WO2006041155A1 - Dérivé de squarylium, matériau de conversion photoélectrique incluant ledit dérivé, élément de conversion photoélectrique, et cellule photoélectrochimique - Google Patents

Dérivé de squarylium, matériau de conversion photoélectrique incluant ledit dérivé, élément de conversion photoélectrique, et cellule photoélectrochimique 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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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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Publication of WO2006041155A1 publication Critical patent/WO2006041155A1/fr

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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

La présente invention a pour objet un dérivé de squarylium de formule générale (I) ci-après [où R1 et R2 représentent chacun un hydrogène, un alkyle éventuellement substitué, etc., ces deux groupements pouvant être différents l’un de l’autre ; R3, R4, R5 et R6 représentent chacun un hydrogène, un alkyle éventuellement substitué, etc., ces groupements pouvant être différents les uns des autres ; et X représente par exemple un groupement de formule générale (II) (où R7 représente un hydrogène, un alkyle éventuellement substitué, etc. ; R8 représente un halogène, etc. ; a est un entier compris entre 0 et 4 ; R9 et R10 représentent chacun un hydrogène, un alkyle éventuellement substitué, etc., ces deux groupements pouvant être différents l’un de l’autre ; b est un entier compris entre 0 et 4 ; A représente un groupement acide ; et c est un entier entre 1 et 5)].
PCT/JP2005/018951 2004-10-14 2005-10-14 Dérivé de squarylium, matériau de conversion photoélectrique incluant ledit dérivé, élément de conversion photoélectrique, et cellule photoélectrochimique WO2006041155A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1698916A1 (fr) * 2003-12-18 2006-09-06 Kyowa Hakko Chemical Co., Ltd. Filtre pour affichage electronique
WO2007049579A1 (fr) * 2005-10-24 2007-05-03 Kyowa Hakko Chemical Co., Ltd. Compose squarylium et composition photopolymerisable pour source lumineuse a ondes courtes l’utilisant

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0317047A (ja) * 1989-05-30 1991-01-25 Xerox Corp 光導電性画像形成部材及びその部材を使用する画像形成方法
JPH03126581A (ja) * 1989-10-12 1991-05-29 Canon Inc 光学記録媒体
WO1994001806A1 (fr) * 1992-07-13 1994-01-20 Kyowa Hakko Kogyo Co., Ltd. Composition photopolymerisable
JPH11168229A (ja) * 1997-12-04 1999-06-22 Kyowa Hakko Kogyo Co Ltd 光電変換材料
JP2000299139A (ja) * 1999-04-14 2000-10-24 Fuji Photo Film Co Ltd 光電変換素子および光電気化学電池
WO2001044375A1 (fr) * 1999-12-16 2001-06-21 Kyowa Hakko Kogyo Co., Ltd. Composes de squarylium et supports d'information optiques a base de ces composes
JP2001322356A (ja) * 2000-03-07 2001-11-20 Ricoh Co Ltd 光記録媒体及びこれを用いる光記録方法
WO2005059608A1 (fr) * 2003-12-18 2005-06-30 Kyowa Hakko Chemical Co., Ltd. Filtre pour affichage electronique

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0317047A (ja) * 1989-05-30 1991-01-25 Xerox Corp 光導電性画像形成部材及びその部材を使用する画像形成方法
JPH03126581A (ja) * 1989-10-12 1991-05-29 Canon Inc 光学記録媒体
WO1994001806A1 (fr) * 1992-07-13 1994-01-20 Kyowa Hakko Kogyo Co., Ltd. Composition photopolymerisable
JPH11168229A (ja) * 1997-12-04 1999-06-22 Kyowa Hakko Kogyo Co Ltd 光電変換材料
JP2000299139A (ja) * 1999-04-14 2000-10-24 Fuji Photo Film Co Ltd 光電変換素子および光電気化学電池
WO2001044375A1 (fr) * 1999-12-16 2001-06-21 Kyowa Hakko Kogyo Co., Ltd. Composes de squarylium et supports d'information optiques a base de ces composes
JP2001322356A (ja) * 2000-03-07 2001-11-20 Ricoh Co Ltd 光記録媒体及びこれを用いる光記録方法
WO2005059608A1 (fr) * 2003-12-18 2005-06-30 Kyowa Hakko Chemical Co., Ltd. Filtre pour affichage electronique

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1698916A1 (fr) * 2003-12-18 2006-09-06 Kyowa Hakko Chemical Co., Ltd. Filtre pour affichage electronique
EP1698916A4 (fr) * 2003-12-18 2010-01-27 Kyowa Hakko Chemical Co Ltd Filtre pour affichage electronique
WO2007049579A1 (fr) * 2005-10-24 2007-05-03 Kyowa Hakko Chemical Co., Ltd. Compose squarylium et composition photopolymerisable pour source lumineuse a ondes courtes l’utilisant

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