WO2006041155A1 - Squarylium compound, photo-electric converting material comprising the same, photo-electric converting element, and photoelectrochemical cell - Google Patents

Squarylium compound, photo-electric converting material comprising the same, photo-electric converting element, and photoelectrochemical cell Download PDF

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WO2006041155A1
WO2006041155A1 PCT/JP2005/018951 JP2005018951W WO2006041155A1 WO 2006041155 A1 WO2006041155 A1 WO 2006041155A1 JP 2005018951 W JP2005018951 W JP 2005018951W WO 2006041155 A1 WO2006041155 A1 WO 2006041155A1
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group
substituent
compound according
squarylium compound
same
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French (fr)
Japanese (ja)
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Ikuo Shimizu
Masanori Ikuta
Shigeaki Kato
Yutaka Osedo
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Kyowa Hakko Chemical Co., Ltd.
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Priority to JP2006540981A priority Critical patent/JPWO2006041155A1/en
Publication of WO2006041155A1 publication Critical patent/WO2006041155A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/40—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino groups bound to carbon atoms of at least one six-membered aromatic ring and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/44—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino groups bound to carbon atoms of at least one six-membered aromatic ring and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton with carboxyl groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by unsaturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C229/56—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in ortho-position
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/68—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H01M14/005—Photoelectrochemical storage cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/652—Cyanine dyes
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a squarylium compound that can be used for a photoelectric conversion element, a photoelectrochemical cell using the squarylium compound, and the like.
  • This battery is a wet solar battery using a ruthenium complex as a photosensitizer and a porous titanium dioxide thin film as a working electrode (see, for example, Patent Document 1 and Non-Patent Document 1).
  • a ruthenium complex of the sensitizing dye is expensive, development of a photoelectric conversion element that is sensitized by an inexpensive organic dye is desired.
  • Patent Document 1 U.S. Pat.No. 4,927,721
  • Patent Document 2 JP-A-11-86916
  • Patent Document 3 European Patent No. 911841 Specification
  • Patent Document 4 Japanese Patent Laid-Open No. 2001-76773
  • Non-Patent Document 1 “Nature”, 1991, No. 353, p. 737-740 Disclosure of the Invention
  • An object of the present invention is to provide a squaryum compound that can be used in a photoelectric conversion element that is inexpensive and has high energy conversion efficiency, a photoelectrochemical cell that uses the squarymium compound, and the like. Means for solving the problem
  • the present invention provides the following (1) to (30).
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, a substituent, or an aralkyl group or a substituent.
  • R 3 , R 4 R 5 and R 6 are the same or different and are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, and an optionally substituted aralkyl.
  • a group, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a hydroxyl group, or a halogen atom, R 3 And R 5 , or R 4 and R 6 may have a substituent together with two adjacent carbon atoms, or may have a hydrocarbon ring or a substituent.
  • R 1 and R 3 , or R 2 and R 4 which may form a heterocyclic ring, together with the adjacent N—C—C, may have a substituent.
  • X may have the general formula (II) [0010] [Chemical 3]
  • R ′ may have a hydrogen atom, an alkyl group which may have a substituent, or a substituent! /, An aralkyl group, having a substituent! /, Or an aryl group or a heterocyclic group which may have a substituent! / R 8 may have a halogen atom or a substituent.
  • An optionally substituted alkyl group, an optionally substituted alkoxyl group, an optionally substituted aralkyl group, an optionally substituted aryl group, a nitro group, a cyano group, a hydroxyl group A group, a substituent, or an amino group or a substituent, a heterocyclic group, a represents an integer of 0 to 4, wherein a is 2 to 4
  • each R 8 may be the same or different, and two adjacent R 8 s may be combined with two adjacent carbon atoms, each having a substituent, or carbonized.
  • Yogu R 9 and R 1C also form a heterocyclic ring> are the same or different
  • Y represents an aryl group or cyano group
  • b represents an integer of 0 to 4
  • each R 9 and each R 1 (> may be the same or different
  • c represents an integer of 1 to 5, and in the case where the length is 2 to 5, each A and each general formula (A)
  • a group represented by the formula (wherein R 9 , R 1 () and b are as defined above may be the same or different), or a group represented by the general formula ( ⁇ )
  • R 11 is a hydrogen atom, an alkyl group which may have a substituent, may have a substituent! /, An aralkyl group, or a substituent! /,
  • R 12 and R 13 may be the same or different, and may be a halogen atom, an alkyl group which may have a substituent, An alkoxyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, a nitro group, a cyano group, a hydroxyl group, and a substituent
  • An optionally substituted amino group or an optionally substituted heterocyclic group
  • p represents an integer of 0 to 3, and when p is 2 to 3, each R 12 is the same Or q may be an integer from 0 to 3, and when q is 2 to 3, each R 13 may be the same or different.
  • R 14 and R 15 are the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, a carboxyl group, an alkoxycarbonyl group, an aralkyl group which may have a substituent, or a substituent.
  • Y represents an acidic group
  • s represents an integer of 1 to 4, and when s is 2 to 4, each E and each general formula (B)
  • R 1 R ′ R ′′, R 14 , R L E, p, q, r and s each represent the same group as defined above] Compound.
  • R 7 , R 8 , RR 10 , A, a, b and c each represents the same group as defined above].
  • (20) a is 0 from (15) to (19)! / The squarylium compound described in any one of them.
  • a photoelectric conversion material comprising the squarylium compound according to any one of (1) to (27) and a semiconductor.
  • a photoelectrochemical cell comprising the photoelectric conversion element according to (29).
  • the squarylium compound represented by the general formula (I) may be expressed as a compound (I).
  • Other compounds of the formula number may be expressed in the same manner.
  • a squarylium compound that can be used in a photoelectric conversion element that is inexpensive and has high energy conversion efficiency, a photoelectrochemical cell that uses the squarylium compound, and the like.
  • examples of the alkyl group and the alkyl moiety in the alkoxyl group and alkoxycarbonyl group include, for example, a linear or branched alkyl group having 1 to 6 carbon atoms or Examples thereof include cyclic alkyl groups having 3 to 8 carbon atoms, and specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec butyl group, tert butyl group, pentyl group, isopentyl group.
  • Examples of the aralkyl group include aralkyl groups having 7 to 15 carbon atoms, and specific examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group.
  • Examples of the aryl group include aryl groups having 6 to 14 carbon atoms, and specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, and an azulenyl group.
  • halogen atom examples include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.
  • heterocyclic ring in the heterocyclic group examples include, for example, a 5-membered or 6-membered monocyclic aromatic or aliphatic heterocyclic ring containing at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and 3 to 8 members.
  • heterocyclic ring in the heterocyclic group examples include condensed bicyclic or tricyclic condensed rings containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and specific examples thereof.
  • heterocyclic ring formed by combining R 1 and R 2 with the adjacent nitrogen atom examples include, for example, a 5-membered or 6-membered monocyclic heterocyclic ring containing at least one nitrogen atom (including A monocyclic heterocycle may contain other nitrogen, oxygen or sulfur atoms), a bicyclic or tricyclic condensed 3- to 8-membered ring and containing at least one nitrogen atom.
  • Cyclic heterocyclic rings (the condensed heterocyclic rings may contain other nitrogen, oxygen or sulfur atoms), and specific examples thereof include pyrrolidine ring, piperidine ring, piperidine ring, and the like.
  • the formed heterocycle include a 5-membered or 6-membered monocyclic heterocycle containing at least one nitrogen atom (the monocyclic heterocycle contains other nitrogen atoms, oxygen atoms or sulfur atoms).
  • a condensed heterocyclic ring containing a bicyclic or tricyclic condensed at least one nitrogen atom fused with a 3- to 8-membered ring (the condensed heterocyclic ring is another nitrogen atom, And may include an oxygen atom or a sulfur atom), and specific examples thereof include a pyrroline ring, 1, 2, 3, 4-tetrahydropyridine ring, 1, 2, 3, 4-tetrahydropyrazine ring, 2,3 dihydronoroxazine ring, 2,3 dihydro-1,4 thiazine ring, tetrahydroazepine ring, tetrahydrazepine ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, pyrrole ring, imidazole ring, pyrazole ring, indole ring, etc. That.
  • the heterocyclic ring formed together with the atom include, for example, a 5- or 6-membered monocyclic aromatic heterocyclic ring containing at least one atom selected from a nitrogen atom, an oxygen atom and sulfur nuclear power, 3 to Specific examples are bicyclic or tricyclic condensed 8-membered rings containing at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur nuclear atom.
  • a hydrocarbon ring formed by R 3 and R 5 or R 4 and R 6 together with two adjacent carbon atoms, and two R 8 adjacent to each other are two adjacent to each other.
  • Examples of the hydrocarbon ring formed together with the carbon atom include unsaturated hydrocarbon rings having 5 to 10 carbon atoms, and specific examples thereof include a cyclopentene ring, a cyclohexene ring, and a cycloheptene. And a ring, a cyclooctene ring, a benzene ring, a naphthalene ring, and the like.
  • a heterocycle formed by R 3 and R 5 , or R 4 and R 6 together with two adjacent carbon atoms, and two R 8 adjacent to each other are each Heterocyclic ring formed with two adjacent carbon atoms, hydrocarbon ring formed with R 3 and R 5 , or R 4 and R 6 with two adjacent carbon atoms, respectively ,
  • a hydrocarbon ring formed by two adjacent R 8 s together with two adjacent carbon atoms, and R 1 and R 3 , or R 2 and R 4 are adjacent N—C—
  • Examples of the substituent of the heterocyclic ring formed together with C include, for example, the same or different 1 to 5 substituents, specifically, a hydroxyl group, a carboxyl group, a halogen atom, an alkyl group.
  • Alkoxyl group Alkoxyl group, nitro group, alkyl substitution Other amino group of non-substitution, and the like.
  • a halogen atom, an alkyl group and an alkoxyl group have the same meanings as described above, and the alkyl part of the alkyl-substituted amino group has the same meaning as the alkyl group.
  • Examples of the substituent of the alkyl group and the alkoxyl group include the same or different one to three substituents, specifically, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxyl group and the like.
  • a halogen atom and an alkoxyl group are as defined above.
  • substituent of the amino group examples include one or two alkyl groups which are the same or different, and the alkyl group in this case is as defined above.
  • the acidic group refers to a group having a hydrogen atom that can be dissociated, and examples thereof include a carboxyl group, a hydroxyl group, a phosphono group, and a sulfo group. These groups may form salts with alkali metal ions, ammonium ions, organic ammonium ions and the like. Further, an intramolecular complex salt may be formed. Examples of the alkali metal in the alkali metal ion include lithium, sodium, and potassium. Examples of organic ammonia include tetraptyl ammonium.
  • R ⁇ R 2, R 3 , R 4, R 5, R 6, R 7, R 8, R 9, R 10, 1, R 12, R 13, R 14, R 15, A ⁇ E , A, b, c, p, q, r and s are as defined above
  • W is a halogen atom such as chlorine or bromine, or OR 16 (wherein R 16 represents an alkyl group, The group is as defined above)
  • Compound (VII) is obtained by reacting Compound (V) with 1 to 2 moles of Compound (VI) in a solvent at 0 to 40 ° C for 1 to 20 hours in the presence of 1 to 2 moles of a base. Can be obtained.
  • Examples of the solvent include halogenated hydrocarbons such as chloroform, dichloromethane and 1,2-dichloroethane, ethers such as jetyl ether and tert-butyl methyl ether, and aromatics such as toluene and benzene.
  • halogenated hydrocarbons such as chloroform, dichloromethane and 1,2-dichloroethane
  • ethers such as jetyl ether and tert-butyl methyl ether
  • aromatics such as toluene and benzene.
  • hydrocarbons examples include hydrocarbons, alcohols such as methanol, ethanol and propanol, tetrahydrofuran, ethyl acetate, dimethylformamide, dimethylsulfoxide (DMSO) and the like.
  • Examples of the base include organic bases such as quinoline, triethylamine, and pyridine, and inorganic bases such as potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium hydroxide, and sodium hydroxide. .
  • Compound (VI) can be obtained, for example, as a commercial product.
  • Compound (VIII) is obtained by mixing Compound (VII) in 50 to 90% by volume of acetic acid aqueous solution at 90 to 120 ° C. for 0.1 to 7 hours, or in 50 to 99% by weight of trifluoroacetic acid aqueous solution. It is obtained by treating at 50 ° C for 0.1 to 3 hours.
  • Compound (la) is prepared by combining compound (VIII) with 1 to 2 moles of compound (IX) in the presence of 1 to 2 moles of a base in a solvent at 80 to 120 ° C. It is obtained by reacting for 15 minutes to 15 minutes.
  • Examples of the solvent include only alcohol solvents having 2 to 8 carbon atoms such as ethanol, propanol, isopropyl alcohol, butanol and octanol, or a mixed solvent of the alcohol solvent and benzene or toluene (alcohol 40). Volume% or more) is used.
  • alcohol solvents having 2 to 8 carbon atoms such as ethanol, propanol, isopropyl alcohol, butanol and octanol, or a mixed solvent of the alcohol solvent and benzene or toluene (alcohol 40). Volume% or more) is used.
  • Examples of the base include organic bases such as quinoline, triethylamine, and pyridine, and inorganic bases such as potassium carbonate, potassium bicarbonate, and sodium bicarbonate.
  • Compound (IX) can be produced, for example, according to a known method (German Published Publication No. 2406333 etc.) or similar methods, but is also commercially available.
  • the compound (la) is further purified by a method usually used in organic synthetic chemistry (column chromatography, recrystallization, washing with a solvent, etc.), if necessary, by evaporating or filtering the solvent. Thus, it can be isolated and purified.
  • Compound (lb) is obtained by mixing Compound (VIII) with 1 to 2 moles of Compound (X), if necessary, in the presence of 1 to 2 moles of a base in a solvent at 80 to 120 ° C. It can be obtained by reacting for ⁇ 15 hours.
  • Examples of the solvent include only alcohol solvents having 2 to 8 carbon atoms such as ethanol, propanol, isopropyl alcohol, butanol, and octanol, or a mixed solvent of the alcohol solvent and benzene or toluene (alcohol 40). Volume% or more) is used.
  • Examples of the base include organic bases such as quinoline, triethylamine, and pyridine, and inorganic bases such as potassium carbonate, potassium bicarbonate, and sodium bicarbonate.
  • Compound (X) can be obtained, for example, by a known method ["Chemical Research in Chinese Universities", 1991, 7th, No. 3, page 197, etc. Or can be produced according to them, but can also be obtained as a commercial product.
  • the compound (lb) is further purified by, for example, distilling off the solvent or filtering, and if necessary, by a method usually used in organic synthesis chemistry (column chromatography, recrystallization, washing with a solvent, etc.). Thus, it can be isolated and purified.
  • Compound (IVa) is obtained by mixing compound (VII) with 1 to 2 moles of compound (IX) in the presence of 1 to 2 moles of a base in a solvent at 80 to 120 ° C. It is obtained by reacting for 15 minutes to 15 minutes.
  • Examples of the solvent include alcohol solvents having 2 to 8 carbon atoms such as ethanol, propanol, isopropyl alcohol, butanol and octanol, or a mixed solvent of the alcohol solvent and benzene or toluene (alcohol 40). Volume% or more) is used.
  • alcohol solvents having 2 to 8 carbon atoms such as ethanol, propanol, isopropyl alcohol, butanol and octanol, or a mixed solvent of the alcohol solvent and benzene or toluene (alcohol 40). Volume% or more) is used.
  • Examples of the base include organic bases such as quinoline, triethylamine, and pyridine, and inorganic bases such as potassium carbonate, potassium bicarbonate, and sodium bicarbonate.
  • the compound (IVa) is further distilled, for example, by distilling off the solvent or filtering, and if necessary, by a method usually used in organic synthetic chemistry (column chromatography, recrystallization, washing with a solvent, etc.). It can be isolated and purified by purification treatment.
  • Compound (IVb) is compound (VII) and 1 to 2 moles of Compound (X), if necessary, in the presence of 1 to 2 moles of a base in a solvent at 80 to 120 ° C. It can be obtained by reacting for ⁇ 15 hours.
  • Examples of the solvent include alcohol-based solvents having 2 to 8 carbon atoms such as ethanol, propanol, isopropyl alcohol, butanol, and octanol, or a mixed solvent of the alcohol-based solvent and benzene or toluene (alcohol 40). Volume% or more) is used.
  • Examples of the base include organic bases such as quinoline, triethylamine, and pyridine, and inorganic bases such as potassium carbonate, potassium bicarbonate, and sodium bicarbonate.
  • the compound (IVb) is, for example, distilled off or filtered, and if necessary, a method usually used in organic synthetic chemistry (column chromatography, recrystallization, washing with a solvent, etc.) ) Can be isolated and purified by further purification treatment.
  • the photoelectric conversion material of the present invention contains compound (I) or (IV) and a semiconductor.
  • the photoelectric conversion element of the present invention comprises a conductive support, a compound installed on the conductive support (
  • the photoelectrochemical cell according to the present invention is one in which this photoelectric conversion element can be used for a battery used for work in an external circuit. That is, the photoelectrochemical cell of the present invention is such that an external circuit connected to the conductive support and the counter electrode of the photoelectric conversion element of the present invention via a lead works.
  • the photoelectrochemical cell is preferably sealed on the side with a polymer, an adhesive or the like in order to prevent deterioration of the constituents and volatilization of the electrolyte used for the charge transfer layer.
  • the semiconductor used for the photoelectric conversion material is a so-called photoconductor, which absorbs light and separates charges to generate electrons and holes.
  • semiconductors sensitized by compound (I) or (IV) light absorption and the generation of electrons and holes thereby occurs mainly in compound (I) or (IV), and the semiconductor receives and transmits these electrons. Take a role.
  • the semiconductor is not particularly limited, but for example, single oxides such as titanium oxide, indium oxide, tin oxide, bismuth oxide, zirconium oxide, tantalum oxide, niobium oxide, tandasten oxide, iron oxide, gallium oxide, nickel oxide, etc.
  • the semiconductor thin film is preferably a compound semiconductor having a nanoporous structure with nanoparticle force, and can be manufactured using the semiconductors listed above [Journal of American 'Ceramic' Society (Journal of American Ceramic Society), 1997, No. 80, No. 12, p. 3157].
  • the semiconductor thin film electrode used in the photoelectric conversion element of the present invention is prepared, for example, by preparing a transparent electrode as a conductive support, laminating a semiconductor thin film on the transparent electrode, and forming the compound (I ) Or (IV) can be adsorbed.
  • the transparent electrode is not particularly limited as long as it has conductivity.
  • a transparent or translucent glass substrate or plastic plate for example, fluorine or antimony-doped oxide oxide, tin-doped indium oxide, zinc oxide, etc.
  • Those coated with a conductive transparent oxide semiconductor thin film preferably those coated with a fluorine-doped tin oxide thin film are used.
  • Examples of a method of placing the compound semiconductor on the conductive support include a method of applying a dispersion or a colloidal solution of the compound semiconductor on the conductive support. Method, dipping method, air knife method, blade method, spin method, spray method and the like.
  • the compound semiconductor is preferably heat-treated in order to electronically contact the semiconductor fine particles after being applied to the conductive support, and to improve the coating film strength and the adhesion to the support.
  • a preferable heat treatment temperature range is 100 to 600 ° C.
  • the heat treatment time is 10 minutes to 10 hours.
  • a method of performing heat treatment a method of applying a dispersion of a compound semiconductor or a mixture of a colloidal solution and a titanium salt (for example, tetrasalt-titanium) to a conductive support and then hydrothermally treating the compound semiconductor with a polar organic solvent (For example, terf-butanol, etc.) Dispersed in electrophoresis, electrophoretic deposition by electrophoresis, dispersion of compound semiconductor or colloidal solution is applied to conductive support, and then pressed under pressure of about 98070 kPa For example, a method of irradiating a microwave of about 28 GHz after applying a dispersion or colloidal solution of a compound semiconductor to a conductive support is used.
  • the film thickness of the semiconductor thin film is preferably 0.1-100 ⁇ m, more preferably 2-25 ⁇ m.
  • the compound (I) or (IV) is adsorbed onto the semiconductor thin film by immersing the semiconductor thin film coated on the support in the compound (I) or (IV) solution, and at room temperature for 1 minute to 2 days. Alternatively, it can be carried out by leaving it for 1 minute to 24 hours under heating conditions.
  • the solvent used when the compound (I) or (IV) is adsorbed on the semiconductor thin film is not particularly limited as long as it is a solvent that dissolves the compound (I) or (IV).
  • mixed solvents thereof may be used.
  • the concentration of the compound (I) or (IV) solution is preferably 0. OlmmolZl or more 0.1-1. Ommol / 1 It is more preferable that
  • the compound (I) or (IV) and a known dye such as a ruthenium complex dye or other organic dye (for example, Polymethine dyes) and the like may be used in combination.
  • a steroid-like compound having a carboxyl group for example, chenodeoxycholic acid
  • the charge transfer layer is a layer having a function of replenishing electrons to the oxidant of the compound (I) or (IV).
  • the compound (I) or (IV) which has absorbed light has an electron Will be converted to an oxidant to release.
  • Examples of the charge transfer layer used in the photoelectric conversion element of the present invention include a liquid (electrolytic solution) obtained by dissolving a redoxion pair in an organic solvent, and a gel electrolyte obtained by impregnating a polymer in a liquid obtained by dissolving a redox ion pair in an organic solvent. And a molten salt containing a redox ion pair, a solid electrolyte, an inorganic compound semiconductor, an organic hole transport material, and the like.
  • redox ion pair examples include, but are not limited to, iodine redox, bromine redox, iron redox, tin redox, chromium redox, vanadium redox, sulfide ion redox, anthraquinone redox, and the like. More specifically, iodine redox includes imidazolium iodide derivatives, lithium iodide, potassium iodide, tetraalkyl ammonium salt and the like, and iodine bromide. Bromine redox includes imidazolium bromide.
  • Examples thereof include a mixture of a derivative, lithium bromide, potassium bromide, tetraalkylammonium bromide salt and bromine.
  • a mixture of iodine with lithium iodide, imidazolium iodide derivatives, etc. is preferred.
  • the organic solvent that dissolves the redox ion pair is not limited as long as it is a stable solvent that dissolves the redox ion pair.
  • Organic solvents such as carbonate, propylene carbonate, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, nitromethane and the like can be used, and a mixed solvent thereof may be used.
  • acetonitrile, methoxyacetonitrile, propio-tolyl, methoxypropio-tolyl are used.
  • Redox ion pair concentration in the electrolyte The degree is preferably 0.01-5. Omol / 1, more preferably 0.05-1.
  • the electrolytic solution may contain a basic compound such as tert-butylpyridine, 2-picoline, 2,6-lutidine.
  • concentration of the basic compound is preferably 0.01 to 5.
  • Examples of the polymer used for the gel electrolyte include polyacrylonitrile and polyvinylidene fluoride.
  • Examples of the molten salt include 1-butyl-3-methylpyridyumumudide, 1-butyl-3-methylimidazoliummide, lithium iodide such as lithium iodide, lithium acetate, and lithium perchlorate.
  • the fluidity at room temperature may be improved by mixing a polymer such as polyethylene oxide with the polymer.
  • solid electrolyte examples include polymers such as polyethylene oxide derivatives.
  • Examples of the inorganic compound semiconductor include copper iodide, copper bromide, and copper thiocyanide.
  • the inorganic compound semiconductor may contain a molten salt such as triethyl ammonium thiocyanate.
  • organic hole transport material examples include polythiophene derivatives and polypyrrole derivatives.
  • a titanium dioxide thin film may be applied as an undercoat layer (short-circuit prevention layer) by using a method such as spray pyrolysis to prevent a short circuit.
  • a counter electrode is first bonded to a semiconductor thin film electrode on which a dye is adsorbed, and a liquid charge transfer layer is injected into the gap. It is a method to do. The other is a method in which a charge transfer layer is directly applied to a semiconductor thin film electrode, and a counter electrode is subsequently applied.
  • a normal pressure process utilizing capillary action and a vacuum process in which the gas phase is replaced with a liquid phase at a pressure lower than normal pressure can be used.
  • a counter electrode is provided without being dried, and measures for preventing liquid leakage at the edge are also taken.
  • a gel electrolyte there is also a method in which it is applied in a wet manner and fixed by a method such as polymerization, in which case it is dried and fixed after sealing. A pole can also be applied.
  • the method for applying the electrolyte, wet organic hole transport material or gel electrolyte is the same as that for applying the semiconductor thin film electrode and the dye, dipping method, roller method, dipping method, air knife method, blade method, spin method. Method, spray method and the like.
  • a solid electrolyte, an inorganic compound semiconductor, or a solid organic hole transport material a solution obtained by dissolving them in a solvent or the like is dropped onto a heated semiconductor thin film electrode and dried by vaporizing the solvent on the semiconductor thin film electrode.
  • a counter electrode can be applied after the charge transfer layer is formed by forming a solidified charge transfer layer, or by forming a charge transfer layer by a dry film forming process such as a vacuum deposition method or a CVD method (chemical vapor deposition method).
  • Examples of the counter electrode used in the photoelectric conversion element of the present invention include platinum, rhodium, ruthenium, carbon, and oxide semiconductor electrode coated in a thin film on a conductive substrate. Platinum, carbon electrodes and the like coated in a thin film on a conductive substrate are preferred.
  • the photoelectric conversion element of the present invention is not limited as long as it prevents contact between the semiconductor thin film electrode and the counter electrode, which may use a spacer.
  • a polymer film such as polyethylene is used.
  • the raw material 3-chloro opening 4- (N, N-jetylaminophenol) cyclobutene 1,1,2-dione was obtained in the same manner as in Example 5.
  • Transparent conductive glass coated with tin oxide doped with fluorine made by Nippon Sheet Glass, surface resistance is about 15 ⁇ / cm 2
  • titanium dioxide dioxide paste (Solaronix, SA Ti-Nanoxide T) was applied using a glass rod, dried at room temperature for 30 minutes, and then baked in an electric furnace at 450 ° C for 30 minutes.
  • the film thickness of titanium dioxide was 10 / zm.
  • the titanium dioxide electrode substrate (1 cm X 3 cm) prepared as described above was superposed on a platinum-deposited glass of the same size.
  • an electrolyte solution iodine 0. O5 mol / U lithium iodide 0.1 mol / U iodide dimethylpropylimidazole 0.62 mol Zl and tert-butyryridine 0.5 mol / l acetonitrile solution
  • a photoelectrochemical cell was obtained by impregnating the gap using a capillary phenomenon and introducing it between the titanium dioxide electrode and the counter electrode.
  • Table 2 shows the characteristics of the photoelectrochemical cell using the compounds (1) to (7).
  • a squarylium compound that can be used in a photoelectric conversion element having low cost and high energy conversion efficiency, a photoelectrochemical cell using the squarylium compound, and the like are provided. You can do it.

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Abstract

A squarylium compound represented by the following general formula (I) [wherein R1 and R2 are the same or different and each represents hydrogen, optionally substituted alkyl, etc.; R3, R4, R5, and R6 are the same or different and each represents hydrogen, optionally substituted alkyl, etc.; and X represents e.g., a group represented by the general formula (II) (wherein R7 represents hydrogen, optionally substituted alkyl, etc.; R8 represents halogeno, etc.; a is an integer of 0-4; R9 and R10 are the same or different and each represents hydrogen, optionally substituted alkyl, etc.; b is an integer of 0-4; A represents an acid group; and c is an integer of 1-5)].

Description

明 細 書  Specification
スクァリリウム化合物ならびにこれを用いた光電変換材料、光電変換素子 および光電気化学電池  SQUARYLIUM COMPOUND AND PHOTOELECTRIC CONVERSION MATERIAL, PHOTOELECTRIC CONVERSION ELEMENT AND PHOTOELECTROCHEMICAL CELL
技術分野  Technical field
[0001] 本発明は、光電変換素子に使用できるスクァリリウム化合物、該スクァリリウム化合 物を用いた光電気化学電池等に関する。  The present invention relates to a squarylium compound that can be used for a photoelectric conversion element, a photoelectrochemical cell using the squarylium compound, and the like.
背景技術  Background art
[0002] 太陽光発電においては単結晶シリコン太陽電池、多結晶シリコン太陽電池、ァモル ファスシリコン太陽電池等の太陽電池が実用ィ匕もしくは主な研究開発の対象となって いるが、普及させる上で製造コスト、原材料確保等の問題点を克服する必要がある。 一方、フィルム化や低価格ィ匕を指向した有機材料を用いた太陽電池もこれまでに多 く提案されているが、エネルギー変換効率が低ぐ耐久性も悪いという問題があった。 こうした状況の中で、色素によって増感された半導体薄膜電極を用いた光電変換素 子および光電気化学電池、ならびにこれらを作成するための材料および製造技術が 知られている。この電池はルテニウム錯体を光増感剤とし、二酸化チタン多孔質薄膜 を作用電極とする湿式太陽電池である (例えば、特許文献 1、非特許文献 1参照)。し 力しながら、増感色素のルテニウム錯体が高価なことから、安価な有機色素によって 増感される光電変換素子の開発が望まれている。  [0002] In solar power generation, solar cells such as single crystal silicon solar cells, polycrystalline silicon solar cells, amorphous silicon solar cells, etc. are the subject of practical use or main research and development. It is necessary to overcome problems such as manufacturing costs and securing raw materials. On the other hand, many solar cells using organic materials aimed at film formation and low cost have been proposed, but there is a problem that the energy conversion efficiency is low and the durability is poor. Under such circumstances, photoelectric conversion elements and photoelectrochemical cells using semiconductor thin film electrodes sensitized with a dye, and materials and manufacturing techniques for producing them are known. This battery is a wet solar battery using a ruthenium complex as a photosensitizer and a porous titanium dioxide thin film as a working electrode (see, for example, Patent Document 1 and Non-Patent Document 1). However, since the ruthenium complex of the sensitizing dye is expensive, development of a photoelectric conversion element that is sensitized by an inexpensive organic dye is desired.
[0003] また、増感色素として有機色素を用いる試みも行われているが、エネルギー変換効 率が低い等の問題があり、実用上満足されるものではない (例えば、特許文献 2、特 許文献 3参照)。 [0003] Also, attempts have been made to use organic dyes as sensitizing dyes, but there are problems such as low energy conversion efficiency, which is not satisfactory in practice (for example, Patent Document 2, Patents). Reference 3).
また、スクアリン酸誘導体を光電変換素子に使用することが知られている（例えば、 特許文献 4参照)。  In addition, it is known to use a squaric acid derivative for a photoelectric conversion element (see, for example, Patent Document 4).
特許文献 1 :米国特許第 4927721号明細書  Patent Document 1: U.S. Pat.No. 4,927,721
特許文献 2：特開平 11― 86916号公報  Patent Document 2: JP-A-11-86916
特許文献 3：欧州特許第 911841号明細書  Patent Document 3: European Patent No. 911841 Specification
特許文献 4：特開 2001 - 76773号公報 非特許文献 1：「ネイチヤー（Nature)」、 1991年、第 353卷、 p. 737— 740 発明の開示 Patent Document 4: Japanese Patent Laid-Open No. 2001-76773 Non-Patent Document 1: “Nature”, 1991, No. 353, p. 737-740 Disclosure of the Invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0004] 本発明の目的は、安価かつ高いエネルギー変換効率を有する光電変換素子に使 用できるスクァリリゥム化合物、該スクァリリゥム化合物を用 、た光電気化学電池等を 提供することである。 課題を解決するための手段 [0004] An object of the present invention is to provide a squaryum compound that can be used in a photoelectric conversion element that is inexpensive and has high energy conversion efficiency, a photoelectrochemical cell that uses the squarymium compound, and the like. Means for solving the problem
[0005] 本発明は、以下の（1)〜（30)を提供する。 [0005] The present invention provides the following (1) to (30).
(1)一般式 (I)  (1) General formula (I)
[0006] [化 1] [0006] [Chemical 1]
Figure imgf000004_0001
Figure imgf000004_0001
[0007] または一般式 (IV)  [0007] or general formula (IV)
[0008] [化 2] [0008] [Chemical 2]
Figure imgf000004_0002
Figure imgf000004_0002
[0009] {式中、 R1および R2は同一または異なって、水素原子、置換基を有していてもよいァ ルキル基、置換基を有して 、てもよ 、ァラルキル基または置換基を有して 、てもよ ヽ ァリール基を表す力、 R1および R2が隣接する窒素原子と一緒になつて置換基を有し ていてもよい複素環を形成し、 R3、 R4、 R5および R6は同一または異なって、水素原 子、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシル 基、置換基を有していてもよいァラルキル基、置換基を有していてもよいァリール基、 置換基を有していてもよい複素環基、ヒドロキシル基、またはハロゲン原子を表し、 R3 および R5、または R4および R6はそれぞれが隣接する 2つの炭素原子と一緒になつて 置換基を有して ヽてもよ 、炭化水素環または置換基を有して ヽてもよ ヽ複素環を形 成してもよぐ R1および R3、または R2および R4はそれぞれが隣接する N— C— Cと一 緒になって、置換基を有していてもよい複素環を形成してもよぐ Xは、一般式 (II) [0010] [化 3] [Wherein, R 1 and R 2 are the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, a substituent, or an aralkyl group or a substituent. , A force representing a aryl group, R 1 and R 2 together with the adjacent nitrogen atom form an optionally substituted heterocyclic ring, R 3 , R 4 R 5 and R 6 are the same or different and are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, and an optionally substituted aralkyl. A group, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a hydroxyl group, or a halogen atom, R 3 And R 5 , or R 4 and R 6 may have a substituent together with two adjacent carbon atoms, or may have a hydrocarbon ring or a substituent. R 1 and R 3 , or R 2 and R 4 , which may form a heterocyclic ring, together with the adjacent N—C—C, may have a substituent. X may have the general formula (II) [0010] [Chemical 3]
Figure imgf000005_0001
Figure imgf000005_0001
[0011] [式中、 R'は水素原子、置換基を有していてもよいアルキル基、置換基を有していて もよ！/、ァラルキル基、置換基を有して!/、てもよ 、ァリール基または置換基を有して!/ヽ てもよい複素環基を表し、 R8はハロゲン原子、置換基を有していてもよいアルキル基 、置換基を有していてもよいアルコキシル基、置換基を有していてもよいァラルキル 基、置換基を有していてもよいァリール基、ニトロ基、シァノ基、ヒドロキシル基、置換 基を有して 、てもよ 、ァミノ基または置換基を有して 、てもよ 、複素環基を表し、 aは 0〜4の整数を表し、ここに aが 2〜4の場合、それぞれの R8は同一または異なっても よぐさらに互いに隣り合う 2つの R8がそれぞれが隣接する 2つの炭素原子と一緒に なって、置換基を有して 、てもよ 、炭化水素環または置換基を有して 、てもよ 、複素 環を形成してもよぐ R9および R1C>は同一または異なって、水素原子、置換基を有して いてもよいアルキル基、カルボキシル基、アルコキシカルボ-ル基、置換基を有して V、てもよ 、ァラルキル基、置換基を有して 、てもよ 、ァリール基またはシァノ基を表し 、 bは 0〜4の整数を表し、ここに bが 2〜4の場合、それぞれの R9およびそれぞれの R 1(>は同一または異なってもよぐ Aは酸性基を表し、 cは 1〜5の整数を表し、ここにじが 2〜5の場合、それぞれの Aおよびそれぞれの一般式 (A) [In the formula, R ′ may have a hydrogen atom, an alkyl group which may have a substituent, or a substituent! /, An aralkyl group, having a substituent! /, Or an aryl group or a heterocyclic group which may have a substituent! / R 8 may have a halogen atom or a substituent. An optionally substituted alkyl group, an optionally substituted alkoxyl group, an optionally substituted aralkyl group, an optionally substituted aryl group, a nitro group, a cyano group, a hydroxyl group A group, a substituent, or an amino group or a substituent, a heterocyclic group, a represents an integer of 0 to 4, wherein a is 2 to 4 In this case, each R 8 may be the same or different, and two adjacent R 8 s may be combined with two adjacent carbon atoms, each having a substituent, or carbonized. a hydrocarbon ring or a substituent, I also, Yogu R 9 and R 1C also form a heterocyclic ring> are the same or different A hydrogen atom, an alkyl group which may have a substituent, a carboxyl group, an alkoxycarbonyl group, a substituent having V, a aralkyl group, or a substituent. Y represents an aryl group or cyano group, b represents an integer of 0 to 4, and when b is 2 to 4, each R 9 and each R 1 (> may be the same or different A Represents an acidic group, c represents an integer of 1 to 5, and in the case where the length is 2 to 5, each A and each general formula (A)
[0012] [化 4]
Figure imgf000006_0001
[0012] [Chemical 4]
Figure imgf000006_0001
[0013] (式中、 R9、 R1()および bはそれぞれ前記と同義である）で表される基は同一または異 なってもよい]で表される基、または一般式 (ΠΙ) A group represented by the formula (wherein R 9 , R 1 () and b are as defined above may be the same or different), or a group represented by the general formula (ΠΙ)
[0014] [化 5] [0014] [Chemical 5]
Figure imgf000006_0002
Figure imgf000006_0002
[0015] (式中、 R11は水素原子、置換基を有していてもよいアルキル基、置換基を有していて もよ！/、ァラルキル基、置換基を有して!/、てもよ 、ァリール基または置換基を有して!/ヽ てもよい複素環基を表し、 R12および R13は同一または異なって、ハロゲン原子、置換 基を有していてもよいアルキル基、置換基を有していてもよいアルコキシル基、置換 基を有していてもよいァラルキル基、置換基を有していてもよいァリール基、ニトロ基 、シァノ基、ヒドロキシル基、置換基を有していてもよいアミノ基または置換基を有して いてもよい複素環基を表し、 pは 0〜3の整数を表し、ここに pが 2〜3の場合、それぞ れの R12は同一または異なってもよぐ qは 0〜3の整数を表し、ここに qが 2〜3の場合 、それぞれの R13は同一または異なってもよぐ R14および R15は同一または異なって、 水素原子、置換基を有していてもよいアルキル基、カルボキシル基、アルコキシカル ボニル基、置換基を有していてもよいァラルキル基、置換基を有していてもよいァリー ル基またはシァノ基を表し、 rは 0〜4の整数を表し、ここに rが 2〜4の場合、それぞれ の R14およびそれぞれの R15は同一または異なってもよぐ Eは酸性基を表し、 sは 1〜 4の整数を表し、ここに sが 2〜4の場合、それぞれの Eおよびそれぞれの一般式（B)(Wherein R 11 is a hydrogen atom, an alkyl group which may have a substituent, may have a substituent! /, An aralkyl group, or a substituent! /, In addition, it represents an aryl group or a heterocyclic group which may have a substituent, and R 12 and R 13 may be the same or different, and may be a halogen atom, an alkyl group which may have a substituent, An alkoxyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, a nitro group, a cyano group, a hydroxyl group, and a substituent An optionally substituted amino group or an optionally substituted heterocyclic group, p represents an integer of 0 to 3, and when p is 2 to 3, each R 12 is the same Or q may be an integer from 0 to 3, and when q is 2 to 3, each R 13 may be the same or different. R 14 and R 15 are the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, a carboxyl group, an alkoxycarbonyl group, an aralkyl group which may have a substituent, or a substituent. Represents an aryl group or a cyan group which may have, r represents an integer of 0 to 4, and when r is 2 to 4, each R 14 and each R 15 may be the same or different. Y represents an acidic group, s represents an integer of 1 to 4, and when s is 2 to 4, each E and each general formula (B)
[0016] [化 6]
Figure imgf000007_0001
[0016] [Chemical 6]
Figure imgf000007_0001
[0017] (式中、 R14、 R15および rはそれぞれ前記と同義である）で表される基は同一または異 なってもよい]で表される基を表す }で表されるスクァリリウム化合物。 [Wherein the groups represented by R 14 , R 15 and r are as defined above may be the same or different]] a squarylium compound represented by .
(2)—般式 (la)  (2) —General formula (la)
[0018] [化 7]  [0018] [Chemical 7]
Figure imgf000007_0002
Figure imgf000007_0002
[0019] 〔式中、
Figure imgf000007_0003
R2、 R3、 R4、 R5および R6は、それぞれ前記と同義であり、 X1は、一般式 ([0019] [wherein
Figure imgf000007_0003
R 2 , R 3 , R 4 , R 5 and R 6 are as defined above, and X 1 is a group represented by the general formula (
II) II)
[0020] [化 8]  [0020] [Chemical 8]
Figure imgf000007_0004
Figure imgf000007_0004
[0021] (式中、 R7、 R8、 R9、 R10, A、 a、 bおよび cは、それぞれ前記と同義である）で表される 基を表す〕で表されるスクァリリウム化合物。 [Wherein R 7 , R 8 , R 9 , R 10 , A, a, b and c each represents the same group as defined above], and a squarylium compound represented by:
(3) Aがカルボキシル基である（2)記載のスクァリリウム化合物。  (3) The squarylium compound according to (2), wherein A is a carboxyl group.
(4) R9および R1Gが水素原子である（2)または（3)記載のスクァリリウム化合物。 (4) The squarylium compound according to (2) or (3), wherein R 9 and R 1G are hydrogen atoms.
(5) bが 0または 1である（2)から (4)の 、ずれかに記載のスクァリリウム化合物。  (5) The squarylium compound according to any one of (2) to (4), wherein b is 0 or 1.
(6) cが 1である（2)から（5)の 、ずれかに記載のスクァリリウム化合物。  (6) The squarylium compound according to any one of (2) to (5), wherein c is 1.
(7) aが 0である（2)から（6)の 、ずれかに記載のスクァリリウム化合物。  (7) The squarylium compound according to any one of (2) to (6), wherein a is 0.
(8)—般式 (lb)  (8) —General formula (lb)
[0022] [化 9]
Figure imgf000008_0001
[0022] [Chemical 9]
Figure imgf000008_0001
[0023] 〔式中、
Figure imgf000008_0002
R2、 R3、 R4、 R5および R6は、それぞれ前記と同義であり、 X2は、一般式 ( III) [0023] [wherein
Figure imgf000008_0002
R 2 , R 3 , R 4 , R 5 and R 6 have the same meanings as defined above, and X 2 represents the general formula (III)
[0024] [化 10]  [0024] [Chemical 10]
Figure imgf000008_0003
Figure imgf000008_0003
[0025] (式中、 1、 R' R"、 R14、 RL E、 p、 q、 rおよび sは、それぞれ前記と同義である) で表される基を表す〕で表されるスクァリリウム化合物。 [Wherein, R 1 R ′ R ″, R 14 , R L E, p, q, r and s each represent the same group as defined above] Compound.
(9) Eがカルボキシル基である（8)記載のスクァリリウム化合物。  (9) The squarylium compound according to (8), wherein E is a carboxyl group.
(10) R14および R15が水素原子である（8)または（9)記載のスクァリリウム化合物。(10) The squarylium compound according to (8) or (9), wherein R 14 and R 15 are hydrogen atoms.
(11) rが 0である（8)から（10)のいずれかに記載のスクァリリウム化合物。 (11) The squarylium compound according to any one of (8) to (10), wherein r is 0.
(12) sが 1である（8)から（11)の 、ずれかに記載のスクァリリウム化合物。  (12) The squarylium compound according to any one of (8) to (11), wherein s is 1.
(13) pが 0である（8)から（12)のいずれかに記載のスクァリリウム化合物。  (13) The squarylium compound according to any one of (8) to (12), wherein p is 0.
(14) qが 0である（8)から（13)の 、ずれかに記載のスクァリリウム化合物。  (14) The squarylium compound according to any one of (8) to (13), wherein q is 0.
(15)—般式(1¥&) (15) —General Formula (1 ¥ & )
[0026] [化 11] [0026] [Chemical 11]
Figure imgf000008_0004
Figure imgf000008_0004
[0027] 〔式中、
Figure imgf000008_0005
R5および R6は、それぞれ前記と同義であり、 X3は、一般式 ( II) [0027] [wherein
Figure imgf000008_0005
R 5 and R 6 have the same meanings as defined above, and X 3 represents the general formula (II)
[0028] [化 12]
Figure imgf000009_0001
[0028] [Chemical 12]
Figure imgf000009_0001
[0029] (式中、 R7、 R8、 R R10, A、 a、 bおよび cは、それぞれ前記と同義である）で表される 基を表す〕で表されるスクァリリウム化合物。 [Wherein, R 7 , R 8 , RR 10 , A, a, b and c each represents the same group as defined above].
( 16) Aがカルボキシル基である（ 15)記載のスクァリリウム化合物。  (16) The squarylium compound according to (15), wherein A is a carboxyl group.
( 17) R9および R1Gが水素原子である（ 15)または（ 16)記載のスクァリリウム化合物。(17) The squarylium compound according to (15) or (16), wherein R 9 and R 1G are hydrogen atoms.
(18) bが 0または 1である（ 15)から（ 17)の!、ずれかに記載のスクァリリウム化合物。(18) The squarylium compound according to any one of (15) to (17), wherein b is 0 or 1.
(19) cが 1である（15)から（18)の 、ずれかに記載のスクァリリウム化合物。 (19) The squarylium compound according to any one of (15) to (18), wherein c is 1.
(20) aが 0である（15)から（19)の！/、ずれかに記載のスクァリリウム化合物。  (20) a is 0 from (15) to (19)! / The squarylium compound described in any one of them.
(21)—般式 (IVb)  (21) —General formula (IVb)
[0030] [化 13] [0030] [Chemical 13]
Figure imgf000009_0002
Figure imgf000009_0002
[0031] 〔式中、
Figure imgf000009_0003
R5および R。は、それぞれ前記と同義であり、 X4は、一般式 ( III) [0031] [wherein
Figure imgf000009_0003
R 5 and R. Are as defined above, and X 4 represents the general formula (III)
[0032] [化 14]  [0032] [Chemical 14]
Figure imgf000009_0004
Figure imgf000009_0004
[0033] (式中、 1、 R"、 R , RM、 R15、 E、 p、 q、 rおよび sは、それぞれ前記と同義である) で表される基を表す〕で表されるスクァリリウム化合物。 (22) Eがカルボキシル基である（21)記載のスクァリリウム化合物。 [In the formula, 1 , R ″, R 1 , R M , R 15 , E, p, q, r and s each represent the same group as defined above] Squarylium compounds. (22) The squarylium compound according to (21), wherein E is a carboxyl group.
(23) R14および R15が水素原子である（21)または（22)記載のスクァリリウム化合物。(23) The squarylium compound according to (21) or (22), wherein R 14 and R 15 are hydrogen atoms.
(24) rが 0である（21)から（23)のいずれかに記載のスクァリリウム化合物。 (24) The squarylium compound according to any one of (21) to (23), wherein r is 0.
(25) sが 1である（21)から（24)の 、ずれかに記載のスクァリリウム化合物。  (25) The squarylium compound according to any one of (21) to (24), wherein s is 1.
(26) pが 0である（21)から（25)の 、ずれかに記載のスクァリリウム化合物。  (26) The squarylium compound according to any one of (21) to (25), wherein p is 0.
(27) qが 0である（21)から（26)の 、ずれかに記載のスクァリリウム化合物。  (27) The squarylium compound according to any one of (21) to (26), wherein q is 0.
(28) (1)〜（27)の 、ずれかに記載のスクァリリウム化合物と半導体とを含む光電変 換材料。  (28) A photoelectric conversion material comprising the squarylium compound according to any one of (1) to (27) and a semiconductor.
(29) (28)記載の光電変換材料を用いた光電変換素子。  (29) A photoelectric conversion element using the photoelectric conversion material according to (28).
(30) (29)記載の光電変換素子を含有する光電気化学電池。  (30) A photoelectrochemical cell comprising the photoelectric conversion element according to (29).
以下、一般式 (I)で表されるスクァリリウム化合物をィ匕合物 (I)と表現することもある。 他の式番号の化合物につ 、ても同様に表現することもある。  Hereinafter, the squarylium compound represented by the general formula (I) may be expressed as a compound (I). Other compounds of the formula number may be expressed in the same manner.
発明の効果  The invention's effect
[0034] 本発明により、安価かつ高いエネルギー変換効率を有する光電変換素子に使用で きるスクァリリウム化合物、該スクァリリウム化合物を用いた光電気化学電池等を提供 することができる。  [0034] According to the present invention, it is possible to provide a squarylium compound that can be used in a photoelectric conversion element that is inexpensive and has high energy conversion efficiency, a photoelectrochemical cell that uses the squarylium compound, and the like.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0035] 前記の一般式における各基の定義において、アルキル基ならびにアルコキシル基お よびアルコキシカルボ-ル基におけるアルキル部分としては、例えば、直鎖または分 岐状の炭素数 1〜6のアルキル基または炭素数 3〜8の環状アルキル基があげられ、 その具体例としては、メチル基、ェチル基、プロピル基、イソプロピル基、ブチル基、 イソブチル基、 sec ブチル基、 tert ブチル基、ペンチル基、イソペンチル基、 1 メチルブチル基、 2—メチルブチル基、 tert ペンチル基、へキシル基、シクロプロピ ル基、シクロブチル基、シクロペンチル基、シクロへキシル基、シクロへプチル基、シ クロォクチル基等があげられる。 [0035] In the definition of each group in the above general formula, examples of the alkyl group and the alkyl moiety in the alkoxyl group and alkoxycarbonyl group include, for example, a linear or branched alkyl group having 1 to 6 carbon atoms or Examples thereof include cyclic alkyl groups having 3 to 8 carbon atoms, and specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec butyl group, tert butyl group, pentyl group, isopentyl group. 1 methylbutyl group, 2-methylbutyl group, tert pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like.
[0036] ァラルキル基としては、例えば、炭素数 7〜15のァラルキル基があげられ、その具 体例としては、ベンジル基、フエネチル基、フエ-ルプロピル基、ナフチルメチル基等 があげられる。 ァリール基としては、例えば、炭素数 6〜14のァリール基があげられ、その具体例と しては、フエ-ル基、ナフチル基、アントリル基、ァズレニル基等があげられる。 [0036] Examples of the aralkyl group include aralkyl groups having 7 to 15 carbon atoms, and specific examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group. Examples of the aryl group include aryl groups having 6 to 14 carbon atoms, and specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, and an azulenyl group.
[0037] ハロゲン原子としては、塩素原子、臭素原子、フッ素原子およびヨウ素原子があげ られる。 [0037] Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.
複素環基における複素環としては、例えば、窒素原子、酸素原子および硫黄原子 力 選ばれる少なくとも 1個の原子を含む 5員または 6員の単環性芳香族または脂肪 族複素環、 3〜8員の環が縮合した二環または三環性で窒素原子、酸素原子および 硫黄原子から選ばれる少なくとも 1個の原子を含む縮環性芳香族または脂肪族複素 環等があげられ、その具体例としては、ピリジン環、ピラジン環、ピリミジン環、ピリダジ ン環、キノリン環、イソキノリン環、フタラジン環、キナゾリン環、キノキサリン環、ナフチ リジン環、シンノリン環、ピロール環、ピラゾール環、イミダゾール環、トリァゾール環、 テトラゾール環、チォフェン環、フラン環、チアゾール環、ォキサゾール環、インドール 環、イソインドール環、インダゾール環、ベンゾイミダゾール環、ベンゾトリアゾール環 、ベンゾチアゾール環、ベンゾォキサゾール環、プリン環、力ルバゾール環、ピロリジ ン環、ピぺリジン環、ピぺラジン環、モルホリン環、チオモルホリン環、ホモピぺリジン 環、ホモピぺラジン環、テトラヒドロピリジン環、テトラヒドロキノリン環、テトラヒドロイソキ ノリン環、テトラヒドロフラン環、テトラヒドロピラン環、ジヒドロべンゾフラン環、テトラヒド ロカルバゾール環等があげられる。  Examples of the heterocyclic ring in the heterocyclic group include, for example, a 5-membered or 6-membered monocyclic aromatic or aliphatic heterocyclic ring containing at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and 3 to 8 members. Examples thereof include condensed bicyclic or tricyclic condensed rings containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and specific examples thereof. Pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, quinoline ring, isoquinoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, naphthyridine ring, cinnoline ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring , Thiophene ring, Furan ring, Thiazole ring, Oxazole ring, Indole ring, Isoindole ring, Indazole ring, Ben Imidazole ring, benzotriazole ring, benzothiazole ring, benzoxazole ring, purine ring, force rubazole ring, pyrrolidine ring, piperidine ring, piperazine ring, morpholine ring, thiomorpholine ring, homopiperidine ring, Examples include a homopiperazine ring, a tetrahydropyridine ring, a tetrahydroquinoline ring, a tetrahydroisoquinoline ring, a tetrahydrofuran ring, a tetrahydropyran ring, a dihydrobenzofuran ring, and a tetrahydrocarbazole ring.
[0038] R1および R2が隣接する窒素原子と一緒になつて形成される複素環としては、例え ば、少なくとも 1個の窒素原子を含む 5員または 6員の単環性複素環 (該単環性複素 環は、他の窒素原子、酸素原子または硫黄原子を含んでいてもよい）、 3〜8員の環 が縮合した二環または三環性で少なくとも 1個の窒素原子を含む縮環性複素環 (該 縮環性複素環は、他の窒素原子、酸素原子または硫黄原子を含んでいてもよい)等 があげられ、その具体例としては、ピロリジン環、ピぺリジン環、ピぺラジン環、モルホ リン環、チオモルホリン環、ホモピぺリジン環、ホモピぺラジン環、テトラヒドロピリジン 環、テトラヒドロキノリン環、テトラヒドロイソキノリン環、ピロール環、イミダゾール環、ピ ラゾール環、インドール環、インドリン環、イソインドール環等があげられる。 [0038] Examples of the heterocyclic ring formed by combining R 1 and R 2 with the adjacent nitrogen atom include, for example, a 5-membered or 6-membered monocyclic heterocyclic ring containing at least one nitrogen atom (including A monocyclic heterocycle may contain other nitrogen, oxygen or sulfur atoms), a bicyclic or tricyclic condensed 3- to 8-membered ring and containing at least one nitrogen atom. Cyclic heterocyclic rings (the condensed heterocyclic rings may contain other nitrogen, oxygen or sulfur atoms), and specific examples thereof include pyrrolidine ring, piperidine ring, piperidine ring, and the like. Perazine ring, morpholine ring, thiomorpholine ring, homopiperidine ring, homopiperazine ring, tetrahydropyridine ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, pyrrole ring, imidazole ring, pyrazole ring, indole ring, indoline ring, I Indole ring, and the like.
[0039] R1および R3、または R2および R4がそれぞれが隣接する N— C— Cと一緒になつて 形成される複素環としては、例えば、少なくとも 1個の窒素原子を含む 5員または 6員 の単環性複素環 (該単環性複素環は、他の窒素原子、酸素原子または硫黄原子を 含んでいてもよい）、 3〜8員の環が縮合した二環または三環性で少なくとも 1個の窒 素原子を含む縮環性複素環 (該縮環性複素環は、他の窒素原子、酸素原子または 硫黄原子を含んでいてもよい）等があげられ、その具体例としては、ピロリン環、 1, 2 , 3, 4ーテトラヒドロピリジン環、 1, 2, 3, 4ーテトラヒドロピラジン環、 2, 3 ジヒドロノ ラオキサジン環、 2, 3 ジヒドロー 1, 4 チアジン環、テトラヒドロアゼピン環、テトラヒ ドロジァゼピン環、テトラヒドロキノリン環、テトラヒドロイソキノリン環、ピロール環、イミダ ゾール環、ピラゾール環、インドール環等があげられる。 [0039] R 1 and R 3 , or R 2 and R 4 together with adjacent N— C— C Examples of the formed heterocycle include a 5-membered or 6-membered monocyclic heterocycle containing at least one nitrogen atom (the monocyclic heterocycle contains other nitrogen atoms, oxygen atoms or sulfur atoms). A condensed heterocyclic ring containing a bicyclic or tricyclic condensed at least one nitrogen atom fused with a 3- to 8-membered ring (the condensed heterocyclic ring is another nitrogen atom, And may include an oxygen atom or a sulfur atom), and specific examples thereof include a pyrroline ring, 1, 2, 3, 4-tetrahydropyridine ring, 1, 2, 3, 4-tetrahydropyrazine ring, 2,3 dihydronoroxazine ring, 2,3 dihydro-1,4 thiazine ring, tetrahydroazepine ring, tetrahydrazepine ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, pyrrole ring, imidazole ring, pyrazole ring, indole ring, etc. That.
[0040] R3および R5、または R4および R6がそれぞれが隣接する 2つの炭素原子と一緒にな つて形成される複素環ならびに互いに隣り合う 2つの R8がそれぞれが隣接する 2つの 炭素原子と一緒になつて形成される複素環としては、例えば、窒素原子、酸素原子 および硫黄原子力 選ばれる少なくとも 1個の原子を含む 5員または 6員の単環性芳 香族複素環、 3〜8員の環が縮合した二環または三環性で窒素原子、酸素原子およ び硫黄原子力ゝら選ばれる少なくとも 1個の原子を含む縮環性芳香族複素環等があげ られ、その具体例としては、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、キノリ ン環、イソキノリン環、フタラジン環、キナゾリン環、キノキサリン環、ナフチリジン環、シ ンノリン環、ピロール環、ピラゾール環、イミダゾール環、トリァゾール環、チォフェン環 、フラン環、チアゾール環、ォキサゾール環、インドール環、イソインドール環、インダ ゾール環、ベンゾイミダゾール環、ベンゾトリアゾール環、ベンゾチアゾール環、ベン ゾォキサゾール環、プリン環、力ルバゾール環等があげられる。 [0040] A heterocycle in which R 3 and R 5 , or R 4 and R 6 are each formed together with two adjacent carbon atoms, and two R 8 adjacent to each other are two adjacent carbons. Examples of the heterocyclic ring formed together with the atom include, for example, a 5- or 6-membered monocyclic aromatic heterocyclic ring containing at least one atom selected from a nitrogen atom, an oxygen atom and sulfur nuclear power, 3 to Specific examples are bicyclic or tricyclic condensed 8-membered rings containing at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur nuclear atom. Pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, quinoline ring, isoquinoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, naphthyridine ring, cinnoline ring, pyrrole ring, pyrazole ring, imida ring Ring, triazole ring, thiophene ring, furan ring, thiazole ring, oxazole ring, indole ring, isoindole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzothiazole ring, benzoxazole ring, purine ring, force And a rubazole ring.
[0041] R3および R5、または R4および R6がそれぞれが隣接する 2つの炭素原子と一緒にな つて形成される炭化水素環ならびに互いに隣り合う 2つの R8がそれぞれが隣接する 2 つの炭素原子と一緒になつて形成される炭化水素環としては、例えば、炭素数 5〜1 0の不飽和の炭化水素環があげられ、その具体例としては、シクロペンテン環、シクロ へキセン環、シクロヘプテン環、シクロオタテン環、ベンゼン環、ナフタレン環等があ げられる。 [0041] A hydrocarbon ring formed by R 3 and R 5 or R 4 and R 6 together with two adjacent carbon atoms, and two R 8 adjacent to each other are two adjacent to each other. Examples of the hydrocarbon ring formed together with the carbon atom include unsaturated hydrocarbon rings having 5 to 10 carbon atoms, and specific examples thereof include a cyclopentene ring, a cyclohexene ring, and a cycloheptene. And a ring, a cyclooctene ring, a benzene ring, a naphthalene ring, and the like.
[0042] ァラルキル基、ァリール基、複素環基、 R1および R2が隣接する窒素原子と一緒にな つて形成される複素環、 R3および R5、または R4および R6がそれぞれが隣接する 2つ の炭素原子と一緒になつて形成される複素環、互いに隣り合う 2つの R8がそれぞれ が隣接する 2つの炭素原子と一緒になつて形成される複素環、 R3および R5、または R 4および R6がそれぞれが隣接する 2つの炭素原子と一緒になつて形成される炭化水 素環、互いに隣り合う 2つの R8がそれぞれが隣接する 2つの炭素原子と一緒になつて 形成される炭化水素環ならびに R1および R3、または R2および R4がそれぞれが隣接 する N— C— Cと一緒になつて形成される複素環の置換基としては、例えば、同一ま たは異なって 1〜5個の置換基、具体的には、ヒドロキシル基、カルボキシル基、ハロ ゲン原子、アルキル基、アルコキシル基、ニトロ基、アルキル置換または非置換のアミ ノ基等があげられる。ハロゲン原子、アルキル基およびアルコキシル基は、それぞれ 前記と同義であり、アルキル置換アミノ基のアルキル部分は前記アルキル基と同義で ある。 [0042] The aralkyl group, aryl group, heterocyclic group, R 1 and R 2 together with the adjacent nitrogen atom A heterocycle formed by R 3 and R 5 , or R 4 and R 6 together with two adjacent carbon atoms, and two R 8 adjacent to each other are each Heterocyclic ring formed with two adjacent carbon atoms, hydrocarbon ring formed with R 3 and R 5 , or R 4 and R 6 with two adjacent carbon atoms, respectively , A hydrocarbon ring formed by two adjacent R 8 s together with two adjacent carbon atoms, and R 1 and R 3 , or R 2 and R 4 are adjacent N—C— Examples of the substituent of the heterocyclic ring formed together with C include, for example, the same or different 1 to 5 substituents, specifically, a hydroxyl group, a carboxyl group, a halogen atom, an alkyl group. , Alkoxyl group, nitro group, alkyl substitution Other amino group of non-substitution, and the like. A halogen atom, an alkyl group and an alkoxyl group have the same meanings as described above, and the alkyl part of the alkyl-substituted amino group has the same meaning as the alkyl group.
[0043] アルキル基およびアルコキシル基の置換基としては、例えば、同一または異なって 1〜3個の置換基、具体的には、ヒドロキシル基、カルボキシル基、ハロゲン原子、ァ ルコキシル基等があげられる。ハロゲン原子およびアルコキシル基は、それぞれ前記 と同義である。  [0043] Examples of the substituent of the alkyl group and the alkoxyl group include the same or different one to three substituents, specifically, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxyl group and the like. A halogen atom and an alkoxyl group are as defined above.
ァミノ基の置換基としては、例えば、同一または異なって 1〜2個のアルキル基があ げられ、この場合のアルキル基は前記と同義である。  Examples of the substituent of the amino group include one or two alkyl groups which are the same or different, and the alkyl group in this case is as defined above.
[0044] 酸性基とは解離することができる水素原子を有して 、る基を指し、例えば、カルボキ シル基、ヒドロキシル基、ホスホノ基、スルホ基等があげられる。これらの基はアルカリ 金属イオン、アンモ-ゥムイオン、有機アンモ-ゥムイオン等と塩を形成したものであ つてもよい。また、分子内錯塩を形成してもよい。アルカリ金属イオンにおけるアルカリ 金属としては、リチウム、ナトリウム、カリウム等があげられる。有機アンモ-ゥムとして は、テトラプチルアンモ -ゥム等があげられる。  [0044] The acidic group refers to a group having a hydrogen atom that can be dissociated, and examples thereof include a carboxyl group, a hydroxyl group, a phosphono group, and a sulfo group. These groups may form salts with alkali metal ions, ammonium ions, organic ammonium ions and the like. Further, an intramolecular complex salt may be formed. Examples of the alkali metal in the alkali metal ion include lithium, sodium, and potassium. Examples of organic ammonia include tetraptyl ammonium.
[0045] 化合物（I)、 (la)および (lb)は、公知の方法 (WO01Z44233等）で、またはそれ らに準じて製造できる。以下、化合物 (1)、 (la)ゝ (lb)ゝ (IV)、（IVa)および (IVb)の 製造法の例について説明する。  [0045] Compounds (I), (la) and (lb) can be produced by a known method (WO01Z44233 or the like) or according to them. Hereinafter, examples of production methods of the compounds (1), (la) ゝ (lb) ゝ (IV), (IVa) and (IVb) will be described.
（a) [0046] [化 15] (A) [0046] [Chemical 15]
Figure imgf000014_0001
Figure imgf000014_0001
[0048] [化 16] [0048] [Chemical 16]
化合物 （V I I)
Figure imgf000014_0002
Compound (VII)
Figure imgf000014_0002
[0049] 反応式（c)  [0049] Reaction formula (c)
[0050] [化 17] [0050] [Chemical 17]
化合物 （VI I I) + 化合物 （l a)
Figure imgf000014_0003
Compound (VI II) + Compound (la)
Figure imgf000014_0003
[0051]  [0051]
[0052] [化 18] [0052] [Chemical 18]
化合物 （VI I I) + 化合物 （l b)
Figure imgf000014_0004
Compound (VI II) + Compound (lb)
Figure imgf000014_0004
(X)  (X)
[0053] f^i^(e) [0054] [化 19] 化合物 ( VI I ) + 化合物 ( IX ) *- 化合物 （IVa ) [0053] f ^ i ^ (e) [0054] [Chem. 19] Compound (VI I) + Compound (IX) *-Compound (IVa)
[0055] [0055]
[0056] [化 20] 化合物 (VI I ) + 化合物 (X) *- 化合物 （IVb)  [0056] [Chemical Formula 20] Compound (VI I) + Compound (X) *-Compound (IVb)
[式中、 R\ R2、 R3、 R4、 R5、 R6、 R7、 R8、 R9、 R10、 1、 R12、 R13、 R14、 R15、 Aゝ E、 a 、 b、 c、 p、 q、 rおよび sは、それぞれ前記と同義であり、 Wは塩素、臭素等のハロゲン 原子、または OR16 (式中、 R16はアルキル基を表し、該アルキル基は、前記と同義で ある）を表す] Wherein, R \ R 2, R 3 , R 4, R 5, R 6, R 7, R 8, R 9, R 10, 1, R 12, R 13, R 14, R 15, AゝE , A, b, c, p, q, r and s are as defined above, W is a halogen atom such as chlorine or bromine, or OR 16 (wherein R 16 represents an alkyl group, The group is as defined above)
反応式（a)  Reaction formula (a)
化合物（VII)は、化合物（V)と 1〜2倍モルの化合物（VI)とを、 1〜2倍モルの塩基 存在下で、溶媒中、 0〜40°Cで 1〜20時間反応させることにより得られる。  Compound (VII) is obtained by reacting Compound (V) with 1 to 2 moles of Compound (VI) in a solvent at 0 to 40 ° C for 1 to 20 hours in the presence of 1 to 2 moles of a base. Can be obtained.
[0058] 溶媒としては、例えば、クロ口ホルム、ジクロロメタン、 1, 2—ジクロロェタン等のハロ ゲン化炭化水素類、ジェチルエーテル、 tert—ブチルメチルエーテル等のエーテル 類、トルエン、ベンゼン等の芳香族炭化水素、メタノール、エタノール、プロパノール 等のアルコール類、テトラヒドロフラン、酢酸ェチル、ジメチルホルムアミド、ジメチルス ルホキシド（DMSO)等があげられる。  [0058] Examples of the solvent include halogenated hydrocarbons such as chloroform, dichloromethane and 1,2-dichloroethane, ethers such as jetyl ether and tert-butyl methyl ether, and aromatics such as toluene and benzene. Examples thereof include hydrocarbons, alcohols such as methanol, ethanol and propanol, tetrahydrofuran, ethyl acetate, dimethylformamide, dimethylsulfoxide (DMSO) and the like.
[0059] 塩基としては、例えばキノリン、トリェチルァミン、ピリジン等の有機塩基または炭酸 カリウム、炭酸水素カリウム、炭酸ナトリウム、炭酸水素ナトリウム、水酸ィ匕カリウム、水 酸ィ匕ナトリウム等の無機塩基があげられる。  [0059] Examples of the base include organic bases such as quinoline, triethylamine, and pyridine, and inorganic bases such as potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium hydroxide, and sodium hydroxide. .
化合物 (VI)は、例えば、市販品として、入手が可能である。 化合物（VIII)は、化合物（VII)を 50〜90容量％の酢酸水溶液中で、 90〜120°C で 0. 1〜7時間、または 50〜99重量％のトリフルォロ酢酸水溶液中で、 45〜50°C で 0. 1〜3時間処理することにより得られる。  Compound (VI) can be obtained, for example, as a commercial product. Compound (VIII) is obtained by mixing Compound (VII) in 50 to 90% by volume of acetic acid aqueous solution at 90 to 120 ° C. for 0.1 to 7 hours, or in 50 to 99% by weight of trifluoroacetic acid aqueous solution. It is obtained by treating at 50 ° C for 0.1 to 3 hours.
（c) 化合物 (la)は、化合物 (VIII)と 1〜2倍モルの化合物 (IX)とを、必要に応じて、 1 〜2倍モルの塩基存在下で、溶媒中、 80〜120°Cで 10分間〜 15時間反応させるこ とにより得られる。 (C) Compound (la) is prepared by combining compound (VIII) with 1 to 2 moles of compound (IX) in the presence of 1 to 2 moles of a base in a solvent at 80 to 120 ° C. It is obtained by reacting for 15 minutes to 15 minutes.
[0060] 溶媒としては、例えば、エタノール、プロパノール、イソプロピルアルコール、ブタノ ール、ォクタノール等の炭素数 2〜8のアルコール系溶媒のみ、または該アルコール 系溶媒とベンゼンもしくはトルエンとの混合溶媒 (アルコール 40容量％以上)等が用 いられる。  [0060] Examples of the solvent include only alcohol solvents having 2 to 8 carbon atoms such as ethanol, propanol, isopropyl alcohol, butanol and octanol, or a mixed solvent of the alcohol solvent and benzene or toluene (alcohol 40). Volume% or more) is used.
塩基としては、例えば、キノリン、トリェチルァミン、ピリジン等の有機塩基または炭酸 カリウム、炭酸水素カリウム、炭酸水素ナトリウム等の無機塩基があげられる。  Examples of the base include organic bases such as quinoline, triethylamine, and pyridine, and inorganic bases such as potassium carbonate, potassium bicarbonate, and sodium bicarbonate.
[0061] 化合物 (IX)は、例えば、公知の方法 (ドイツ公開公報 2406333号等)またはそれら に準じて製造することもできるが、市販品としても、入手が可能である。 [0061] Compound (IX) can be produced, for example, according to a known method (German Published Publication No. 2406333 etc.) or similar methods, but is also commercially available.
反応後、化合物 (la)は、例えば、溶媒の留去または濾過を行い、必要により有機合 成化学で通常用いられる方法 (カラムクロマトグラフィー、再結晶、溶媒での洗浄等） でさらに精製処理することにより、単離精製することができる。 化合物（lb)は、化合物 (VIII)と 1〜2倍モルの化合物 (X)とを、必要に応じて、 1〜 2倍モルの塩基存在下で、溶媒中、 80〜120°Cで 1〜15時間反応させることにより 得られる。  After the reaction, for example, the compound (la) is further purified by a method usually used in organic synthetic chemistry (column chromatography, recrystallization, washing with a solvent, etc.), if necessary, by evaporating or filtering the solvent. Thus, it can be isolated and purified. Compound (lb) is obtained by mixing Compound (VIII) with 1 to 2 moles of Compound (X), if necessary, in the presence of 1 to 2 moles of a base in a solvent at 80 to 120 ° C. It can be obtained by reacting for ~ 15 hours.
[0062] 溶媒としては、例えば、エタノール、プロパノール、イソプロピルアルコール、ブタノ ール、ォクタノール等の炭素数 2〜8のアルコール系溶媒のみ、または該アルコール 系溶媒とベンゼンもしくはトルエンとの混合溶媒 (アルコール 40容量％以上)等が用 いられる。  [0062] Examples of the solvent include only alcohol solvents having 2 to 8 carbon atoms such as ethanol, propanol, isopropyl alcohol, butanol, and octanol, or a mixed solvent of the alcohol solvent and benzene or toluene (alcohol 40). Volume% or more) is used.
塩基としては、例えば、キノリン、トリェチルァミン、ピリジン等の有機塩基または炭酸 カリウム、炭酸水素カリウム、炭酸水素ナトリウム等の無機塩基があげられる。  Examples of the base include organic bases such as quinoline, triethylamine, and pyridine, and inorganic bases such as potassium carbonate, potassium bicarbonate, and sodium bicarbonate.
[0063] 化合物 (X)は、例えば、公知の方法 [「ケミカル 'リサーチ 'イン 'チャイニーズ ·ュ- ノ ーシアイズ (Chemical Research in Chinese Universities)」、 1991年、 7卷、第 3号、 197頁等]またはそれらに準じて製造することもできるが、市販品として も、入手が可能である。 反応後、化合物 (lb)は、例えば、溶媒の留去または濾過を行い、必要により有機合 成化学で通常用いられる方法 (カラムクロマトグラフィー、再結晶、溶媒での洗浄等） でさらに精製処理することにより、単離精製することができる。 [0063] Compound (X) can be obtained, for example, by a known method ["Chemical Research in Chinese Universities", 1991, 7th, No. 3, page 197, etc. Or can be produced according to them, but can also be obtained as a commercial product. After the reaction, the compound (lb) is further purified by, for example, distilling off the solvent or filtering, and if necessary, by a method usually used in organic synthesis chemistry (column chromatography, recrystallization, washing with a solvent, etc.). Thus, it can be isolated and purified.
（e)  (E)
化合物 (IVa)は、化合物 (VII)と 1〜2倍モルの化合物 (IX)とを、必要に応じて、 1 〜2倍モルの塩基存在下で、溶媒中、 80〜120°Cで 10分間〜 15時間反応させるこ とにより得られる。  Compound (IVa) is obtained by mixing compound (VII) with 1 to 2 moles of compound (IX) in the presence of 1 to 2 moles of a base in a solvent at 80 to 120 ° C. It is obtained by reacting for 15 minutes to 15 minutes.
[0064] 溶媒としては、例えば、エタノール、プロパノール、イソプロピルアルコール、ブタノ ール、ォクタノール等の炭素数 2〜8のアルコール系溶媒のみ、または該アルコール 系溶媒とベンゼンもしくはトルエンとの混合溶媒 (アルコール 40容量％以上)等が用 いられる。  [0064] Examples of the solvent include alcohol solvents having 2 to 8 carbon atoms such as ethanol, propanol, isopropyl alcohol, butanol and octanol, or a mixed solvent of the alcohol solvent and benzene or toluene (alcohol 40). Volume% or more) is used.
塩基としては、例えば、キノリン、トリェチルァミン、ピリジン等の有機塩基または炭酸 カリウム、炭酸水素カリウム、炭酸水素ナトリウム等の無機塩基があげられる。  Examples of the base include organic bases such as quinoline, triethylamine, and pyridine, and inorganic bases such as potassium carbonate, potassium bicarbonate, and sodium bicarbonate.
[0065] 反応後、化合物 (IVa)は、例えば、溶媒の留去または濾過を行 、、必要により有機 合成化学で通常用いられる方法 (カラムクロマトグラフィー、再結晶、溶媒での洗浄等 )でさらに精製処理することにより、単離精製することができる。 化合物 (IVb)は、化合物 (VII)と 1〜2倍モルの化合物 (X)とを、必要に応じて、 1 〜2倍モルの塩基存在下で、溶媒中、 80〜120°Cで 1〜15時間反応させることによ り得られる。 [0065] After the reaction, the compound (IVa) is further distilled, for example, by distilling off the solvent or filtering, and if necessary, by a method usually used in organic synthetic chemistry (column chromatography, recrystallization, washing with a solvent, etc.). It can be isolated and purified by purification treatment. Compound (IVb) is compound (VII) and 1 to 2 moles of Compound (X), if necessary, in the presence of 1 to 2 moles of a base in a solvent at 80 to 120 ° C. It can be obtained by reacting for ~ 15 hours.
[0066] 溶媒としては、例えば、エタノール、プロパノール、イソプロピルアルコール、ブタノ ール、ォクタノール等の炭素数 2〜8のアルコール系溶媒のみ、または該アルコール 系溶媒とベンゼンもしくはトルエンとの混合溶媒 (アルコール 40容量％以上)等が用 いられる。  [0066] Examples of the solvent include alcohol-based solvents having 2 to 8 carbon atoms such as ethanol, propanol, isopropyl alcohol, butanol, and octanol, or a mixed solvent of the alcohol-based solvent and benzene or toluene (alcohol 40). Volume% or more) is used.
塩基としては、例えば、キノリン、トリェチルァミン、ピリジン等の有機塩基または炭酸 カリウム、炭酸水素カリウム、炭酸水素ナトリウム等の無機塩基があげられる。  Examples of the base include organic bases such as quinoline, triethylamine, and pyridine, and inorganic bases such as potassium carbonate, potassium bicarbonate, and sodium bicarbonate.
[0067] 反応後、化合物 (IVb)は、例えば、溶媒の留去または濾過を行い、必要により有機 合成化学で通常用いられる方法 (カラムクロマトグラフィー、再結晶、溶媒での洗浄等 )でさらに精製処理することにより、単離精製することができる。 [0067] After the reaction, the compound (IVb) is, for example, distilled off or filtered, and if necessary, a method usually used in organic synthetic chemistry (column chromatography, recrystallization, washing with a solvent, etc.) ) Can be isolated and purified by further purification treatment.
本発明の化合物 (I)または (IV)の具体例を表 1に例示するが、本発明の化合物 (I) または (IV)は、これらに限定されるものではない。また、表 1中、 Etはェチル基、 Bu はブチル基を表す。 Specific examples of the compound (I) or (IV) of the present invention are illustrated in Table 1, but the compound (I) or (IV) of the present invention is not limited thereto. In Table 1, Et represents an ethyl group, and Bu represents a butyl group.
[表 1-1] [Table 1-1]
Figure imgf000018_0001
[0069] [表 1-2]
Figure imgf000018_0001
[0069] [Table 1-2]
Figure imgf000019_0001
Figure imgf000019_0001
[0070] 次に、本発明の光電変換材料、光電変換素子および光電気化学電池について詳 述する。 [0070] Next, the photoelectric conversion material, photoelectric conversion element and photoelectrochemical cell of the present invention will be described in detail.
本発明の光電変換材料は、化合物 (I)または (IV)と半導体とを含む。  The photoelectric conversion material of the present invention contains compound (I) or (IV) and a semiconductor.
本発明の光電変換素子は、導電性支持体、導電性支持体上に設置される化合物 ( The photoelectric conversion element of the present invention comprises a conductive support, a compound installed on the conductive support (
I)または (IV)により増感された半導体からなる半導体薄膜電極、電荷移動層、対極 等から構成される。この光電変換素子を外部回路で仕事をさせる電池用途に使用で きるようにしたものが本発明の光電気化学電池である。すなわち、本発明の光電気化 学電池は、本発明の光電変換素子の導電性支持体および対極にリードを介して接 続された外部回路に仕事をさせるようにしたものである。該光電気化学電池は構成 物の劣化や電荷移動層に用いられる電解液の揮散を防止するために、側面をポリマ 一、接着剤等で密封されているのが好ましい。 [0071] 光電変換材料に用いる半導体はいわゆる感光体であり、光を吸収して電荷分離さ れ電子と正孔を生ずる役割を担う。化合物 (I)または (IV)により増感された半導体で は、光吸収およびこれによる電子および正孔の発生は主として化合物 (I)または (IV) において起こり、半導体はこの電子を受け取り、伝達する役割を担う。 It consists of a semiconductor thin film electrode made of a semiconductor sensitized by I) or (IV), a charge transfer layer, a counter electrode and the like. The photoelectrochemical cell according to the present invention is one in which this photoelectric conversion element can be used for a battery used for work in an external circuit. That is, the photoelectrochemical cell of the present invention is such that an external circuit connected to the conductive support and the counter electrode of the photoelectric conversion element of the present invention via a lead works. The photoelectrochemical cell is preferably sealed on the side with a polymer, an adhesive or the like in order to prevent deterioration of the constituents and volatilization of the electrolyte used for the charge transfer layer. [0071] The semiconductor used for the photoelectric conversion material is a so-called photoconductor, which absorbs light and separates charges to generate electrons and holes. In semiconductors sensitized by compound (I) or (IV), light absorption and the generation of electrons and holes thereby occurs mainly in compound (I) or (IV), and the semiconductor receives and transmits these electrons. Take a role.
半導体としては、特に限定されないが、例えば、酸化チタン、酸化インジウム、酸ィ匕 スズ、酸化ビスマス、酸化ジルコニウム、酸化タンタル、酸化ニオブ、酸化タンダステ ン、酸化鉄、酸化ガリウム、酸化ニッケル等の単一金属酸化物、チタン酸ストロンチウ ム、チタン酸バリウム、ニオブ酸カリウム、タンタル酸ナトリウム等の複合酸ィ匕物、ヨウ 化銀、臭化銀、ヨウ化銅、臭化銅等の金属ハロゲン化物、硫化亜鉛、硫ィ匕チタン、硫 ィ匕インジウム、硫ィ匕ビスマス、硫ィ匕カドミウム、硫ィ匕ジルコニウム、硫化タンタル、硫ィ匕 銀、硫化スズ、硫化タングステン、硫ィ匕モリブデン、セレン化カドミウム、セレンィ匕ジル コ-ゥム、セレン化亜鉛、セレン化チタン、セレン化インジウム、セレン化タングステン 、セレン化モリブデン、セレン化ビスマス、テルル化カドミウム、テルル化タングステン 、テルル化モリブデン、テルル化亜鉛、テルル化ビスマス等のカルコゲナイド化合物 等があげられる。  The semiconductor is not particularly limited, but for example, single oxides such as titanium oxide, indium oxide, tin oxide, bismuth oxide, zirconium oxide, tantalum oxide, niobium oxide, tandasten oxide, iron oxide, gallium oxide, nickel oxide, etc. Metal oxides, composite oxides such as strontium titanate, barium titanate, potassium niobate, sodium tantalate, metal halides such as silver iodide, silver bromide, copper iodide, copper bromide, sulfide Zinc, titanium sulfate, titanium indium, copper bismuth, copper cadmium sulfate, zirconium sulfate, tantalum sulfide, silver sulfide, tin sulfide, tungsten sulfide, molybdenum sulfide, cadmium selenide, Selenium chloride, zinc selenide, titanium selenide, indium selenide, tungsten selenide, molybdenum selenide Den, bismuth selenide, cadmium telluride, tellurium, tungsten, tellurium, molybdenum, zinc telluride, chalcogenide compounds such as bismuth telluride and the like.
[0072] 前記の半導体は、単独でまたは二種類以上混合して用いられる。  [0072] The semiconductors described above are used alone or in combination of two or more.
半導体薄膜は、ナノ粒子力 なるナノポーラス構造を有する化合物半導体であるの が好ましく、前記にあげた半導体を用 、て製造することができる [「ジャーナル ·ォブ · アメリカン 'セラミック'ソサイエティ一 (Journal of American Ceramic Society) 」、 1997年、第 80卷、第 12号、 p. 3157]。  The semiconductor thin film is preferably a compound semiconductor having a nanoporous structure with nanoparticle force, and can be manufactured using the semiconductors listed above [Journal of American 'Ceramic' Society (Journal of American Ceramic Society), 1997, No. 80, No. 12, p. 3157].
[0073] 本発明の光電変換素子に使用される半導体薄膜電極は、例えば、導電性支持体 として透明電極を用意し、その上に半導体薄膜を積層し、その半導体薄膜に本発明 による化合物 (I)または (IV)を吸着させること〖こより製造することができる。  [0073] The semiconductor thin film electrode used in the photoelectric conversion element of the present invention is prepared, for example, by preparing a transparent electrode as a conductive support, laminating a semiconductor thin film on the transparent electrode, and forming the compound (I ) Or (IV) can be adsorbed.
透明電極としては、導電性を有するものであればよぐ例えば、透明または半透明 のガラス基板やプラスチック板上に、例えば、フッ素またはアンチモンドープの酸化ス ズ、スズドープの酸化インジウム、酸化亜鉛等の導電性透明酸化物半導体薄膜をコ ートしたもの、好ましくは、フッ素ドープの酸化スズ薄膜をコートしたもの等が用いられ る。 [0074] 化合物半導体を導電性支持体上に設置する方法としては、例えば、前記化合物半 導体の分散液またはコロイド溶液を導電性支持体上に塗布する方法等があげられる 塗布方法としては、ローラ法、ディップ法、エアーナイフ法、ブレード法、スピン法、 スプレー法等があげられる。 The transparent electrode is not particularly limited as long as it has conductivity. For example, on a transparent or translucent glass substrate or plastic plate, for example, fluorine or antimony-doped oxide oxide, tin-doped indium oxide, zinc oxide, etc. Those coated with a conductive transparent oxide semiconductor thin film, preferably those coated with a fluorine-doped tin oxide thin film are used. [0074] Examples of a method of placing the compound semiconductor on the conductive support include a method of applying a dispersion or a colloidal solution of the compound semiconductor on the conductive support. Method, dipping method, air knife method, blade method, spin method, spray method and the like.
化合物半導体は、導電性支持体に塗布した後に半導体微粒子同士を電子的にコ ンタタトさせるため、および塗膜強度の向上や支持体との密着性を向上させるために 、加熱処理することが好ましい。好ましい加熱処理温度の範囲は 100〜600°Cである 。また、加熱処理時間は 10分間〜 10時間である。ポリマーフィルム等の融点や軟ィ匕 点の低い導電性支持体を用いる場合は、高温処理は該支持体の劣化を招くため、 5 nm以下の小さい半導体微粒子の併用ゃ鉱酸の存在下での加熱処理を行う方法、 化合物半導体の分散液またはコロイド溶液とチタン塩 (例えば、四塩ィ匕チタン等）の 混合物を導電性支持体に塗布後、水熱処理を行う方法、化合物半導体を極性有機 溶媒 (例えば、 tert—ブタノール等）に分散させ、電気泳動により泳動電着を行う方 法、化合物半導体の分散液またはコロイド溶液を導電性支持体に塗布後、約 98070 kPaの圧力で加圧プレスする方法、化合物半導体の分散液またはコロイド溶液を導 電性支持体に塗布後、約 28GHzのマイクロ波を照射する方法等が用いられる。半導 体薄膜の膜厚は 0. 1-100 μ mであるのが好ましぐより好ましくは 2〜25 μ mであ る。  The compound semiconductor is preferably heat-treated in order to electronically contact the semiconductor fine particles after being applied to the conductive support, and to improve the coating film strength and the adhesion to the support. A preferable heat treatment temperature range is 100 to 600 ° C. The heat treatment time is 10 minutes to 10 hours. When using a conductive support having a low melting point or soft melting point such as a polymer film, the high temperature treatment causes deterioration of the support. Therefore, a combination of small semiconductor fine particles of 5 nm or less is used in the presence of mineral acid. A method of performing heat treatment, a method of applying a dispersion of a compound semiconductor or a mixture of a colloidal solution and a titanium salt (for example, tetrasalt-titanium) to a conductive support and then hydrothermally treating the compound semiconductor with a polar organic solvent (For example, terf-butanol, etc.) Dispersed in electrophoresis, electrophoretic deposition by electrophoresis, dispersion of compound semiconductor or colloidal solution is applied to conductive support, and then pressed under pressure of about 98070 kPa For example, a method of irradiating a microwave of about 28 GHz after applying a dispersion or colloidal solution of a compound semiconductor to a conductive support is used. The film thickness of the semiconductor thin film is preferably 0.1-100 μm, more preferably 2-25 μm.
[0075] 化合物 (I)または (IV)の半導体薄膜上への吸着は、化合物 (I)または (IV)溶液中 に支持体に塗布された半導体薄膜を浸し、室温で 1分間〜 2日間、または加熱条件 下で 1分間〜 24時間放置することにより行うことができる。化合物 (I)または (IV)を半 導体薄膜上に吸着させる場合に用いる溶媒としては、化合物 (I)または (IV)を溶解 する溶媒であれば、特に限定されないが、例えば、メタノール、エタノール等のアルコ ール溶媒、ベンゼン等の炭化水素溶媒、テトラヒドロフラン、ァセトニトリル等の有機溶 媒等があげられ、それらの混合溶媒を用いてもよぐ好ましくは、ァセトニトリル等があ げられる。化合物 (I)または (IV)を半導体薄膜上に吸着させる場合の化合物 (I)また は（IV)溶液の濃度は 0. OlmmolZl以上であるのが好ましぐ 0. 1〜1. Ommol/1 であるのがより好ましい。 [0075] The compound (I) or (IV) is adsorbed onto the semiconductor thin film by immersing the semiconductor thin film coated on the support in the compound (I) or (IV) solution, and at room temperature for 1 minute to 2 days. Alternatively, it can be carried out by leaving it for 1 minute to 24 hours under heating conditions. The solvent used when the compound (I) or (IV) is adsorbed on the semiconductor thin film is not particularly limited as long as it is a solvent that dissolves the compound (I) or (IV). For example, methanol, ethanol, etc. Alcohol solvents, hydrocarbon solvents such as benzene, organic solvents such as tetrahydrofuran and acetonitrile, and the like. Preferably, mixed solvents thereof may be used. When the compound (I) or (IV) is adsorbed on the semiconductor thin film, the concentration of the compound (I) or (IV) solution is preferably 0. OlmmolZl or more 0.1-1. Ommol / 1 It is more preferable that
[0076] 光電変換の波長域をできるだけ広くし、かつエネルギー変換効率を上げるため、化 合物 (I)または (IV)と公知の色素、例えば、ルテニウム錯体色素、他の有機色素（例 えば、ポリメチン色素）等を併用してもよい。  [0076] In order to make the wavelength range of photoelectric conversion as wide as possible and increase the energy conversion efficiency, the compound (I) or (IV) and a known dye such as a ruthenium complex dye or other organic dye (for example, Polymethine dyes) and the like may be used in combination.
また、会合等色素同士の相互作用を低減する目的でカルボキシル基を有するステ ロイドィ匕合物 (例えば、ケノデォキシコール酸)等を半導体薄膜に共吸着させてもょ 、 。さらに、紫外線吸収剤を併用してもよい。  In addition, for the purpose of reducing the interaction between dyes such as association, a steroid-like compound having a carboxyl group (for example, chenodeoxycholic acid) or the like may be co-adsorbed on the semiconductor thin film. Furthermore, you may use a ultraviolet absorber together.
[0077] 電荷移動層は、化合物 (I)または (IV)の酸化体に電子を補充する機能を有する層 である [光を吸収した化合物 (I)または (IV)は増感作用によって、電子を放出するた め、酸化体に変換される]。  [0077] The charge transfer layer is a layer having a function of replenishing electrons to the oxidant of the compound (I) or (IV). [The compound (I) or (IV) which has absorbed light has an electron Will be converted to an oxidant to release.
本発明の光電変換素子に使用される電荷移動層としては、例えば、レドックスィォ ン対を有機溶媒に溶解した液体 (電解液)、レドックスイオン対を有機溶媒に溶解した 液体にポリマーを含浸したゲル電解質、レドックスイオン対を含有する溶融塩、固体 電解質、無機化合物半導体、有機正孔輸送材料等があげられる。  Examples of the charge transfer layer used in the photoelectric conversion element of the present invention include a liquid (electrolytic solution) obtained by dissolving a redoxion pair in an organic solvent, and a gel electrolyte obtained by impregnating a polymer in a liquid obtained by dissolving a redox ion pair in an organic solvent. And a molten salt containing a redox ion pair, a solid electrolyte, an inorganic compound semiconductor, an organic hole transport material, and the like.
[0078] レドックスイオン対としては、例えば、ヨウ素レドックス、臭素レドックス、鉄レドックス、 スズレドックス、クロムレドックス、バナジウムレドックス、硫化物イオンレドックス、アント ラキノンレドックス等があげられるが、これらに限定されない。より具体的には、ヨウ素 レドックスとしては、ヨウ化イミダゾリゥム誘導体、ヨウ化リチウム、ヨウ化カリウム、ヨウ化 テトラアルキルアンモ-ゥム塩等とヨウ素との混合物、また、臭素レドックスとしては、 臭化イミダゾリゥム誘導体、臭化リチウム、臭化カリウム、臭化テトラアルキルアンモ- ゥム塩等と臭素との混合物等があげられる。中でも、ヨウ化リチウム、ヨウ化イミダゾリウ ム誘導体等とヨウ素との混合物が好まし 、。レドックスイオン対を溶解する有機溶媒と しては、安定でかつレドックスイオン対を溶解する溶媒ならば限定されないが、例え ば、ァセトニトリル、メトキシァセトニトリル、プロピオ二トリル、メトキシプロピオ二トリル、 エチレンカーボネート、プロピレンカーボネート、ジメチルスルホキシド、ジメチルホル ムアミド、テトラヒドロフラン、ニトロメタン等の有機溶媒があげられ、それらの混合溶媒 を用いてもよぐ好ましくは、ァセトニトリル、メトキシァセトニトリル、プロピオ-トリル、メ トキシプロピオ-トリル等があげられる。前記電解液におけるレドックスイオン対の濃 度は、好ましくは 0. 01-5. Omol/1、より好ましくは、 0. 05-1. Omol/1である。 Examples of the redox ion pair include, but are not limited to, iodine redox, bromine redox, iron redox, tin redox, chromium redox, vanadium redox, sulfide ion redox, anthraquinone redox, and the like. More specifically, iodine redox includes imidazolium iodide derivatives, lithium iodide, potassium iodide, tetraalkyl ammonium salt and the like, and iodine bromide. Bromine redox includes imidazolium bromide. Examples thereof include a mixture of a derivative, lithium bromide, potassium bromide, tetraalkylammonium bromide salt and bromine. Among these, a mixture of iodine with lithium iodide, imidazolium iodide derivatives, etc. is preferred. The organic solvent that dissolves the redox ion pair is not limited as long as it is a stable solvent that dissolves the redox ion pair.For example, acetonitrile, methoxyacetonitrile, propionitol, methoxypropionitol, ethylene Organic solvents such as carbonate, propylene carbonate, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, nitromethane and the like can be used, and a mixed solvent thereof may be used. Preferably, acetonitrile, methoxyacetonitrile, propio-tolyl, methoxypropio-tolyl are used. Etc. Redox ion pair concentration in the electrolyte The degree is preferably 0.01-5. Omol / 1, more preferably 0.05-1.
[0079] 前記電解液は tert—ブチルピリジン、 2—ピコリン、 2, 6—ルチジン等の塩基性ィ匕 合物を含有していてもよい。塩基性化合物の濃度は、好ましくは 0. 01〜5. Omol/1 、より好ましくは 0. 1〜1. OmolZlである。 [0079] The electrolytic solution may contain a basic compound such as tert-butylpyridine, 2-picoline, 2,6-lutidine. The concentration of the basic compound is preferably 0.01 to 5. Omol / 1, more preferably 0.1 to 1. OmolZl.
ゲル電解質に使用されるポリマーとしては、ポリアクリロニトリル、ポリビ-リデンフル オリド等があげられる。  Examples of the polymer used for the gel electrolyte include polyacrylonitrile and polyvinylidene fluoride.
[0080] 溶融塩としては、 1ーブチルー 3—メチルピリジ-ゥムョーダイド、 1ーブチルー 3—メ チルイミダゾリゥムョーダイド、ヨウ化リチウム、酢酸リチウム、過塩素酸リチウム等のリ チウム塩等があげられ、これらにポリエチレンォキシド等のポリマーを混合することに より、室温での流動性を高めてもよい。  [0080] Examples of the molten salt include 1-butyl-3-methylpyridyumumudide, 1-butyl-3-methylimidazoliummide, lithium iodide such as lithium iodide, lithium acetate, and lithium perchlorate. The fluidity at room temperature may be improved by mixing a polymer such as polyethylene oxide with the polymer.
固体電解質としては、ポリエチレンォキシド誘導体等のポリマーがあげられる。  Examples of the solid electrolyte include polymers such as polyethylene oxide derivatives.
[0081] 無機化合物半導体としては、ヨウ化銅、臭化銅、チォシアン化銅等があげられる。 [0081] Examples of the inorganic compound semiconductor include copper iodide, copper bromide, and copper thiocyanide.
無機化合物半導体中にチォシアン酸トリェチルアンモ -ゥム等の溶融塩を含んで 、 てもよい。  The inorganic compound semiconductor may contain a molten salt such as triethyl ammonium thiocyanate.
有機正孔輸送材料としては、ポリチォフェン誘導体、ポリピロール誘導体等があげ られる。  Examples of the organic hole transport material include polythiophene derivatives and polypyrrole derivatives.
無機化合物半導体や有機正孔輸送材料を使用する場合は、短絡防止のためスプ レーパイロリシス等の手法を用いて二酸ィ匕チタン薄膜を下塗り層（短絡防止層）として 塗設してちよい。  In the case of using an inorganic compound semiconductor or an organic hole transport material, a titanium dioxide thin film may be applied as an undercoat layer (short-circuit prevention layer) by using a method such as spray pyrolysis to prevent a short circuit.
[0082] 電荷移動層の形成方法に関しては 2通りの方法があげられ、ひとつは色素を吸着さ せた半導体薄膜電極に先に対極を貼り合わせておき、その間隙に液状の電荷移動 層を注入する方法である。もうひとつは、半導体薄膜電極に直接電荷移動層を付与 する方法で、対極はその後付与することになる。  [0082] There are two methods for forming the charge transfer layer, and one is that a counter electrode is first bonded to a semiconductor thin film electrode on which a dye is adsorbed, and a liquid charge transfer layer is injected into the gap. It is a method to do. The other is a method in which a charge transfer layer is directly applied to a semiconductor thin film electrode, and a counter electrode is subsequently applied.
前者の場合の電荷移動層の注入方法としては、毛細管現象を利用する常圧プロセ スと常圧より低い圧力にして気相を液相に置換する真空プロセスが利用できる。後者 の場合は、湿式の電荷移動層においては未乾燥のまま対極を付与し、エッジ部の液 漏洩防止措置も施すことになる。また、ゲル電解質の場合には、湿式で塗布して重 合等の方法により固定ィ匕する方法もあり、その場合には、乾燥し、固定ィ匕した後に対 極を付与することもできる。電解液、湿式有機正孔輸送材料またはゲル電解質を付 与する方法としては、半導体薄膜電極や色素の付与の際と同様に、浸漬法、ローラ 法、ディップ法、エアーナイフ法、ブレード法、スピン法、スプレー法等をあげることも できる。固体電解質、無機化合物半導体または固体の有機正孔輸送材料の場合に は、これらを溶媒等に溶解したものを加熱された半導体薄膜電極に滴下し、半導体 薄膜電極上で溶媒を気化させることにより乾固された電荷移動層を形成したり、真空 蒸着法、 CVD法 (化学気相成長法)等のドライ成膜処理により、電荷移動層を形成し た後、対極を付与することもできる。 As the injection method of the charge transfer layer in the former case, a normal pressure process utilizing capillary action and a vacuum process in which the gas phase is replaced with a liquid phase at a pressure lower than normal pressure can be used. In the latter case, in the wet charge transfer layer, a counter electrode is provided without being dried, and measures for preventing liquid leakage at the edge are also taken. In the case of a gel electrolyte, there is also a method in which it is applied in a wet manner and fixed by a method such as polymerization, in which case it is dried and fixed after sealing. A pole can also be applied. The method for applying the electrolyte, wet organic hole transport material or gel electrolyte is the same as that for applying the semiconductor thin film electrode and the dye, dipping method, roller method, dipping method, air knife method, blade method, spin method. Method, spray method and the like. In the case of a solid electrolyte, an inorganic compound semiconductor, or a solid organic hole transport material, a solution obtained by dissolving them in a solvent or the like is dropped onto a heated semiconductor thin film electrode and dried by vaporizing the solvent on the semiconductor thin film electrode. A counter electrode can be applied after the charge transfer layer is formed by forming a solidified charge transfer layer, or by forming a charge transfer layer by a dry film forming process such as a vacuum deposition method or a CVD method (chemical vapor deposition method).
[0083] 本発明の光電変換素子に使用される対極としては、導電性基板上に薄膜状にコー トした白金、ロジウム、ルテニウム、カーボン、酸化物半導体電極等があげられ、中で も、導電性基板上に薄膜状にコートした白金、カーボン電極等が好ましい。 [0083] Examples of the counter electrode used in the photoelectric conversion element of the present invention include platinum, rhodium, ruthenium, carbon, and oxide semiconductor electrode coated in a thin film on a conductive substrate. Platinum, carbon electrodes and the like coated in a thin film on a conductive substrate are preferred.
本発明の光電変換素子においては、スぺーサーを用いてもよぐ半導体薄膜電極 と対極との接触を防ぐものであれば限定されないが、例えば、ポリエチレン等のポリマ 一フィルムが用いられる。  The photoelectric conversion element of the present invention is not limited as long as it prevents contact between the semiconductor thin film electrode and the counter electrode, which may use a spacer. For example, a polymer film such as polyethylene is used.
また、化合物 (I)および (IV)は、安価である。  In addition, compounds (I) and (IV) are inexpensive.
[0084] 以下、実施例により、本発明をさらに具体的に説明する。 [0084] Hereinafter, the present invention will be described more specifically with reference to Examples.
実施例 1  Example 1
[0085] 3, 4 ジクロロ一 3 シクロブテン一 1, 2 ジオン 33mgをジクロロメタン 2mLに溶 力した。この溶液にピリジン 17mgおよび N, N—ジ n—ブチルァ-リン 45mgをカロえ、 25°Cで 5時間攪拌した。その後、濃縮により溶媒を留去し、得られた残渣に酢酸 2m Lおよび水 lmLをカ卩え、 110°Cで 2時間攪拌した。析出した不溶物を濾取することに より、 4一（N, N ジ n—ブチルァミノフエ二ル）一 3 ヒドロキシシクロブテン一 1, 2— ジオン 40mgを得た。  [0085] 33 mg of 3,4 dichloro-1,3 cyclobutene-1,2,2 dione was dissolved in 2 mL of dichloromethane. To this solution, 17 mg of pyridine and 45 mg of N, N-di-n-butylaline were added and stirred at 25 ° C. for 5 hours. Thereafter, the solvent was distilled off by concentration, and 2 mL of acetic acid and 1 mL of water were added to the resulting residue, followed by stirring at 110 ° C. for 2 hours. The precipitated insoluble material was collected by filtration to obtain 40 mg of 4- (N, N-di-n-butylaminophenyl) 1-3 hydroxycyclobutene-1,2-dione.
[0086] 4— (N, N—ジ n—ブチルァミノフエ-ル） 3 ヒドロキシシクロブテン一 1, 2 ジ オン 40mgおよび 4 ァミノ安息香酸 18mgに n—ブタノール 1. 5mlおよびトルエン 1 . 5mlをカ卩え、 110°Cで 1時間加熱した後、析出物を濾取することにより、化合物（1) 42mgを得た。  [0086] 4- (N, N-di-n-butylaminophenol) 3 hydroxycyclobutene 1,2 dione 40 mg and 4-aminobenzoic acid 18 mg with n-butanol 1.5 ml and toluene 1.5 ml After heating at 110 ° C. for 1 hour, the precipitate was collected by filtration to obtain 42 mg of Compound (1).
JH NMR(DMSO- d ) δ ppm: 0.93 (6H, t, J = 7.1 Hz), 1.35 (4H, q, J = 7.3 Hz) •(s 'Ηΐ) SZ'Zl '(ΖΗ 0·6 = f 'P 'HZ J H NMR (DMSO- d) δ ppm: 0.93 (6H, t, J = 7.1 Hz), 1.35 (4H, q, J = 7.3 Hz) • ( s 'Ηΐ) SZ'Zl' ( Ζ Η 0 · 6 = f 'P' HZ
) WT8 '(ΖΗ 8·8 = f 'P ΉΖ) 66· '(ΖΗ 8·8 = f 'P 'HZ) LL'L '(ΖΗ Γ9Ϊ = f 'P 'Ηΐ) ZS" l '(ΖΗ ε·6 = f 'P ΉΖ) 28"9 '(ΖΗ Γ9Ϊ = f 'P 'Ηΐ) '(^ 'H WZ '(^ 'H IS'I ' (ZH Z'L = f 'b 'Η ) ZZ'\ '(ΖΗ Z' L = f '； 'Η9) S6 ： ^dcj g (9p-OS a)H N HT ) WT8 '( Ζ Η 8 ・ 8 = f' P ΉΖ) 66 · '(ΖΗ 8 ・ 8 = f' P 'HZ) LL'L' ( Ζ Γ Γ9Ϊ = f 'P' Ηΐ) ZS "l '( Ζ Η ε · 6 = f ' P ΉΖ) 28 "9' (Ζ Η Γ9Ϊ = f 'P' Ηΐ) '(^' H WZ '(^' H IS'I '(ZH Z'L = f' b 'Η) ZZ' \ '( Ζ Η Z' L = f ';' Η9) S6: ^ dcj g ( 9 p-OS a) HNH T
9(ε)呦
Figure imgf000025_0001
9 (ε) 呦
Figure imgf000025_0001
ui0Sベu i 0S
Figure imgf000025_0002
'N)—
Figure imgf000025_0002
'N) —
^/i ^^ ^— ε— ( ェ , ^ ^ : -U-/ -N 'Ν)- [8800] x_rao-x_(l/lOUI) 00899 ： (os va)凝、 ^ / i ^^ ^ — ε— (, ^ ^: -U- / -N 'Ν)-[8800] x_ rao - x _ (l / l OUI ) 00899: (os va)
^osf ： (ospva)誉¾¾1¾ 軎 ^ osf: (ospva) Honor ¾¾1¾ 軎
•(s 'Ηΐ) OL'Zl '(ΖΗ ε·8 = f 'Ρ 'Ηΐ) SS"8 '(ω Ήε) 30"8 '(ΖΗ 9"Ζ = f 'Ρ 'Ηΐ) • (s 'Ηΐ) OL'Zl' ( Ζ Η ε · 8 = f 'Ρ' Ηΐ) SS "8 '(ω Ήε) 30"8' ( Ζ Η 9 "Ζ = f 'Ρ' Ηΐ)
•Ζ '(ΖΗ 9"Ζ = f 'Ηΐ) LZ'L '(ΖΗ 8·8 = f 'Ρ 'ΗΖ) 98·9 '(ω Ή^) £V£ '(ω Ή^) SS'I ' (ZH Z'L = f 'b 'Η ) SS"T '(ΖΗ ΓΖ = f 'Η9) S6 ： ^dcj g (9p-OS a)H N Ητ
Figure imgf000025_0003
ι、 · • Ζ '(ΖΗ 9 "Ζ = f' Ηΐ) LZ'L '(ΖΗ 8 · 8 = f' Ρ 'ΗΖ) 98 · 9' (ω Ή ^) £ V £ '(ω Ή ^) SS'I '(ZH Z'L = f' b 'Η) SS "T' (ΖΗ ΓΖ = f 'Η9) S6: ^ dcj g ( 9 p-OS a) HN Η τ
Figure imgf000025_0003
ι, ·
' I -
Figure imgf000025_0004
'N)—'I-
Figure imgf000025_0004
'N) —
^ ^^ ^ - ε - ( /—^Δ ^ /-^/ - U/ - N 'N)— : ^ U 800]  ^ ^^ ^-ε-(/ — ^ Δ ^ /-^ /-U /-N 'N) —: ^ U 800]
x_rao-x_(l/lOUI) 00^92 ： (OS Va)凝、 x_ rao - x _ (l / l OUI ) 00 ^ 92: (OS Va)
•(s 'Ηΐ) Z6 ΐ '(ZH 6"S = f 'P 'Η 90·8 '(ΖΗ 9"S = f 'P 'HZ) fO •8 '(ZH Γ8 = f 'P Ή2) 86· '(ZH 9·8 = f 'P 'HZ) S8"9 '(ω Ή^) ZYZ '(ω Ή^) SS'I ' • (s' Ηΐ) Z6 ΐ '(ZH 6 "S = f' P 'Η 90 · 8' ( Ζ Η 9" S = f 'P' HZ) fO • 8 '(ZH Γ8 = f' P Ή2) 86 · '(ZH 9 · 8 = f' P 'HZ) S8 "9' (ω Ή ^) ZYZ '(ω Ή ^) SS'I'
TS68l0/S00Zdf/X3d 83 S 贿 900Ζ OAV •(s 'Ηΐ) 08 ΐ '(ΖΗ 9·8 TS68l0 / S00Zdf / X3d 83 S 贿 900 Ζ OAV • ( s 'Ηΐ) 08 ΐ' ( Ζ Η 9 · 8
= f 'Ρ 'ΗΖ) SO'8 '(ΖΗ 8·8 = f 'Ρ 'ΗΖ) £6Ί '(ΖΗ 9·8 = f 'Ρ 'ΗΖ) 9VL '(ΖΗ 0·6 = f 'Ρ = f 'Ρ' ΗΖ) SO'8 '( Ζ Η 8 ・ 8 = f' Ρ 'ΗΖ) £ 6Ί' ( Ζ Η 9 ・ 8 = f 'Ρ' ΗΖ) 9VL '( Ζ Η 0 ・ 6 = f 'Ρ
'ΗΖ) 08·9 '(ω 'Η ) 9V2 '(ΖΗ ΓΖ = f 'Η9) fVl ： ^dcj g (9p-OS a)H N HT
Figure imgf000026_0001
·〇べェ'ΗΖ) 08 · 9' (ω 'Η) 9V2' ( Ζ Η ΓΖ = f 'Η9) fVl ： ^ dcj g ( 9 p-OS a) HNH T
Figure imgf000026_0001
· Bee
4¾QT¾:iraQ
Figure imgf000026_0002
、3
Figure imgf000026_0003
4¾QT¾: iraQ
Figure imgf000026_0002
, 3
Figure imgf000026_0003
。 ¾¾3raogベ^ S 'l
Figure imgf000026_0004
. ¾¾3raogbe ^ S 'l
Figure imgf000026_0004
( / ェ , ^ ^エ — N 'Ν) )T^ -¾ -¾l¾¾^¾^、"¥
Figure imgf000026_0005
翻 s、 つ。
Figure imgf000026_0006
x_rao-x_(l/lOUI)06Z8S： (os va)凝、 (/, ^ ^ Et — N 'Ν)) T ^ -¾ -¾l¾¾ ^ ¾ ^ 、 "¥
Figure imgf000026_0005
S.
Figure imgf000026_0006
x_ rao - x _ (l / l OUI ) 06Z8S: (os va)
•(s 'Ηΐ) 80·εΐ ' (s 'Ηΐ) 09·8 ' (s 'Ηΐ) 9 ·8 '(ΖΗ 8·8 = f 'Ρ ' Ηΐ) 82"8 '(ΖΗ 8·8 = f 'Ρ 'Ηΐ) 02"8 '(ΖΗ 0·6 = f 'Ρ 'ΗΖ) 80·8 '(ΖΗ S'8 = f 'Ρ 'Ηΐ) 00 •8 '(ΖΗ S'8 = f 'Ρ 'Ηΐ) 96· '(ΖΗ 0·6 = f 'Ρ 'ΗΖ) 38"9 '(ω Ή^) 1£ '(ω Ή^) 93"ΐ ' (ΖΗ 9"Ζ = f 'b 'Η ) SS"T '(ΖΗ Ζ' L = f '； 'Η9) 6·0： ^dcj g (9p-OS a)H N Ητ • ( s ' Ηΐ) 80 · εΐ '( s ' Ηΐ) 09 · 8' ( s ' Ηΐ) 9 8 '( Ζ Η 8 ・ 8 = f' Ρ 'Ηΐ) 82 "8' ( Ζ Η 8 8 = f 'Ρ' Ηΐ) 02 "8 '( Ζ Η 0 · 6 = f' Ρ 'ΗΖ) 80 · 8' ( Ζ Η S'8 = f 'Ρ' Ηΐ) 00 • 8 '( Ζ Η S '8 = f' Ρ 'Ηΐ) 96 ·' (ΖΗ 0 · 6 = f 'Ρ' ΗΖ) 38 "9 '(ω Ή ^) 1 £' (ω Ή ^) 93" ΐ '(ΖΗ 9 "Ζ = f 'b' Η) SS "T '(ΖΗ Ζ' L = f ';' Η9) 6 · 0: ^ dcj g ( 9 p-OS a) HN Η τ
Figure imgf000026_0007
Figure imgf000026_0008
^ : N [6800]
Figure imgf000026_0007
Figure imgf000026_0008
^: N [6800]
,_m ',_{ / om)^^ ^ '■ (os va)凝、 , _ m ', _ {/ om ) ^^ ^' ■ (os va)
TS68l0/S00Zdf/X3d z S 贿 900Z OAV モル吸光係数（DMSO)： 63257 (molZD 'cm TS68l0 / S00Zdf / X3d z S 贿 900Z OAV Molar extinction coefficient (DMSO): 63257 (molZD 'cm
実施例 6  Example 6
[0092] 原料である 3—クロ口一 4— (N, N—ジェチルァミノフエ-ル）シクロブテン一 1, 2— ジオンは実施例 5と同様の操作により得た。  [0092] The raw material 3-chloro opening 4- (N, N-jetylaminophenol) cyclobutene 1,2-dione was obtained in the same manner as in Example 5.
3—クロ口一 4— (N, N—ジェチルァミノフエ-ル）シクロブテン一 1, 2—ジオン 50m g、 2—ァミノ安息香酸 26mgおよびキノリン 25mgに n—ブタノール 0. 5mlおよびトル ェン 0. 5mlをカ卩え、 110°Cで 2時間加熱した後、析出物を濾取することにより、化合 物（6) 13mgを得た。  3—Black Mouth 4— (N, N-Jetylaminophenol) Cyclobutene 1,2-Dione 50 mg, 2-Aminobenzoic acid 26 mg and Quinoline 25 mg, n-Butanol 0.5 ml and Toluene 0.5 ml was added and heated at 110 ° C. for 2 hours, and then the precipitate was collected by filtration to obtain 13 mg of Compound (6).
JH NMR(DMSO-d ) δ ppm: 1.09 (6H, t, J = 7.1 Hz), 3.46 (4H, m), 6.84 (2H, J H NMR (DMSO-d) δ ppm: 1.09 (6H, t, J = 7.1 Hz), 3.46 (4H, m), 6.84 (2H,
6  6
d, J = 9.3 Hz), 7.37 (IH, t, J = 7.6 Hz), 7.74 (IH, d, J = 7.6 Hz), 8.02 (2H, d, J = d, J = 9.3 Hz), 7.37 (IH, t, J = 7.6 Hz), 7.74 (IH, d, J = 7.6 Hz), 8.02 (2H, d, J =
8.3 Hz), 8.07 (IH, d, J = 7.6 Hz), 8.44 (IH, d, J = 8.3 Hz). 8.3 Hz), 8.07 (IH, d, J = 7.6 Hz), 8.44 (IH, d, J = 8.3 Hz).
最大吸収波長（DMSO)： 436nm  Maximum absorption wavelength (DMSO): 436nm
モル吸光係数（DMSO)： 44784 (mol/Ι) "1 · cm"1 Molar extinction coefficient (DMSO): 44784 (mol / Ι) " 1 · cm" 1
実施例 7  Example 7
[0093] 原料である 3—クロ口一 4— (N, N—ジェチルァミノフエ-ル）シクロブテン一 1, 2— ジオンは実施例 5と同様の操作により得た。  The raw material 3-chloro opening 4- (N, N-jetylaminophenol) cyclobutene 1,1,2-dione was obtained in the same manner as in Example 5.
3—クロ口一 4— (N, N—ジェチルァミノフエ-ル）シクロブテン一 1, 2—ジオン 50m g、 4—アミノケィ皮酸 31mgおよびキノリン 25mgに n—ブタノール 0. 5mlおよびトル ェン 0. 5mlをカ卩え、 110°Cで 2時間加熱した後、析出物を濾取することにより、化合 物（7) 52mgを得た。  3—Black mouthpiece 4— (N, N-Jetylaminophenol) cyclobutene 1,2-Dione 50 mg, 4-Aminocacin acid 31 mg and Quinoline 25 mg, n-Butanol 0.5 ml and Toluene 0.5 ml was added and heated at 110 ° C. for 2 hours, and the precipitate was collected by filtration to obtain 52 mg of Compound (7).
JH NMR(DMSO-d ) δ ppm: 1.14 (6H, t, J = 6.6 Hz), 3.46 (4H, m), 6.48 (IH, J H NMR (DMSO-d) δ ppm: 1.14 (6H, t, J = 6.6 Hz), 3.46 (4H, m), 6.48 (IH,
6  6
d, J = 16.1 Hz), 6.79 (2H, d, J = 9.0 Hz), 7.41 (2H, d, J = 8.6 Hz), 7.57 (IH, d, J = 15.9 Hz), 7.70 (2H, d, J = 8.8 Hz), 7.91 (2H, d, J = 8.3 Hz), 12.32 (IH, s).  d, J = 16.1 Hz), 6.79 (2H, d, J = 9.0 Hz), 7.41 (2H, d, J = 8.6 Hz), 7.57 (IH, d, J = 15.9 Hz), 7.70 (2H, d, J = 8.8 Hz), 7.91 (2H, d, J = 8.3 Hz), 12.32 (IH, s).
最大吸収波長（DMSO)： 427nm  Maximum absorption wavelength (DMSO): 427nm
モル吸光係数（DMSO)： 71575 (mol/Ι) "1 · cm"1 Molar extinction coefficient (DMSO): 71575 (mol / Ι) " 1 · cm" 1
実施例 8  Example 8
[0094] フッ素をドープした酸化スズをコーティングした透明導電性ガラス (日本板硝子製、 表面抵抗は約 15 Ω /cm2)の導電面側に二酸ィ匕チタンペースト（Solaronix製、 SA Ti-Nanoxide T)をガラス棒を用いて塗布し、室温で 30分間乾燥した後、電気 炉で 450°Cにて 30分間焼成した。二酸ィ匕チタンの膜厚は 10 /z mであった。ガラスを 取り出し冷却した後、実施例 1〜7で製造したィ匕合物（1)〜（7)のそれぞれとケノデォ キシコール酸を混合したァセトニトリル溶液 (ィ匕合物 0. lmmol/1,ケノデォキシコー ル酸 lOmmolZDに 75°Cで 30分間浸漬した。色素の吸着したガラスをァセトニトリル で洗浄し自然乾燥させた。 [0094] Transparent conductive glass coated with tin oxide doped with fluorine (made by Nippon Sheet Glass, surface resistance is about 15 Ω / cm 2 ) on the conductive surface side of titanium dioxide dioxide paste (Solaronix, SA Ti-Nanoxide T) was applied using a glass rod, dried at room temperature for 30 minutes, and then baked in an electric furnace at 450 ° C for 30 minutes. The film thickness of titanium dioxide was 10 / zm. After the glass was taken out and cooled, acetonitrile solution in which each of the compounds (1) to (7) prepared in Examples 1 to 7 and chenodeoxycholic acid were mixed (the compound 0.1 lmmol / 1, chenodeoxychol) It was immersed in acid lOmmolZD for 30 minutes at 75 ° C. The dye-adsorbed glass was washed with acetonitrile and allowed to air dry.
[0095] 上述のようにして作成した二酸化チタン電極基板（1cm X 3cm)をこれと同じ大きさ の白金蒸着ガラスと重ね合わせた。次に、電解液 (ヨウ素 0. O5mol/Uヨウ化リチウ ム 0. lmol/Uヨウ化ジメチルプロピルイミダゾリゥム 0. 62molZlおよび tert—ブチ ルビリジン 0. 5mol/lのァセトニトリル溶液)を、両ガラスの隙間に毛細管現象を利用 して染み込ませて二酸化チタン電極と対極の間に導入することにより、光電気化学電 池を得た。この光電気化学電池について、 500Wクセノンショートアークランプ（ゥシ ォ電機製)を用い、 lOOmWZcm2の擬似太陽光を照射し、 I—Vカーブトレーサー（ 英弘精機製)にてその特性を評価した。 [0095] The titanium dioxide electrode substrate (1 cm X 3 cm) prepared as described above was superposed on a platinum-deposited glass of the same size. Next, an electrolyte solution (iodine 0. O5 mol / U lithium iodide 0.1 mol / U iodide dimethylpropylimidazole 0.62 mol Zl and tert-butyryridine 0.5 mol / l acetonitrile solution) was added to both glasses. A photoelectrochemical cell was obtained by impregnating the gap using a capillary phenomenon and introducing it between the titanium dioxide electrode and the counter electrode. About this photoelectrochemical cell, using 500W xenon short arc lamp (manufactured by Usio Electric Co., Ltd.), irradiating pseudo sunlight of lOOmWZcm 2 and evaluating its characteristics with IV curve tracer (manufactured by Eihiro Seiki).
[0096] 表 2に化合物（1)〜（7)を用いた光電気化学電池の特性を示す。  [0096] Table 2 shows the characteristics of the photoelectrochemical cell using the compounds (1) to (7).
[0097] [表 2]  [0097] [Table 2]
^ 2 ^ 2
Figure imgf000028_0001
Figure imgf000028_0001
産業上の利用可能性 Industrial applicability
本発明により、安価かつ高いエネルギー変換効率を有する光電変換素子に使用で きるスクァリリウム化合物、該スクァリリウム化合物を用いた光電気化学電池等を提供 することがでさる。 According to the present invention, a squarylium compound that can be used in a photoelectric conversion element having low cost and high energy conversion efficiency, a photoelectrochemical cell using the squarylium compound, and the like are provided. You can do it.

Claims

請求の範囲 The scope of the claims
[1] 一般式 (I)  [1] General formula (I)
[化 21]  [Chemical 21]
Figure imgf000030_0001
Figure imgf000030_0001
または一般式 (IV)  Or general formula (IV)
[化 22]  [Chemical 22]
Figure imgf000030_0002
Figure imgf000030_0002
{式中、 R1および R2は同一または異なって、水素原子、置換基を有していてもよいァ ルキル基、置換基を有して 、てもよ 、ァラルキル基または置換基を有して 、てもよ ヽ ァリール基を表す力、 R1および R2が隣接する窒素原子と一緒になつて置換基を有し ていてもよい複素環を形成し、 R3、 R4、 R5および R6は同一または異なって、水素原 子、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシル 基、置換基を有していてもよいァラルキル基、置換基を有していてもよいァリール基、 置換基を有していてもよい複素環基、ヒドロキシル基、またはハロゲン原子を表し、 R3 および R5、または R4および R6はそれぞれが隣接する 2つの炭素原子と一緒になつて 置換基を有して ヽてもよ 、炭化水素環または置換基を有して ヽてもよ ヽ複素環を形 成してもよぐ R1および R3、または R2および R4はそれぞれが隣接する N— C— Cと一 緒になって、置換基を有していてもよい複素環を形成してもよぐ Xは、一般式 (II) [化 23]
Figure imgf000031_0001
{In the formula, R 1 and R 2 are the same or different and have a hydrogen atom, an alkyl group which may have a substituent, or a substituent, which may have an aralkyl group or a substituent. The force representing the aryl group, R 1 and R 2 together with the adjacent nitrogen atom form an optionally substituted heterocyclic ring, and R 3 , R 4 , R 5 And R 6 are the same or different and are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, an optionally substituted aralkyl group, and a substituted group. Represents an aryl group that may have a group, a heterocyclic group that may have a substituent, a hydroxyl group, or a halogen atom, and R 3 and R 5 , or R 4 and R 6 are adjacent to each other Together with two carbon atoms may have a substituent, a hydrocarbon ring or a substituent R 1 and R 3 , or R 2 and R 4, together with adjacent N—C—C, may be substituted. X may form a heterocyclic ring which may have a group. X is represented by the general formula (II)
Figure imgf000031_0001
[式中、 R7は水素原子、置換基を有していてもよいアルキル基、置換基を有していて もよ！/、ァラルキル基、置換基を有して!/、てもよ 、ァリール基または置換基を有して!/ヽ てもよい複素環基を表し、 R8はハロゲン原子、置換基を有していてもよいアルキル基 、置換基を有していてもよいアルコキシル基、置換基を有していてもよいァラルキル 基、置換基を有していてもよいァリール基、ニトロ基、シァノ基、ヒドロキシル基、置換 基を有して 、てもよ 、ァミノ基または置換基を有して 、てもよ 、複素環基を表し、 aは 0〜4の整数を表し、ここに aが 2〜4の場合、それぞれの R8は同一または異なっても よぐさらに互いに隣り合う 2つの R8がそれぞれが隣接する 2つの炭素原子と一緒に なって、置換基を有して 、てもよ 、炭化水素環または置換基を有して 、てもよ 、複素 環を形成してもよぐ R9および R1C>は同一または異なって、水素原子、置換基を有して いてもよいアルキル基、カルボキシル基、アルコキシカルボ-ル基、置換基を有して V、てもよ 、ァラルキル基、置換基を有して 、てもよ 、ァリール基またはシァノ基を表し 、 bは 0〜4の整数を表し、ここに bが 2〜4の場合、それぞれの R9およびそれぞれの R 1(>は同一または異なってもよぐ Aは酸性基を表し、 cは 1〜5の整数を表し、ここにじが 2〜5の場合、それぞれの Aおよびそれぞれの一般式 (A) [Wherein R 7 may have a hydrogen atom, an alkyl group which may have a substituent, or a substituent! /, An aralkyl group, having a substituent! /, Or an aryl group or a heterocyclic group which may have a substituent! / R 8 may have a halogen atom or a substituent. An optionally substituted alkyl group, an optionally substituted alkoxyl group, an optionally substituted aralkyl group, an optionally substituted aryl group, a nitro group, a cyano group, a hydroxyl group A group, a substituent, or an amino group or a substituent, a heterocyclic group, a represents an integer of 0 to 4, wherein a is 2 to 4 In this case, each R 8 may be the same or different. Further, two R 8 adjacent to each other may be substituted with two adjacent carbon atoms, each having a substituent, or carbonization. a hydrocarbon ring or a substituent, I also, Yogu R 9 and R 1C also form a heterocyclic ring> are the same or different A hydrogen atom, an alkyl group which may have a substituent, a carboxyl group, an alkoxycarbonyl group, a substituent having V, a aralkyl group, or a substituent. Y represents an aryl group or cyano group, b represents an integer of 0 to 4, and when b is 2 to 4, each R 9 and each R 1 (> may be the same or different A Represents an acidic group, c represents an integer of 1 to 5, and in the case where the length is 2 to 5, each A and each general formula (A)
[化 24] [Chemical 24]
Figure imgf000031_0002
Figure imgf000031_0002
(式中、 R9、 R1C>および bはそれぞれ前記と同義である）で表される基は同一または異 なってもよい]で表される基、または一般式 (III) (Wherein R 9 , R 1C> and b are as defined above, respectively, may be the same or different)] or a group represented by the general formula (III)
[化 25]
Figure imgf000032_0001
[Chemical 25]
Figure imgf000032_0001
(式中、 R11は水素原子、置換基を有していてもよいアルキル基、置換基を有していて もよ！/、ァラルキル基、置換基を有して!/、てもよ 、ァリール基または置換基を有して!/ヽ てもよい複素環基を表し、 R12および R13は同一または異なって、ハロゲン原子、置換 基を有していてもよいアルキル基、置換基を有していてもよいアルコキシル基、置換 基を有していてもよいァラルキル基、置換基を有していてもよいァリール基、ニトロ基 、シァノ基、ヒドロキシル基、置換基を有していてもよいアミノ基または置換基を有して いてもよい複素環基を表し、 pは 0〜3の整数を表し、ここに pが 2〜3の場合、それぞ れの R12は同一または異なってもよぐ qは 0〜3の整数を表し、ここに qが 2〜3の場合 、それぞれの R13は同一または異なってもよぐ R14および R15は同一または異なって、 水素原子、置換基を有していてもよいアルキル基、カルボキシル基、アルコキシカル ボニル基、置換基を有していてもよいァラルキル基、置換基を有していてもよいァリー ル基またはシァノ基を表し、 rは 0〜4の整数を表し、ここに rが 2〜4の場合、それぞれ の R14およびそれぞれの R15は同一または異なってもよぐ Eは酸性基を表し、 sは 1〜 4の整数を表し、ここに sが 2〜4の場合、それぞれの Eおよびそれぞれの一般式（B) [化 26] (Wherein R 11 is a hydrogen atom, an alkyl group which may have a substituent, may have a substituent! /, An aralkyl group or a substituent! /, Represents an aryl group or a heterocyclic group which may have a substituent, and R 12 and R 13 may be the same or different and each represents a halogen atom, an optionally substituted alkyl group or a substituent. An alkoxyl group which may have, an aralkyl group which may have a substituent, an aryl group which may have a substituent, a nitro group, a cyano group, a hydroxyl group, or a substituent. Represents a good amino group or an optionally substituted heterocyclic group, p represents an integer of 0 to 3, and when p is 2 to 3, each R 12 is the same or different. Moqoku represents an integer from 0 to 3, where when q is 2 to 3, each R 13 may be the same or different R 1 4 and R 15 are the same or different and each has a hydrogen atom, an alkyl group which may have a substituent, a carboxyl group, an alkoxycarbonyl group, an aralkyl group which may have a substituent, or a substituent. May represent an aryl group or a cyano group, and r represents an integer of 0 to 4, and when r is 2 to 4, each R 14 and each R 15 may be the same or different. E represents an acidic group, s represents an integer of 1 to 4, and when s is 2 to 4, each E and each general formula (B) [Chemical Formula 26]
Figure imgf000032_0002
Figure imgf000032_0002
(式中、 R14、 R1&および rはそれぞれ前記と同義である）で表される基は同一または異 なってもよい]で表される基を表す }で表されるスクァリリウム化合物。 (Wherein R 14 , R 1 & and r have the same meanings as defined above, respectively) may represent the same or different groups].
[2] 一般式 (la) [2] General formula (la)
[化 27]
Figure imgf000033_0001
[Chemical 27]
Figure imgf000033_0001
〔式中、
Figure imgf000033_0002
R2、 R3、 R4、 R5および R6は、それぞれ前記と同義であり、 X1は、一般式 ([Where,
Figure imgf000033_0002
R 2 , R 3 , R 4 , R 5 and R 6 are as defined above, and X 1 is a group represented by the general formula (
II) II)
[化 28]  [Chemical 28]
Figure imgf000033_0003
Figure imgf000033_0003
(式中、 R'、 R8、 R9、 R10, A、 a、 bおよび cは、それぞれ前記と同義である）で表される 基を表す〕で表されるスクァリリウム化合物。 (Wherein R ′, R 8 , R 9 , R 10 , A, a, b and c each represents the same group as defined above), a squarylium compound represented by:
[3] Aがカルボキシル基である請求項 2記載のスクァリリウム化合物。 [3] The squarylium compound according to [2], wherein A is a carboxyl group.
[4] R9および R1Gが水素原子である請求項 2または 3記載のスクァリリウム化合物。 [4] according to claim 2 or 3 Sukuaririumu compound according R 9 and R 1G is a hydrogen atom.
[5] bが 0または 1である請求項 2から 4のいずれかに記載のスクァリリウム化合物。  [5] The squarylium compound according to any one of claims 2 to 4, wherein b is 0 or 1.
[6] cが 1である請求項 2から 5のいずれかに記載のスクァリリウム化合物。  [6] The squarylium compound according to any one of claims 2 to 5, wherein c is 1.
[7] aが 0である請求項 2から 6の 、ずれかに記載のスクァリリウム化合物。  [7] The squarylium compound according to any one of claims 2 to 6, wherein a is 0.
[8] 一般式 (lb)  [8] General formula (lb)
[化 29]  [Chemical 29]
Figure imgf000033_0004
Figure imgf000033_0004
〔式中、
Figure imgf000033_0005
R2、 R3、 R4、 R5および R6は、それぞれ前記と同義であり、 X2は、一般式 ([Where,
Figure imgf000033_0005
R 2 , R 3 , R 4 , R 5 and R 6 are as defined above, and X 2 is a group represented by the general formula (
III) III)
[化 30]
Figure imgf000034_0001
[Chemical 30]
Figure imgf000034_0001
(式中、 R"、 R"、 R"、 R14、 R , E、 p、 q、 rおよび sは、それぞれ前記と同義である) で表される基を表す〕で表されるスクァリリウム化合物。 (Wherein R ′, R ″, R ″, R 14 , R 1, E, p, q, r and s each have the same meaning as described above)) .
[9] Eがカルボキシル基である請求項 8記載のスクァリリウム化合物。 9. The squarylium compound according to claim 8, wherein E is a carboxyl group.
[10] R14および R15が水素原子である請求項 8または 9記載のスクァリリウム化合物。 [10] according to claim 8 or 9 Sukuaririumu compound according R 14 and R 15 are hydrogen atoms.
[11] rが 0である請求項 8から 10のいずれかに記載のスクァリリウム化合物。 [11] The squarylium compound according to any one of claims 8 to 10, wherein r is 0.
[12] sが 1である請求項 8から 11のいずれかに記載のスクァリリウム化合物。 [12] The squarylium compound according to any one of claims 8 to 11, wherein s is 1.
[13] pが 0である請求項 8から 12のいずれかに記載のスクァリリウム化合物。 [13] The squarylium compound according to any one of claims 8 to 12, wherein p is 0.
[14] qが 0である請求項 8から 13のいずれかに記載のスクァリリウム化合物。 [14] The squarylium compound according to any one of claims 8 to 13, wherein q is 0.
[15] 一般式 (IVa) [15] General formula (IVa)
[化 31]  [Chemical 31]
Figure imgf000034_0002
Figure imgf000034_0002
〔式中、
Figure imgf000034_0003
R5および R6は、それぞれ前記と同義であり、 X3は、一般式 ([Where,
Figure imgf000034_0003
R 5 and R 6 are as defined above, and X 3 is a group represented by the general formula (
II) II)
[化 32]  [Chemical 32]
Figure imgf000034_0004
Figure imgf000034_0004
(式中、 R7、 R8、 R9、 R10, A、 a、 bおよび cは、それぞれ前記と同義である）で表される 基を表す〕で表されるスクァリリウム化合物。 Aが力ルポキシル基である請求項 15記載のスクァリリウム化合物。 (Wherein R 7 , R 8 , R 9 , R 10 , A, a, b and c each represents the same group as defined above), a squarylium compound represented by: 16. The squarylium compound according to claim 15, wherein A is a strong lpoxyl group.
R9および R1Gが水素原子である請求項 15または 16記載のスクァリリウム化合物。 bが 0または 1である請求項 15から 17のいずれかに記載のスクァリリウム化合物。 cが 1である請求項 15から 18のいずれかに記載のスクァリリウム化合物。 aが 0である請求項 15から 19のいずれかに記載のスクァリリウム化合物。 一般式 (IVb) The squarylium compound according to claim 15 or 16, wherein R 9 and R 1G are hydrogen atoms. The squarylium compound according to any one of claims 15 to 17, wherein b is 0 or 1. The squarylium compound according to any one of claims 15 to 18, wherein c is 1. The squarylium compound according to any one of claims 15 to 19, wherein a is 0. Formula (IVb)
[化 33]  [Chemical 33]
Figure imgf000035_0001
Figure imgf000035_0001
〔式中、 R\ R2、 R3、 R4、 R5および R6は、それぞれ前記と同義であり、 X4は、一般式 ([Wherein R \ R 2 , R 3 , R 4 , R 5 and R 6 have the same meanings as defined above, and X 4 represents the general formula (
III) III)
[化 34]  [Chemical 34]
Figure imgf000035_0002
Figure imgf000035_0002
(式中、 1、 R12、 R13、 R14、 R15、 E、 p、 q、 rおよび sは、それぞれ前記と同義である) で表される基を表す〕で表されるスクァリリウム化合物。 (Wherein each represents a group represented by 1 , R 12 , R 13 , R 14 , R 15 , E, p, q, r, and s are as defined above), a squarylium compound represented by .
[22] Eがカルボキシル基である請求項 21記載のスクァリリゥム化合物。 22. The squaryum compound according to claim 21, wherein E is a carboxyl group.
[23] R14および R15が水素原子である請求項 21または 22記載のスクァリリウム化合物。 [23] according to claim 21 or 22 Sukuaririumu compound according R 14 and R 15 are hydrogen atoms.
[24] rが 0である請求項 21から 23のいずれかに記載のスクァリリウム化合物。 [24] The squarylium compound according to any one of items 21 to 23, wherein r is 0.
[25] sが 1である請求項 21から 24のいずれかに記載のスクァリリウム化合物。 [25] The squarylium compound according to any one of items 21 to 24, wherein s is 1.
[26] pが 0である請求項 21から 25の!、ずれかに記載のスクァリリウム化合物。 [27] qが 0である請求項 21から 26の!、ずれかに記載のスクァリリウム化合物。 [26] The squarylium compound according to any one of claims 21 to 25, wherein p is 0. [27] The squarylium compound according to any one of claims 21 to 26, wherein q is 0.
[28] 請求項 1〜27のいずれかに記載のスクァリリウム化合物と半導体とを含む光電変換 材料。 [28] A photoelectric conversion material comprising the squarylium compound according to any one of claims 1 to 27 and a semiconductor.
[29] 請求項 28記載の光電変換材料を用いた光電変換素子。  [29] A photoelectric conversion device using the photoelectric conversion material according to [28].
[30] 請求項 29記載の光電変換素子を含有する光電気化学電池。 30. A photoelectrochemical cell comprising the photoelectric conversion element according to claim 29.
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