JP4542741B2 - Semiconductor thin film electrode, photoelectric conversion element and photoelectrochemical solar cell using organic dye as photosensitizer - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a semiconductor thin film electrode, a photoelectric conversion element, and a photoelectrochemical solar cell using the same, using an organic dye as a photosensitizer.
[0002]
[Prior art]
  In 1993, Prof. Graetzel et al. Of Lausanne University of Technology in Switzerland reported a dye-sensitized solar cell exhibiting a conversion efficiency of 7 to 10% (for example, see Non-Patent Document 1). This dye-sensitized solar cell uses a metal complex such as ruthenium or an organic dye as a photosensitizer, and has an oxide semiconductor thin film electrode having a large band gap such as nano-particle titanium dioxide and zinc oxide, an iodine redox electrolyte, and Consists of a counter electrode. So far, highly efficient dye-sensitized photoelectric conversion elements have been mainly studied and reported as solar cells. In recent years, it has attracted attention as a next-generation solar cell because of its high conversion efficiency and low cost in production.
[0003]
  In conventional dye-sensitized solar cells, ruthenium complexes have mainly been used as photosensitizers (see, for example, Non-Patent Document 2). However, since ruthenium, a precious metal, is used, a large amount of ruthenium complex is required for large-scale power generation using dye-sensitized solar cells using these ruthenium complexes. Become.
[0004]
  So far, dye-sensitized solar cells using an organic dye containing no precious metal such as ruthenium as a photosensitizer have been studied. Examples of organic dyes that have been used include phenylxanthene dyes, phthalocyanine dyes, coumarin dyes, cyanine dyes, merocyanine dyes, porphyrin dyes, and proflavine dyes (for example, see Non-Patent Document 3). .) These organic dyes have advantages as photosensitizers such as a large absorption coefficient compared to metal complexes, low cost, and the ability to control absorption characteristics by the diversity of structures. However, since the absorption wavelength region is limited to a relatively short wavelength region, the solar energy conversion efficiency is greatly inferior to that using a ruthenium complex.
[0005]
[Non-Patent Document 1]
  Nature, 1991, 353, 583-585, J. Am. Am. Chem. Soc. 1993, 115, 6382-6390.
[Non-Patent Document 2]
  J. et al. Am. Chem. Soc. 1993, 115, 6382-6390, Chem. Commun. 1997, 1705-1706, Langmuir, 2001, 17, 5992-5999, etc.
[Non-Patent Document 3]
  Chem. Lett. 1998, 753-754, Sol. Energy Mater. Sol. Cells, 2000, 64, 115-134, New J. et al. Chem. , 2001, 25, 200-202, etc.
[0006]
[Problems to be solved by the invention]
  The present invention provides an inexpensive solar cell exhibiting high photoelectric conversion efficiency in a dye-sensitized solar cell using a semiconductor thin film electrode sensitized with an organic dye, and a photoelectric conversion element used in the battery and the photoelectric conversion It is an object of the present invention to provide a semiconductor thin film electrode used for an element.
[0007]
[Means for Solving the Problems]
  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
[0008]
  ADVANTAGE OF THE INVENTION According to this invention, the semiconductor thin film electrode shown below, the photoelectric conversion element using this electrode, and the high performance photoelectrochemical solar cell using this element are provided.
  ADVANTAGE OF THE INVENTION According to this invention, the semiconductor thin film electrode shown below, the photoelectric conversion element using this electrode, and the high performance photoelectrochemical solar cell using this element are provided.
  (1) In a semiconductor thin film electrode sensitized by the action of an organic dye, the organic dye represented by the following general formula (2) having a cyano group and a carbon group substituted with COOM at the end is composed of nanoparticles, and is nanoporous. A semiconductor thin film electrode characterized in that it is in a state of being adsorbed on the surface of a compound semiconductor particle having a structure and sensitized.
[Chemical Formula 3]
  (L₁Is a group selected from the following a, b, c, or d.
  a group selected from -CH = or -CH = CH-CH =,
  a group consisting of b-A-CH = (wherein A is a thiophene ring, a furan ring or a heterocyclic compound selected from a pyrrole ring substituted by a hydrogen atom or a methyl group, and 2 or 3 A ring compound may be continuous, or a benzene or benzothiazole may be bonded to the end of the heterocyclic compound).
  a group consisting of c—CH═CH—A—CH═C═ (wherein A is a heterocyclic compound selected from a thiophene ring or a furan ring. The same two heterocyclic compounds may be linked). ) Group represented by
  d—A—CH═CH—B = (in the formula, A represents a thiophene ring, and B represents a heterocyclic compound composed of a methyl-substituted pyran ring).
  R₁~ R₃And R₅Independently represents a hydrogen atom or a methyl, ethyl or halogenated methyl group, R₆, R₇Independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,₁~ R₃And R₅~ R₇Any two of them may be bonded to each other to form a nitrogen-containing ring.
  M is a hydrogen atom or hydrogen-substituted pyridine. )
  (2) In the semiconductor thin film electrode sensitized by the action of an organic dye, the following general formula having a cyano group and a carbon group substituted by COOM at the end(4)A semiconductor thin film electrode characterized in that an organic dye represented by the formula is composed of nanoparticles and is adsorbed on the surface of a compound semiconductor particle having a nanoporous structure and sensitized.
[Formula 4]
  (Where L₂Is a group selected from the following a, b, c, d or e.
  a group selected from = CH-CH =, = CH-CH = CH-CH = or = CH-CH = CH-CH = CH-CH =,
  b = CH = CH-A-CH = CH =, = CH = CH-A-A-CH = CH =, or = CH = CH-A-A-A-CH = CH = (where A is thiophene) One or two selected from a ring, or a pyrrole ring substituted with a hydrogen atom or a methyl grouptypeIt is a heterocyclic compound. ) A group selected from
  a group consisting of c = CH═CH—A—CH═CH—A—CH═ (wherein A is a heterocyclic compound comprising a thiophene ring),
  d = CH = CH-CH = B = (in the formula, B represents a cyclohexyl group).
  R₈~ R₁₀, R₁₂~ R₁₃And R₁₅~ R₁₇Independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;₁₈~ R₂₁Independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;₈~ R₁₀, R₁₂~ R₁₃And R₁₅~ R₂₁Any two of them may be bonded to each other to form a ring containing N.
  M represents a hydrogen atom, a tributylamino group, or a pyridine group substituted with hydrogen. )
  (3) A photoelectric conversion element using the semiconductor thin film electrode according to any one of (1) to (3).
  (4) A substrate coated with a conductive transparent oxide semiconductor thin film in contact with one surface of the layer formed of the semiconductor thin film electrode, a layer formed of an electrolytic solution containing a Redox ion pair in contact with the other surface, The photoelectric conversion element as described in (3) above, comprising an electrode coated on the outside with a compound selected from platinum, rhodium, ruthenium, carbon or an oxide semiconductor on a conductive transparent glass substrate.
  (5) A photoelectrochemical solar cell using the photoelectric conversion element according to (4).
[0009]
DETAILED DESCRIPTION OF THE INVENTION
  When general formula (1) which is a reference example of the present invention is used, it is as follows.
[Chemical formula 5]
  In the general formula (1), L₁Represents an electron transporting linking group containing at least one heterocyclic ring selected from thiophene ring, furan ring and pyrrole ring (hereinafter also simply referred to as heterocyclic ring A). The electron transporting linking group in this case means a linking group having an action of transferring electrons on one side of the linking group to the other side, and such a linking group is well known in the art. is there.
  Examples of the linking group include those composed of a heterocyclic ring A, those having a structure in which the heterocyclic ring A and an electron transporting chain (hereinafter also simply referred to as chain B) are combined, and the heterocyclic ring A and the chain B and electron transporting property. A structure in which a ring (hereinafter, also simply referred to as ring C) is combined, a structure in which a heterocyclic ring A and ring C are combined, and the like are included.
[0010]
  Chain B includes a carbon chain having an unsaturated bond. As such a chain B, the following can be shown.
[Chemical 6]
[Chemical 7]
[Chemical 8]
[Chemical 9]
[0011]
  In the above formula, X¹~ X⁴Represents a hydrogen atom or a substituent. n represents a number of 1 to 6, preferably 1 to 3.
[0012]
  Ring C includes monocyclic and polycyclic rings. The polycycle includes fused polycycles and chain polycycles.
  Ring C includes carbocycles and heterocycles. Carbocycles include aromatic carbocycles and aliphatic carbocycles. The heterocyclic ring includes an aromatic heterocyclic ring and an aliphatic heterocyclic ring.
  In the monocycle, the ring constituent elements are 4 to 8, preferably 5 to 6.
  In the condensed polycycle, the number of single-ring bonds is 2 to 4, preferably 2 to 3.
  The heterocyclic ring is a cyclic compound containing one or more (2 to 3) heteroatoms such as sulfur, oxygen, nitrogen and selenium as constituent elements.
  The ring C may have various substituents that can be bonded to carbon.
[0013]
  Specific examples of the ring C include the following. Examples of the aromatic carbocycle include a benzene ring and a naphthalene ring. Examples of the aliphatic carbocycle include a cyclobutene ring, a cyclobutane ring, a cyclopentene ring, a cyclopentane ring, a cyclohexene ring, and a cyclohexane ring.
[0014]
  As aromatic heterocycles, pyridine ring, quinoxaline ring, purine ring, oxazole ring, benzoxazole ring, naphthoxazole ring, thiazole ring, benzothiazole ring, naphthothiazole ring, selenazole ring, benzoselenazole ring, naphthoselenazole ring, Examples include imidazole ring, benzimidazole ring, naphthimidazole ring, quinoline ring, quinoxaline ring, purine ring, acridine ring, phenanthroline ring and the like.
[0015]
  Examples of the aliphatic heterocycle include a pyrazoline ring, a pyrrolidine ring, a piperidine ring, an indoline ring, a morpholine ring, a pyran ring, an imidazolidine ring, a thiazoline ring, an imidazoline ring, and an oxazoline ring.
[0016]
  In the ring C, the existing structural isomers are not limited, and the ring C can be composed of various structural isomers.
[0017]
  Electron-transferring linking group L containing heterocycle A₁Specific examples of these are as follows.
[0018]
  (1) A linking group containing a thiophene ring
  As this linking group, the following general formula (a¹) Can be shown.
[Chemical Formula 10]
  In the above formula, R¹And R²Represents a hydrogen atom or a substituent, and X¹Represents a hydrogen atom or a substituent. n represents an integer of 1 to 6, preferably 1 to 3.
[0019]
  (2) A linking group containing a furan ring
  As this linking group, the following general formula (a²).
Embedded image
  In the above formula, R¹And R²Represents a hydrogen atom or a substituent. X¹Represents a hydrogen atom or a substituent. n represents an integer of 1 to 6, preferably 1 to 3.
[0020]
  (3) A linking group containing a pyrrole ring
  As this linking group, the following general formula (a³) Can be shown.
Embedded image
  In the above formula, R¹And R²Represents a hydrogen atom or a substituent. X¹Represents a hydrogen atom or a substituent. X represents a hydrogen atom or a hydrocarbon group which may have a substituent.
  The hydrocarbon group in this case includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group. In the aliphatic hydrocarbon group, the carbon number is 1 to 12, preferably 1 to 8. The aliphatic hydrocarbon group includes an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, preferably 4 to 8 carbon atoms, 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms. An alkenyl group having 3 to 12 carbon atoms, preferably 4 to 8 carbon atoms.
  In the aromatic hydrocarbon group, the carbon number is 6-18, preferably 6-12. The aromatic hydrocarbon group includes an aryl group having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms, and an arylalkyl group having 7 to 18 carbon atoms, preferably 7 to 12 carbon atoms.
[0021]
  (4) A linking group containing at least two heterocyclic rings A selected from a thiophene ring, a furan ring and a pyrrole ring.
  As this linking group, the following general formula (a⁴) Can be shown.
Embedded image
[0022]
  In the above formula, A¹, A², A³Represents a heterocyclic ring A composed of at least one selected from a thiophene ring, a furan ring and a pyrrole ring, and at least two of them are different from each other. n, m, and p represent an integer of 0 to 6, and at least two of them represent an integer of 1 or more. n + m + p is 2 to 18, preferably 2 to 9, and more preferably 2 to 6.
[0023]
  (5) Linking group containing heterocyclic ring A and vinylene chain
  This linking group has the following general formula (a⁵) ~ (A⁷) Are included.
Embedded image
Embedded image
Embedded image
  In the above formula, A¹And A²Represents a heterocyclic ring A composed of at least one selected from a thiophene ring, a furan ring and a pyrrole ring;¹, X²And X³Represents a hydrogen atom or a substituent. A¹And A²May be the same or different. n and m represent an integer of 1 to 6, preferably 1 to 3. n + m is 2 to 12, preferably 2 to 6. q is an integer of 1 to 6, preferably 1 to 3.
[0024]
  (6) A linking group containing a heterocycle A and another ring C
  As this linking group, what is represented by the following general formula can be shown.
[0025]
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
[0026]
  In the above formula, A¹Represents a heterocyclic ring A composed of at least one selected from a thiophene ring, a furan ring and a pyrrole ring. C¹Represents a ring other than the heterocycle A. n and m represent an integer of 1 to 6, preferably 1 to 3. q represents an integer of 1 to 6, preferably 1 to 3. X¹~ X³Represents a hydrogen atom or a substituent. Y¹Represents a linking chain giving ring Y.
  Connecting chain Y¹Can consist of carbon atoms and / or heteroatoms. Ring Y is a 5- to 8-membered ring, preferably a 5- to 6-membered carbocyclic or heterocyclic ring. Further, the ring Y may have various substituents that can be bonded to the ring Y.
[0027]
  The electron transfer linking group L₁The substituents shown in connection with are hydrocarbon group (R-), hydrocarbon oxy group (RO-), acyl group (RCO-), hydrocarbon oxycarbonyl group (ROCO-), acyloxy group (RCOO- ), Hydrocarbon thio group (RS-), hydrocarbon-substituted amino group (RNH-, RNR-), halogen atom (chlorine, bromine, iodine, fluorine), hydroxyl group, carboxyl group, thiol group, amino group, cyano Groups, nitro groups and the like are included.
[0028]
  The hydrocarbon group (R-) and the hydrocarbon-containing group (RO-, RCO-, ROCO-, RCOO-, R-S-, R-NH-, etc.) in the hydrocarbon group (R-) have a carbon number. Various hydrocarbon groups of 1-18, preferably 1-12, more preferably 1-8 are included. Such materials include alkyl groups having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (methyl, ethyl, propyl, butytil, amyl, hexyl, octyl, etc.), 2 to 18 carbon atoms. , Preferably 2 to 12, more preferably 2 to 8 alkenyl groups (vinyl, propenyl, hexenyl, octynyl, etc.), cycloalkyl having 3 to 18 carbon atoms, preferably 4 to 12 carbon atoms, more preferably 5 to 8 carbon atoms. In addition to aliphatic hydrocarbon groups such as cycloalkenyl groups (cyclopentyl, cyclohexyl, cyclooctyl, cyclohexenyl, etc.), aryl groups having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms (phenyl, o-tolyl, p-cumenyl, Naphthyl, biphenylyl, etc.), arylalkyl groups having 7 to 18 carbon atoms, preferably 7 to 12 carbon atoms (benzyl, phenethyl, naphthyl) Aromatic hydrocarbon groups chill etc.), and the like. These hydrocarbon groups can have a substituent as described above.
[0029]
  In the substituent, examples of the hydrocarbon oxy group (RO-) include methoxy, ethoxy, propoxy, butoxy, pentyloxy, benzyloxy, phenoxy and the like. Examples of the acyl group (RCO-) include acetyl, propionyl, hexylcarbonyl, benzoyl and the like. Examples of the hydrocarbon oxycarbonyl group (ROCO-) include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl and the like. Examples of the acyloxy group (RCOO-) include acetyloxy, hexylcarbonyloxy, benzoyloxy, phenylcarbonyloxy and the like. Examples of the hydrocarbon thio group (RS-) include methylthio, ethylthio, propylthio, hexylthio, octylthio, phenylthio, benzylthio, naphthylthio and the like. Examples of the substituted amino group (RNH-, RNR-) include methylamino, ethylamino, propylamino, hexylamino, octylamino, phenylamino, benzylamino, dimethylamino, diethylamino, dipropylamino, diphenylamino, methylethylamino, Examples include methylhexylamino and methylbenzylamino.
[0030]
  In the general formula (1), R₁~ R₅Is a hydrogen atom or a substituent. In this case, examples of the substituent and specific examples thereof include an electron transfer linking group L₁The various substituents shown above in connection with, and specific examples thereof can be shown.
[0031]
  In the general formula (1), R₁~ R₅2 adjacent to each other can be bonded to each other to form a ring. In this case, the ring includes, in addition to carbocyclic rings having 4 to 10, preferably 5 to 8, ring constituent elements. Includes 4-8, preferably 5-6 heterocycles. The heterocyclic ring in this case includes those containing at least one hetero atom such as sulfur, oxygen, nitrogen, selenium or the like as a ring constituent element.
  R₁~ R₅A combination of two adjacent groups of₁And R₂, R₂And R₃, R₃And R₄, R₄And R₅Can be shown.
[0032]
  In the general formula (1), M represents a hydrogen atom or a salt-forming cation (cation). In this case, examples of the salt-forming cation include alkali metals such as lithium, sodium, and potassium, calcium, and magnesium. In addition to cations derived from alkaline earth metals such as strontium and other metals, ammonium cations and amine-derived organic ammonium cations are included.
  The ammonium cation can be represented by the following general formula (7).
Embedded image
  In the above formula, A¹~ A⁴Represents a hydrogen atom or an alkyl or alkenyl group having 1 to 22 carbon atoms, preferably 1 to 12 carbon atoms, at least one of which is an alkyl group or an alkenyl group.
[0033]
  (1) In a semiconductor thin film electrode sensitized by the action of an organic dye, the organic dye represented by the following general formula (2) having a cyano group and a carbon group substituted by COOM at the end is composed of nanoparticles, and is nanoporous. A semiconductor thin film electrode characterized in that it is in a state of being adsorbed on the surface of a compound semiconductor particle having a structure and sensitized.
Embedded image
  (L₁Is the followingB, C or dThe
  b  A group consisting of -A-CH =, wherein A is a thiophene ring, a furan ring or a heterocyclic compound selected from a pyrrole ring substituted by a hydrogen atom or a methyl group, and 2 or 3 heterocyclic rings A compound may be linked, and a benzene or benzothiazole may be bonded to the terminal of the heterocyclic compound.)
  c  -CH = CH-A-CH =A group represented by the formula: wherein A is a heterocyclic compound selected from a thiophene ring or a furan ring, and the same two heterocyclic compounds may be linked;
  d—A—CH═CH—B = (in the formula, A represents a thiophene ring, and B represents a heterocyclic compound composed of a methyl-substituted pyran ring).
  R₁~ R₃And R₅Independently represents a hydrogen atom or a methyl, ethyl or halogenated methyl group, R₆, R₇Independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,₁~ R₃And R₅~ R₇Any two of them may be bonded to each other to form a nitrogen-containing ring.
  M is a hydrogen atom or hydrogen-substituted pyridine. )
[0034]
  In the general formula (2), R₁~ R₃And R₅Represents a hydrogen atom or a substituent. In this case, examples of the substituent and specific examples thereof include those shown in relation to the general formula (1).
[0035]
  In the general formula (2), R₆, R₇Represents a hydrogen atom or a hydrocarbon group which may have a substituent.
  The hydrocarbon group in this case includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group. In an aliphatic hydrocarbon group, the carbon number is 1-18, Preferably it is 1-12, More preferably, it is 1-8. Specific examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, 3 to 12 carbon atoms, preferably 4 to 12 carbon atoms, and more preferably 5 to 5 carbon atoms. An cycloalkyl group having 8 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and a cycloalkenyl group having 3 to 12 carbon atoms, preferably 4 to 12 carbon atoms, more preferably 5 to 8 carbon atoms. Is included.
[0036]
  In the aromatic hydrocarbon group, the carbon number is 6-18, preferably 6-12. Specific examples of the aromatic hydrocarbon group include an aryl group having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms, and an arylalkyl group having 7 to 18 carbon atoms, preferably 7 to 12 carbon atoms.
[0037]
  In the general formula (2), R₁~ R₃And R₅~ R₇2 adjacent to each other can be bonded to each other to form a ring. In this case, the ring includes, in addition to carbocyclic rings having 4 to 10, preferably 5 to 8, ring constituent elements. Includes 4-8, preferably 5-6 heterocycles. The heterocyclic ring in this case includes those containing at least one hetero atom such as sulfur, oxygen, nitrogen, selenium or the like as a ring constituent element. R₁~ R₃And R₅~ R₇Of two adjacent groups of R₁And R₂, R₂And R₃, R₃And R₆, R₆And R₇, R₇And R₅Can be shown.
[0038]
  In the general formula (2), M represents a hydrogen atom or a salt-forming cation (cation). Specific examples of the salt-forming cation in this case are shown in relation to the general formula (1). Can be mentioned.
[0039]
  The case represented by the general formula (3) shown below is a reference example.
  In general formula (3)
Embedded image
  (Where L₂Is a group selected from any of the following a, b, c, d, e, or f.
  a group selected from = CH-CH =, = CH-CH = CH-CH =, or = CH-CH = CH-CH = CH-CH =,
  b = CH-CH = CH-CH =, CH-CH = CH-CH = CH-CH =, or a group selected from CH-CH = CH-CH = CH-CH = CH-CH =
  c = CH-A-CH =, = CH-AA-CH =, or = CH-AAAACH = (wherein A is a thiophene ring or furan ring heterocyclic compound). The group chosen,
  d = CH-A1-A2-CH =, = CH-A1-A2-CH =, wherein A1 and A2 are selected from a thiophene ring, a furan ring, or a pyrrole ring substituted with a hydrogen atom or a methyl group. A group selected from two types of heterocyclic compounds),
  e= CH-A-CH =, = CH-A-A-CH =Or = CH-A-A-A-CH = (wherein A is a heterocyclic compound selected from a thiophene ring, a furan ring, or a pyrrole ring substituted with a hydrogen atom or a methyl group.) A group selected from
  f = CH-A1-CH = CH-A2-CH = (wherein A1 and A2 are two kinds of heterocyclic compounds selected from a thiophene ring, a furan ring, or a pyrrole ring substituted with a hydrogen atom or a methyl group. A group consisting of:
  R₈~ R₁₇Independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;₈~ R₁₇Two adjacent to each other may be bonded to each other and two adjacent to each other may be bonded to each other to form a nitrogen-containing ring. M represents a hydrogen atom or a salt-forming cation. )
  M represents a hydrogen atom or a salt-forming cation. )
[0040]
  (1) Linking group consisting of carbon chain B
This linking group has the following general formula (d¹) To (d²) Are included.
Embedded image
  In the above formula, X¹And X²Represents a hydrogen atom or a substituent, and q represents an integer of 1 to 6, preferably 1 to 3.
Embedded image
  In the above formula, X¹~ X⁴Represents a hydrogen atom or a substituent, and q represents an integer of 1 to 6, preferably 1 to 3.
[0041]
  (2) A linking group comprising heterocycle A and / or ring C and carbon chain B
This linking group has the following general formula (d³) To (d¹⁷) Are included.
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
[0042]
  In the above formula, A¹And A²Represents a heterocyclic ring A composed of at least one selected from a thiophene ring, a furan ring and a pyrrole ring. C¹Represents a ring other than the heterocycle A. n and m represent an integer of 1 to 6, preferably 1 to 3. q represents an integer of 1 to 6, preferably 1 to 3. X¹~ X⁴Represents a hydrogen atom or a substituent. Y¹Represents a linking chain giving ring Y.
  Connecting chain Y¹Can consist of carbon atoms and / or heteroatoms. Ring Y consists of a 5- to 8-membered ring, preferably a 5- to 6-membered ring. Ring Y may have various substituents that can be bonded thereto.
[0043]
  (3) Linking group consisting of ring C
  This linking group has the following general formula (d¹⁸) Are included.
Embedded image
  In the above formula, Y¹Represents a linking chain giving ring Y. Y¹And Y have the same meaning as described above.
[0044]
  In the general formula (3), R₈~ R₁₇Is a hydrogen atom or a substituent. In this case, examples of the substituent and specific examples thereof include an electron transfer linking group L₁The various substituents shown above in connection with, and specific examples thereof can be shown.
[0045]
  In the general formula (3), R₈~ R₁₇2 adjacent to each other can be bonded to each other to form a ring. In this case, the ring includes, in addition to carbocyclic rings having 4 to 10, preferably 5 to 8, ring constituent elements. Includes 4-8, preferably 5-6 heterocycles. The heterocyclic ring in this case includes those containing at least one hetero atom such as sulfur, oxygen, nitrogen, selenium or the like as a ring constituent element.
  R₈~ R₁₇A combination of two adjacent groups of₈And R₉, R₉And R₁₀, R₁₀And R₁₁, R₁₁And R₁₂, R₁₂And R₁₃, R₁₃And R₁₄, R₁₄And R₁₅, R₁₅And R₁₆, R₁₆And R₁₇Can be shown.
[0046]
  In the general formula (3), M represents a hydrogen atom or a salt-forming cation (cation). Specific examples of the salt-forming cation in this case are shown in relation to the general formula (1). Can be mentioned.
[0047]
  In a semiconductor thin film electrode sensitized by the action of an organic dye, an organic dye represented by the following general formula (4) having a cyano group and a carbon group substituted by COOM at the end is composed of nanoparticles and has a nanoporous structure. A semiconductor thin film electrode which is sensitized by being adsorbed on the surface of a compound semiconductor particle.
Embedded image
  (Where L₂Is a group selected from the following a, b, c, d or e.
  a group selected from = CH-CH =, = CH-CH = CH-CH = or = CH-CH = CH-CH = CH-CH =,
  b = CH = CH-A-CH = CH =, = CH = CH-A-A-CH = CH =, or = CH = CH-AA-A-CH = CH = (where A is thiophene) One or two selected from a ring, or a pyrrole ring substituted with a hydrogen atom or a methyl grouptypeIt is a heterocyclic compound. ) A group selected from
  a group consisting of c = CH═CH—A—CH═CH—A—CH═ (wherein A is a heterocyclic compound comprising a thiophene ring),
  d = CH = CH-CH = B = (in the formula, B represents a cyclohexyl group).
  R₈~ R₁₀, R₁₂~ R₁₃And R₁₅~ R₁₇Independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;₁₈~ R₂₁Independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;₈~ R₁₀, R₁₂~ R₁₃And R₁₅~ R₂₁Any two of them may be bonded to each other to form a ring containing N.
  M represents a hydrogen atom, a tributylamino group, or a pyridine group substituted with hydrogen. )
[0048]
  In the general formula (4), R₈~ R₁₀, R₁₂~ R₁₃And R₁₅~ R₂₁Represents a hydrogen atom or a substituent, and examples of the substituent and specific examples in this case include those shown in relation to the general formula (1).
[0049]
  In the general formula (4), R₁₈~ R₂₁Represents a hydrogen atom or a hydrocarbon group which may have a substituent. In this case, for the types and specific examples of the hydrocarbon group which may have a substituent, the general formula (2) Can be mentioned in connection with.
[0050]
  In the general formula (4), R₈~ R₁₀, R₁₂~ R₁₃And R₁₅~ R₂₁2 adjacent to each other can be bonded to each other to form a ring. In this case, the ring includes, in addition to carbocyclic rings having 4 to 10, preferably 5 to 8, ring constituent elements. Includes 4-8, preferably 5-6 heterocycles. The heterocyclic ring in this case includes those containing at least one hetero atom such as sulfur, oxygen, nitrogen, selenium or the like as a ring constituent element.
  R₈~ R₁₀, R₁₂~ R₁₃And R₁₅~ R₂₁A combination of two adjacent groups of₈And R₉, R₉And R₁₀, R₁₀And R₁₈, R₁₈And R₁₉, R₁₉And R₁₂, R₁₂And R₁₃, R₁₃And R₂₀, R₂₀And R₂₁, R₂₁And R₁₅, R₁₅And R₁₆, R₁₆And R₁₇Can be shown.
[0051]
  In the general formula (4), M represents a hydrogen atom or a salt-forming cation (cation). Specific examples of the salt-forming cation in this case are those shown in the general formula (1). Can be mentioned.
[0052]
  In the general formula (5) (which is a reference example), L₂Represents an electron-transporting linking group. Examples of the linking group and specific examples thereof include those shown in connection with the general formula (3).
Embedded image
  (Where L₂Represents an electron transfer linking group, R₂₂~ R₂₇Independently represents a hydrogen atom or a substituent, R₂₂~ R₂₇Adjacent two of them may be bonded to each other to form a ring, and M represents a hydrogen atom or a salt-forming cation)
[0053]
  In the general formula (5), R₂₂~ R₂₇Represents a hydrogen atom or a substituent, and examples of the substituent and specific examples in this case include those shown in relation to the general formula (1).
[0054]
  In the general formula (5), R₂₂~ R₂₇2 adjacent to each other can be bonded to each other to form a ring. In this case, the ring includes, in addition to carbocyclic rings having 4 to 10, preferably 5 to 8, ring constituent elements. Includes 4-8, preferably 5-6 heterocycles. The heterocyclic ring in this case includes those containing at least one hetero atom such as sulfur, oxygen, nitrogen, selenium or the like as a ring constituent element.
  R₂₂~ R₂₇Of two adjacent groups of R₂₂And R₂₃, R₂₃And R₂₄, R₂₄And R₂₅, R₂₅And R₂₆, R₂₆And R₂₇Can be shown.
[0055]
  In the general formula (5), M represents a hydrogen atom or a salt-forming cation (cation). Specific examples of the salt-forming cation in this case are those shown in the general formula (1). Can be mentioned.
[0056]
  In general formula (6) (which is a reference example),
Embedded image
  L₂Represents an electron-transporting linking group. Examples of the linking group and specific examples thereof include those shown in connection with the general formula (3).
[0057]
  In the general formula (6), R₂₂~ R₂₃And R₂₅~ R₂₇Represents a hydrogen atom or a substituent, and examples of the substituent and specific examples in this case include those shown in relation to the general formula (1).
[0058]
  In the general formula (6), R₂₈, R₂₉Represents a hydrogen atom or a hydrocarbon group which may have a substituent. In this case, for the types and specific examples of the hydrocarbon group which may have a substituent, the general formula (2) Can be mentioned in connection with.
[0059]
  In the general formula (6), R₂₂~ R₂₃And R₂₅~ R₂₉2 adjacent to each other can be bonded to each other to form a ring. In this case, the ring includes, in addition to carbocyclic rings having 4 to 10, preferably 5 to 8, ring constituent elements. Includes 4-8, preferably 5-6 heterocycles. The heterocyclic ring in this case includes those containing at least one hetero atom such as sulfur, oxygen, nitrogen, selenium or the like as a ring constituent element.
  R₂₂~ R₂₃And R₂₅~ R₂₉A combination of two adjacent groups of₂₂And R₂₃, R₂₃And R₂₈, R₂₈And R₂₉, R₂₉And R₂₅, R₂₅And R₂₆, R₂₆And R₂₇Can be shown.
[0060]
  In the general formula (6), M represents a hydrogen atom or a salt-forming cation (cation). Specific examples of the salt-forming cation in this case are shown in relation to the general formula (1). Can be mentioned.
[0061]
  Next, specific examples of the compounds (organic dyes) represented by the general formulas (1) to (6) are shown below, but the present invention is not limited thereto.
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
[Chemical Formula 86]
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
[0062]
[Table 1]
  The compound of the general formula (1) according to the present invention (reference example) can be obtained by using a carbonyl compound of the following general formula (1 ′) as a precursor and usually reacting it with cyanoacetic acid. It is not limited to.
Embedded image
  In the above formula, R₁~ R₆Has the same meaning as above. L₁'Is the L₁And the terminal is a group formed in a carbonyl group (-C = O) having reactivity with cyanoacetic acid.
[0063]
  The compound of the general formula (2) according to the present invention can be obtained by using, as a precursor thereof, a carbonyl compound of the following general formula (2 ′), and usually reacting it with cyanoacetic acid. It is not a thing.
Embedded image
  In the above formula, R₁~ R₃And R₅~ R₇Has the same meaning as above. L₁'Is the L₁And the terminal is a group formed in a carbonyl group (-C = O) having reactivity with cyanoacetic acid.
[0064]
  The compound of the general formula (3) according to the present invention can be obtained by using a carbonyl compound of the following general formula (3 ′) as a precursor and reacting it with cyanoacetic acid. However, the present invention is limited to this. It is not a thing.
Embedded image
  In the above formula, R₈~ R₁₇Has the same meaning as above. L₂'Is the L₂And the terminal is a group formed in a carbonyl group (-C = O) having reactivity with cyanoacetic acid.
[0065]
  The compound of the general formula (4) according to the present invention can be obtained by using a carbonyl compound of the following general formula (4 ′) as a precursor and reacting it with cyanoacetic acid. However, the present invention is limited to this. It is not a thing.
Embedded image
  In the above formula, R₈~ R₁₀, R₁₂~ R₁₃And R₁₅~ R₂₁Has the same meaning as above. L₂'Is the L₂And the terminal is a group formed in a carbonyl group (-C = O) having reactivity with cyanoacetic acid.
[0066]
  The compound of the general formula (5) according to the present invention (reference example) can be obtained by using a carbonyl compound of the following general formula (5 ′) as a precursor and usually reacting it with cyanoacetic acid. However, the present invention is not limited to this.
Embedded image
  In the above formula, R₂₂~ R₂₇Has the same meaning as above. L₂'Is the L₂And the terminal is a group formed in a carbonyl group (-C = O) having reactivity with cyanoacetic acid.
[0067]
  The compound of the general formula (6) according to the present invention (reference example) can be obtained by using a carbonyl compound of the following general formula (6 ′) as a precursor and reacting it with cyanoacetic acid. It is not limited to.
Embedded image
  In the above formula, R₂₂~ R₂₃And R₂₅~ R₂₉Has the same meaning as above. L₂'Is the L₂And the terminal is a group formed in a carbonyl group (-C = O) having reactivity with cyanoacetic acid.
[0068]
  The compounds of the general formulas (1 ') to (6') are L₁'And L₂According to the specific structure of ′, it can be synthesized by a conventionally known method using an appropriate raw material compound. In general, the L₁'And L₂It is possible to obtain a compound having a terminal structure from which carbonyl group bonded to the terminal is removed from ′ and reacting it usually with a Vilsmeier reagent.
[0069]
  The substrate of the semiconductor thin film electrode used in the present invention is a glass or plastic substrate coated with a conductive transparent oxide semiconductor thin film such as fluorine or antimony-doped tin oxide (NESA), tin-doped indium oxide (ITO), or zinc oxide. is there. Preferred is a fluorine-doped tin oxide thin film coated glass.
[0070]
  The semiconductor thin film electrode used in the present invention is composed of a compound semiconductor composed of nanoparticles and having a nanoporous structure. The material used is, for example, TiO₂, ZnO, In₂O₃, SnO₂, Bi₂O₃, ZrO₂, Ta₂O₅, Nb₂O₅, WO₃, Fe₂O₃, Ga₂O₃, SrTiO₃Metal oxides and composite oxides such as, metal halides such as AgI, AgBr, CuI, CuBr, ZnS, TiS₂, In₂S₃, Bi₂S₃, CdS, ZrS₂, TaS₂, Ag₂S, Cu₂S, SnS₂, WS₂, MoS₂Metal sulfides such as CdSe, CdTe, ZrSe₂, ZeSe, TiSe₂, Bi₂Se₃, In₂Se₃, WSe₂, WTe₂, MoSe₂, MoTe₂And metal selenides, tellurides, and the like. An oxide semiconductor material such as titanium dioxide, zinc oxide, or tin oxide is preferable.
[0071]
  For example, commercially available titanium oxide particles such as P25 (Degussa or Nippon Aerosil) and ST-01 (Ishihara Sangyo) may be used. Am. Ceram. Soc. 1997, 80, 3157-3171, crystalline titanium oxide particles obtained by hydrolysis, autoclaving, etc. from titanium alkoxide by a sol-gel method may be used. Titanium oxide particles obtained from a titanium alkoxide by a sol-gel method are preferred.
[0072]
  The semiconductor nanoparticles constituting the semiconductor thin film have a particle diameter of 8 to 500 nm, preferably 10 to 300 nm.
[0073]
  For example, methods for forming an oxide semiconductor thin film electrode include the following methods, but are not limited thereto. Oxide semiconductor nanoparticles are mixed well with water, a polymer such as polyethylene glycol, a surfactant and the like to form a slurry, which is applied onto the substrate by a method called a doctor blade method. Further, a polymer as a binder and an organic solvent may be mixed and applied onto the substrate by a screen printing method. An oxide semiconductor thin film electrode can be obtained by baking a substrate coated with an oxide semiconductor at about 450 to 500 ° C. in air or oxygen.
  The film thickness of the semiconductor thin film electrode is usually 2 to 100 μm, preferably 8 to 20 μm.
[0074]
  The organic dye sensitizer is adsorbed on the surface of the semiconductor fine particles by immersing the semiconductor thin film in a dye solution and leaving it at room temperature for 5 hours or more, or by leaving it under heating conditions for 1 hour to 2 hours. The method is preferably left at room temperature for 12 hours or more.
[0075]
  The dye adsorption solvent is an alcohol solvent such as methanol, ethanol, n-propanol, isopropanol, t-butanol, or n-butanol, an organic solvent such as chloroform, acetone, acetonitrile, or tetrahydrofuran, and a mixed solvent thereof. Preferred are ethanol, chloroform, and t-butanol-acetonitrile mixed solvent.
[0076]
  The density | concentration of the said pigment | dye solution is 0.05-0.5 mM normally, Preferably, it is 0.2-0.3 mM.
[0077]
  During the dye adsorption, cholic acid, deoxycholic acid, chenodeoxycholic acid, taurochenodeoxycholic acid, lysocholic acid, ursochoic acid are used in order to prevent association of the dyes on the semiconductor electrode and to perform electron injection efficiently. A cholic acid derivative such as deoxycholic acid and dehydrocholic acid, a sodium salt thereof, a surfactant such as Triton X, and glucose may be dissolved in the dye solution and co-adsorbed with the dye. The concentration of the coadsorbent in the dye solution is usually 2 to 100 mM, preferably 5 to 20 mM.
[0078]
  The electrolyte solution used in the dye-sensitized photoelectric conversion element and the photoelectrochemical solar cell of the present invention includes a redox ion pair. The redox ion pair is I⁻/ I₃ ⁻, Br⁻/ Br₂, Fe²⁺/ Fe³⁺, Sn²⁺/ Sn⁴⁺, Cr²⁺/ Cr³⁺, V²⁺/ V³⁺, S^2-/ S₂ ^2-And anthraquinone. As an electrolyte, in the case of iodine redox, imidazolium derivatives containing these ions (such as dimethylpropylimidazolium iodide), lithium iodide, potassium iodide, a mixture of tetraalkylammonium iodide and iodine, bromine redox In some cases, a mixture of lithium bromide, potassium bromide, tetraalkylammonium bromide and bromine containing these ions is used. Preferred are lithium iodide, tetraalkylammonium and imidazolium iodide derivatives of iodine redox.
[0079]
  The concentration of the redox electrolyte is usually 0.05 to 1M, preferably 0.1 to 0.5M.
[0080]
  The electrolyte solvent for dissolving the redox electrolyte is an alcohol solvent such as methanol, ethanol or isopropanol, a nitrile solvent such as acetonitrile, methoxyacetonitrile, propionitrile, or methoxypropionitrile, or a carbonate solvent such as ethylene carbonate or propylene carbonate. A solvent, an organic solvent such as dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, nitromethane, n-methylpyrrolidone, or a mixed solvent thereof. Nitrile solvents are preferred.
[0081]
  In order to improve photoelectric conversion characteristics, a basic additive such as a pyridine derivative such as t-butylpyridine may be added to the redox electrolyte solution used in the photoelectric conversion element and the photoelectrochemical solar cell of the present invention. The concentration of the additive in the electrolytic solution at that time is usually 0.05 to 1M, preferably 0.1 to 0.5M.
[0082]
  1-ethyl-3-methylimidazolium iodide, 1-n-propyl-3-methylimidazolium iodide containing no solvent instead of the redox electrolyte used in the photoelectric conversion element and the photoelectrochemical solar cell of the present invention Even a mixture of iodide and iodine of an imidazolium derivative which is a room temperature molten salt such as 1-n-butyl-3-methylimidazolium iodide, 1-n-hexyl-3-methylimidazolium iodide, etc. good.
[0083]
  In the above, when a room temperature molten salt electrolyte is used instead of the charged solution, Chem. Commun. , 2002, 374-375, etc., various gelling agents may be used to make the electrolyte quasi-solid.
[0084]
  Instead of the redox electrolyte used in the photoelectric conversion element and the photoelectrochemical solar cell of the present invention, J. Org. Photochem. Photobiol. A: Chem. Inorganic p-type semiconductor hole transport materials such as copper iodide, copper bromide, and copper thiocyanide used in US, 1998, 117, 137-142, etc., or 2 used in Nature, 1998, 395, 583-585. , 2 ′, 7,7′-tetrakis (N, N-di-p-methoxyphenylamine) 9,9′-spirobifluorene and polypyrrole (Sol. Energy Mater. Sol. Cells, 1998, 55, 113-125). ), Organic hole transport materials such as polythiophene may be used.
[0085]
  The counter electrode used in the photoelectric conversion element and the photoelectrochemical solar cell of the present invention is platinum, rhodium, ruthenium, carbon, or an oxide semiconductor electrode coated in a thin film on a conductive transparent glass substrate. A platinum or carbon electrode is preferable.
[0086]
  The spacer used for the photoelectric conversion element and the photoelectrochemical solar cell of the present invention is a polymer film such as polyethylene, polypropylene, and ethylene vinyl acetate, and the film thickness is usually 15 to 120 μm, preferably 15 to 30 μm.
[0087]
  Next, the present invention will be described in detail with reference examples and examples. In addition, No. 48-No. The 67 compounds are specifically shown below.
[0088]
  Reference example 1
  No. 48 g of 4-dimethylaminocinnamaldehyde represented by 48 and 3.7 g of cyanoacetic acid were heated in acetonitrile and completely dissolved at 45 ° C., 0.9 ml of piperidine was added dropwise, and the mixture was reacted for 1 hour by heating under reflux. Cool and collect the precipitated crystals by filtration. The obtained crude crystals are dissolved in methanol at room temperature, and 4.85 ml of triethylamine is added and dissolved. Then, 4.0 ml of acetic acid is added to precipitate crystals, which are collected by filtration. The obtained crude crystals were heated to reflux in methanol for 10 minutes, and filtered while hot. 1.5 g of purple crystals represented by 28 were obtained. A part of the crystal was taken and its melting point was measured by a conventional method, and it was 221 to 223 ° C. In the visible absorption spectrum in the methanol solution, an absorption maximum was observed at 453 nm. In heavy N, N-dimethylformamide (hereinafter abbreviated as heavy DMF)¹The H-NMR spectrum is as follows.
  δ (TMS, ppm) 3.07 (12H, s), 6.81 (2H, d), 7.04 (1H, dd), 7.55 (1H, d), 7.61 (2H, d) , 8.05 (1H, d)
[0089]
  Reference example 2
  After cooling 200 ml of N, N-dimethylformamide (hereinafter abbreviated as DMF) and dropping 42 ml of phosphorus oxychloride (5 to 10 ° C.), the mixture is reacted at room temperature for 1 hour to synthesize a Vilsmeier reagent. No. 100 g of an ethylene derivative represented by 49 is dissolved in DMF at 36 ° C., and the above-mentioned Vilsmeier reagent is added dropwise over 1 hour (36 to 45 ° C.). After reacting at a reaction temperature of 50 ° C. for 1.5 hours, the reaction solution is poured into ice water, neutralized with an aqueous sodium hydroxide solution, and the precipitated crystals are collected by filtration. The obtained crystals were dissolved in benzene, washed with water, dried over magnesium sulfate, filtered, the solvent was distilled off under reduced pressure, and recrystallization was carried out with methanol. 66 g of an intermediate represented by 50 was obtained.
  No. 50 g of the intermediate of 50 and 2.17 g of cyanoacetic acid were completely dissolved in acetonitrile at 60 ° C., 0.5 ml of piperidine was added dropwise, and the mixture was reacted for 1.5 hours with heating under reflux. Crystals deposited upon cooling were collected by filtration. The obtained crude crystals were heated and completely dissolved in a mixed solution of chloroform: methanol = 1: 1 and filtered, and then the solvent was distilled off by heating with 25 ml. After cooling, the precipitated crystals were collected by filtration. 0.9 g of reddish purple crystals represented by 35 was obtained. A part of the crystal was taken and its melting point was measured by a conventional method. In the visible absorption spectrum in the methanol solution, an absorption maximum was observed at 450 nm. In deuterated chloroform¹The H-NMR spectrum is as follows.
  δ (TMS, ppm) 3.05 (6H, s), 3.06 (6H, s) 6.65 (2H, d), 6.73 (2H, d), 7.01 (1H, d), 7.13 (2H, d), 7.36 (2H, d), 8.00 (1H, d)
[0090]
  Reference example 3
  No. synthesized in Reference Example 2 15 g of 50 intermediates and 30.9 g of methyltriphenylphosphonium iodide were dissolved in DMF165m, and 15.6 ml of 28% sodium methylate solution was added dropwise at 20 ° C. Then, it was made to react at 60 degreeC for 2 hours. After completion of the reaction, the reaction solution was poured into ice water, and the precipitated crystals were collected by filtration. 30 g of the obtained crude crystals were dissolved in ethyl acetate, washed with water, dried over magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure. 28 g of the intermediate represented by 51 was obtained.
  While 45 ml of DMF was cooled, 14.2 ml of phosphorus oxychloride was added dropwise (5 to 10 ° C.), and then reacted at room temperature for 1 hour to synthesize a Vilsmeier reagent. No. Said Vilsmeier reagent was dripped at the DMF solution of the intermediate body 28g represented by 51 for 1 hour (4-12 degreeC). Thereafter, the mixture was reacted at room temperature for 1.5 hours and further reacted at 50 ° C. for 1 hour. After completion of the reaction, the reaction solution was poured into ice water, neutralized with an aqueous sodium hydroxide solution, and the precipitated crystals were collected by filtration. The obtained crystals were dissolved in ethyl acetate, washed with water and dried over magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure. 27.3 g of the obtained oil component was purified with a silica gel column and then recrystallized with acetonitrile. 3.88 g of the intermediate represented by 52 was obtained.
  No. 3 g of the intermediate represented by 52 and 1.59 g of cyanoacetic acid were heated and completely dissolved in acetonitrile at 60 ° C., and 2.8 ml of piperidine was added dropwise and reacted for 20 minutes under heating and reflux. Under cooling, 3.2 ml of acetic acid was added for crystallization, and the mixture was collected by filtration. 3.4 g of the resulting crude crystals were dispersed in 68 ml of acetonitrile at room temperature, 7.34 ml of a 15% methanol-hydrochloric acid solution was added dropwise, and the mixture was sufficiently stirred and collected by filtration. The obtained crystals were completely dissolved by adding 9.8 ml of triethylamine in acetonitrile. Under stirring, 6.2 ml of acetic acid was added dropwise, and the precipitated crystals were collected by filtration. The obtained crystals (1.37 g) were dispersed in acetic acid at room temperature and collected by filtration, and further heated to reflux with acetone and then collected by filtration under heat. 1 g of black purple crystals represented by 39 was obtained. A part of the crystal was taken and its melting point was measured by a conventional method. In the visible absorption spectrum in the methanol solution, an absorption maximum was observed at 458 nm. In heavy DMF¹The H-NMR spectrum is as follows.
  δ (TMS, ppm) 3.01 (6H, s), 3.03 (6H, s), 6.75 (2H, d), 6.82-6.85 (3H, m), 7.01 ( 1H, d), 7.12 (2H, d), 7.24-7.31 (1H, m), 7.32 (2H, d), 7.92 (1H, d)
[0091]
  Reference example 4
  No. No. 53, 2-bromomethylthiophene (41.05 g) and triethyl phosphite (43 g) were reacted in an oil bath at 80 ° C. for 19.5 hours. 54.92 g of 54 liquid reagents were obtained.
  No. No. 55 was dispersed in 44 g of a ketone derivative represented by No. 55 and 16.06 g of potassium t-butoxy in tetrahydrofuran (hereinafter abbreviated as THF). A THF solution of 33.52 g of the reagent represented by 54 was added dropwise, followed by reaction at an internal temperature of 70 ° C. for 23 hours. The reaction solution was poured into water, extracted with chloroform, washed with water, dried over magnesium sulfate, and filtered, and the solvent was distilled off under reduced pressure. 46.35 g of the obtained crude crystals were purified by silica gel column. 28 g of an intermediate represented by 56 was obtained.
  While cooling 63 ml of DMF, 20 ml of phosphorus oxychloride was added dropwise (5 to 10 ° C.), and then reacted at room temperature for 30 minutes to synthesize a Vilsmeier reagent. No. The above-mentioned Vilsmeier reagent is added dropwise to a DMF solution of 25 g of the intermediate represented by 56 (4 to 12 ° C.). Thereafter, the reaction was allowed to proceed at room temperature for 5 hours, the reaction solution was poured into ice water, neutralized with an aqueous sodium hydroxide solution, and the precipitated crystals were collected by filtration. The obtained crystals were dissolved in ethyl acetate, washed with water and dried over magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure. The obtained oil component (39.7 g) was purified through a silica gel column and recrystallized from acetonitrile. 4.8 g of an intermediate represented by 57 was obtained.
  No. 3 g of the intermediate represented by 57 and 1.02 g of cyanoacetic acid were completely dissolved in acetonitrile at 60 ° C., 0.93 ml of piperidine was added dropwise, and the mixture was reacted with heating under reflux for 5.5 hours. Crystals precipitated after cooling were collected by filtration. After 3.89 g of the obtained crude crystals were purified by a silica gel column, the crystals were completely dissolved in chloroform, crystallized by adding acetic acid and acetonitrile, and collected by filtration. 2.25 g of the obtained crystals were dispersed in acetonitrile at room temperature, dissolved by adding 15 ml of tributylamine and isopropyl ether, filtered, and 6.4 ml of acetic acid was added with stirring to precipitate crystals, which were collected by filtration. 1.89 g of dark green crystals represented by 40 were obtained. A part of the crystal was taken and its melting point was measured by a conventional method, and it was 235 to 238 ° C. In the visible absorption spectrum in the methanol solution, an absorption maximum was observed at 485 nm. With heavy DMF¹The H-NMR spectrum is as follows.
  δ (TMS, ppm) 2.99 (6H, s), 3.05 (6H, s), 6.65 (2H, d), 6.86 (2H, d), 6.90 (1H, d) 7.08 (2H, d), 7.13 (1H, s), 7.29 (2H, d), 7.66 (1H, d), 8.04 (1H, s)
[0092]
  Reference Example 5
  No. obtained in Reference Example 4 After completely dissolving 40 products of the present invention in chloroform, piperidine was added and dispersed at room temperature, acetonitrile was added to crystallize and collected by filtration. 2.3 g of vermilion crystals represented by 41 were obtained. A part of the crystal was taken and its melting point was measured by a conventional method, and it was 225 to 228 ° C. In the visible absorption spectrum in the methanol solution, an absorption maximum was observed at 465 nm. In heavy DMF¹The H-NMR spectrum is as follows.
  δ (TMS, ppm) 1.65 (2H, m), 1.84 (4H, m), 2.97 (6H, s), 3.04 (6H, s), 3.16 (4H, t) 6.64 (2H, d), 6.79-6.82 (3H, m), 7.06-7.08 (3H, m), 7.27 (2H, d), 7.58 (1H) , D), 7.96 (1H, s)
[0093]
  Reference Example 6
  No. No. 58 and 15.2 g of 4-diethylaminosalicylaldehyde represented by No. In DMF, 12.3 g of the thiophene derivative represented by 59 was added with 17 ml of acetic acid and 33.5 ml of piperidine, and reacted for 2 hours with heating under reflux. The reaction was poured into water. The mixture was extracted with ethyl acetate, washed with water, dried and the solvent was distilled off under reduced pressure. The precipitated crystals were dispersed in ethanol and collected by filtration. The obtained crude crystals were recrystallized with a chloroform-methanol mixed solvent. 15.3 g of dark green crystals of a coumarin derivative represented by 60 were obtained.
  No. 60 g of a coumarin derivative represented by 60 was dissolved in DMF, and a separately prepared Vilsmeyer reagent (synthesized by a conventional method using 2 ml of DMF and 0.7 ml of phosphorus oxychloride) was added dropwise at 8 to 14 ° C. Thereafter, the mixture was reacted at room temperature for 2 hours and then reacted at 40 ° C. for 1 hour. The reaction solution was poured into ice water, neutralized with an aqueous sodium hydroxide solution, heated to 60 ° C. and cooled, and the precipitated crystals were collected by filtration. The obtained crystals were recrystallized from isopropyl alcohol. 1.18 g of an intermediate represented by 61 was obtained.
  No. 1 g of the intermediate represented by 61 and 0.39 g of cyanoacetic acid were added to 0.5 ml of piperidine in acetonitrile and reacted for 3 hours with heating under reflux. The crystals that precipitated upon cooling were collected by filtration. To the obtained crude crystals, 11.2 ml of acetic acid was added and dispersed at room temperature and collected by filtration. Thereafter, silica gel column purification was performed. 0.48 g of dark green crystals represented by 1 was obtained. A part of the crystal was taken and its melting point was measured by a conventional method, and it was 270 to 275 ° C. In the visible absorption spectrum in the methanol solution, an absorption maximum was observed at 474 nm.
  In heavy DMF¹The H-NMR spectrum is as follows.
  δ (TMS, ppm) 1.23 (6H, t), 3.59 (4H, q), 6.67 (1H, d), 6.9 (1H, dd), 7.64 (1H, d) 7.97 (1H, d), 8.05 (1H, d), 8.49 (1H, s), 8.75 (1H, s)
[0094]
  Reference Example 7
  No. No. 62 and 27.34 g of a salicylaldehyde derivative represented by No. In DMF, 12.3 g of the thiophene derivative represented by 59 was added with 17 ml of acetic acid and 33.5 ml of piperidine, and heated to reflux for 3 hours. The reaction solution was poured into water, extracted with isopropyl ether and washed with water. After drying, the solvent was distilled off under reduced pressure to obtain an oil component. After purification on a silica gel column, crystallization was performed with isopropyl ether. 10.3 g of a coumarin derivative represented by 63 was obtained.
  No. obtained 9 g of a coumarin derivative represented by 63 was dissolved in 90 ml of DMF, and 6.6 ml of phosphorus oxychloride was added dropwise at 20 to 23 ° C. Thereafter, the reaction was carried out at 30 to 35 ° C. for 1.5 hours. The reaction solution was poured into ice water, neutralized with an aqueous sodium hydroxide solution, stirred at 40 to 45 ° C. for 30 minutes, and the precipitated crystals were collected by filtration. The obtained crude crystals were recrystallized from isopropyl alcohol. 8.65 g of an intermediate represented by 64 was obtained.
  No. Into acetonitrile, 0.5 ml of piperidine was added to 1.5 g of the intermediate represented by 64 and 0.47 g of cyanoacetic acid, and the mixture was heated to reflux for 2 hours. Thereafter, the solvent was distilled off under reduced pressure, and a mixed solution of acetic acid: water: acetonitrile = 1: 2: 2 was added for crystallization, followed by filtration. The obtained crystals were purified by silica gel column, recrystallized from DMF-methanol and collected by filtration. 0.21 g of dark green crystals represented by 4 was obtained. A part of the crystal was taken and its melting point was measured by a conventional method, and it was 272 to 277 ° C. In the visible absorption spectrum in the methanol solution, an absorption maximum was observed at 494 nm.
  In heavy DMF¹The H-NMR spectrum is as follows.
δ (TMS, ppm) 1.29 (6H, s), 1.52 (6H, s), 1.74-1.83 (4H, m), 3.35-3.46 (4H, m), 7.52 (1H, s) 7.91-8.04 (2H, m), 8.46 (1H, s), 8.66 (1H, s)
[0095]
  Reference Example 8
  No. No. 65 synthesized in Reference Example 4 was prepared by dispersing 15 g of a coumarin derivative represented by 65 and 6.21 g of t-butoxypotassium at 55 ° C. in THF. A THF solution of 12.96 g of the reagent represented by 54 was added dropwise, and then reacted at an internal temperature of 70 ° C. for 23 hours. The reaction solution was poured into water, extracted with chloroform, washed with water, dried over magnesium sulfate, and filtered, and the solvent was distilled off under reduced pressure. The obtained oil component (27.02 g) was purified through a silica gel column. 10.13 g of an intermediate represented by 66 was obtained.
  Under cooling of 22 ml of DMF, 7.0 ml of phosphorus oxychloride was added dropwise (5 to 10 ° C.), and then reacted at room temperature for 30 minutes to synthesize a Vilsmeier reagent. Separately, no. A DMF solution of 10.13 g of the intermediate represented by 66 was added dropwise (4-12 ° C.) to the above-mentioned Vilsmeier reagent. Thereafter, the mixture was reacted at room temperature for 1 hour and then reacted at 45 ° C. for 3.5 hours. Thereafter, the reaction solution was poured into ice water, neutralized with an aqueous sodium hydroxide solution, and the precipitated crystals were collected by filtration. The obtained crystals were dissolved in ethyl acetate, washed with water and dried over magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure. After 11.4 g of the obtained oil component was purified by silica gel column, it was recrystallized from acetonitrile. 3.4 g of the intermediate represented by 67 was obtained.
  No. 3 g of the intermediate represented by 67 and 0.88 g of cyanoacetic acid were completely dissolved in acetonitrile at 60 ° C., and 0.21 ml of piperidine was added dropwise, followed by reaction with heating under reflux for 3.5 hours. The precipitated crystals were collected by filtration while hot. After 3.2 g of the obtained crude crystals were purified by column, they were dissolved in chloroform, crystallized by adding acetic acid and acetonitrile, and collected by filtration. 1.6 g of dark green crystals represented by 16 was obtained. A part of the crystal was taken and its melting point was measured by a conventional method, and it was 263 to 267 ° C. In the visible absorption spectrum in the methanol solution, an absorption maximum was observed at 494 nm.
  In heavy DMF¹The H-NMR spectrum is as follows.
  δ (TMS, ppm) 1.28 (6H, s), 1.51 (6H, s), 1.73-1.79 (4H, m), 3.32 (2H, t) 3.39 (2H) , T), 7.19 (1H, d) 7.38-7.42 (2H, m), 7.81-7.90 (2H, m), 8.12 (1H, s), 8.41. (1H, s)
[0096]
Embedded image
Embedded image
Embedded image
Embedded image
[0097]
Embedded image
Embedded image
Embedded image
Embedded image
[0098]
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
[0099]
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
[0100]
Embedded image
Embedded image
[0101]
  Example 1
  (1) Preparation of titanium oxide thin film electrode with dye adsorbed
  Crystalline titanium oxide nanoparticles were obtained by autoclaving a titanium oxide colloid prepared by hydrolysis of titanium tetraisopropoxide. An organic paste mixed with ethyl cellulose as a binder and α-terpineol as a solvent was applied onto a tin oxide-coated conductive glass by a screen printing method. By baking in air at 500 ° C. for 1 to 2 hours, a titanium oxide thin film electrode having a thickness of 10 to 14 microns was obtained. This electrode was immersed in a 0.3 mM organic dye solution (the solvent was a mixed solvent of t-butanol and acetonitrile 1: 1) and left at room temperature for 10 hours or more to obtain a dye-adsorbed titanium oxide thin film electrode. Further, at the time of dye adsorption, 5 to 20 mM deoxycholic acid was appropriately added to the dye solution according to the kind of the dye.
[0102]
  (2) Fabrication of photoelectrochemical solar cells and evaluation of photoelectric conversion characteristics
  The dye-adsorbed titanium oxide thin film electrode obtained in the above (1) and the tin oxide coated conductive glass sputtered with platinum are overlapped with a polyethylene film sandwiched between them, and 0.6M 1,2-dimethyl iodide as an electrolyte solution is placed in the gap. A methoxyacetonitrile solution of -3-propylimidazolium-0.1M lithium iodide-0.05M iodine was injected and stopped with a Zem clip. Moreover, according to the kind of pigment | dye, the acetonitrile solution which added 0.05-0.5M t-butyl pyridine to said composition was used for electrolyte solution. Photoelectric conversion characteristics were measured using a solar simulator composed of a xenon lamp and an AM filter as a light source, and photocurrent voltage characteristics were measured using a source meter.
[0103]
[Table 2]
[0104]
Embedded image
[0105]
  Table 1 shows the photoelectric conversion characteristics of the photoelectrochemical solar cell using the organic dye sensitizer synthesized according to the present invention under AM1.5 conditions. Here, Jsc is the optical short-circuit current density, Voc is the optical open-circuit voltage, Fill factor is the form factor, and η is the photoelectric conversion efficiency. As shown in Table 1, the photoelectric conversion characteristics of the photochemical solar cell using the novel organic dye sensitizer synthesized according to the present invention are compared with those using the conventional commercially available Coumarin 343 (No. 68). Greatly improved. In particular, Jsc has improved dramatically. This is considered to be because the absorption wavelength region of the dye is greatly expanded by the expansion of the conjugated system. These photoelectric conversion efficiencies are comparable to solar cells using a ruthenium complex sensitizer.
[0106]
【The invention's effect】
  According to the present invention, there are provided a dye-sensitized photoelectric conversion element using a ruthenium complex photosensitizer, an organic dye-sensitized photoelectric conversion element showing a photoelectric conversion efficiency comparable to a photoelectrochemical solar cell, and a photoelectrochemical solar cell. I was able to.
[Brief description of the drawings]
FIG. 1 shows an example of a configuration diagram of a photoelectrochemical solar cell used in Examples.
[Explanation of symbols]
1 Platinum sputtered conductive glass layer
2 Redox electrolyte layer
3 Dye adsorption semiconductor thin film electrode layer
4 Conductive transparent glass

Claims (5)

In a semiconductor thin film electrode sensitized by the action of an organic dye, the organic dye represented by the following general formula (2) having a cyano group and a carbon group substituted by COOM at the end is composed of nanoparticles and has a nanoporous structure. A semiconductor thin film electrode which is sensitized by being adsorbed on the surface of a compound semiconductor particle.
(L ₁ is a group selected from the following b, c, or d.
a group consisting of b-A-CH = (wherein A is a thiophene ring, a furan ring or a heterocyclic compound selected from a pyrrole ring substituted by a hydrogen atom or a methyl group, and 2 or 3 A ring compound may be continuous, or a benzene or benzothiazole may be bonded to the end of the heterocyclic compound).
a group consisting of c—CH═CH—A—CH═ (wherein A is a heterocyclic compound selected from a thiophene ring or a furan ring; the same two heterocyclic compounds may be linked). The group represented,
d—A—CH═CH—B = (in the formula, A represents a thiophene ring, and B represents a heterocyclic compound composed of a methyl-substituted pyran ring).
R ₁ to R ₃ and R ₅ represents hydrogen or a methyl, ethyl or a halogenated methyl group independently, R _6, R ₇ are independently a hydrogen atom, an alkyl group of from 1 to 4 carbon atoms, if Depending on the case, any one or both of R _{1 to} R ₃ and R _{5 to} R ₇ may be bonded to each other to form a nitrogen-containing ring.
M is a hydrogen atom or hydrogen-substituted pyridine. ) In a semiconductor thin film electrode sensitized by the action of an organic dye, the organic dye represented by the following general formula (4) having a cyano group and a carbon group substituted by COOM at the end is composed of nanoparticles and has a nanoporous structure. A semiconductor thin film electrode which is sensitized by being adsorbed on the surface of a compound semiconductor particle.
(In the formula, L ₂ is a group selected from the following a, b, c, d or e.
a group selected from: = CH-CH =, = CH-CH = CH-CH = or = CH-CH = CH-CH = CH-CH =,
b = CH-A-CH =, = CH-AA-CH =, or = CH-AA-A-CH = (wherein A is substituted with a thiophene ring, a hydrogen atom or a methyl group) A group selected from 1 type or 2 types of heterocyclic compounds selected from pyrrole rings.
a group consisting of c = CH—A—CH═CH—A—CH═ (wherein A is a heterocyclic compound comprising a thiophene ring),
d = CH—CH═B = (wherein B represents a cyclohexyl group).
R _{8 to} R ₁₀ , R _{12 to} R ₁₃ and R _{15 to} R ₁₇ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R _{18 to} R ₂₁ independently represent a hydrogen atom or carbon number 1 Or any one of R _{8 to} R ₁₀ , R _{12 to} R ₁₃ and R _{15 to} R ₂₁ may be bonded to each other to form a ring containing N. Good.
M represents a hydrogen atom, a tributylamino group or a hydrogen-substituted pyridine group. )   A photoelectric conversion element using the semiconductor thin film electrode according to claim 1.   A substrate coated with a conductive transparent oxide semiconductor thin film in contact with one surface of the layer made of the semiconductor thin film electrode, a layer made of an electrolytic solution containing a Redox ion pair in contact with the other surface, and further on the outside thereof 4. The photoelectric conversion element according to claim 3, comprising an electrode obtained by coating a conductive transparent glass substrate with a compound selected from platinum, rhodium, ruthenium, carbon or an oxide semiconductor.   A photoelectrochemical solar cell using the photoelectric conversion element according to claim 4.