atom or a nitrogen atom, and the bond between Z 1 and N atom in Ring A and the bond between Z 2 and N atom in Ring C are Independently, each may be a single bond or a double bond.
  • Ring A and ring C are connected to ring B by these Z 1 and Z 2 .
  • Z 1 and Z 2 are particularly preferably both carbon atoms.
  • Ring A, ring B, and ring C may each be any nitrogen-containing aromatic heterocycle as long as it can bind to metal ion M.
  • a nitrogen-containing aromatic heterocycle is preferably a 5-membered ring or a 6-membered ring.
  • These nitrogen-containing aromatic heterocycles may be other rings, for example, an aryl group or a heterocyclic group of the substituent T described later, or a non-aromatic heterocyclic group ring or a non-aromatic hydrocarbon ring group described later. It does not matter if it is condensed.
  • the ring-forming hetero atom of the nitrogen-containing aromatic heterocycle may be 2 to 6 nitrogen atoms, or may contain other hetero atoms such as an oxygen atom and a sulfur atom in addition to the nitrogen atom.
  • the 6-membered nitrogen-containing aromatic heterocycle include a pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, quinoline ring, isoquinoline ring, and quinazoline ring, and a 5-membered nitrogen-containing aromatic ring.
  • heterocycle examples include a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, an indoline ring, an indazole ring, a triazole ring, a tetrazole ring, an isoxazole ring, Examples include isothiazole ring, furazane ring, indole ring, benzopyrrole ring, isoindole ring, benzotriazole ring, oxadiazole ring, and thiadiazole ring.
  • Ring A and ring C are preferably a non-condensed 5- or 6-membered ring or a condensed (preferably benzene-fused) 5-membered ring having a lone electron pair that is not conjugated to the ⁇ electron of ring A or ring C.
  • An aromatic heterocycle is particularly preferred.
  • Examples of the nitrogen-containing aromatic heterocycle having a lone pair of electrons include a pyridine ring, pyrimidine ring, triazine ring, imidazole ring, oxazole ring, thiazole ring, benzothiazole ring, oxadiazole ring, thiadiazole ring, isoxazole ring, Examples include isothiazole ring, triazole ring, pyrazole ring, pyridine ring, pyrimidine ring, triazine ring, imidazole ring, oxazole ring, thiazole ring, oxadiazole ring, thiadiazole ring, isoxazole ring, isothiazole ring, triazole ring.
  • Ring B is preferably a non-condensed 6-membered ring, for example, a pyridine ring, a pyrazine ring, a pyrimidine ring or a triazole ring is more preferred, and a pyridine ring or a pyrimidine ring is particularly preferred.
  • At least one of Z 1 and Z 2 is preferably a carbon atom, and more preferably both are carbon atoms.
  • Z 1 or Z 2 is a nitrogen atom
  • ring A or ring C is preferably a pyrazole ring or a triazole ring, respectively.
  • Ring A, ring B and ring C may be the same or different from each other, and ring A and ring C may be different but are preferably the same.
  • Examples of combinations of ring A, ring B and ring C include, for example, ring A-ring B-ring C in this order: pyridine ring-pyridine ring-pyridine ring, pyridine ring-pyridine ring-pyrimidine ring, pyridine ring-pyridine ring- Benzothiazole ring, pyridine ring-pyridine ring-imidazole ring, pyridine ring-pyrimidine ring-pyridine ring, pyrimidine ring-pyridine ring-pyrimidine ring, triazine ring-pyridine ring-triazine ring, pyridine ring-pyrazine ring-pyridine ring, pyridine Ring-pyridine ring-pyrazine ring, pyrazine ring-pyridine ring-pyrazine ring,
  • pyridine ring-pyridine ring-pyridine ring pyridine ring-pyridine ring
  • pyridine ring-pyridine ring-pyrimidine ring Pyridine ring-pyridine ring-benzothiazole ring
  • pyridine ring-pyridine ring-imidazole Ring pyridine ring - pyrimidine ring - pyridine ring
  • pyridine ring - pyridine ring - pyridine ring is more preferable.
  • Ring A, ring B, and ring C may have substituents R 1 , R 2, and R 3 that do not have Anc 1 , Anc 2, and Anc 3, respectively.
  • substituent T examples include the following.
  • substituent T when each group, for example, an alkyl group is only described, Preferred ranges and specific examples of the corresponding group of the substituent T are applied.
  • alkyl group preferably having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, trifluoromethyl, etc.
  • Alkenyl groups preferably having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.
  • alkynyl groups preferably having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.
  • cycloalkyl groups preferably Has 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl and the like, cycloalkenyl group (preferably having 5 to 20 carbon atoms, for example, cyclopenten
  • alkoxycarbonyl group preferably having 2 to 20 carbon atoms such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.
  • a cycloalkoxycarbonyl group preferably having 4 to 20 carbon atoms such as cyclopropyloxycarbonyl, cyclopentyloxycarbonyl, etc.
  • Cyclohexyloxycarbonyl, etc. aryloxycarbonyl groups (preferably having 6 to 20 carbon atoms, such as phenyloxycarbonyl, naphthyloxycarbonyl, etc.)
  • amino groups preferably having 0 to 20 carbon atoms, alkylamino groups, alkenyls
  • An acyl group preferably having 1 to 20 carbon atoms such as acetyl, cyclohexylcarbonyl, benzoyl, etc.
  • an acyloxy group preferably having 1 to 20 carbon atoms such as acetyloxy, cyclohexylcarbonyloxy).
  • Benzoyloxy, etc. carbamoyl group (preferably an carbamoyl group having 1 to 20 carbon atoms, alkyl, cycloalkyl or aryl, such as N, N-dimethylcarbamoyl, N-cyclohexylcarbamoyl, N-phenylcarbamoyl, etc.)
  • N, N-dimethylcarbamoyl, N-cyclohexylcarbamoyl, N-phenylcarbamoyl, etc.
  • An acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, cyclohexylcarbonylamino, benzoylamino, etc.), a sulfonamide group (preferably an alkyl, cycloalkyl or aryl sulfonamide having 0 to 20 carbon atoms) Groups such as methanesulfonamide, benzenesulfonamide, N-methylmethanesulfonamide, N-cyclohexylsulfonamide, N-ethylbenzenesulfonamide, etc., alkylthio groups (preferably having 1 to 20 carbon atoms, eg, methylthio , Ethylthio, isopropylthio, benzylthio, etc.), cycloalkylthio groups (preferably having 3 to 20 carbon atoms, such as cyclopropylthio, cyclopent
  • a silyl group (preferably a silyl group having 1 to 20 carbon atoms and substituted by alkyl, aryl, alkoxy and aryloxy, such as triethylsilyl, triphenylsilyl, diethylbenzylsilyl, dimethylphenylsilyl, etc.), silyloxy group ( Preferably, it is a silyloxy group having 1 to 20 carbon atoms and substituted with alkyl, aryl, alkoxy and aryloxy, such as triethylsilyloxy, triphenylsilyloxy, diethylbenzylsilyloxy, dimethylphenylsilyloxy, etc.), hydroxyl group , Cyano group, nitro group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group, sulfo group, phosphonyl group, phosphoryl group, boric acid group, more
  • the substituent T may be a group formed by combining a plurality of the aforementioned groups.
  • an aryl group substituted with one or more alkoxy groups an aryl group or heterocyclic group having one or more alkyl groups, and an aryl group or heterocyclic group having one or more alkyl groups And alkenyl groups.
  • substituent T or the compound contains an alkyl group, an alkenyl group or the like, these may be linear or branched, and may be substituted or unsubstituted.
  • substituent T or the compound may be linear or branched, and may be substituted or unsubstituted.
  • aryl group, a heterocyclic group, or the like may be monocyclic or condensed, and may be substituted or unsubstituted.
  • an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group and a halogen atom are preferable, and an alkyl group, an alkenyl group and an aryl group are particularly preferable.
  • substituents R 1 to R 3 may be bonded to each other directly or via a linking group to form a ring.
  • n1 and n3 each independently represents an integer of 0 to 4, and n2 represents an integer of 0 to 3.
  • n1 to n3 are each preferably 0 or 1.
  • Linking group X 1 is a linking group, connecting the ring with A bonded atoms ANC1.
  • X 3 is a single bond or a linking group, and connects the bond atom of Anc 3 and ring C.
  • X 1 and X 3 are synonymous except for whether or not a single bond is included, and preferable ones are also the same, so the linking group in X 1 and X 3 will be described below.
  • the valence of the linking groups X 1 and X 3 varies depending on the number of substitutions of the acidic groups Anc1 and Anc3 and the number of substitutions of the substituents R 1 and R 3 and is at least divalent.
  • a linking group is not particularly limited, and examples thereof include an acyclic hydrocarbon group having an unsaturated bond or a cyclic hydrocarbon group having an unsaturated bond, a non-aromatic heterocyclic group, and an aromatic heterocyclic group.
  • Specific examples of the acyclic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, and the cyclic hydrocarbon group having an unsaturated bond includes a non-aromatic hydrocarbon ring group. And aromatic hydrocarbon ring groups.
  • the linking groups X 1 and X 3 can be expected to have an effect of improving the absorption characteristics due to the extension of the ⁇ -conjugated system, and are a conjugated chain that ⁇ -couples the bonding atom of Anc1 and the ring A or the bonding atom of Anc3 and the ring C.
  • the linking group is preferably a linking group comprising a conjugated chain that is ⁇ -conjugated. Therefore, the linear or branched aliphatic hydrocarbon group, non-aromatic hydrocarbon ring group and non-aromatic heterocyclic group preferably have an unsaturated bond at a position ⁇ -conjugated with ring A or ring C.
  • the aromatic hydrocarbon ring group and the aromatic heterocyclic group are preferably on the same plane as the ring A or ring C to be bonded and ⁇ -conjugated.
  • Examples of the linear or branched aliphatic hydrocarbon group include an aliphatic hydrocarbon group having one or more carbon-carbon double bonds and / or carbon-carbon triple bonds.
  • Suitable aliphatic hydrocarbon groups include, for example, hydrocarbon groups having one or more carbon-carbon double bonds, hydrocarbon groups having one or more carbon-carbon triple bonds, and the like.
  • Examples of the hydrocarbon group having one carbon-carbon double bond include an alkenylene group represented by the following formula (3), for example, ethenylene group.
  • Examples of the hydrocarbon group having two or more carbon-carbon double bonds include hydrocarbon groups having an even number of ⁇ -conjugated methine chains as skeletons, such as hydrocarbons represented by formulas (4) to (6) described later. Groups.
  • Examples of the hydrocarbon group having one carbon-carbon triple bond include alkynylene groups such as an ethynylene group.
  • non-aromatic hydrocarbon ring group examples include a hydrocarbon ring group having one or more carbon-carbon double bonds or carbon-carbon triple bonds so as not to satisfy the Hückel rule.
  • ring-constituting atom contains an oxo group (> C ⁇ O)
  • it can take an enol structure as a tautomer and formally, for example, 6 ⁇ conjugate, but these are classified as non-aromatic hydrocarbon ring groups.
  • Suitable non-aromatic hydrocarbon ring groups include, for example, cycloalkenylene groups having one or more carbon-carbon double bonds, cycloalkynylene groups having one or more carbon-carbon triple bonds, etc. Is mentioned.
  • Examples of the cycloalkenylene group and the cycloalkynylene group include a cycloalkenylene group and a cycloalkynylene group having 4 to 6 carbon atoms constituting the ring.
  • the carbon atom bonded to ring A or ring C is preferably a carbon atom forming a carbon-carbon double bond or a carbon-carbon triple bond because the ⁇ -conjugated system can be extended. .
  • aromatic hydrocarbon ring group examples include divalent or higher valent groups corresponding to the aryl group of the substituent T, and specific examples include a benzene ring group and a naphthalene ring group.
  • non-aromatic heterocyclic group examples include a heterocyclic group having one or more carbon-carbon double bonds and / or carbon-hetero double bonds and not satisfying the Hückel rule, such as a pyrroline ring group , An imidazoline ring group, a heterocyclic group represented by the following formula, and the like.
  • a heterocyclic group having one or more carbon-carbon double bonds and / or carbon-hetero double bonds and not satisfying the Hückel rule such as a pyrroline ring group , An imidazoline ring group, a heterocyclic group represented by the following formula, and the like.
  • the non-aromatic hydrocarbon ring group the case where the ring-constituting atom of the non-aromatic heterocyclic group includes an oxo group (> C ⁇ O) is also classified as a non-aromatic heterocyclic group.
  • An atom bonded to ring A or ring C in a non-aromatic heterocyclic group is carbon-carbon A carbon atom or a hetero atom forming a double bond or a carbon-hetero double bond is preferable because the ⁇ -conjugated system can be extended.
  • R 11 and R 12 represents a substituent.
  • substituent R 11 include the substituent T
  • substituent R 12 include an electron-withdrawing group among the substituent T.
  • a cyano group is preferable.
  • aromatic heterocyclic group examples include a divalent or higher valent group corresponding to the nitrogen-containing aromatic heterocyclic ring of ring A to ring C and a divalent or higher valent group corresponding to the heterocyclic group of substituent T.
  • a bivalent or higher-valent aromatic heterocyclic group corresponding to a pyridine ring, a pyrimidine ring, a triazine ring, a triazole ring, a pyrazole ring, or the like or a group having a thiophene ring structure (thiophene ring group, benzothiophene ring group, thiophene) 1-oxide ring group, thiophene, 1,1-dioxide ring group, etc.) and furan ring group and the like.
  • the linking groups X 1 and X 3 may be a linking group formed by combining a plurality of the linking groups described above (hereinafter sometimes referred to as a composite linking group).
  • a composite linking group includes, for example, a bond linking group formed by bonding a plurality of the linking groups, a substituted linking group in which the linking group is substituted with at least one substituent that does not have Anc1, Anc2, and Anc3. Can be mentioned.
  • These composite linking groups are preferably ⁇ -conjugated with ring A or ring C.
  • Examples of the bond linking group include a bond linking group in which a linear or branched aliphatic hydrocarbon group is bonded to an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and a bond in which aromatic heterocyclic groups are bonded to each other.
  • Examples thereof include a linking group.
  • Examples of such a linking group include a group having a benzene ring group in which a hydrogen atom is substituted with an ethenylene group or an ethynylene group, a group having a thiophene ring structure, or a group having two or more thiophene ring structures. It is done.
  • the linking group bonded to the acidic group may be an ethenylene group or an ethynylene group, or may be a group having a benzene ring group or a thiophene ring structure.
  • substituent of the substituted linking group include a substituent T. When m3 is 0, the substituent T is electron withdrawing (for example, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, a substituted group).
  • an unsubstituted aminocarbonyl group a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted aminosulfonyl group, or a cyano group
  • m3 1 or more
  • the substituent T is preferably a hydrogen atom. The reason is that the photoelectric conversion efficiency is improved and the variation in performance can be reduced.
  • the linking groups X 1 and X 3 are linear or branched unsaturated aliphatic hydrocarbon groups, aromatic heterocyclic groups, or these, in that the metal complex dye exhibits a higher photoelectric conversion efficiency ( ⁇ ). It is preferably a composite linking group.
  • straight-chain or branched-chain aliphatic hydrocarbon groups hydrocarbon groups having an even number of ⁇ -conjugated methine chains represented by the following formulas (3) to (6) are preferred, and the formula (3) is More preferred.
  • aromatic heterocyclic groups an aromatic 5-membered heterocyclic group is preferable, a furan ring and a thiophene ring are more preferable, and a group having a thiophene ring skeleton represented by the following formulas (7) to (9). Is more preferable.
  • the linking groups X 1 and X 3 are also preferably a composite linking group represented by the formula (3) and the following formulas (7) to (10).
  • the composite linking group of the formula (3) and the following formula (7) Is more preferable, and as a composite order, a composite linking group in which ** of the formula (7) is bonded to * of the formula (3) is more preferable.
  • R 31 to R 102 represent a hydrogen atom or a substituent, and a plurality of substituents may be bonded directly or via a linking group to form a ring.
  • substituent of R 31 to R 102 include the substituent T.
  • the linking group X 2 is a group linking ring B and Anc2, and includes, for example, —O—, —S—, —NR ′ (R ′ represents a hydrogen atom or a substituent) —, a saturated aliphatic group, It is a group formed by an unsaturated aliphatic group having an unsaturated group that is not ⁇ -conjugated with ring B, a non-aromatic hydrocarbon ring group, a non-aromatic heterocyclic group, or a combination thereof.
  • R ′ can include a hydrogen atom or the above-described substituent T.
  • the connecting group X 2 may have a substituent T.
  • saturated aliphatic group may be linear, branched or cyclic.
  • a particularly preferred saturated aliphatic group is an alkylene group, and specific examples include alkylene groups having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, and a butylene group.
  • the unsaturated aliphatic group having an unsaturated group that is not ⁇ -conjugated with ring B only needs to have an unsaturated group that is not ⁇ -conjugated with an atom bonded to Anc2 and ring B. For example, one or two or more In the position where the ring B is not ⁇ -conjugated.
  • Examples of the unsaturated bond include a carbon-carbon double bond and / or a carbon-carbon triple bond.
  • Examples of such a group include unsaturated aliphatic groups in which the carbon atom bonded to ring B is a carbon atom having an sp 3 hybrid orbital, that is, a saturated carbon atom.
  • the unsaturated group of the unsaturated aliphatic group may or may not be ⁇ -conjugated with another unsaturated group as long as it is not ⁇ -conjugated with ring B.
  • Specific examples of the particularly preferred unsaturated aliphatic group include alkenylene groups having 3 or more carbon atoms, alkynylene groups having 3 or more carbon atoms, and the like.
  • Examples of the alkenylene group having 3 or more carbon atoms include 1-propenylene group (—CH ⁇ CH—CH 2 —) and the like, and examples of the alkynylene group having 3 or more carbon atoms include 1-propynylene group (—C ⁇ C—CH 2 —) and the like.
  • the carbon atom bonded to the ring B is a carbon atom having an sp 3 hybrid orbital as described above, for example, a methylene carbon atom.
  • Non-aromatic hydrocarbon ring group the a same meaning as the non-aromatic hydrocarbon ring group of the linking group X 1 and X 3, it is preferable also the same.
  • the non-aromatic heterocyclic group is synonymous with the non-aromatic heterocyclic group in the linking groups X 1 and X 3 , and preferred ones are also the same.
  • Group formed by the combination include a group formed by combining the groups described as the linking group X 2 1 or more.
  • linking group X 2 even if the atom bonded to the ring B is a carbon atom or heteroatom forming a carbon-carbon double bond or a carbon-hetero double bond, other atoms such as sp It may be a carbon atom having three hybrid orbitals.
  • the acidic groups represented by Anc1, Anc2 and Anc3 are substituents having a dissociative proton, and are groups having a pKa of 11 or less. Examples thereof include acidic groups such as —COOH, —SO 3 H, —PO 3 H 2 , —OH, and —SH. Further, the acidic group may take a form of releasing a proton and dissociating, or may be a salt.
  • the acidic group is preferably —COOH, —SO 3 H, —PO 3 H 2, —OH or —SH, or a salt thereof.
  • the counter ion when the salt is converted is not particularly limited, and examples thereof include positive ions represented by counter ion Y in formula (I).
  • Anc1, Anc2 and Anc3 are each preferably —COOH or —OH, more preferably —COOH from the viewpoints of adsorption stability and electron injection.
  • nx represents an integer of 1 to 3.
  • Ra1 and Ra2 each independently represent a substituent. Note that —OH in the above formula may form a salt.
  • Ra1 and Ra2 are more preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, or a sulfamoyl group, and an alkyl group, an aryl group, or a cyano group is more preferable. Further preferred.
  • the group represented by the formula (Anc) is preferably a group represented by any of the following formulas (Anc-1) to (Anc-5).
  • Ra1 to Ra4 each independently represent a substituent.
  • —OH may form a salt.
  • Ra1 to Ra4 have the same meanings as Ra1 and Ra2 described above, and the preferred ranges are also the same.
  • groups represented by the formulas (Anc-1) to (Anc-5) groups represented by the formulas (Anc-1) and (Anc-5) are preferable, and represented by the formula (Anc-1) Group is particularly preferred.
  • the metal complex dye represented by the formula (I) of the present invention has a plurality of acidic groups essentially including at least one Anc1 from the viewpoint of adsorption stability, that is, durability and reduction in performance variation. It is preferable that the plurality of acidic groups may be bonded to the same linking group or ring, or may be bonded to another linking group or ring.
  • the ring A may have a plurality of Anc1s, and in addition to Anc1, it may have Anc2 or Anc3.
  • ring A has at least one Ancl and ring C has at least one Anc3.
  • l1 and l3 each independently represents an integer of 1 to 4, and l2 represents an integer of 1 to 5.
  • l1 and l3 are preferably each independently 1 or 2, and l2 is preferably 1 or 2.
  • m1 represents an integer of 1 to 4
  • m2 represents an integer of 0 to 3
  • m3 represents an integer of 0 to 4.
  • metal complex dye when m3 is an integer of 1 to 4 are represented by the formula (I-1), the linking group X 3 and Anc3 coupled to the linking group X 1 and Anc1 and ring C is connected to the ring A is essential It becomes. The reason is as described above.
  • the metal complex dye is represented by the formula (I-2).
  • linking groups X 1 and Anc1 linked to ring A is required if m3 is 0.
  • m1 is preferably 1
  • m2 is preferably from 0 to 2, more preferably 0, and even more preferably 0, and m3 is preferably 1.
  • m31 represents an integer of 1 to 4 and is preferably 1.
  • L 1 , L 2 and L 3 represent ligands and are bidentate ligands in which L 1 and L 2 are bonded to each other, or L 1 , L 2 and L 3 are bonded to each other It is a tridentate ligand.
  • the ligands L 1 to L 3 are all ligands having no acidic group and are also referred to as “donor ligands”.
  • L 1 , L 2 and L 3 each represent a ligand that binds to the metal ion M, and one or two of L 1 to L 3 are ligands having an anionic coordination atom.
  • L 1 and L 2 are bidentate ligands bonded to each other, at least one of the coordination atoms is anionic, and L 1 , L 2 and L 3 are bonded to each other.
  • one or two of the coordination atoms are anionic.
  • the level of the highest occupied orbital and the lowest unoccupied orbital of the metal complex dye is moderated, and preferable absorption characteristics are exhibited. Or the effect that a voltage becomes high can be expected. As a result, the photoelectric conversion efficiency of the photoelectric conversion element is improved.
  • the ligands L 1 , L 2 and L 3 have a conjugated structure in that the photoelectric conversion efficiency of the photoelectric conversion element is further increased.
  • These ligands (La) to (Lf) are the same or different from each other to form a bidentate or tridentate ligand, preferably a bidentate or tridentate arrangement in which they are linked by a single bond. It is a rank.
  • these ligands may have a substituent which does not inhibit the characteristics of each ligand. Examples of such a substituent include a substituent other than the adsorptive group adsorbed on the surface of the semiconductor fine particles, and examples thereof include a substituent T.
  • the nitrogen-containing aromatic ring group (La) may have a substituent T that is not anionic.
  • Preferred examples of the substituent T include an alkyl group, an alkenyl group, a perfluoroalkyl group, an alkoxy group, an aryl group, a heterocyclic group, a cyano group, a nitro group, a halogen atom, and a group formed by combining a plurality of these. It is. This substituent T may be bonded to each of two adjacent rings and condensed with them.
  • the nitrogen-containing aromatic ring group (La) in which the atom bonded to the metal ion M has a lone electron pair and has no anionic property at least one of the ring constituent atoms has a nitrogen atom having a lone electron pair
  • a ring atom in addition to a nitrogen atom, an oxygen atom, a sulfur atom (—S—, —SO—, —SO 2 —), a selenium atom, or the like may be contained.
  • the lone electron pair in the nitrogen-containing aromatic ring group (La) having a lone electron pair is not a ⁇ electron on the aromatic ring but a lone electron pair not involved in the bond.
  • This nitrogen-containing aromatic ring group (La) does not have an anionic carbon atom or nitrogen atom as a ring constituent atom bonded to the metal ion M, and does not have an anionic functional group. It is a cyclic group. An anionic carbon atom or nitrogen atom and an anionic functional group will be described later.
  • the ring in the nitrogen-containing aromatic ring group (La) is preferably a 5- to 7-membered ring and may be condensed. Examples of the ring of such a nitrogen-containing aromatic ring group (La) include an anionic carbon atom or nitrogen as a ring-constituting atom bonded to the metal ion M in the nitrogen-containing aromatic heterocycle described in ring A or the like.
  • the thing which does not have an atom is mentioned.
  • Specific examples include an oxazole ring, a thiazole ring, a pyridine ring, a quinoline ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, and a pyrazole ring group in which the atom bonded to the metal ion M is a nitrogen atom at the 2-position.
  • a pyridine ring is preferred.
  • the nitrogen-containing aromatic ring group (La) may have a substituent T.
  • the nitrogen-containing aromatic ring group (La) has a substituent T. It is preferable.
  • the substituent T of the nitrogen-containing aromatic ring group (La) is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an aryl group substituted with one or two or more alkoxy groups, and one or two or more alkyl groups.
  • An aryl group or heterocyclic group having one, an aryl group having one or more alkyl groups or an alkenyl group substituted with a heterocyclic group is preferred.
  • the nitrogen-containing aromatic ring group (Lb) having an anionic nitrogen atom as a ring-constituting atom bonded to the metal ion M is incorporated as a ligand of a metal complex dye, at least one of the nitrogen-containing aromatic ring groups A carbocyclic aromatic group in which the nitrogen atom —NH— moiety becomes an anion —N ⁇ —.
  • the nitrogen-containing aromatic ring group (Lb) is preferably one in which the —NH— moiety becomes an anion —N ⁇ — and binds to or can bind to the metal ion M.
  • this nitrogen-containing aromatic ring group (Lb) is a nitrogen-containing aromatic ring group in which the nitrogen atom that is a ring-constituting atom bonded to the metal ion M has active hydrogen.
  • the ring in the nitrogen-containing aromatic ring group (Lb) is preferably a 5- to 7-membered ring and may be condensed.
  • Examples of the ring of the nitrogen-containing aromatic ring group (Lb) include those having an anionic nitrogen atom among the nitrogen-containing aromatic hetero rings described in Ring A and the like.
  • imidazole Ring groups triazole ring groups, benzimidazole ring groups, 1H-indazole ring groups, purine ring groups, pyrrole ring groups, pyrazole ring groups in which the atom bonded to the metal ion M is the 1st nitrogen atom, and the like.
  • a cyclic group, a triazole ring group, a pyrrole ring group, and a pyrazole ring group in which the atom bonded to the metal ion M is the nitrogen atom at the 1-position are preferable.
  • This nitrogen-containing aromatic ring group (Lb) is represented by the following formulas (a-1) to (a-5) derived from an imidazole ring group, a pyrazole ring group, a triazole ring group, or a pyrrole ring group, among the above-mentioned ones.
  • the group represented by (a-1), (a-2) or (a-5) is more preferred, and the group represented by (a-2) is particularly preferred.
  • Rd represents a substituent.
  • b1 represents an integer of 0 to 2
  • b2 represents an integer of 0 to 3
  • b3 represents 0 or 1.
  • b1 is 2 or b2 is 2 or more
  • a plurality of Rd's may be bonded to each other to form a ring.
  • Rd the above-mentioned substituent T is mentioned, for example.
  • Rd and b1 to b3 have the same meanings as Rd and b1 to b3 in the formulas (a-1) to (a-5) described above, and preferred ranges are also the same.
  • b4 represents an integer of 0 to 4
  • b5 represents an integer of 0 to 5.
  • Rd represents not only a benzene ring but also a pyrrole ring.
  • Rd is preferably a linear or branched alkyl group, a cycloalkyl group, an alkenyl group, a fluoroalkyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, or a group formed by combining these, more preferably A straight chain or branched alkyl group, a cycloalkyl group, an alkenyl group, a fluoroalkyl group, an aryl group or a group formed by combining these, particularly preferably a linear or branched alkyl group, a cycloalkyl group, an alkenyl group, a fluoro group. An alkyl group and a group formed by a combination thereof.
  • an aromatic ring group (Lc) other than a nitrogen-containing aromatic ring group (Lb) having an anionic carbon atom as a ring-constituting atom bonded to the metal ion M is incorporated as a ligand of a metal complex dye
  • any ring having a carbon atom as a ring constituent atom bonded to the metal ion M and exhibiting aromaticity may be used, for example, an aromatic hydrocarbon ring group
  • the ring group atom bonded to the heterocyclic group and the metal ion M include a nitrogen-containing aromatic ring group having no nitrogen atom.
  • an aryl group of the substituent T having an anionic carbon atom as a ring-constituting atom particularly an m, m-difluorobenzene ring, o, p-difluorobenzene ring, p-fluoro
  • substituent T having an anionic carbon atom as a ring-constituting atom, particularly an m, m-difluorobenzene ring, o, p-difluorobenzene ring, p-fluoro
  • examples thereof include a benzene ring, a p-cyanobenzene ring, a p-nitrobenzene ring, a cyclopentadiene ring, a naphthalene ring, and an unsubstituted benzene ring.
  • substitution positions o, m and p of the benzene ring represent positions with respect to the carbon atom bonded to the metal ion M.
  • the heterocyclic group among the heterocyclic groups of the substituent T, those in which a carbon atom becomes anionic as a ring constituent atom, for example, furan, thiophene and the like can be mentioned.
  • examples of the nitrogen-containing aromatic ring group in which the ring-constituting atom bonded to the metal ion M is not a nitrogen atom include a pyrazole ring group in which the atom bonded to the metal ion M is a carbon atom at the 5-position, A pyridine ring group in which is a 4-position carbon atom.
  • aromatic hydrocarbon ring group (Ld) substituted with a functional group having an anionic nitrogen atom, oxygen atom or sulfur atom, the nitrogen atom of the functional group when incorporated as a ligand of a metal complex dye An aromatic hydrocarbon ring group in which at least one —XH— or —XH moiety (X represents N, O or S) of an oxygen atom or sulfur atom becomes an anion —X ⁇ — or —X 2 — . Then, the aromatic hydrocarbon Hajime Tamaki (Ld), the -XH- or -XH moiety anion -X - - or -X - bonded to the metal ion M becomes, or it can bond.
  • this aromatic hydrocarbon ring group (Ld) is an aromatic hydrocarbon ring group in which at least one nitrogen atom, oxygen atom or sulfur atom constituting the functional group has active hydrogen.
  • the ring in the aromatic hydrocarbon ring group (Ld) include a ring composed of the aryl group of the substituent T, and the ring may have the substituent T.
  • Examples of the functional group possessed by such an aromatic hydrocarbon ring group (Ld) include a hydroxyl group, a thiol group, an amino group, a substituted amino group, a hydroxyalkyl group, a mercaptoalkyl group, and an aminoalkyl group. , A thiol group, an amino group, and a substituted amino group are preferable.
  • Specific examples of the aromatic hydrocarbon ring group (Ld) having such a functional group include a phenol ring group, a thiophenol ring group, an aniline ring group, a substituted aniline ring group, a hydroxyalkylbenzene ring group, and a mercaptoalkylbenzene ring. Group, anomialkylbenzene ring group and the like.
  • the substituted amino group is an amino group in which one of its hydrogen atoms is substituted, and examples thereof include —NHSO 2 Ry (Ry represents a substituent).
  • Ry include the above-described substituent T, and among them, an alkyl group is preferable.
  • Specific examples of —NHSO 2 Ry include —NHSO 2 CH 3 , —NHSO 2 C 2 H 5 , —NHSO 2 C 3 H 7 and the like.
  • the hydroxyalkyl group is an alkyl group in which at least one of its hydrogen atoms is substituted with a hydroxyl group, and examples thereof include a hydroxymethyl group and a hydroxyethyl group.
  • the mercaptoalkyl group is an alkyl group in which at least one of its hydrogen atoms is substituted with a thiol group, and examples thereof include a mercaptomethyl group and a mercaptoethyl group.
  • An aminoalkyl group is an alkyl group in which at least one of its hydrogen atoms is substituted with an amino group, and examples thereof include an aminomethyl group and an aminoethyl group.
  • the carbon atom of the alkyl group to which the hydroxy group, mercapto group or amino group is bonded is not particularly limited, but considering the ease of coordination with the metal ion M
  • the terminal carbon atom of the alkyl group is preferable.
  • a nitrogen-containing aromatic ring group in which at least one —XH— or —XH moiety (X represents N, O or S) of an oxygen atom or sulfur atom becomes an anion —X ⁇ — or —X 2 — .
  • the nitrogen-containing aromatic Hajime Tamaki (Le) the -XH- or -XH moiety anion -X - - or -X - bonded to the metal ion M becomes, or it can bond.
  • this nitrogen-containing aromatic ring group (Le) is a nitrogen-containing aromatic ring group in which at least one nitrogen atom, oxygen atom or sulfur atom constituting the functional group has active hydrogen.
  • This nitrogen-containing aromatic ring group (Le) is synonymous with the aromatic hydrocarbon ring group (Ld) except that it has a nitrogen-containing aromatic ring group instead of the aromatic hydrocarbon ring group.
  • the functional group of the nitrogen-containing aromatic ring group (Le) is synonymous with the functional group of the aromatic hydrocarbon ring group (Ld), and preferred ones are also the same.
  • the nitrogen-containing aromatic ring group of the nitrogen-containing aromatic ring group (Le) may be the same ring as the ring of the nitrogen-containing aromatic ring group (La) or the ring of the nitrogen-containing aromatic ring group (Lb). A ring similar to the ring of the nitrogen-containing aromatic ring group (La) having no active hydrogen is preferable.
  • This nitrogen-containing aromatic ring group (Le) may have a substituent T, for example.
  • the ligand (Lf) may be any ligand other than (La) to (Le), for example, an inorganic ligand, or a nitrogen-containing aromatic ring group or ligand (Ld) and (Le And an organic ligand having no functional group.
  • an inorganic compound or an anion, atom or compound derived from the inorganic compound is referred to as an inorganic ligand, and the organic compound or the organic compound bonded to the metal ion M other than the nitrogen-containing aromatic ring group or this functional group
  • the derived anion is called an organic ligand.
  • Examples of such ligands include known ligands without any particular limitation.
  • An anion selected from or a monodentate ligand bonded by these groups, or a halogen atom, cyano, ether, thioether, sulfoxide, carbonyl, Alkyl ketones, carboxylic amides represents a monodentate ligand selected from the group of anions consisting of thio carboxylic amides and thioureas, atom or compound (including a compound anion
  • this ligand (Lf) contains an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, etc.
  • these may be linear, branched or cyclic, and may be substituted or unsubstituted.
  • a ligand (Lf) contains an aryl group, a heterocyclic group, a cycloalkyl group, etc., they may be substituted or unsubstituted, and may be monocyclic or condensed.
  • the ligand (Lf) is preferably an anion such as a cyanate anion, an isocyanate anion, a thiocyanate anion, and an isothiocyanate anion, more preferably an isocyanate anion and an isothiocyanate anion, and particularly preferably an isothiocyanate anion.
  • the ligands L 1 , L 2 and L 3 are each selected from the group consisting of (La) to (Lf), one or two of which have anionic coordination atoms as ligands such as ( Lb) to (Le) and (Lf) are selected from the group consisting of anions, and the remaining two or one is selected from (La) and optionally from the group consisting of compounds of (Lf).
  • the ligands L 1 and L 2 are directly bonded to form a bidentate ligand, and the ligands L 1 , L 2 and L 3 are directly bonded to form a tridentate ligand.
  • the ligand L 2 is selected from (La) and coordinated.
  • the child L 1 is preferably an anionic ligand with a coordination atom selected from (Lb) to (Le), and the ligand L 3 is selected from the ligand (Lf). Is particularly preferred.
  • the ligand L 2 is selected from (La).
  • the coordination atom selected from the above (Lb) to (Le) is preferably an anionic ligand.
  • the bidentate ligand in which L 1 and L 2 are bonded to each other is preferably a bidentate ligand represented by any of the following formulas (2L-1) to (2L-5).
  • Ring D represents an aromatic ring.
  • a 111 to A 141 each represents an anionic nitrogen atom or carbon atom, and A 151 represents any one of an anionic nitrogen atom, oxygen atom or sulfur atom.
  • R 111 to R 154 each represent a hydrogen atom or a substituent that does not have Anc1, Anc2, and Anc3.
  • a 111 to A 141 are a carbon anion or a nitrogen anion from which a hydrogen atom bonded to the nitrogen atom or carbon atom constituting the ring D is eliminated.
  • a 151 is synonymous with a residue obtained by removing active hydrogen from a (substituted) amino group, hydroxyl group or thiol group among the functional groups in the aromatic hydrocarbon ring group (Ld) and the nitrogen-containing aromatic ring group (Le).
  • examples of ring D include aromatic carbocycles, oxygen-containing aromatic heterocycles, sulfur-containing aromatic heterocycles, and nitrogen-containing aromatic heterocycles.
  • This aromatic ring is, for example, a nitrogen-containing aromatic ring composed of a nitrogen-containing aromatic ring group (Lb) or an aromatic hydrocarbon ring composed of an aromatic hydrocarbon ring group of (Lc), ( A heterocyclic ring composed of a heterocyclic group of Lc), or a nitrogen-containing aromatic ring composed of a nitrogen-containing aromatic ring group having no nitrogen atom as a ring-constituting atom bonded to the metal ion M of (Lc) Etc., and preferable examples are also the same.
  • Ring D before A 111 to A 141 are anionized and Ring D substituted by A 151 in Formula (2L-5) are, for example, a benzene ring, m, m-difluorobenzene ring, o, p-difluorobenzene ring, p-fluorobenzene ring, p-cyanobenzene ring, p-nitrobenzene ring or thiophene ring, furan ring, or formulas (a-1) to (a-5) ), (A-1a), (a-2a), (a-1b) and a ring in which the anion portion of the group represented by (a-4a) is substituted with a hydrogen atom.
  • Examples of the substituent of R 111 to R 154 include a substituent T, among which a heterocyclic group, an aromatic carbocyclic group, an ethenyl group, an ethynyl group, a halogen atom, an alkyl group, an amino group (an alkylamino group, A dialkylamino group, an arylamino group, a diarylamino group, an N-alkyl-arylamino group, etc.), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and a silyl group, preferably a heterocyclic group, an aromatic carbocycle Group, ethenyl group, alkyl group and amino group (including alkylamino group, dialkylamino group, arylamino group, diarylamino group, N-alkyl-arylamino group and the like) are more preferable.
  • a substituent T among which a heterocyclic group
  • the remaining ligand is a ligand in which at least one of the ligands L 1 to L 3 has an anionic coordination atom. It is preferably selected from (La) to (Lf) so that it is not a ligand, and an NCS (isothiocyanate) ligand is selected.
  • the tridentate ligand in which L 1 , L 2 and L 3 are bonded to each other is preferably a tridentate ligand represented by any of the following formulas (3L-1) to (3L-5).
  • a 211 to A 242 represent a nitrogen atom or a carbon atom
  • a 251 and A 252 represent any of a nitrogen atom, an oxygen atom, or a sulfur atom.
  • at least one of A 211 and A 212 , A 221 and A 222 , A 231 and A 232 , A 241 and A 242 , and A 251 and A 252 is anionic.
  • R 211 to R 253 represent a hydrogen atom or a substituent having no Anc1, Anc2, and Anc3.
  • a 211 to A 242 those which are anionic are synonymous with A 111 to A 141 in the formulas (2L-1) to (2L-5).
  • those having no anionic property are carbon atoms or nitrogen atoms not having a hydrogen atom.
  • a 251 and A 252 have the same meanings as A 151 in the formula (2L-5).
  • the ring D in the formulas (3L-1) to (3L-5) has the same meaning as the ring D in the formulas (2L-1) to (2L-5), specifically, any one of A 211 to A 242
  • two rings D may be the same or different.
  • the substituents R 211 to R 253 are synonymous with the substituents R 111 to R 154 in formulas (2L-1) to (2L-5), and preferred ones are also the same.
  • -Counter ion Y- Y in the formula (I) represents a charge neutralizing counter ion when a counter ion is required to neutralize the charge.
  • a dye is a cation or an anion or has a net ionic charge depends on the metal, ligand and substituent in the metal complex dye.
  • the metal complex dye represented by the formula (I) may be dissociated and have a negative charge because the substituent has a dissociable group. In this case, the charge of the whole metal complex dye represented by the formula (I) is electrically neutralized by Y.
  • the counter ion Y is a positive counter ion
  • the counter ion Y is an inorganic or organic ammonium ion (for example, tetraalkylammonium ion, pyridinium ion, etc.), phosphonium ion (for example, tetraalkylphosphonium ion, alkyltriphenylphosphonium ion). Etc.), alkali metal ions or protons.
  • the counter ion Y may be an inorganic anion or an organic anion.
  • a halogen anion eg, fluoride ion, chloride ion, bromide ion, iodide ion, etc.
  • substituted aryl sulfonate ion eg, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion, etc.
  • aryl disulfone Acid ions for example, 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion, etc.
  • alkyl sulfate ions for example, methyl sulfate ion
  • sulfate ions thiocyanate ions Perchlorate ion
  • ionic polymer or another dye having a charge opposite to that of the dye may be used as the charge balance counter ion, and a metal complex ion (for example, bisbenzene-1,2-dithiolatonickel (III)) can also be used.
  • Y is preferably an inorganic or organic ammonium ion, particularly tetrabutylammonium ion, sodium ion or proton.
  • the counter ion Y may be a number necessary to neutralize the charge, and is usually selected from integers of 0 to 2.
  • the maximum absorption wavelength in the solution is preferably in the range of 300 to 1000 nm, more preferably in the range of 350 to 950 nm, and particularly preferably in the range of 370 to 900 nm.
  • the metal complex dye of the present invention is disclosed in JP-A No. 2001-291534 and a method according to the method cited in the publication, Chem. Commun. , 2009, 5844-5846, Angew. Chem. Int. Ed. , 50, 2054 to 2058 (2011), or a method analogous thereto.
  • a precursor represented by the formula (IIA) is synthesized.
  • This precursor is a precursor of a tridentate acceptor ligand composed of ring A to ring C having at least an aldehyde group or an acetal group in ring A.
  • Ring A, ring B and ring C each independently represent a nitrogen-containing aromatic heterocycle.
  • Z 1 and Z 2 each independently represent a carbon atom or a nitrogen atom.
  • the bond between Z 1 and the N atom and the bond between Z 2 and the N atom may be a single bond or a double bond.
  • R 1 to R 3 each independently represents a substituent.
  • n1 and n3 each independently represents an integer of 0 to 4, and n2 represents an integer of 0 to 3.
  • X 10 and X 30 each independently represent a single bond or a linking group.
  • X 20 is a single bond or —O—, —S—, —NR ′ (R ′ represents a hydrogen atom or a substituent) —, a saturated aliphatic group, or an unsaturated group that does not have a ⁇ -conjugated unsaturated group with the ring B.
  • R ′ represents a hydrogen atom or a substituent
  • a saturated aliphatic group, a non-aromatic hydrocarbon ring group, a non-aromatic heterocyclic group, or a combination thereof is represented.
  • G represents an acetal group which may have an aldehyde group or a substituent.
  • p1 represents an integer of 1 to 4
  • p2 represents an integer of 0 to 3
  • p3 represents an integer of 0 to 4, respectively.
  • Ring A, ring B and ring C are the same as ring A, ring B and ring C in formula (I), respectively, and preferred ranges are also the same.
  • Z 1 and Z 2 has the same meaning as Z 1 and Z 2 in each formula (I).
  • R 1 to R 3 each have the same meaning as R 1 to R 3 in formula (I), and the preferred range is also the same.
  • n1 to n3 each have the same meaning as n1 to n3 in formula (I), and the preferred range is also the same.
  • X 10 is synonymous with X 1 in formula (I) except that it contains a single bond, and the preferred range is also the same, and particularly preferably an aromatic hydrocarbon ring group, an aromatic heterocyclic group or a single bond.
  • X 20 is synonymous with X 2 in formula (I) except that it contains a single bond, and the preferred range is also the same, and particularly preferably a single bond.
  • X 30 has the same meaning as X 3 in formula (I), and the preferred range is also the same, and particularly preferably an aromatic hydrocarbon ring group, an aromatic heterocyclic group or a single bond.
  • G represents an aldehyde group or an acetal group which is represented by any one of the following structures and may have a substituent.
  • R ⁇ G > represents an alkyl group each independently. * Represents a bonding position with X 10 , X 20 or X 30 .
  • R G each independently represents an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 or 2 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, butyl, hexyl, octyl and the like.
  • the substituent T may be mentioned as the substituent that the acetal group may have.
  • P1 to p3 have the same meanings as m1 to m3 in formula (I), respectively, and preferred ones are also the same.
  • This precursor is coordinated to a compound of metal ion M, and if desired, a bidentate ligand in which L 1 and L 2 are separately bonded or a tridentate in which L 1 , L 2 and L 3 are bonded to each other
  • a ligand is coordinated to the metal ion M to synthesize a metal complex represented by the following formula (II) as a synthetic intermediate.
  • ring A to ring C, Z 1 , Z 2 , R 1 to R 3 , n1 to n3, X 10 to X 30 , G, p1 to p3, Y, and n are as defined in formula (IIA).
  • M represents a metal ion.
  • L 1 to L 3 each represents a ligand, each of which is a monodentate ligand, a bidentate ligand in which L 1 and L 2 are bonded to each other, or L 1 , L 2 and L 3 are bonded to each other It is a tridentate ligand.
  • one or two of L 1 to L 3 represent a ligand having an anionic coordination atom.
  • Y represents a counter ion necessary for neutralizing the charge
  • n represents an integer of 0 to 2.
  • L 1 to L 3 in the formula (II) may be a monodentate ligand as long as one or two of them have an anionic coordination atom.
  • the metal complex in which L 1 to L 3 are all monodentate ligands can be obtained by coordinating the precursor represented by the formula (IIA) to the compound of the metal ion M.
  • L 1 to L 3 which are monodentate ligands are synonymous with the ligands (La) to (Lf) in the formula (I), and the availability or preparation of the compound of the metal ion M
  • the ligand (Lf) is preferable among the ligands (La) to (Lf) in the formula (I), more preferably an inorganic compound or an anion derived from an inorganic compound, particularly a chlorine anion (Cl - is preferably a) -) and isothiocyanate anion (NCS.
  • the compound of the metal ion M is not particularly limited, and examples thereof include a halide of the metal ion M.
  • a metal complex which is a bidentate ligand in which L 1 and L 2 are bonded to each other among L 1 to L 3 in the formula (II) is converted into a compound of the metal ion M by using a precursor represented by the formula (IIA). It can be obtained by coordinating the metal ion M with a bidentate ligand in which L 1 and L 2 synthesized separately after coordination are bonded to each other.
  • bidentate ligands L 1 and L 2 are bonded to each other has the same meaning as ligand bidentate where L 1 and L 2 in formula (I) bonded to each other, preferably those same It is.
  • the ligand L 3 is selected from the ligands (La) to (Lf), and is preferably selected from the ligand (Lf).
  • a metal complex which is a tridentate ligand in which L 1 , L 2 and L 3 are bonded to each other among L 1 to L 3 in the formula (II) is represented by a metal ion M as a precursor represented by the formula (IIA). It is obtained by coordinating the metal ion M with a tridentate ligand in which L 1 , L 2 and L 3 which are separately synthesized are coordinated with each other, and then synthesized.
  • L 1, L 2 and L 3 are tridentate ligand bound to each other, tridentate ligands synonymous the L 1, L 2 and L 3 in formula (I) bonded to each other
  • the preferred ones are also the same.
  • Metal ion M has the same meaning as M in formula (I), and preferred ones are also the same.
  • the metal complex can be reacted with compounds corresponding to the linking groups X 1 to X 3 and the acidic groups Anc1 to Anc3 to synthesize a metal complex dye represented by the formula (I).
  • a metal complex dye represented by the formula (I) for example, when the portion to which the acidic group Anc is bonded in the linking group is an ethenylene group (including the linking linking group), an active methylene compound such as cyanoacetic acid and the metal complex represented by the formula (II) Is subjected to, for example, a Knoevenagel condensation reaction to synthesize a metal complex dye represented by the formula (I).
  • G of the metal complex represented by the formula (II) is an acetal group, it is preferably deprotected by hydrolysis or the like to be an aldehyde group.
  • the conductive support is preferably a support made of glass or plastic having a conductive film layer on the surface, such as a metal, which is conductive in itself.
  • the plastic support include a transparent polymer film described in paragraph No. 0153 of JP-A No. 2001-291534.
  • the support in addition to glass and plastic, ceramic (Japanese Patent Laid-Open No. 2005-135902) or conductive resin (Japanese Patent Laid-Open No. 2001-160425) may be used.
  • the surface may be provided with a light management function. For example, an antireflection film in which high refractive films and low refractive index oxide films described in JP-A-2003-123859 are alternately laminated Or a light guide function described in JP-A-2002-260746.
  • the thickness of the conductive film layer is preferably 0.01 to 30 ⁇ m, more preferably 0.03 to 25 ⁇ m, and particularly preferably 0.05 to 20 ⁇ m.
  • the conductive support is substantially transparent.
  • substantially transparent means that the light transmittance is 10% or more, preferably 50% or more, particularly preferably 80% or more.
  • a glass or plastic coated with a conductive metal oxide is preferable.
  • the metal oxide tin oxide is preferable, and indium-tin oxide and fluorine-doped oxide are particularly preferable.
  • the coating amount of the conductive metal oxide at this time is preferably 0.1 to 100 g per 1 m 2 of the glass or plastic support. When a transparent conductive support is used, light is preferably incident from the support side.
  • the semiconductor fine particles are preferably metal chalcogenide (for example, oxide, sulfide, selenide, etc.) or perovskite fine particles.
  • metal chalcogenide for example, oxide, sulfide, selenide, etc.
  • perovskite fine particles Preferred examples of the metal chalcogenide include titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, tantalum oxide, cadmium sulfide, cadmium selenide, and the like.
  • Preferred perovskites include strontium titanate and calcium titanate. Of these, titanium oxide (titania), zinc oxide, tin oxide, and tungsten oxide are particularly preferable.
  • titania examples include anatase type, brookite type, and rutile type, and anatase type and brookite type are preferable. Titania nanotubes, nanowires, and nanorods may be mixed with titania fine particles or used as a semiconductor electrode.
  • the particle diameters of the semiconductor fine particles are 0.001 to 1 ⁇ m as primary particles and 0.01 to 100 ⁇ m as the average particle diameter of the dispersion as the average particle diameter using the diameter when the projected area is converted into a circle. preferable.
  • Examples of the method for coating the semiconductor fine particles on the conductive support include a wet method, a dry method, and other methods.
  • the semiconductor fine particles preferably have a large surface area so that many dyes can be adsorbed.
  • the surface area is preferably 10 times or more, more preferably 100 times or more the projected area.
  • the preferred thickness of the photoreceptor layer which is a semiconductor layer, varies depending on the use of the device, but is typically 0.1 to 100 ⁇ m. When used as a dye-sensitized solar cell, it is preferably 1 to 50 ⁇ m, more preferably 3 to 30 ⁇ m.
  • the semiconductor fine particles may be fired at a temperature of 100 to 800 ° C. for 10 minutes to 10 hours in order to adhere the particles to each other after being applied to the support. When glass is used as the support, the film forming temperature is preferably 60 to 400 ° C.
  • the coating amount of semiconductor fine particles per 1 m 2 of support is preferably 0.5 to 500 g, more preferably 5 to 100 g.
  • the total amount of the dye used is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, and particularly preferably 0.1 to 10 mmol per 1 m 2 of the support.
  • the amount of the metal complex dye of the present invention is preferably 5 mol% or more.
  • the adsorption amount of the dye to the semiconductor fine particles is preferably 0.001 to 1 mmol, more preferably 0.1 to 0.5 mmol, with respect to 1 g of the semiconductor fine particles. By using such a dye amount, the sensitizing effect in the semiconductor fine particles can be sufficiently obtained.
  • the counter ion of the specific metal complex dye is not particularly limited, and examples thereof include alkali metal ions and quaternary ammonium ions.
  • the surface of the semiconductor fine particles may be treated with amines.
  • amines include pyridines (for example, 4-tert-butylpyridine, polyvinylpyridine) and the like. These may be used as they are in the case of a liquid, or may be used by dissolving in an organic solvent.
  • the photoelectric conversion element for example, the photoelectric conversion element 10
  • the dye-sensitized solar cell for example, the photoelectrochemical cell 20
  • at least the metal complex dye of the present invention is used.
  • the metal complex dye of the present invention may be used in combination with another dye.
  • the dye used in combination include Ru complex dyes described in JP-A-7-500630 (particularly the dyes synthesized in Examples 1 to 19 on page 5, lower left column, line 5 to page 7, upper right column, line 7). ), Ru complex dyes described in JP-T-2002-512729 (especially dyes synthesized in Examples 1 to 16 from the third line to the 29th page and the 23rd line from the bottom of page 20), JP-A-2001- Ru complex dyes described in Japanese Patent No. 59062 (particularly dyes described in paragraphs 0087 to 0104), Ru complex dyes described in Japanese Patent Application Laid-Open No.
  • Dyes described in JP-A-2007-287694 organic dyes described in JP-A No. 2007-287694 (especially dyes described in paragraphs 0091-0096), organic dyes described in JP-A-2008-71648 (in particular, Pigments described in paragraphs 0030 to 0034), organic dyes described in WO 2007/119525 pamphlet (particularly, the dye described in [0024]), Angew. Chem. Int. Ed. , 49, 1-5 (2010), etc., Angew. Chem. Int. Ed. , 46, 8358 (2007), and the like.
  • the dye used in combination is preferably a Ru complex dye, a squarylium cyanine dye, or an organic dye.
  • the ratio of the mass of the metal complex dye of the present invention to the mass of the other dye is preferably 95/5 to 10/90, and 95/5 to 50/50. Is more preferable, 95/5 to 60/40 is further preferable, 95/5 to 65/35 is particularly preferable, and 95/5 to 70/30 is most preferable.
  • the charge transfer layer used in the photoelectric conversion element of the present invention is a layer having a function of replenishing electrons to the dye oxidant, and is provided between the light receiving electrode and the counter electrode (counter electrode).
  • the charge transfer layer includes an electrolyte.
  • the electrolyte include a liquid electrolyte obtained by dissolving a redox couple in an organic solvent, a so-called gel electrolyte obtained by impregnating a polymer matrix obtained by dissolving a redox couple in an organic solvent, and a molten salt containing the redox couple. .
  • a liquid electrolyte is preferable.
  • a nitrile compound As the solvent for the liquid electrolyte, a nitrile compound, an ether compound, an ester compound or the like is used, and a nitrile compound is preferable, and acetonitrile and methoxypropionitrile are particularly preferable.
  • iodine and iodide iodide salt, ionic liquid is preferable, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, methylpropylimidazolium iodide are preferable
  • alkyl viologen for example, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate
  • polyhydroxybenzenes for example, hydroquinone, naphthohydroquinone, etc.
  • divalent And trivalent iron complexes for example, red blood salt and yellow blood salt
  • divalent and trivalent cobalt complexes and the like.
  • the cobalt complex is preferably a complex represented by the following formula (CC).
  • LL represents a bidentate or tridentate ligand.
  • X represents a monodentate ligand.
  • ma represents an integer of 0 to 3.
  • mb represents an integer of 0-6.
  • CI represents a counter ion when a counter ion is required to neutralize the charge.
  • CI includes CI in the formula (I).
  • LL is preferably a ligand represented by the following formula (LC).
  • X LC1 and X LC3 each independently represent a carbon atom or a nitrogen atom.
  • X LC1 N
  • X LC3 N
  • X LC1 N
  • X LC3 N
  • Z LC1 , Z LC2 and Z LC3 each independently represent a nonmetallic atom group necessary for forming a 5-membered ring or a 6-membered ring.
  • Z LC1 , Z LC2 and Z LC3 may have a substituent and may be closed with an adjacent ring via the substituent.
  • q represents 0 or 1; Examples of the substituent include the substituent T described later.
  • the carbon atom at the position where X LC3 is bonded to the 5-membered ring or 6-membered ring formed by Z LC2 is a hydrogen atom or a substituent other than the heterocyclic group formed by Z LC3 Join.
  • X is preferably a halogen ion.
  • the ligand represented by the above formula (LC) is more preferably a ligand represented by the following formulas (LC-1) to (LC-4).
  • R LC1 to R LC11 each independently represents a substituent.
  • q1, q2, q6 and q7 each independently represents an integer of 0 to 4.
  • q3, q5, q10 and q11 each independently represents an integer of 0 to 3.
  • q4 represents an integer of 0-2.
  • examples of the substituent represented by R LC1 to R LC11 include an aliphatic group, an aromatic group, and a heterocyclic group.
  • Specific examples of the substituent include alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, and heterocyclic rings.
  • Preferred examples include alkyl groups (eg methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl, benzyl etc.), aryl groups (eg phenyl, tolyl, naphthyl).
  • alkyl groups eg methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl, benzyl etc.
  • aryl groups eg phenyl, tolyl, naphthyl
  • alkoxy groups eg methoxy, ethoxy, isopropoxy, butoxy etc.
  • alkylthio groups eg methylthio, n-butylthio, n-hexylthio, 2-ethylhexylthio etc.
  • aryloxy groups eg phenoxy, naphthoxy etc.
  • arylthio groups eg, phenylthio, naphthylthio, etc.
  • heterocyclic groups eg, 2-thienyl, 2-furyl, etc.
  • cobalt complex having a ligand represented by the formula (LC) include the following complexes.
  • iodine and iodide When a combination of iodine and iodide is used as the electrolyte, it is preferable to further use an iodine salt of a 5-membered or 6-membered nitrogen-containing aromatic cation.
  • organic solvent for dissolving the redox couple these are aprotic polar solvents (for example, acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, sulfolane, 1,3-dimethylimidazolinone, 3-methyloxazolidinone, etc. ) Is preferred.
  • aprotic polar solvents for example, acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, sulfolane, 1,3-dimethylimidazolinone, 3-methyloxazolidinone, etc.
  • the polymer used for the matrix of the gel electrolyte include polyacrylonitrile and polyvinylidene fluoride.
  • the molten salt include those imparted with fluidity at room temperature by mixing polyethylene oxide with lithium iodide and at least one other lithium salt (such as lithium acetate and lithium perchlorate). It is
  • aminopyridine compounds As an additive to the electrolyte, in addition to the aforementioned 4-tert-butylpyridine, aminopyridine compounds, benzimidazole compounds, aminotriazole compounds and aminothiazole compounds, imidazole compounds, aminotriazine compounds, urea derivatives, Amide compounds, pyrimidine compounds and nitrogen-free heterocycles can be added.
  • a method of controlling the moisture of the electrolytic solution may be taken.
  • Preferred methods for controlling moisture include a method for controlling the concentration and a method in which a dehydrating agent is allowed to coexist.
  • an inclusion compound of iodine and cyclodextrin may be used, or a method of constantly supplying water may be used.
  • Cyclic amidine may be used, and an antioxidant, hydrolysis inhibitor, decomposition inhibitor, and zinc iodide may be added.
  • a molten salt may be used as the electrolyte, and preferred molten salts include ionic liquids containing imidazolium or triazolium type cations, oxazolium-based, pyridinium-based, guanidinium-based, and combinations thereof. These cationic systems may be combined with specific anions. Additives may be added to these molten salts. You may have a liquid crystalline substituent. Further, a quaternary ammonium salt-based molten salt may be used.
  • molten salt other than these for example, flowability at room temperature was imparted by mixing polyethylene oxide with lithium iodide and at least one other lithium salt (for example, lithium acetate, lithium perchlorate, etc.). And the like.
  • the electrolyte may be quasi-solidified by adding a gelling agent to an electrolyte solution composed of an electrolyte and a solvent for gelation.
  • a gelling agent include organic compounds having a molecular weight of 1000 or less, Si-containing compounds having a molecular weight in the range of 500 to 5000, organic salts made of a specific acidic compound and a basic compound, sorbitol derivatives, and polyvinylpyridine.
  • the matrix polymer is preferably a polymer having a nitrogen-containing heterocyclic ring in the main chain or side chain repeating unit, a crosslinked product obtained by reacting these with an electrophilic compound, a polymer having a triazine structure, or a ureido structure.
  • polymers liquid crystal compounds, ether-bonded polymers, polyvinylidene fluoride, methacrylate / acrylate, thermosetting resins, crosslinked polysiloxane, polyvinyl alcohol (PVA), polyalkylene glycol and dextrin
  • PVA polyvinyl alcohol
  • Examples include compounds, systems to which oxygen-containing or sulfur-containing polymers are added, natural polymers, and the like.
  • An alkali swelling polymer, a polymer having a compound capable of forming a charge transfer complex between a cation moiety and iodine in one polymer, and the like may be added thereto.
  • a system containing a cross-linked polymer obtained by reacting a functional group such as a hydroxyl group, an amino group, or a carboxyl group with one or more functional isocyanate as one component may be used.
  • a crosslinking method in which a crosslinked polymer composed of a hydrosilyl group and a double bond compound, polysulfonic acid, polycarboxylic acid, or the like is reacted with a divalent or higher valent metal ion compound may be used.
  • Examples of the solvent that can be preferably used in combination with the quasi-solid electrolyte include a specific phosphate ester, a mixed solvent containing ethylene carbonate, and a solvent having a specific dielectric constant.
  • the liquid electrolyte solution may be held in a solid electrolyte membrane or pores, and preferred methods thereof include conductive polymer membranes, fibrous solids, and cloth-like solids such as filters.
  • a solid charge transport layer such as a p-type semiconductor or a hole transport material, for example, CuI, CuNCS, or the like can be used. Also, Nature, vol. 486, p. The electrolyte described in 487 (2012) or the like may be used. An organic hole transport material may be used as the solid charge transport layer.
  • the hole transport layer is preferably a conductive polymer such as polythiophene, polyaniline, polypyrrole and polysilane, and a spiro compound in which two rings share a tetrahedral structure such as C or Si, an aromatic such as triarylamine Examples include amine derivatives, triphenylene derivatives, nitrogen-containing heterocyclic derivatives, and liquid crystalline cyano derivatives.
  • a preferable concentration is 0.01 mol / L or more in total, more preferably 0.1 mol / L or more, and particularly preferably 0.3 mol / L or more.
  • the upper limit in this case is not particularly limited, but is usually about 5 mol / L.
  • a coadsorbent In the photoelectric conversion element of this invention, it is preferable to use a coadsorbent with the metal complex dye of this invention or the pigment
  • a co-adsorbent a co-adsorbent having at least one acidic group (preferably a carboxyl group or a salt group thereof) is preferable, and examples thereof include a compound having a fatty acid or a steroid skeleton.
  • the fatty acid may be a saturated fatty acid or an unsaturated fatty acid, and examples thereof include butanoic acid, hexanoic acid, octanoic acid, decanoic acid, hexadecanoic acid, dodecanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid.
  • Examples of the compound having a steroid skeleton include cholic acid, glycocholic acid, chenodeoxycholic acid, hyocholic acid, deoxycholic acid, lithocholic acid, ursodeoxycholic acid and the like. Preferred are cholic acid, deoxycholic acid and chenodeoxycholic acid, and more preferred are chenodeoxycholic acid.
  • a preferred co-adsorbent is a compound represented by the following formula (CA).
  • R A1 represents a substituent having an acidic group.
  • R A2 represents a substituent.
  • nA represents an integer of 0 or more.
  • An acidic group is synonymous with what was shown previously, and its preferable range is also the same.
  • R A1 is preferably a carboxyl group or an alkyl group substituted with a sulfo group or a salt thereof, —CH (CH 3 ) CH 2 CH 2 CO 2 H, —CH (CH 3 ) CH 2 CH 2 CONHCH More preferred is 2 CH 2 SO 3 H.
  • R A2 examples include the substituent T described later. Among them, an alkyl group, a hydroxy group, an acyloxy group, an alkylaminocarbonyloxy group, and an arylaminocarbonyloxy group are preferable, and an alkyl group, a hydroxy group, and an acyloxy group are more preferable. . nA is preferably 2 to 4.
  • These specific compounds include the compounds exemplified as the compounds having the steroid skeleton described above.
  • the co-adsorbent of the present invention has an effect of suppressing inefficient association of dyes by adsorbing to semiconductor fine particles and an effect of preventing reverse electron transfer from the surface of the semiconductor fine particles to the redox system in the electrolyte.
  • the amount of coadsorbent used is not particularly limited, but it is preferably 1 to 200 mol, more preferably 10 to 150 mol, and particularly preferably 20 to 50 mol with respect to 1 mol of the dye. It is preferable from the viewpoint of being effectively expressed.
  • the counter electrode is preferably a positive electrode of a dye-sensitized solar cell (photoelectrochemical cell).
  • the counter electrode is usually synonymous with the conductive support described above, but the support is not necessarily required in a configuration in which the strength is sufficiently maintained.
  • As the structure of the counter electrode a structure having a high current collecting effect is preferable.
  • at least one of the conductive support and the counter electrode described above must be substantially transparent.
  • the conductive support is preferably transparent, and sunlight is preferably incident from the support side. In this case, it is more preferable that the counter electrode has a property of reflecting light.
  • a counter electrode of the dye-sensitized solar cell glass or plastic on which metal or conductive oxide is vapor-deposited is preferable, and glass on which platinum is vapor-deposited is particularly preferable.
  • the dye-sensitized solar cell it is preferable to seal the side surface of the battery with a polymer, an adhesive or the like in order to prevent the constituents from evaporating.
  • the present invention is disclosed in Japanese Patent No. 4260494, Japanese Patent Application Laid-Open No. 2004-146425, Japanese Patent Application Laid-Open No. 2000-340269, Japanese Patent Application Laid-Open No. 2002-289274, Japanese Patent Application Laid-Open No. 2004-152613, and Japanese Patent Application Laid-Open No. 9-27352. It can apply to the described photoelectric conversion element and a dye-sensitized solar cell.
  • the metal complex dye of the present invention is dissolved in a solvent and may contain a co-adsorbent and other components as necessary.
  • the solvent to be used include, but are not particularly limited to, the solvents described in JP-A No. 2001-291534.
  • an organic solvent is preferable, and alcohols, amides, nitriles, hydrocarbons, and a mixed solvent of two or more of these are preferable.
  • a mixed solvent of an alcohol and a solvent selected from amides, nitriles or hydrocarbons is preferable. Further preferred are alcohols and amides, mixed solvents of alcohols and hydrocarbons, and particularly preferred are mixed solvents of alcohols and amides. Specifically, methanol, ethanol, propanol, butanol, dimethylformamide, and dimethylacetamide are preferable.
  • the dye solution preferably contains a co-adsorbent.
  • the co-adsorbent the above-mentioned co-adsorbent is preferable, and among them, the compound represented by the formula (CA) is preferable.
  • the dye solution of the present invention is preferably one in which the concentration of the metal complex dye or coadsorbent is adjusted so that the solution can be used as it is when producing a photoelectric conversion element or a dye-sensitized solar cell.
  • the metal complex dye of the present invention is preferably contained in an amount of 0.001 to 0.1% by mass.
  • the water content of the dye solution is particularly preferably adjusted. Therefore, in the present invention, the water content (content ratio) is preferably adjusted to 0 to 0.1% by mass. Similarly, the adjustment of the water content of the electrolyte in the photoelectric conversion element or the dye-sensitized solar cell is also preferable in order to effectively exhibit the effect of the present invention. For this reason, the water content (content rate) of the electrolyte solution is It is preferable to adjust to 0 to 0.1% by mass.
  • the electrolyte is particularly preferably adjusted with a dye solution.
  • a dye adsorption electrode which is a semiconductor electrode for a dye-sensitized solar cell in which a metal complex dye is supported on the surface of a semiconductor fine particle provided in a semiconductor electrode using the dye solution is preferable. That is, a dye-adsorbing electrode for a dye-sensitized solar cell is obtained by applying a composition obtained from the dye solution onto a conductive support provided with semiconductor fine particles, and curing the composition after application. What was made into the photoreceptor layer is preferable.
  • a dye-sensitized solar cell by using the dye-adsorbing electrode for the dye-sensitized solar cell, preparing an electrolyte and a counter electrode, and assembling them using these.
  • This compound (6) is a tridentate ligand in which L 1 , L 2 and L 3 are bonded to each other, and G is an acetal group and is a metal complex represented by the formula (II).
  • the obtained compound (6) was identified by 1 H-NMR and ESI-MS.
  • This compound (7) is a tridentate ligand in which L 1 , L 2, and L 3 are bonded to each other, and G is a metal complex represented by the formula (II), in which G is an aldehyde group.
  • the obtained compound (7) was identified by 1 H-NMR.
  • Metal complex dye Dye-4 was synthesized by the following synthesis scheme.
  • a metal complex dye Dye-5 was synthesized according to the following synthesis scheme. First, the following compound (25) was synthesized according to the following synthesis scheme.
  • a metal complex dye Dye-8 was synthesized in the same manner as the metal complex dye Dye-7.
  • the synthesized metal complex dyes Dye-1 to 9 were adjusted with a 340 ⁇ mol / L tetrabutylammonium hydroxide methanol solvent so that the dye concentration would be 17 ⁇ mol / L, and spectral absorption measurement was performed. As a result, it was confirmed that all of the metal complex dyes Dye-1 to Dye-9 had a maximum absorption wavelength ( ⁇ max) at 650 nm or more in the long wavelength region.
  • the ultraviolet-visible absorption spectra of Dye-1, 2, 4, 5 and 6 are shown in FIGS.
  • Dye-1 is FIG. 10
  • Dye-2 is FIG. 11
  • Dye-4 is FIG. 12
  • Dye-5 is FIG. 13
  • Dye-6 is FIG.
  • the molar absorption coefficient ⁇ is large in the long wavelength region of 700 nm or more, and in particular, those having two Ancs (two of Anc1 to Anc3) exhibit larger absorption characteristics.
  • FIG. 15 to 17 show visible absorption spectra of a model semiconductor film (titanium oxide film on which a metal complex dye is adsorbed) according to Example 2 below.
  • FIG. 15 shows Dye-1
  • FIG. 16 shows Dye-5
  • FIG. 17 shows Dye-6.
  • Example 2 [Dye-sensitized solar cell] The following comparative compounds (1) and (2) were used as comparative metal complex dyes. Comparative compound (1) is DCSC9 described in International Publication No. 2009/082163. Comparative compound (2) is compound I-25 described in JP-A-2008-266639.
  • a photoelectrode having the same configuration as that of the photoelectrode 12 shown in FIG. 5 described in JP-A-2002-289274 is prepared by the following procedure, and further, using the photoelectrode, A 10 mm ⁇ 10 mm scale dye-sensitized solar cell 1 having the same configuration as that of the dye-sensitized solar cell 20 except for the photoelectrode described in 3 was prepared.
  • a specific configuration is shown in FIG. 2 attached to the present application. In FIG.
  • 41 is a transparent electrode
  • 42 is a semiconductor electrode
  • 43 is a transparent conductive film
  • 44 is a substrate
  • 45 is a semiconductor layer
  • 46 is a light scattering layer
  • 40 is a photoelectrode
  • 20 is a dye-sensitized solar cell
  • CE is a counter electrode
  • E is an electrolyte
  • S is a spacer.
  • a titania slurry was prepared by placing spherical TiO 2 particles (anatase, average particle size; 25 nm, hereinafter referred to as spherical TiO 2 particles A) in a nitric acid solution and stirring. Next, a cellulose binder as a thickener was added to the titania slurry and kneaded to prepare a paste.
  • a paste was prepared.
  • a transparent electrode 41 having a fluorine-doped SnO 2 conductive film (film thickness: 500 nm) 43 formed on a glass substrate 44 was prepared. Then, on the SnO 2 conductive film 43, the paste 1 of the above screen printing and then dried. Then, it baked on the conditions of 450 degreeC in the air. Further, by repeating the firing and the screen printing using a paste 2, the area of the semiconductor electrode (light receiving surface of the same structure as the semiconductor electrode 42 shown in FIG.
  • the semiconductor electrode 42 is immersed in this solution for several hours to several tens of hours, and the immersed semiconductor electrode 42 is pulled up from the solution and dried at 50 ° C., so that the photoelectrode 40 having the dye adsorbed on the semiconductor electrode 42 is obtained. Each completed.
  • IPCE Quantum yield
  • IPCE at 800 nm is shown in Table 1.
  • IPCE is expressed as “A” in terms of IPCE of the comparative compound (1), with 1.50 times or more of this IPCE being expressed as “A”, 1.01 or more and less than 1.50 times being “B”, 1.01 times Less than “C” was assigned.
  • Table 1 The results are summarized in Table 1 below.
  • the photoelectric conversion efficiency ( ⁇ (%)) is 1.50 times or more with respect to the comparative compound (2) as “A”, 1.10 times or more and less than 1.50 times is “B”, 1.00 “C” is defined as “double” or more and less than 1.10 times, and “D” is defined as less than 1.00 times.
  • the dye-sensitized solar cell of the present invention using the metal complex dyes Dye-1 to Dye-9 of the present invention is different from the dye-sensitized solar cell using each comparative compound.
  • IPCE quantum yield
  • ⁇ photoelectric conversion efficiency

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Abstract

La présente invention concerne un élément de conversion photoélectrique qui comprend un corps de support conducteur, une couche photosensible qui contient de fines particules de semi-conducteur chargées avec un colorant de complexe métallique représenté par la formule (I), une couche de transfert de charge, et une contre-électrode ; un colorant pour complexe métallique ; un complexe métallique ; une solution de colorant ; une électrode à adsorption de colorant ; une cellule solaire à colorant ; et un procédé de fabrication de ladite cellule solaire à colorant. formule (I) Dans la formule (I), M représente un ion métallique ; chacune des anneaux A à C représente un hétéro-anneau aromatique qui contient de l'azote ; chacun parmi Z1 et Z2 représente un atome de C ou de N ; chacun parmi R1-R3 représente un substituant ; X1 représente un groupe de liaison autre qu'une liaison simple ; X2 représente un groupe de liaison ; X3 représente une liaison simple ou un groupe de liaison ; chacun parmi Anc1-3 représente un groupe acide ; un ou deux parmi L1-L3 représente(nt) chacun un ligand anionique ; Y représente un ion ; chacun parmi n1 et n3 représente un entier de 0 à 4 ; n2 représente un entier de 0 à 3 ; chacun parmi l1 et l3 représente un entier de 1 à 4 ; l2 représente un entier de 1 à 5 ; m1 représente un entier de 1 à 4 ; m2 représente un entier de 0 à 3 ; m3 représente un entier de 0 à 4 ; et n représente un entier de 0 à 2.
PCT/JP2013/080884 2012-11-16 2013-11-15 Complexe métallique, colorant pour complexe métallique, élément de conversion photoélectrique, cellule solaire à colorant, solution de colorant, électrode à adsorption de colorant, et procédé de fabrication d'une cellule solaire à colorant WO2014077357A1 (fr)

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EP3273456A4 (fr) * 2015-03-17 2018-01-24 FUJI-FILM Corporation Élément de conversion photoélectrique, cellule solaire sensibilisé au colorant, colorant de complexe de ruthénium, et solution de colorant
JPWO2016143507A1 (ja) * 2015-03-09 2018-01-25 富士フイルム株式会社 光電変換素子、色素増感太陽電池、金属錯体色素および色素溶液
US10153442B2 (en) * 2015-12-31 2018-12-11 National Tsing Hua University Iridium complex, OLED using the same, and nitrogen-containing tridentate ligand having carbene unit

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JP6310558B2 (ja) * 2014-06-11 2018-05-16 富士フイルム株式会社 光電変換素子、色素増感太陽電池、金属錯体色素、色素溶液、およびターピリジン化合物またはそのエステル化物
WO2020071415A1 (fr) * 2018-10-03 2020-04-09 コニカミノルタ株式会社 Composition de résine et dispositif electronique

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JP2008222747A (ja) * 2007-03-08 2008-09-25 National Institute Of Advanced Industrial & Technology 色素及びそれを用いた色素増感太陽電池
JP2008266639A (ja) * 2007-03-29 2008-11-06 Sumitomo Chemical Co Ltd 化合物、光電変換素子及び光電気化学電池

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JP2008222747A (ja) * 2007-03-08 2008-09-25 National Institute Of Advanced Industrial & Technology 色素及びそれを用いた色素増感太陽電池
JP2008266639A (ja) * 2007-03-29 2008-11-06 Sumitomo Chemical Co Ltd 化合物、光電変換素子及び光電気化学電池

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2016143507A1 (ja) * 2015-03-09 2018-01-25 富士フイルム株式会社 光電変換素子、色素増感太陽電池、金属錯体色素および色素溶液
EP3270391A4 (fr) * 2015-03-09 2018-04-11 FUJIFILM Corporation Élément de conversion photoélectrique, cellule solaire à colorant, colorant au complexe métallique et solution de colorant
EP3273456A4 (fr) * 2015-03-17 2018-01-24 FUJI-FILM Corporation Élément de conversion photoélectrique, cellule solaire sensibilisé au colorant, colorant de complexe de ruthénium, et solution de colorant
US10153442B2 (en) * 2015-12-31 2018-12-11 National Tsing Hua University Iridium complex, OLED using the same, and nitrogen-containing tridentate ligand having carbene unit

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