JP2017166067A - Water decomposition optical electrochemical cell, hydrogen manufacturing device and hydrogen peroxide manufacturing device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water decomposition optical electrochemical cell capable of achieving optical water decomposition without a metallic oxidation catalyst and a hydrogen manufacturing device and a hydrogen peroxide manufacturing device using the same.SOLUTION: The water decomposition optical electrochemical cell is a water decomposition optical electrochemical cell 10 having a photoelectrode 3 containing compound semiconductor fine particles and a dye carried on the compound semiconductor fine particles, the dye is an organic dye compound consisting of at least one semi-metal element including carbon and at least one non-metal element including hydrogen or a salt thereof.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a water-splitting photoelectrochemical cell, a hydrogen production apparatus and a hydrogen peroxide production apparatus using the same.

  In recent years, in order to overcome the shortage of fossil fuels in the future, it has become inevitable to develop efficient devices for converting water into hydrogen fuel using solar energy. Therefore, in recent years, a technique for producing hydrogen by performing water splitting with light energy using a photocatalyst or a photoelectrochemical cell has attracted attention.

Such a photo-water splitting technique is based on (a) “photocatalyst in which fine particles acting as a catalyst such as platinum (Pt) fine particles are joined as hydrogen generation sites on compound semiconductor fine particles such as titanium oxide (TiO ₂ ) fine particles. And the “photoelectrode” system using a semiconductor for the photoelectrode and platinum or the like for the counter electrode.

(A) Photocatalytic system A photocatalytic system in which a catalyst such as platinum, rhodium (Rh), nickel oxide (NiO), ruthenium dioxide (RuO ₂ ) is supported on a semiconductor powder can simultaneously generate hydrogen and oxygen for a long time. . For example, Graetzel et al. Have a platinum catalyst and a ruthenium dioxide catalyst supported on a colloidal titania (TiO ₂ ) support and a photocatalytic system using a ruthenium complex such as (Ru (bipy) ₃ ) ²⁺ as a sensitizing dye. Has been reported (see Non-Patent Document 1). However, this photocatalytic system has a drawback that a reaction (surface back reaction (SBR)) in which the produced hydrogen and oxygen are catalytically returned to water on the platinum catalyst occurs.

Therefore, at present, in photocatalytic systems using sensitizing dyes, research focusing on hydrogen generation (4H ⁺ + 4e → 2H ₂ ) seems to be mainstream.

  For example, as a photocatalytic system that combines compound semiconductor fine particles and sensitizing dyes, a compound semiconductor fine particle such as titanium oxide fine particles carries a platinum catalyst and a carbazole-based metal-free organic dye as a sensitizing dye, and a sacrificial reagent is used. A photocatalytic system that has been reported has been reported (Non-Patent Document 2). The photocatalytic system of Non-Patent Document 2 is a fine particle photocatalyst in which platinum is bonded to semiconductor fine particles as a hydrogen generation site (reduction site), and is supplied with electrons from a sacrificial reagent.

  In addition, hydrogen generation in a simple photocatalytic system in which a nickel complex is used as a catalyst, an iridium complex is used as a sensitizing dye, and the catalyst, sensitizing dye, and sacrificial reagent are dissolved in a solvent has been reported ( Non-patent document 3). However, the water decomposition reaction by these photocatalytic systems is irreversible and not complete water decomposition.

  A photocatalytic system using a ruthenium complex alone as a catalyst has also been reported (Patent Document 1).

(B) Photoelectrode system (PEC)
An example of successful decomposition of water using a semiconductor as a photoelectrode is the Honda-Fujishima effect (Non-Patent Document 4). In a photoelectrode system using a titanium oxide semiconductor electrode as a photoelectrode (negative electrode) and platinum as a counter electrode, when the titanium oxide semiconductor electrode is irradiated with light having a wavelength of 410 nm or less, oxygen is generated from the surface of the photoelectrode, and from the counter electrode It has been found that hydrogen is generated.

  However, because the band gap of titanium oxide is large (> 3.0 eV), the photoelectrode system can only use near ultraviolet light. Further, the photoelectrode system has low water splitting efficiency, and it is necessary to use an external voltage or neutralization energy of acid / base.

  For this reason, a dye-sensitized photoelectrode system in which a sensitizing dye is adsorbed on a semiconductor surface and the sensitizing dye is photoexcited has been reported.

  As such a dye-sensitized photoelectrode system, one in which two kinds of ruthenium complexes cooperate with each other as a sensitizing dye and a water oxidation catalyst to advance a water splitting reaction has been reported. For example, Papanikolas et al. Have covalently linked two ruthenium complexes, a ruthenium complex that acts as a sensitizer and a ruthenium complex that acts as a water oxidation catalyst, and the molecular system is titanium oxide. It has been reported that a water-splitting reaction was carried out using a dye-sensitized photoelectrode system adsorbed on (Non-patent Document 5, Patent Document 2).

  On the other hand, Sun et al. Have proposed a dye-sensitized photoelectrode system in which a ruthenium complex acting as a sensitizer (sensitizing dye) and a ruthenium complex acting as a water oxidation catalyst are co-adsorbed on titanium oxide. Reported that water was photolyzed (Non-patent Document 6).

  Recently, a negative electrode in which a ruthenium complex that functions as a water oxidation catalyst and an organic dye that functions as a sensitizer are adsorbed on titanium oxide, a cobalt complex that functions as a water reduction catalyst, and an organic dye that functions as a sensitizer are nickel oxide. A tandem dye-sensitized photoelectrode system in combination with a positive electrode adsorbed on a non-patent document 7 has been reported. However, in this tandem dye-sensitized photoelectrode system, a decrease in the photocurrent value has been observed in the long-time light irradiation, and stability is an issue.

International Publication No. 2012/050436 US Patent Application Publication No. 2015/0072852

E. Borgarello, J. Kiwi, E. Pelizzetti, M. Visca ,, and M. Graetzel, Nature, 1981, 289, p.158-160 M. Watanabe, H. Hagiwara, Y. Ogata, A. Staykov, SR Bishop, NH Perry, YJ Chang, S. Ida, K. Tanaka, and T. Ishihara, Journal of Materials Chemistry A, 2015, 3, p. 21713-21721 Y.-J. Yuan, J.-R. Tu, H.-W. Lu, Z.-T. Yu, X.-X. Fan, and Z.-G. Zou, Dalton Transactions, 2016, 45, p.1359-1363 A. Fujishima, and K. Honda, Nature, 1972, 238, p.37-38 L. Wang, D. L. Ashford, D. W. Thompson, T. J. Meyer, and J. M. Papanikolas, The Journal of Physical Chemistry C, 2013, 117, p.24250-24258 Y. Gao, X. Ding, J. Liu, L. Wang Z. Lu, L. Li, and L. Sun, Journal of the American Chemical Society, 2013, 135, p.4219-4222 F. Li, K. Fan, B. Xu, E. Gabrielsson, Q. Daniel, L. Li, L. Sun, Journal of the American Chemical Society, 2015, 137, p.9153-9159

  However, conventional photo-water splitting techniques include metal compound catalysts that function as oxidation catalysts (nickel oxide, ruthenium dioxide, etc.), and metal complex catalysts that function as oxidation catalysts (ruthenium complexes, nickel complexes) (hereinafter collectively referred to as these). Depending on at least one of the "metal oxidation catalysts").

  The present invention has been made in view of the above problems, and its object is to provide a water-splitting photoelectrochemical cell capable of realizing photo-water splitting without a metal-based oxidation catalyst, and a hydrogen production apparatus and hydrogen peroxide production using the same. To provide an apparatus.

  As a result of intensive studies, the present inventors have found that an organic dye compound or a salt thereof comprising at least one metalloid element containing carbon and at least one nonmetal element containing hydrogen as a sensitizing dye is a compound semiconductor fine particle. By using the photoelectrode supported on the photocatalyst, it has been found that photohydrolysis occurs without a metal-based oxidation catalyst that has been conventionally required, and the present invention has been completed.

  In order to solve the above problems, the water-splitting photoelectrochemical cell of the present invention is a water-splitting photoelectrochemical device provided with a photoelectrode comprising compound semiconductor fine particles and a sensitizing dye supported on the compound semiconductor fine particles. The cell is characterized in that the sensitizing dye is an organic dye compound or a salt thereof comprising at least one metalloid element containing carbon and at least one nonmetal element containing hydrogen.

  According to the present invention, photowater decomposition can be realized without a metal-based oxidation catalyst. By eliminating the need for a metal-based oxidation catalyst that has been conventionally required, it is possible to expect cost reduction and stability improvement.

It is a figure which shows the structure of the water splitting photoelectrochemical cell which concerns on one Embodiment of this invention. It is a figure which shows typically the operation | movement principle of the water splitting in the water splitting photoelectrochemical cell which concerns on one Embodiment of this invention. It is a figure which shows the structure of the water-splitting photoelectrochemical cell for experiment which concerns on the Example of this invention. It is a figure which shows the photocurrent waveform of the water-splitting photoelectrochemical cell and control cell which concern on the Example of this invention.

  Hereinafter, the present invention will be described in detail.

(Water-splitting photoelectrochemical cell)
The water-splitting photoelectrochemical cell of the present invention is a water-splitting photoelectrochemical cell provided with a photoelectrode comprising compound semiconductor fine particles and a sensitizing dye supported on the compound semiconductor fine particles, the sensitizing dye Is an organic dye compound or a salt thereof comprising at least one metalloid element containing carbon and at least one nonmetal element containing hydrogen. Therefore, the sensitizing dye supported on the compound semiconductor fine particles is metal-free except for a metal ion (for example, sodium ion) that is sometimes included as a counter ion of a salt, unlike a metal complex dye that requires a central metal. . In the application documents of the present application, “metalloid element” means an element having intermediate properties between a metal element and a nonmetal element. Specifically, boron, carbon, aluminum, silicon, germanium, arsenic , Selenium, antimony, tellurium, polonium, and astatine.

(Organic dye compound)
When the organic dye compound has an acidic group or a basic group, a salt thereof may be used. Examples of the salt of the organic dye compound include (1) an organic dye compound having at least one acidic group (carboxy group, phosphate group, sulfo group, hydroxy group on an aromatic ring, etc.), and at least one acidic group. Deprotonated conjugate base to form a salt between this conjugate base (anion) and counter cation, (2) an organic dye compound having at least one basic group (for example, amino group), Examples thereof include those in which at least one basic group is protonated to form a cation, and a salt is formed between this cation and a counter anion (for example, chloride ion). Examples of the counter cation include alkali metal ions such as lithium ion, sodium ion and potassium ion; alkaline earth metal ions such as magnesium ion and calcium ion; tetramethylammonium ion, tetrabutylammonium ion, pyridinium ion and imidazolium. Examples thereof include organic cations such as quaternary ammonium ions such as ions, piperazinium ions, and piperidinium ions.

で表されるメロシアニン系色素、特開平１１−１６７９３７号公報に記載のメロシアニン系色素、特開平１１−２３８９０５号公報に記載のメロシアニン系色素等のメロシアニン系色素（荒川裕則企画監修、「色素増感型太陽電池の最新技術」、株式会社シーエムシー、２００１年のｐ．１３６−１４１参照）；ロダシアニン系色素（特開平１１−１８５８３６号公報参照）、無金属ポルフィリン系色素（荒川裕則企画監修、「色素増感型太陽電池の最新技術」、株式会社シーエムシー、２００１年のｐ．１７０−１７３及びｐ．３０４−３０７参照）等が挙げられる。 As an organic pigment | dye compound or its salt used by this invention, in the compound represented by the general formula (1) or general formula (2) mentioned later, C is a substituent represented by a formula (C-1), for example. Aniline dyes such as compounds; dipyrromethene dyes (for example, compounds in which C is a substituent represented by formula (C-2) in the compound represented by formula (1) or formula (2) described later) Eosin Y (sodium salt; see JP-A-10-92477) converted to free acid, 9-phenylxanthene dye described in JP-A-11-97725, JP-A-11-67285 9-phenylxanthene dyes such as 9-phenylxanthene dyes such as rhodamines; triphenylmethane dyes such as modern blue 29 (see JP-A-10-093118); Kridine dye (see JP-A-10-093118); Coumarin dye (see JP-A-10-093118); Metal-free phthalocyanine dye; Oxazine dye (see JP-A-11-074003); Indigo Dyes (see JP-A-11-074003); cyanine dyes (JP-A-11-126717, JP-A-11-144773, Hironori Arakawa, supervised), "Latest Dye-sensitized Solar Cell Technology" , See CMC Corporation, p. 136-141 in 2001)));

Merocyanine dyes such as merocyanine dyes described in JP-A-11-167937, merocyanine dyes described in JP-A-11-238905, etc. Latest Technology of Sensitive Solar Cells ”, CMC Co., Ltd., 2001, p.136-141); rhodacyanine dyes (see JP-A-11-185836), metal-free porphyrin dyes (supervised by Hironori Arakawa , “Latest technology of dye-sensitized solar cell”, see CMC Corporation, p. 170-173 and p. 304-307 in 2001).

  As the organic dye compound or a salt thereof, A-B-C (wherein A represents an electron conjugated group A, B represents a conjugated bond group, represents an adsorption group (anchor site), and A represents B. The structure may be a structure in which it is directly bonded to C without intervention).

  Among the organic dye compounds of the type described above or salts thereof, compounds represented by the following general formula (1) or the following general formula (2) or salts thereof are particularly preferred.

［前記一般式（１）中におけるｍ１は１乃至４の整数を表し、
前記一般式（２）中におけるｍ２は２乃至３の整数を表し、
前記一般式（１）及び（２）中におけるｒは０又は１を表し、
前記一般式（１）及び（２）中におけるＡは、カルボキシ基、リン酸基、シアノ基、アルコキシカルボニル基、アシル基、ニトロ基、アルコキシシリル基、ヒドロキシ基、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい複素環基、又は下記式（Ａ−１）乃至（Ａ−５）の何れか１つで表される置換基を表し、

（式（Ａ−１）乃至（Ａ−５）中、^*Ｂは前記一般式（１）及び（２）におけるＢとの結合部位を表し、Ｘ₁、Ｘ₂、Ｙ₁、及びＹ₂はそれぞれ独立に、置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい複素環基、アミノ基、ヒドロキシ基、アルコキシ基、水素原子、ハロゲン原子、カルボキシ基、シアノ基、リン酸基、スルホ基、アルコキシカルボニル基、アシル基、又はカルボンアミド基を表し、Ｒ₁乃至Ｒ₈はそれぞれ独立に、置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい複素環基、アミノ基、ヒドロキシ基、アルコキシ基、水素原子、ハロゲン原子、シアノ基、リン酸基、アルコキシカルボニル基、アシル基、カルボンアミド基、アミド基、アリールオキシ基、又はカルボキシメチル基を表し、Ｒ₈はベンゼン環上の４つの基（水素原子を含む）を表し、互いに同一でも異なっていてもよく、Ｚ₁乃至Ｚ₅はそれぞれ独立に酸素原子、硫黄原子、セレン原子、−ＣＲＲ’−基、−ＣＲ＝ＣＲ’−基、又は−ＮＲ''−基（式中、Ｒ、Ｒ’及びＲ''はそれぞれ独立に水素原子又は置換基を表し、Ｒ及びＲ’は互いに結合を形成してもよい。）を表す。）
前記一般式（１）及び（２）中におけるＢは、下記式（Ｂ−１）乃至（Ｂ−４）の何れか１つで表される置換基を表し、

（式（Ｂ−１）乃至式（Ｂ−４）中、^*Ａは前記一般式（１）及び（２）におけるＡとの結合位置を、^*Ｃは前記一般式（１）及び（２）におけるＣとの結合位置をそれぞれ表し、Ｒ₁₀₁乃至Ｒ₁₀₆はそれぞれ独立に、置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい複素環基、アミノ基、ヒドロキシ基、リン酸基、シアノ基、水素原子、ハロゲン原子、アルコキシ基、アミド基、カルボキシ基、カルボンアミド基、アルコキシカルボニル基、又はアシル基を表し、Ｒ₁₀₅はベンゼン環上の４つの基（水素原子を含む）を表し、互いに同一でも異なっていてもよく、Ｒ₁₀₆はベンゼン環上の２つの基（水素原子を含む）を表し、互いに同一でも異なっていてもよく、Ｚ₁₀₁乃至Ｚ₁₀₄はそれぞれ独立に、酸素原子、硫黄原子、セレン原子、−ＣＲＲ’−基、−ＣＲ＝ＣＲ’−基、又は−ＮＲ''−基（式中、Ｒ、Ｒ’およびＲ''はそれぞれ独立に水素原子又は置換基を表す。）を表し、ｎ１乃至ｎ４はそれぞれ独立に１乃至７の整数を表す。）
前記一般式（１）及び（２）中におけるＣは、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい複素環基、又は下記式（Ｃ−１）若しくは式（Ｃ−２）で表される置換基を表す。

（式（Ｃ−１）中、^*Ｂは、前記一般式（１）及び（２）におけるＢとの結合位置を表し、Ｒ₂₀₁は水素原子又は１個若しくは複数個の置換基を表し、それら複数個の置換基は、互いに同一でも異なっていてもよく、また、互いに結合して又はＲ₂₀₂若しくはＲ₂₀₃と結合して環を形成してもよく、Ｒ₂₀₂及びＲ₂₀₃はそれぞれ独立に、水素原子、置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよい芳香族炭化水素基、又は置換基を有していてもよい複素環基を表す。）

（式（Ｃ−２）中、^*Ｂは、前記一般式（１）及び（２）におけるＢとの結合位置を表し、ｐ１は１乃至４の整数を表し、Ｍ₁はホウ素原子、ケイ素原子、ゲルマニウム原子、ヒ素原子、アンチモン原子、及びテルル原子からなる群より選択される半金属原子を表し、Ｒ₂₀₄乃至Ｒ₂₀₆はそれぞれ独立に、水素原子、置換基を有していてもよい芳香族炭化水素基、又は置換基を有していてもよい複素環基を表し、Ｑ₁及びＱ₂はそれぞれ独立にハロゲン原子を表し、Ａｒ１及びＡｒ２はそれぞれ独立に芳香環を表す。）］

[M1 in the general formula (1) represents an integer of 1 to 4,
M2 in the general formula (2) represents an integer of 2 to 3,
R in the general formulas (1) and (2) represents 0 or 1,
A in the general formulas (1) and (2) may have a carboxy group, a phosphate group, a cyano group, an alkoxycarbonyl group, an acyl group, a nitro group, an alkoxysilyl group, a hydroxy group, or a substituent. A good aromatic hydrocarbon group, a heterocyclic group which may have a substituent, or a substituent represented by any one of the following formulas (A-1) to (A-5);

(In the formulas (A-1) to (A-5), ^* B represents a binding site with B in the general formulas (1) and (2), and X ₁ , X ₂ , Y ₁ , and Y ₂ are Independently, an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, an amino group, Represents a hydroxy group, an alkoxy group, a hydrogen atom, a halogen atom, a carboxy group, a cyano group, a phosphate group, a sulfo group, an alkoxycarbonyl group, an acyl group, or a carbonamido group, and R _{1 to} R ₈ are each independently substituted An aliphatic hydrocarbon group which may have a group, an aromatic hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, an amino group, a hydroxy group, an alkoxy group , Hydrogen atom, halogen atom, cyano group, phosphate group, alkoxycal Group, an acyl group, carbonamido group, an amide group, an aryloxy group, or carboxymethyl group, R ₈ represents 4 radicals on the benzene ring (including a hydrogen atom), be the same or different from each other Z _{1 to} Z ₅ are each independently an oxygen atom, a sulfur atom, a selenium atom, a —CRR′— group, a —CR═CR′— group, or a —NR ″ — group (wherein R, R ′ and R ″ each independently represents a hydrogen atom or a substituent, and R and R ′ may form a bond with each other.)
B in the general formulas (1) and (2) represents a substituent represented by any one of the following formulas (B-1) to (B-4);

(In formulas (B-1) to (B-4), ^* A represents the bonding position with A in formulas (1) and (2), and ^* C represents formulas (1) and (2). Each of R _{101 to} R ₁₀₆ independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, An optionally substituted heterocyclic group, amino group, hydroxy group, phosphoric acid group, cyano group, hydrogen atom, halogen atom, alkoxy group, amide group, carboxy group, carbonamido group, alkoxycarbonyl group, or Represents an acyl group, R ₁₀₅ represents four groups (including hydrogen atoms) on the benzene ring, which may be the same or different from each other, and R ₁₀₆ represents two groups (including hydrogen atoms) on the benzene ring. represents may be the same or different, Z ₁₀₁ or ₁₀₄ are each independently an oxygen atom, a sulfur atom, a selenium atom, -CRR'- group, -CR = CR'- group, or -NR '' - group (wherein, R, R 'and R''are each Independently represents a hydrogen atom or a substituent, and n1 to n4 each independently represents an integer of 1 to 7.)
C in the general formulas (1) and (2) is an aromatic hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or the following formula (C-1 ) Or a substituent represented by the formula (C-2).

(In the formula (C-1), ^* B represents the bonding position with B in the general formulas (1) and (2), R ₂₀₁ represents a hydrogen atom or one or more substituents; The plurality of substituents may be the same or different from each other, and may be bonded to each other or bonded to R ₂₀₂ or R ₂₀₃ to form a ring, and R ₂₀₂ and R ₂₀₃ are each independently A hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent.

(In formula (C-2), ^* B represents the bonding position with B in the general formulas (1) and (2), p1 represents an integer of 1 to 4, M ₁ represents a boron atom, a silicon atom Represents a metalloid atom selected from the group consisting of a germanium atom, an arsenic atom, an antimony atom, and a tellurium atom, and R _{204 to} R ₂₀₆ are each independently a hydrogen atom or an aromatic group optionally having a substituent. A hydrocarbon group or an optionally substituted heterocyclic group, Q ₁ and Q ₂ each independently represent a halogen atom, and Ar 1 and Ar ₂ each independently represent an aromatic ring)]

In the general formula of the present application, the partial structure is enclosed in parentheses, and the symbol indicating the number of repetitions of the partial structure (for example, n1) is attached to the parenthesis with a lower right subscript (for example, the formula (B-1) In the case where the number of repeating partial structures is 2 or more, the groups (for example, R ₁₀₁ ) of the two or more partial structures may be the same or different.

  First, A in the general formulas (1) and (2) will be described.

  The alkoxycarbonyl group represented by A in the general formulas (1) and (2) is preferably an alkoxycarbonyl group having 2 to 10 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, and an n-butyloxycarbonyl group. Is mentioned.

  Examples of the acyl group represented by A include an alkylcarbonyl group having 1 to 10 carbon atoms and an arylcarbonyl group, and an alkylcarbonyl group having 1 to 4 carbon atoms is preferable. Specific examples of the alkylcarbonyl group having 1 to 4 carbon atoms include an acetyl group and a propionyl group.

The alkoxysilyl group A represents, for example _{SiRs m (ORs) 3-m} (Rs represents an alkyl group having 1 to 20 carbon atoms, m represents an integer of 0 to 2, Rs of each other are identical or different May be included). Specific examples of the alkyl group having 1 to 20 carbon atoms represented by Rs include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and a sec-butyl group. , T-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, etc., preferably methyl group, ethyl group, i-propyl Group, n-butyl group, t-butyl group and neopentyl group.

  The aromatic hydrocarbon group represented by A means a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring (aromatic hydrocarbon). Specific examples of the aromatic hydrocarbon ring include a benzene ring, And aromatic rings such as naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, perylene ring, and terylene ring. The aromatic hydrocarbon ring is preferably an aromatic hydrocarbon ring having an aromatic ring having 6 to 16 carbon atoms (a condensed ring including an aromatic hydrocarbon ring and an aromatic hydrocarbon ring).

  The heterocyclic group represented by A means a group obtained by removing one hydrogen atom from a heterocyclic ring. Specific examples of the heterocyclic ring include an indene ring, an azulene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and a pyrazole ring. , Pyrazolidine ring, thiazolidine ring, oxazolidine ring, pyran ring, chromene ring, pyrrole ring, pyrrolidine ring, benzimidazole ring, imidazoline ring, imidazolidine ring, imidazole ring, pyrazole ring, triazole ring, triazine ring, diazole ring, indoline ring Thiophene ring, thienothiophene ring, furan ring, oxazole ring, oxadiazole ring, thiazine ring, thiazole ring, indole ring, benzothiazole ring, benzothiadiazole ring, naphthothiazole ring, benzoxazole ring, naphthoxazole ring, indolenine Ring, benzoindole Down ring, a pyrazine ring, a quinoline ring, and aromatic heterocyclic rings such as quinazoline ring; and a fluorene ring, and condensed aromatic heterocycles carbazole ring, and the like. The heterocyclic ring is preferably a heterocyclic group having an aromatic heterocyclic ring having 5 to 16 carbon atoms (a condensed ring including an aromatic heterocyclic ring and an aromatic heterocyclic ring).

  The substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have is not particularly limited, and examples thereof include a sulfo group, a sulfamoyl group, a cyano group, an isocyano group, a thiocyanato group, an isothiocyanato group, and a nitro group. Group, nitrosyl group, halogen atom, hydroxy group, phosphate group, phosphate ester group, amino group, mercapto group, amide group, alkoxy group, aryloxy group, carboxy group, carbamoyl group, acyl group, aldehyde group, carbonyl group And an aromatic hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, and an aliphatic hydrocarbon group which may have a substituent.

  Examples of the halogen atom as the substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom, a bromine atom, Or a chlorine atom is preferable.

  Examples of the phosphate ester group as a substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have include a phosphoric acid (C 1 to C 4) alkyl ester group. Specific examples of the phosphate ester group include a methyl phosphate group, an ethyl phosphate group, a phosphoric acid (n-propyl) group, and a phosphoric acid (n-butyl) group.

  The amino group as a substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have is an amino group; a mono- or dimethylamino group, a mono- or diethylamino group, and mono- or di (n-propyl) An alkyl-substituted amino group such as an amino group; an aryl-substituted amino group such as a mono- or diphenylamino group and a mono- or dinaphthylamino group; an alkyl group and an aromatic hydrocarbon group such as a monoalkylmonophenylamino group; Amino group substituted one by one; a benzylamino group, an acetylamino group, a phenylacetylamino group, and the like.

  The mercapto group as a substituent which the aromatic hydrocarbon group or heterocyclic group represented by A may have includes a mercapto group; a methyl mercapto group, an ethyl mercapto group, an n-propyl mercapto group, an isopropyl mercapto group, n -Alkyl mercapto groups having 1 to 4 carbon atoms such as butyl mercapto group, isobutyl mercapto group, sec-butyl mercapto group and t-butyl mercapto group; phenyl mercapto group and the like.

  Examples of the amide group as a substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have include an amide group, an acetamido group, an N-methylamide group, an N-ethylamide group, and N- (n-propyl). ) Amide group, N- (n-butyl) amide group, N-isobutylamide group, N- (sec-butylamide) group, N- (t-butyl) amide group, N, N-dimethylamide group, N, N -Diethylamide group, N, N-di (n-propyl) amide group, N, N-di (n-butyl) amide group, N, N-diisobutyramide group, N-methylacetamide group, N-ethylacetamide group, N- (n-propyl) acetamide group, N- (n-butyl) acetamide group, N-isobutylacetamide group, N- (sec-butyl) acetamide group, N- (t-butyl) acetamide N, N-dimethylacetamide group, N, N-diethylacetamide group, N, N-di (n-propyl) acetamide group, N, N-di (n-butyl) acetamide group, N, N-diisobutylacetamide group , Phenylamide group, naphthylamide group, phenylacetamide group, naphthylacetamide group, and the like.

  Examples of the alkoxy group as a substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and an isobutoxy group. , Sec-butoxy group, t-butoxy group and the like.

  Examples of the aryloxy group as a substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have include a phenoxy group and a naphthoxy group, and these include a phenyl group or a methyl group as a substituent. You may have.

  Examples of the acyl group as a substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have include an alkylcarbonyl group having 1 to 10 carbon atoms and an arylcarbonyl group, preferably a carbon number. 1 to 4 alkylcarbonyl groups, and specific examples include an acetyl group, a propionyl group, a trifluoromethylcarbonyl group, a pentafluoroethylcarbonyl group, a benzoyl group, and a naphthoyl group.

  Examples of the carbonyl group as the substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, and n-butoxy. Carbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pentoxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-nonyloxycarbonyl group and n- A decyloxycarbonyl group etc. are mentioned.

  Specific examples of the aromatic hydrocarbon group or heterocyclic group as the substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have include the aromatic hydrocarbon group or heterocyclic group represented by A The same thing is mentioned. In addition, the aromatic hydrocarbon group or heterocyclic group as the substituent which the aromatic hydrocarbon group or heterocyclic group represented by A may have may have a substituent, and Includes the same substituents that the aromatic hydrocarbon group or heterocyclic group represented by A may have.

  Examples of the aliphatic hydrocarbon group as the substituent which the aromatic hydrocarbon group or heterocyclic group represented by A may have include a saturated or unsaturated, linear, branched or cyclic alkyl group. The carbon number is preferably 1 to 36, more preferably 1 to 20, and still more preferably 3 to 18. Examples of the cyclic alkyl group include a cycloalkyl group having 3 to 8 carbon atoms. Specific examples of these aliphatic hydrocarbon groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, and n-pentyl group. N-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group N-hexadecyl group, n-heptadecyl group, n-octadecyl group, cyclohexyl group, vinyl group, propenyl group, pentynyl group, butenyl group, hexenyl group, hexadienyl group, isopropenyl group, isohexenyl group, cyclohexenyl group , Cyclopentadienyl group, ethynyl group, propynyl group, pentynyl group, hexynyl group, isohexynyl group, and cyclohexyl group. Group and the like. The aliphatic hydrocarbon group is particularly preferably a linear alkyl group having 3 to 18 carbon atoms. These aliphatic hydrocarbon groups may have a substituent, and the substituent is the same as the substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have. Is mentioned.

  Next, the substituents represented by the formulas (A-1) to (A-5) will be described.

The “optionally substituted aliphatic hydrocarbon group” represented by X ₁ , X ₂ , Y ₁ and Y _{2 in the} formulas (A-1) to (A-5), “amino group”, “ The “alkoxy group” and “halogen atom” are the “optionally substituted aliphatic hydrocarbon group” as the substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have, “ The same as “amino group”, “alkoxy group” and “halogen atom”. “Aromatic hydrocarbon group optionally having substituent (s)” represented by X ₁ , X ₂ , Y ₁ and Y _{2 in} formulas (A-1) to (A-5) The heterocyclic group, “alkoxycarbonyl group” and “acyl group” which may be substituted may each have an “aromatic hydrocarbon group which may have a substituent” or a “substituent” represented by A. The same as “heterocyclic group”, “alkoxycarbonyl group” and “acyl group”.

The carbonamido group represented by X ₁ , X ₂ , Y ₁ and Y _{2 in the} formulas (A-1) to (A-5) is preferably a carbonamido group having 1 to 10 carbon atoms, for example, acetyl An amino group, a propionylamino group, an n-octanoylamino group, a phenylcarbonylamino group, etc. are mentioned.

The “optionally substituted aliphatic hydrocarbon group”, “amino group”, “alkoxy group” and “halogen atom” represented by R _{1 to} R _{8 in the} formulas (A-1) to (A-5) The “amide group” and “aryloxy group” are each an “optionally substituted aliphatic hydrocarbon group” as the substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have. ”,“ Amino group ”,“ alkoxy group ”,“ halogen atom ”,“ amide group ”and“ aryloxy group ”. “Aromatic hydrocarbon group optionally having substituents” represented by R _{1 to} R _{8 in} formulas (A-1) to (A-5) “Heterocycle optionally having substituents” Group, “alkoxycarbonyl group” and “acyl group” are respectively represented by A “aromatic hydrocarbon group which may have a substituent” “heterocyclic group which may have a substituent” “alkoxycarbonyl” The same as “group” and “acyl group”. The “carbonamido group” represented by R _{1 to} R ₈ in Formulas (A-1) to (A-5) is X ₁ , X ₂ , Y in Formulas (A-1) to (A-5). It is the same as the “carbonamido group” represented by ₁ and Y ₂ .

R, R ′ contained in the —CRR′— group, —CR═CR′— group, or —NR ″ — group represented by Z _{1 to} Z _{5 in the} formulas (A-1) to (A-5). And R ″ each independently represents a hydrogen atom or a substituent, a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. Or a heterocyclic group which may have a substituent. The “aliphatic hydrocarbon group optionally having substituent (s)” represented by R, R ′ and R ″ is the substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have. In the “aliphatic hydrocarbon group optionally having substituent (s)”. The “optionally substituted aromatic hydrocarbon group” and the “optionally substituted heterocyclic group” represented by R, R ′, and R ″ each represent “the substituent group represented by A”. It is the same as the “aromatic hydrocarbon group which may be present” and “the heterocyclic group which may have a substituent”.

  Next, the substituent B represented by any one of the formulas (B-1) to (B-4) in the general formulas (1) and (2) will be described.

The “optionally substituted aliphatic hydrocarbon group”, “amino group”, “alkoxy group”, “halogen atom” represented by R _{101 to} R _{106 in} formulas (B-1) to (B-4) "Amido group" is an "optionally substituted aliphatic hydrocarbon group" or "amino group" as the substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have. ”,“ Alkoxy group ”,“ halogen atom ”and“ amide group ”. “Aromatic hydrocarbon group optionally having substituent (s)” represented by R _{101 to} R _{106 in} formulas (B-1) to (B-4) “complex optionally having substituent (s)” The “ring group”, “alkoxycarbonyl group”, and “acyl group” are respectively represented by “an optionally substituted aromatic hydrocarbon group”, “optionally substituted heterocyclic group”, “alkoxy”. The same as “carbonyl group” and “acyl group”. The “carbonamido group” represented by R _{101 to} R _{106 in} Formulas (B-1) to (B-4) is X ₁ , X ₂ in Formulas (A-1) to (A-5), This is the same as the “carbonamido group” represented by Y ₁ and Y ₂ .

The —CRR′— group, —CR═CR′— group, and —NR ″ — group represented by Z _{101 to} Z _{104 in the} above formulas (B-1) to (B-4) are each represented by the formula ( It is the same as the —CRR′— group, —CR═CR′— group, and —NR ″ — group represented by Z _{1 to} Z _{5 in} A-1) to (A-5).

  Next, C in the general formulas (1) and (2) will be described.

  The “optionally substituted aromatic hydrocarbon group” and the “optionally substituted heterocyclic group” represented by C in the general formulas (1) and (2) are each represented by A This is the same as the “optionally substituted aromatic hydrocarbon group” and “optionally substituted heterocyclic group”.

  Next, the substituent represented by Formula (C-1) will be described.

In the formula (C-1), one or more substituents R ₂₀₁ are an aromatic hydrocarbon group which may have a substituent, and an aromatic heterocyclic group which may have a substituent. , An aliphatic hydrocarbon group which may have a substituent, a cyano group, an acyl group, an amide group, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, Or it is preferable that it is a benzenesulfonyl group which may have a substituent. The “optionally substituted aromatic hydrocarbon group”, “(unsubstituted) alkoxycarbonyl group”, “acyl group” represented by one or more substituents R _{201 in the} formula (C-1) ”Is the same as the“ optionally substituted aromatic hydrocarbon group ”,“ alkoxycarbonyl group ”and“ acyl group ”represented by A, and the alkoxycarbonyl group may have a substituent , A is the same as the substituent which the aromatic hydrocarbon group or heterocyclic group represented by A may have. As the “optionally substituted aromatic heterocyclic group” represented by one or more substituents R _{201 in the} formula (C-1), “having a substituent” Examples of the heterocyclic group which may be mentioned include various aromatic heterocyclic groups, and the substituent that the aromatic heterocyclic group may have is the aromatic hydrocarbon group or heterocyclic ring represented by A It is the same as the substituent which the group may have. The “optionally substituted aliphatic hydrocarbon group”, “(unsubstituted) alkoxy group”, “amide group” represented by one or more substituents R _{201 in the} formula (C-1) Are the “optionally substituted aliphatic hydrocarbon group”, “alkoxy group”, “amide group” as the substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have, respectively. It is the same. The substituent that the benzenesulfonyl group represented by one or more substituents R _{201 in the} formula (C-1) may have is an aromatic hydrocarbon group or a heterocyclic group represented by A. It is the same as the substituent which may be present.

The “optionally substituted aliphatic hydrocarbon group” represented by R ₂₀₂ and R ₂₀₃ in the formula (C-1) has an aromatic hydrocarbon group or a heterocyclic group represented by A. This is the same as the “optionally substituted aliphatic hydrocarbon group” as the substituent. The “aromatic hydrocarbon group which may have a substituent” represented by R ₂₀₂ and R ₂₀₃ in the formula (C-1) is the “aromatic carbon which may have a substituent” represented by A. The same as “hydrogen group”.

  Next, the substituent represented by the formula (C-2) will be described.

In formula (C-2), ^* B represents the bonding position with B in the general formulas (1) and (2). In the general formulas (1) and (2), the bonding position with B is preferably on the aromatic ring Ar ₁ or Ar ₂ . p1 represents an integer of 1 to 4, preferably 1 to 2, and more preferably 2. M ₁ represents a metalloid atom selected from the group consisting of boron atom, silicon atom, germanium atom, arsenic atom, antimony atom, and tellurium atom. Examples of the metalloid atom include a boron atom, a silicon atom, a germanium atom, and an antimony atom. The metalloid atom is preferably a boron atom. The R ₂₀₄ to R ₂₀₆ each independently represent a hydrogen atom, an aromatic optionally substituted hydrocarbon group, or optionally substituted heterocyclic group.

“Aromatic hydrocarbon group optionally having substituent (s)” and “heterocyclic group optionally having substituent (s)” represented by R _{204 to} R ₂₀₆ in formula (C-2) are each represented by A. This is the same as “an aromatic hydrocarbon group which may have a substituent” and “heterocyclic group which may have a substituent”.

R ₂₀₄ in formula (C-2) is preferably a hydrogen atom. R ₂₀₅ and R ₂₀₆ in formula (C-2) are each independently preferably an aromatic hydrocarbon group or an aromatic heterocyclic group, more preferably a phenyl group, a naphthyl group, or a thienyl group. Preferably, it is a phenyl group.

In formula (C-2), Q ₁ and Q ₂ each independently represent a halogen atom. Examples of the halogen atom include those similar to the halogen atom as a substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have, and is preferably a fluorine atom. Q ₁ and R ₂₀₅ , and Q ₂ and R ₂₀₆ in formula (C-2) may be connected to each other to form a ring, and R ₂₀₅ and R ₂₀₆ may be an aromatic hydrocarbon group or In the case of an aromatic heterocyclic group, the aromatic hydrocarbon group or substituent on the aromatic heterocyclic group represented by Q ₁ and R _205, and the aromatic hydrocarbon group or aromatic heterocyclic group represented by Q ₂ and R ₂₀₆ The above substituents may be linked together to form a ring.

In formula (C-2), Ar ₁ and Ar ₂ each independently represent an aromatic ring. Specific examples of the aromatic ring include those similar to the aromatic hydrocarbon ring or heteroaromatic ring described as specific examples in the explanation part of the aromatic hydrocarbon group or heterocyclic group represented by A. Ar ₁ and Ar ₂ are each independently preferably a benzene ring, a naphthalene ring, or a thiophene ring, and more preferably a benzene ring.

  The compound represented by the general formula (1) or the following general formula (2) or a salt thereof is, for example, International Publication No. 02/011213, International Publication No. 03/005481, International Publication No. 2004/082061, Patent No. 4610160, JP 2014-196283 A, International Publication No. 2015/137382, and the like.

  Some preferred embodiments of the compound represented by the general formula (1) or the following general formula (2) or a salt thereof are shown below.

A first preferred form of the compound represented by the general formula (1) or the following general formula (2) or a salt thereof is the compound represented by the general formula (1) or a salt thereof,
The combination of r, A, and B is
(A) r is 0 or 1, A is a substituent represented by the formula (A-1), and X ₁ and Y ₁ in the formula (A-1) are each independently a hydrogen atom. , A carboxy group, a cyano group, a phosphoric acid group, or a sulfonic acid group, and R ₁ in the formula (A-1) is a hydrogen atom, an aliphatic hydrocarbon group, a halogen atom, or an alkoxy group, and B is a substituent but represented by the formula (B-1), the formula (B-1) n1 in is an integer of 1 to 5, R ₁₀₁ and R ₁₀₂ in the formula (B-1) Each independently represents a hydrogen atom, an aliphatic hydrocarbon group, a halogen atom, or an alkoxy group,
(B) r is 1, A is a substituent represented by the formula (A-1), and X ₁ and Y ₁ in the formula (A-1) are each independently a hydrogen atom, carboxy A group, a cyano group, a phosphoric acid group, or a sulfonic acid group, R ₁ in the formula (A-1) is a hydrogen atom, an aliphatic hydrocarbon group, a halogen atom, or an alkoxy group; is a substituent represented by formula (B-2), the formula (B-2) n2 is an integer of 1 to 5 in the formula (B-2) R ₁₀₃ and R ₁₀₄ are each in Independently, a hydrogen atom, an aliphatic hydrocarbon group, a halogen atom, or an alkoxy group, and a combination in which Z ₁₀₁ in the formula (B-2) is an oxygen atom, a sulfur atom, or a selenium atom,
(C) r is 0 or 1, A is a formyl group, B is a substituent represented by the formula (B-2), and n2 in the formula (B-2) is 1 to 5 R ₁₀₃ and R ₁₀₄ in the formula (B-2) are each independently a hydrogen atom, an aliphatic hydrocarbon group, a halogen atom, or an alkoxy group, and in the formula (B-2) In which Z ₁₀₁ is an oxygen atom, a sulfur atom, or a selenium atom,
It is one of these.

で表される化合物（特開２０１４−１９６２８３号公報の化合物１９４）が挙げられる。 Such a compound is described in JP2014-196283A. Examples of such compounds include:

(Compound 194 of JP 2014-196283 A).

で表される基であり、Ｚ₄が硫黄原子である置換基、
（ｅ）前記式（Ａ−３）で表され、Ｒ₅がエチル基であり、Ｒ₆が水素原子であり、Ｚ₂が酸素原子であり、Ｚ₃が−Ｃ（ＣＮ）（ＣＯＯＨ）−基であり、Ｚ₄が硫黄原子である置換基、
（ｆ）前記式（Ａ−３）で表され、Ｒ₅がエチル基であり、Ｒ₆が水素原子であり、Ｚ₂が酸素原子であり、Ｚ₃が−Ｃ（ＣＯＯＨ）₂−基であり、Ｚ₄が硫黄原子である置換基、
（ｇ）前記式（Ａ−３）で表され、Ｒ₅がカルボキシメチル基であり、Ｒ₆が４−（ジフェニルアミノ）フェニル基であり、Ｚ₂及びＺ₃が酸素原子であり、Ｚ₄が硫黄原子である置換基、
（ｈ）前記式（Ａ−３）で表され、Ｒ₅がカルボキシメチル基であり、Ｒ₆がｐ−トリル基であり、Ｚ₂が酸素原子であり、Ｚ₃及びＺ₄が硫黄原子である置換基、
の何れか１つであり、
Ｂが、前記式（Ｂ−１）で表され、Ｒ₁₀₁及びＲ₁₀₂が水素原子であり、
Ｃが、下記式（Ｃ−１−１）

（式（Ｃ−１−１）中、Ｒ₁₅は、下記式（１０１）〜（１０５）

の何れか１つで表される芳香族炭化水素基又は芳香族複素環基を表し、Ｒ₁₆及びＲ₁₇の組み合わせは、
（ｉ）Ｒ₁₆及びＲ₁₇がメチル基である組み合わせ、
（ii）Ｒ₁₆が水素原子、Ｒ₁₇がフェニル基である組み合わせ、
（iii）Ｒ₁₆及びＲ₁₇がフェニル基である組み合わせ、
（iv）Ｒ₁₆及びＲ₁₇がｐ−トリル基である組み合わせ、
（ｖ）Ｒ₁₆が２−チエニル基、Ｒ₁₇が水素原子である組み合わせ、
（vi）Ｒ₁₆及びＲ₁₇が２，４−キシリル基である組み合わせ、
（vii）Ｒ₁₆が１−ナフチル基、Ｒ₁₇が水素原子である組み合わせ、
の何れか１つであり、Ｒ₁₈は水素原子又はフェニル基を表し、Ｒ₁₉及びＲ₂₀は水素原子を表し、Ｘ₃は、アミノ基と共に下記式（１０６）〜（１１０）

の何れか１つで表される環状構造を形成する連結基を示し、ｎは０又は１を示す。）
で表される置換基であるものである。 A second preferred embodiment of the compound represented by the general formula (1) or the following general formula (2) or a salt thereof is the compound represented by the general formula (1) or a salt thereof,
m1 is 1,
A is
(A) a substituent represented by the formula (A-1), wherein X ₁ and Y ₁ are carboxy groups,
(B) a substituent represented by the formula (A-1), wherein _one of X ₁ and Y ₁ is a carboxy group and the other is a cyano group;
(C) Substitution represented by the formula (A-3), wherein R ₅ is a carboxymethyl group, R ₆ is a hydrogen atom, Z ₂ is an oxygen atom, and Z ₃ and Z ₄ are sulfur atoms. Group,
(D) Represented by the formula (A-3), R ₅ is an ethyl group, R ₆ is a hydrogen atom, Z ₂ is an oxygen atom, and Z ₃ is

A substituent represented by: Z ₄ is a sulfur atom,
(E) Represented by the formula (A-3), R ₅ is an ethyl group, R ₆ is a hydrogen atom, Z ₂ is an oxygen atom, and Z ₃ is —C (CN) (COOH) — A substituent, wherein Z ₄ is a sulfur atom,
(F) Represented by the formula (A-3), R ₅ is an ethyl group, R ₆ is a hydrogen atom, Z ₂ is an oxygen atom, and Z ₃ is a —C (COOH) ₂ — group. A substituent in which Z ₄ is a sulfur atom,
(G) Represented by the formula (A-3), R ₅ is a carboxymethyl group, R ₆ is a 4- (diphenylamino) phenyl group, Z ₂ and Z ₃ are oxygen atoms, and Z ₄ A substituent in which is a sulfur atom,
(H) Represented by the formula (A-3), R ₅ is a carboxymethyl group, R ₆ is a p-tolyl group, Z ₂ is an oxygen atom, and Z ₃ and Z ₄ are sulfur atoms. A substituent,
Any one of
B is represented by the formula (B-1), R ₁₀₁ and R ₁₀₂ are hydrogen atoms,
C is the following formula (C-1-1)

(In the formula (C-1-1), R ₁₅ represents the following formulas (101) to (105).

Represents an aromatic hydrocarbon group or an aromatic heterocyclic group represented by any one of the following, and the combination of R ₁₆ and R ₁₇ is:
(I) a combination in which R ₁₆ and R ₁₇ are methyl groups;
(Ii) a combination in which R ₁₆ is a hydrogen atom and R ₁₇ is a phenyl group;
(Iii) a combination in which R ₁₆ and R ₁₇ are phenyl groups;
(Iv) a combination in which R ₁₆ and R ₁₇ are p-tolyl groups;
(V) a combination in which R ₁₆ is a 2-thienyl group and R ₁₇ is a hydrogen atom;
(Vi) a combination in which R ₁₆ and R ₁₇ are 2,4-xylyl groups,
(Vii) a combination in which R ₁₆ is a 1-naphthyl group and R ₁₇ is a hydrogen atom;
R ₁₈ represents a hydrogen atom or a phenyl group, R ₁₉ and R ₂₀ represent a hydrogen atom, and X ₃ together with the amino group is represented by the following formulas (106) to (110):

A linking group that forms a cyclic structure represented by any one of the above, n represents 0 or 1; )
It is a substituent represented by these.

で表される化合物（特許第４６１０１６０号公報の化合物（Ａ−４））が挙げられる。
前記一般式（１）又は下記一般式（２）で表される化合物又はその塩の第３の好ましい形態は、前記一般式（１）で表される化合物又はその塩であり、
ｍ１が１であり、ｒが１であり、
Ａが、前記式（Ａ−１）で表される置換基であり、
前記式（Ａ−１）中のＸ₁及びＹ₁がそれぞれ独立に、水素原子、芳香族炭化水素基、芳香族複素環基、脂肪族炭化水素基、カルボキシ基、リン酸基、スルホ基、シアノ基、アシル基、アミド基、アルコキシカルボニル基、又はフェニルスルホニル基であり、
前記式（Ａ−１）中のＲ₁が、水素原子、芳香族炭化水素基、芳香族複素環基、脂肪族炭化水素基、シアノ基、ハロゲン原子、カルボンアミド基、アミド基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アリールカルボニル基、又はアシル基であり、
Ｂが、下記式（Ｂ−１１）

（式（Ｂ−１１）中、^*Ａは前記一般式（１）におけるＡとの結合位置を、^*Ｃは前記一般式（１）におけるＣとの結合位置をそれぞれ表し、
ｊは０乃至３の整数を表し、ｋは１乃至３の整数を表し、ｑは１乃至５の整数（ただし、ｑはｊ＋ｋ＋ｑ≦７を満たす）を表し、
Ｚ₁₁乃至Ｚ₁₃はそれぞれ独立に、酸素原子、硫黄原子、セレン原子、又は−ＮＲ''−基（式中、Ｒ''はそれぞれ独立に水素原子、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又は置換基を有していてもよい脂肪族炭化水素基を表す。）を表し、
Ａ₄は、水素原子、置換基を有していてもよい脂肪族炭化水素基、シアノ基、ハロゲン原子、カルボンアミド基、アルコキシ基、アミド基、アルコキシカルボニル基、又はアシル基を表し、
Ａ₇乃至Ａ₁₀はそれぞれ独立に、水素原子、置換基を有していてもよい脂肪族炭化水素基、シアノ基、ハロゲン原子、カルボンアミド基、アルコキシ基、アルコキシカルボニル基、又はアシル基を表し、
Ｒ₃₀₁は、下記式（３０２）

（式（３０２）中、ｐは０乃至３の整数を表し、ｑは０乃至６の整数を表し、
Ｘ₄及びＹ₄はそれぞれ独立に、水素原子、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、置換基を有していてもよい脂肪族炭化水素基、カルボキシ基、リン酸基、スルホ基、シアノ基、アシル基、アミド基、アルコキシカルボニル基、又は置換基を有していてもよいベンゼンスルホニル基を表し、
Ｚ₁₄は酸素原子、硫黄原子、セレン原子、又は−ＮＲ₁₂−基（Ｒ₁₂は水素原子、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又は置換基を有していてもよい脂肪族炭化水素基を表す）を表し、
Ａ₁₁及びＡ₁₂はそれぞれ独立に、水素原子、置換基を有していてもよい脂肪族炭化水素基、シアノ基、ハロゲン原子、カルボンアミド基、アルコキシ基、アルコキシカルボニル基、又はアシル基を表し、
Ａ₁₃乃至Ａ₁₅はそれぞれ独立に、水素原子、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、置換基を有していてもよい脂肪族炭化水素基、シアノ基、ハロゲン原子、カルボンアミド基、アミド基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アリールカルボニル基、又はアシル基を表す。）
で表される置換基を表し、
Ｃが、前記式（Ｃ−１）で表される置換基であり、前記式（Ｃ−１）中の１個又は複数個の置換基Ｒ₂₀₁は、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、置換基を有していてもよい脂肪族炭化水素基、シアノ基、アシル基、アミド基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアルコキシカルボニル基、又は置換基を有していてもよいベンゼンスルホニル基であり、前記式（Ｃ−１）中のＲ₂₀₂及びＲ₂₀₃はそれぞれ独立に、下記式（３０１）

（式（３０１）中、Ｒ₁₂及びＲ₁₃はそれぞれ独立に、水素原子、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又は置換基を有していてもよい脂肪族炭化水素基を表す。）
で表される置換基であるものである。 Such compounds are described in Japanese Patent No. 4610160. Examples of such compounds include:

(Compound (A-4) of Japanese Patent No. 4610160).
A third preferred embodiment of the compound represented by the general formula (1) or the following general formula (2) or a salt thereof is the compound represented by the general formula (1) or a salt thereof.
m1 is 1, r is 1,
A is a substituent represented by the formula (A-1),
X ₁ and Y ₁ in the formula (A-1) are each independently a hydrogen atom, an aromatic hydrocarbon group, an aromatic heterocyclic group, an aliphatic hydrocarbon group, a carboxy group, a phosphate group, a sulfo group, A cyano group, an acyl group, an amide group, an alkoxycarbonyl group, or a phenylsulfonyl group,
R ₁ in the formula (A-1) is a hydrogen atom, an aromatic hydrocarbon group, an aromatic heterocyclic group, an aliphatic hydrocarbon group, a cyano group, a halogen atom, a carbonamido group, an amide group, an alkoxy group, An aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group, or an acyl group,
B is the following formula (B-11)

(In the formula (B-11), ^* A represents the bonding position with A in the general formula (1), ^* C represents the bonding position with C in the general formula (1),
j represents an integer of 0 to 3, k represents an integer of 1 to 3, q represents an integer of 1 to 5 (where q satisfies j + k + q ≦ 7),
Z _{11 to} Z ₁₃ are each independently an oxygen atom, a sulfur atom, a selenium atom, or a —NR ″ -group (wherein R ″ is independently a hydrogen atom or an aromatic group optionally having a substituent). Represents an aromatic hydrocarbon group, an aromatic heterocyclic group which may have a substituent, or an aliphatic hydrocarbon group which may have a substituent.
A ₄ represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, a cyano group, a halogen atom, a carbonamido group, an alkoxy group, an amide group, an alkoxycarbonyl group, or an acyl group,
A _{7 to} A ₁₀ each independently represent a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, a cyano group, a halogen atom, a carbonamido group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. ,
R ₃₀₁ represents the following formula (302)

(In Formula (302), p represents an integer of 0 to 3, q represents an integer of 0 to 6,
X ₄ and Y ₄ each independently have a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent. Represents an aliphatic hydrocarbon group, a carboxy group, a phosphate group, a sulfo group, a cyano group, an acyl group, an amide group, an alkoxycarbonyl group, or an optionally substituted benzenesulfonyl group,
Z ₁₄ represents an oxygen atom, a sulfur atom, a selenium atom, or a —NR ₁₂ — group (R ₁₂ represents a hydrogen atom, an aromatic hydrocarbon group that may have a substituent, or an aromatic that may have a substituent. Represents a heterocyclic group or an aliphatic hydrocarbon group optionally having substituent (s),
A ₁₁ and A ₁₂ each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, a cyano group, a halogen atom, a carbonamido group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. ,
A _{13 to} A ₁₅ each independently have a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent. And may represent an aliphatic hydrocarbon group, a cyano group, a halogen atom, a carbonamido group, an amide group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group, or an acyl group. )
Represents a substituent represented by
C is a substituent represented by the formula (C-1), and one or more substituents R ₂₀₁ in the formula (C-1) may have a substituent. An aromatic hydrocarbon group that may have a substituent, an aliphatic hydrocarbon group that may have a substituent, a cyano group, an acyl group, an amide group, and a substituent. An optionally substituted alkoxy group, an optionally substituted alkoxycarbonyl group, or an optionally substituted benzenesulfonyl group, wherein R ₂₀₂ and R ₂₀₃ in formula (C-1) are: Independently, the following formula (301)

(In Formula (301), R ₁₂ and R ₁₃ are each independently a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, Or, it represents an aliphatic hydrocarbon group which may have a substituent.)
It is a substituent represented by these.

—NR ″ — groups represented by Z _{11 to} Z _{13 in} Formula (B-11) are represented by —NR ″ represented by Z _{1 to} Z ₅ in Formulas (A-1) to (A-5), respectively. -Same as group. The “aromatic hydrocarbon group which may have a substituent” represented by Z _{11 to} Z ₁₃ in the formula (B-11) is the “aromatic carbon which may have a substituent” represented by A. The same as “hydrogen group”. As the “aromatic heterocyclic group optionally having substituent (s)” represented by Z _{11 to} Z ₁₃ in the formula (B-11), “heterocyclic ring optionally having substituent (s)” represented by A Various aromatic heterocyclic groups mentioned as examples of the “group” can be mentioned, and the substituent that the aromatic heterocyclic group may have is the aromatic hydrocarbon group or heterocyclic group represented by A. It is the same as the substituent which may be. The “aliphatic hydrocarbon group optionally having substituent (s)” represented by Z _{11 to} Z ₁₃ in the formula (B-11) has an aromatic hydrocarbon group or a heterocyclic group represented by A. This is the same as the “optionally substituted aliphatic hydrocarbon group” as the substituent.

The “optionally substituted aliphatic hydrocarbon group”, “halogen atom”, “alkoxy group”, and “amide group” represented by A ₄ in the formula (B-11) are each an aromatic carbon group represented by A. This is the same as the “optionally substituted aliphatic hydrocarbon group”, “halogen atom”, “alkoxy group”, and “amide group” as the substituent that the hydrogen group or heterocyclic group may have. The “carbonamido group” represented by A ₄ in the formula (B-11) is “carvone group” represented by X ₁ , X ₂ , Y ₁ , and Y _{2 in} the formulas (A-1) to (A-5). The same as “amide group”. The “alkoxycarbonyl group” and “acyl group” represented by A ₄ in the formula (B-11) are the same as the “alkoxycarbonyl group” and “acyl group” represented by A, respectively.

The “optionally substituted aliphatic hydrocarbon group”, “halogen atom” and “alkoxy group” represented by A _{7 to} A ₁₀ in the formula (B-11) are each an aromatic hydrocarbon represented by A. This is the same as the “optionally substituted aliphatic hydrocarbon group”, “halogen atom”, and “alkoxy group” as the substituents that the group or heterocyclic group may have. The “carbonamido group” represented by A _{7 to} A ₁₀ in the formula (B-11) is such that X ₁ , X ₂ , Y ₁ , and Y _{2 in} the formulas (A-1) to (A-5) are This is the same as the “carbonamido group” represented. The “alkoxycarbonyl group” and “acyl group” represented by A _{7 to} A ₁₀ in the formula (B-11) are the same as the “alkoxycarbonyl group” and “acyl group” represented by A, respectively.

The “optionally substituted aromatic hydrocarbon group”, “acyl group”, and “alkoxycarbonyl group” represented by X ₄ and Y ₄ in the above formula (302) have the “substituent group” represented by A. It is the same as the aromatic hydrocarbon group, “acyl group” and “alkoxycarbonyl group” which may be present. As the “aromatic heterocyclic group optionally having substituent (s)” represented by X ₄ and Y ₄ in the formula (302), “heterocyclic group optionally having substituent (s)” represented by A The aromatic heterocyclic group which the aromatic heterocyclic group which A showed may be mentioned and the aromatic heterocyclic group which the aromatic heterocyclic group mentioned as an example may have may have. Similar to good substituents. The “optionally substituted aliphatic hydrocarbon group” and “amide group” represented by X ₄ and Y ₄ in the formula (302) are each an aromatic hydrocarbon group or a heterocyclic group represented by A. This is the same as the “optionally substituted aliphatic hydrocarbon group” and “amide group” as the optionally substituted substituents. The substituent that the benzenesulfonyl group represented by X ₄ and Y ₄ in the formula (302) may have is the substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have It is the same.

The “optionally substituted aromatic hydrocarbon group” represented by R ₁₂ in the —NR ₁₂ — group represented by Z ₁₄ in the formula (302) has the “substituted group” represented by A. It is the same as the “aromatic hydrocarbon group which may be”. As the “aromatic heterocyclic group optionally having substituent (s)” represented by R ₁₂ in the —NR ₁₂ — group as Z ₁₄ in the formula (302), “having a substituent” Examples of the heterocyclic group that may be included include various aromatic heterocyclic groups, and the substituent that the aromatic heterocyclic group may have is an aromatic hydrocarbon group or a heterocyclic group represented by A. This is the same as the substituent that the ring group may have. The “optionally substituted aliphatic hydrocarbon group” represented by R ₁₂ in the —NR ₁₂ — group represented by Z ₁₄ in the formula (302) is an aromatic hydrocarbon group or a complex represented by A This is the same as the “aliphatic hydrocarbon group optionally having substituent (s)” as the substituent that the ring group may have.

The “optionally substituted aliphatic hydrocarbon group”, “halogen atom” and “alkoxy group” represented by A ₁₁ and A ₁₂ in the formula (302) are each an aromatic hydrocarbon group represented by A or This is the same as the “optionally substituted aliphatic hydrocarbon group”, “halogen atom”, and “alkoxy group” as the substituent that the heterocyclic group may have. The “carbonamido group” represented by A ₁₁ and A ₁₂ in the formula (302) is represented by X ₁ , X ₂ , Y ₁ , and Y _{2 in} the formulas (A-1) to (A-5). The same as “carbonamide group”. The “alkoxycarbonyl group” and “acyl group” represented by A ₁₁ and A ₁₂ in the formula (302) are the same as the “alkoxycarbonyl group” and “acyl group” represented by A, respectively.

The “optionally substituted aromatic hydrocarbon group”, “alkoxycarbonyl group”, and “acyl group” represented by A _{13 to} A ₁₅ in the formula (302) are each represented by “having a substituent”. And the same as the aromatic hydrocarbon group, “alkoxycarbonyl group”, and “acyl group”. The “aromatic heterocyclic group which may have a substituent” represented by A _{13 to} A ₁₅ in the formula (302) is “the heterocyclic group which may have a substituent” represented by A. The aromatic heterocyclic group which the aromatic heterocyclic group which A showed may be mentioned and the aromatic heterocyclic group which the aromatic heterocyclic group mentioned as an example may have may have. Similar to good substituents. The “optionally substituted aliphatic hydrocarbon group”, “halogen atom”, “amide group”, “alkoxy group” and “aryloxy group” represented by A _{13 to} A ₁₅ in the formula (302) are respectively “Aliphatic hydrocarbon group optionally having substituent (s)” “halogen atom” “amide group” “alkoxy group” as the substituent that the aromatic hydrocarbon group or heterocyclic group represented by A may have And “aryloxy group”. The “carbonamido group” represented by A _{13 to} A ₁₅ in the formula (302) is represented by X ₁ , X ₂ , Y ₁ , and Y _{2 in} the formulas (A-1) to (A-5). The same as “carbonamide group”.

The aryl group represented by A ₁₃ to A ₁₅ in the formula (302), for example benzoyl, mono- or bicyclic aryl group having 6 to 10-membered, such as naphthoyl carbonyl group substituted.

The “optionally substituted aromatic hydrocarbon group” represented by R ₁₂ and R ₁₃ in the formula (301) represents the “optionally substituted aromatic hydrocarbon group represented by A”. Is the same. As the “aromatic heterocyclic group optionally having substituent (s)” represented by R ₁₂ and R _{13 in} formula (301), “heterocyclic group optionally having substituent (s)” represented by A The aromatic heterocyclic group which the aromatic heterocyclic group which A showed may be mentioned and the aromatic heterocyclic group which the aromatic heterocyclic group mentioned as an example may have may have. Similar to good substituents. The “aliphatic hydrocarbon group optionally having substituent (s)” represented by R ₁₂ and R ₁₃ in the formula (301) may be the aromatic hydrocarbon group or heterocyclic group represented by A. It is the same as the “aliphatic hydrocarbon group which may have a substituent” as a good substituent.

で表される化合物（国際公開第２０１５／１３７３８２号の化合物１）が挙げられる。 Such compounds are described in WO2015 / 137382. Examples of such compounds include:

(Compound 1 of International Publication No. 2015/137382).

(Configuration of water-splitting photoelectrochemical cell)
The water-splitting photoelectrochemical cell of the present invention includes a photoelectrode containing compound semiconductor fine particles and a sensitizing dye (the organic dye compound) supported on the compound semiconductor fine particles.

  As the compound semiconductor particles, oxide semiconductor fine particles are preferable, and metal oxide semiconductor fine particles are more preferable. Specific examples of the metal oxide constituting the metal oxide semiconductor fine particles include oxides of metals such as titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, and vanadium. Of these metal oxides, metal oxides such as titanium, tin, zinc, niobium, and indium are preferable, and titanium oxide, zinc oxide, and tin oxide are most preferable. The average particle size of the compound semiconductor fine particles is usually 1 to 500 nm, preferably 1 to 100 nm. In addition, compound semiconductor fine particles may be used by mixing compound semiconductor fine particles having a large particle size and compound semiconductor fine particles having a small particle size, or by using a compound semiconductor fine particle having a large particle size and a compound semiconductor fine particle having a small particle size as a multilayer. You can also. The compound semiconductor fine particles can be used alone, but can also be used by mixing with other components or coating the surface of the semiconductor.

  The semiconductor particles preferably constitute a photoelectrode by being provided on a substrate as a thin film. The thickness of the semiconductor thin film is usually 1 to 200 μm, preferably 1 to 50 μm.

  As the substrate, a light-transmitting substrate whose surface is conductive is preferable, and such a light-transmitting substrate whose surface is conductive is easily available in the market. Examples of such a light-transmitting substrate having a conductive surface include a conductive metal oxide on the surface of a transparent substrate made of a transparent polymer material such as polyethylene terephthalate or polyether sulfone or glass. An object thin film or a metal thin film can be used. Examples of conductive metal oxide thin films include thin films of conductive metal oxides such as tin oxide doped with indium, fluorine, or antimony. Examples of metal thin films include thin films of metals such as copper, silver, and gold. Is mentioned. The conductive metal oxide thin film is preferably a transparent conductive metal oxide thin film such as tin oxide doped with indium, fluorine, or antimony. Such a translucent substrate having an electrically conductive surface may be any substrate as long as it exhibits an electrical resistance of usually 1000Ω or less, and particularly preferably an electrical resistance of 100Ω or less.

  As a method of forming a thin film of semiconductor particles on a substrate, a compound semiconductor fine particle is directly formed on the substrate by spray spraying or the like, and a compound semiconductor fine particle is electrically formed into a thin film using the substrate as an electrode. A method of depositing on a substrate, a paste containing fine particles obtained by hydrolyzing a precursor of compound semiconductor fine particles such as a slurry of compound semiconductor fine particles or semiconductor alkoxide, and then drying, curing or baking Etc. can be used. In view of the performance of the photoelectrode, a method using a slurry is preferable. In the case of this method, the slurry can be obtained by dispersing secondary agglomerated compound semiconductor fine particles in a dispersion medium so that the average primary particle diameter is 1 to 200 nm by a conventional method.

  The dispersion medium for dispersing the slurry may be anything as long as the compound semiconductor fine particles can be dispersed. Water, alcohols such as ethanol, ketones such as acetone and acetylacetone, hydrocarbons such as hexane, and the like are used. In addition, the use of water is preferable in that the viscosity change of the slurry is reduced. In addition, a dispersion stabilizer can be used for the purpose of stabilizing the dispersion state of the compound semiconductor fine particles. Examples of the dispersion stabilizer that can be used include acids such as acetic acid, hydrochloric acid, and nitric acid, and organic solvents such as acetylacetone, acrylic acid, polyethylene glycol, and polyvinyl alcohol.

  The substrate coated with the slurry may be fired, and the firing temperature is usually 100 ° C. or higher, preferably 200 ° C. or higher, and the upper limit is generally lower than the melting point (softening point) of the material of the substrate. Preferably, it is 600 degrees C or less. The firing time is not particularly limited, but is preferably within 4 hours.

  After the formation of the semiconductor particle thin film, the compound semiconductor fine particle thin film may be subjected to a secondary treatment. For example, when the compound semiconductor fine particles are metal oxide semiconductor particles, the compound semiconductor fine particles together with the substrate directly in a solution of alkoxide, chloride, nitride, sulfide, etc. of the same metal as the metal constituting the metal oxide semiconductor particles The performance of the thin film of compound semiconductor fine particles can be improved by immersing and drying or refiring the thin film. Examples of the metal alkoxide include titanium ethoxide, titanium isopropoxide, titanium t-butoxide, n-dibutyl-diacetyltin, and alcohol solutions thereof are used. Examples of the chloride include titanium tetrachloride, tin tetrachloride, zinc chloride and the like, and an aqueous solution thereof is used. The semiconductor thin film thus obtained is composed of compound semiconductor fine particles.

Next, a method for supporting a sensitizing dye on compound semiconductor fine particles will be described.
As a method of supporting the sensitizing dye on the compound semiconductor fine particles, a sensitizing dye solution obtained by dissolving the sensitizing dye in a solvent capable of dissolving the sensitizing dye, or a sensitizing dye having low solubility is used. For example, a method of immersing a thin film of compound semiconductor fine particles in a sensitizing dye dispersion obtained by dispersing a sensitizing dye is mentioned. When a photoelectrode is formed by providing a thin film of semiconductor particles on a substrate, in this method, the thin film of semiconductor particles provided on the substrate may be immersed in a sensitizing dye solution or dispersion. The immersion temperature is generally from room temperature to the boiling point of the solvent, and the immersion time is about 1 minute to 48 hours. Specific examples of solvents that can be used to dissolve the sensitizing dye include, for example, methanol, ethanol, isopropanol, tetrahydrofuran (THF), acetonitrile, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), acetone, n-butanol, Examples thereof include t-butanol, water, n-hexane, chloroform, dichloromethane, toluene and the like, and can be used alone or in combination according to the solubility of the sensitizing dye. The concentration of the sensitizing dye in the solution is usually 1 × 10 ⁻⁶ M to 1M, and preferably 1 × 10 ⁻⁵ M to ¹ × 10 ⁻¹ M. After immersion, the solvent is removed by air drying or heating if necessary.

  The sensitizing dye supported on the compound semiconductor fine particles may be one kind of sensitizing dye or a mixture of plural kinds of sensitizing dyes. In particular, by mixing a plurality of types of sensitizing dyes having different absorption wavelengths, a wide range of absorption wavelengths can be used, and an efficient water-splitting photoelectrochemical cell can be obtained. When multiple types of sensitizing dyes are used, even if multiple types of sensitizing dyes are sequentially adsorbed on the thin film of compound semiconductor particles, multiple types of sensitizing dyes are mixed and dissolved and adsorbed on the thin film of compound semiconductor particles. May be.

  When the dye is supported on the thin film of compound semiconductor fine particles, it is advantageous to support the sensitizing dye in the presence of the inclusion compound in order to prevent the association between the dyes. Examples of the inclusion compound include steroidal compounds such as cholic acid, crown ether, cyclodextrin, calixarene, polyethylene oxide and the like. Specific examples of preferable compounds include deoxycholic acid, dehydrodeoxycholic acid, chenodeoxycholic acid. And cholic acids such as cholic acid methyl ester and sodium cholate, and polyethylene oxide. Further, after the sensitizing dye is supported, the thin film of compound semiconductor fine particles may be treated with an amine compound such as 4-t-butylpyridine. As a treatment method, for example, a method in which a substrate provided with a thin film of compound semiconductor fine particles carrying a sensitizing dye in an ethanol solution of amine can be used.

  In this manner, a photoelectrode containing compound semiconductor fine particles carrying a sensitizing dye can be obtained.

The water-splitting photoelectrochemical cell of the present invention preferably contains a reducing electrode facing the photoelectrode, an aqueous solution containing an electrolyte, in addition to the photoelectrode, and the water-splitting photoelectric cell A light transmissive container capable of transmitting the light applied to the water-splitting photoelectrochemical cell from the outside of the chemical cell to the photoelectrode, wherein the photoelectrode and the reduction electrode are respectively used as a negative electrode and a positive electrode. Arranged in the light-transmitting container so as to be opposed to each other, the negative electrode and the positive electrode are electrically connected to each other directly or via an external circuit, and the photoelectrode is the compound semiconductor This is a configuration provided with a compound semiconductor thin film composed of fine particles. By irradiating the negative electrode (photoelectrode) with light, water is oxidized at the negative electrode (photoelectrode) to generate hydrogen peroxide, and at the positive electrode (reduction electrode), protons are reduced to generate hydrogen, Is decomposed into hydrogen peroxide (H ₂ O ₂ ) and hydrogen.

  The reduction electrode is preferably one that catalytically advances the reduction reaction of the electrolyte in water. As the reducing electrode, for example, a glass or polymer film deposited with platinum, carbon, rhodium, ruthenium, or the like, or a conductive fine particle coated on glass or a polymer film can be used.

  The inside of the light transmissive container is usually partitioned by a diaphragm into a negative electrode chamber containing a negative electrode and a positive electrode chamber containing a positive electrode. Examples of the membrane include ion exchange membranes such as a copolymer (trade name “NAFION (registered trademark))” of tetrafluoroethylene and perfluoro [2- (fluorosulfonylethoxy) propyl vinyl ether], which are proton-selective membranes. Can be used.

(Embodiment of Water-Splitting Photoelectrochemical Cell)
Next, one embodiment of the water-splitting photoelectrochemical cell will be described with reference to FIGS.

  As shown in FIG. 1, a water-splitting photoelectrochemical cell 10 according to an embodiment of the present invention includes a photoelectrode 3 having the above-described configuration, a reducing electrode 4 facing the photoelectrode 3, and an aqueous solution 1 containing an electrolyte. , And the light that has been applied to the water-splitting photoelectrochemical cell from a light source 6 outside the water-splitting photoelectrochemical cell (such as the sun or an artificial light source (for example, a xenon lamp)). A light transmissive container 2 capable of transmitting to the electrode is provided, and the photo electrode 3 and the reduction electrode 4 are inserted into the light transmissive container 2 so as to be opposed to each other as a negative electrode and a positive electrode, respectively. The electrode 3 and the reduction electrode 4 are electrically connected via an external circuit 5 so that the photoelectrode 3 can receive light from the light source 6. As schematically shown in FIG. 2, the photoelectrode 3 includes a substrate 3a, a compound semiconductor thin film composed of the compound semiconductor fine particles 3b formed on the substrate 3a, and a sensitizing dye supported on the compound semiconductor fine particles 3b. 3c. The external circuit 5 may be any circuit that enables electrical connection between the photoelectrode 3 and the reduction electrode 4, and the external circuit 5 may be replaced with a short-circuit line.

  In the water-splitting photoelectrochemical cell 10, as shown in FIG. 2, when light from the light source 8 is irradiated to the sensitizing dye 3c, the molecules of the sensitizing dye 3c are photoexcited to form electrons into the compound semiconductor fine particles 3b. Inject into the conduction band of the semiconductor. At the photoelectrode 3, the excited sensitizing dye 3c oxidizes water (acquires electrons from water) to generate hydrogen peroxide and protons. On the other hand, the electrons injected into the semiconductor conduction band constituting the compound semiconductor fine particles 3 b reach the reduction electrode 4 through the substrate 3 a and the external circuit 5. Then, protons generated at the photoelectrode 3 receive electrons at the reduction electrode 4 and are reduced to generate hydrogen. The water-splitting photoelectrochemical cell according to the present invention is fundamentally different from the photocatalytic system of Non-Patent Document 2 in that the sensitizing dye itself oxidizes water and acquires electrons from water.

  Since water-splitting photoelectrochemical cells can generate hydrogen by the decomposition of water by light, hydrogen production equipment that produces hydrogen using light energy and hydrogen peroxide that produces hydrogen peroxide using light energy It can be used as a manufacturing device.

  The hydrogen production apparatus of the present invention may be provided with the water-splitting photoelectrochemical cell of the present invention, and is preferably for accommodating a reducing electrode facing the photoelectrode and an aqueous solution containing an electrolyte. A light transmissive container capable of transmitting the light irradiated to the water-splitting photoelectrochemical cell from the outside of the water-splitting photoelectrochemical cell to the photoelectrode, the photoelectrode and the reduction The electrodes are disposed in the light-transmitting container and are electrically connected to each other, and the photoelectrode includes a compound semiconductor thin film composed of the compound semiconductor fine particles, and the light-transmitting container includes An aqueous solution containing an electrolyte is contained in the photoelectrode and the reducing electrode, and the water-splitting photoelectrochemical cell is irradiated with light from outside the water-splitting photoelectrochemical cell. Sometimes said A structure for generating hydrogen under the electrode.

  The hydrogen peroxide production apparatus of the present invention may be provided with the water-splitting photoelectrochemical cell of the present invention, preferably, for containing a reducing electrode facing the photoelectrode and an aqueous solution containing an electrolyte. A light transmissive container capable of transmitting light irradiated to the water-splitting photoelectrochemical cell from the outside of the water-splitting photoelectrochemical cell to the photoelectrode; And the reduction electrode are disposed in the light transmissive container and are electrically connected to each other, and the photoelectrode includes a compound semiconductor thin film composed of the compound semiconductor fine particles, and the light transmissive An aqueous solution containing an electrolyte is contained in a container, and the photoelectrode and the reduction electrode are immersed in the aqueous solution, and light is applied to the water-splitting photoelectrochemical cell from the outside of the water-splitting photoelectrochemical cell. When It is configured to generate hydrogen peroxide in the photoelectrode.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.

[Example 1]
The experimental water-splitting photoelectrochemical cell 10A according to this example is substantially the same as the water-splitting photoelectrochemical cell 10 of FIG. 1 as shown in FIG. 3, but the water-splitting photoelectrochemical cell of FIG. In addition to the constituent elements included in 10, a reference electrode 7 made of Ag / AgCl inserted into the light transmissive container 2 and connected to the external circuit 5 to measure the photocurrent, and the inside of the light transmissive container 2 Is provided with a negative electrode chamber including a photoelectrode (negative electrode) 3 and a positive electrode chamber including a reduction electrode (positive electrode) 4.

で表される化合物（特開２０１４−１９６２８３号公報の化合物１９４；以下、「ＢＯＤＩＰＹ」と略記する）を用い、基板３ａ及び化合物半導体微粒子３ｂとして、フッ素ドープ酸化スズ（ＦＴＯ）薄膜をガラス板上に形成してなる透明導電性ガラス基板上に、酸化チタン微粒子薄膜を９ｍｍ×９ｍｍのサイズで膜厚９μｍとなるように形成してなる半導体薄膜電極（以下、「ＦＴＯ／ＴｉＯ₂」と略記する）を用いた。そして、光電極３を以下のようにして作製した。すなわち、ＢＯＤＩＰＹのメタノール溶液を、ＦＴＯ／ＴｉＯ₂における多孔質酸化チタン膜上に１２時間かけて堆積させることにより、ＢＯＤＩＰＹをＦＴＯ／ＴｉＯ₂に吸着させて、光電極３を作成した。 In this example, the following structural formula is used as the sensitizing dye 3c.

And a fluorine-doped tin oxide (FTO) thin film on a glass plate as the substrate 3a and the compound semiconductor fine particles 3b, using a compound represented by the following formula (Compound 194 of JP-A-2014-196283; hereinafter abbreviated as “BODIPY”): On a transparent conductive glass substrate formed on a semiconductor thin film electrode (hereinafter referred to as “FTO / TiO ₂ ”), a titanium oxide fine particle thin film having a size of 9 mm × 9 mm and a film thickness of 9 μm is formed. ) Was used. And the photoelectrode 3 was produced as follows. That is, a photoelectrode 3 was prepared by adsorbing BODIPY on FTO / TiO ₂ by depositing a methanol solution of BODIPY on a porous titanium oxide film in FTO / TiO ₂ over 12 hours.

  The resulting photoelectrode 3 was used as a working electrode and incorporated into a water-splitting photoelectrochemical cell 10A as shown in FIG. In this example, the reduction electrode 4 was formed by sputtering platinum on a conductive substrate, and the photoelectrode 3 and the reduction electrode 4 were connected via an external circuit 5. In this example, water (sodium sulfate aqueous solution) 1 containing sodium sulfate at a concentration of 0.1 M was used as the electrolyte.

で表される化合物（特許第４６１０１６０号公報の化合物（Ａ−４）；以下、「Ｄ１０２」と略記する）を用いたこと以外は、実施例１と同様にして、実験用の水分解光電気化学セル１０Ａを作製した。 [Example 2]
In this example, as the sensitizing dye 3c, instead of BODIPY, the following structural formula

In the same manner as in Example 1, except that a compound represented by the formula (Compound (A-4) of Japanese Patent No. 4610160; hereinafter abbreviated as “D102”) was used, A chemical cell 10A was produced.

[Control]
A control cell was produced in the same manner as in the production of the water-splitting photoelectrochemical cell 10A in the same manner as in Example 1 except that the sensitizing dye 3c was not used.

[Constant potential measurement of photocurrent]
For each of the water-splitting photoelectrochemical cell of Example 1, the water-splitting photoelectrochemical cell of Example 2, and the control cell, a 300 W xenon lamp (manufactured by Asahi Spectroscopic Co., Ltd.) was used as the light source 6, and this xenon was used. Light from the lamp was applied to the photoelectrode 3 through a 400 nm long-pass filter 9, and the photocurrent waveform at an applied voltage (bias voltage) of 0 V was measured. The measurement results of the water-splitting photoelectrochemical cell of Example 1, the water-splitting photoelectrochemical cell of Example 2, and the control cell are shown by a broken line, a solid line, and an alternate long and short dash line in FIG.

As shown in FIG. 5, the water-splitting photoelectrochemical cell of Example 2 shows a remarkably high photocurrent (600 μA / cm ² ) and is considered to have a high hydrogen generation efficiency, but a photocurrent exceeding 200 μA / cm ^2. The time for maintaining the value was 1500 seconds. The water-splitting photoelectrochemical cell of Example 1 had a low photocurrent of 140 μA / cm ² compared to the water-splitting photoelectrochemical cell of Example ² , but had a photocurrent value exceeding 50 μA / cm ^2. The maintenance time was 1 hour, which was superior to the stability. In addition, it is considered that the decrease in photocurrent with time is due to the detachment of the sensitizing dye molecules from the titanium oxide fine particles (nanoparticles).

[Gas analysis]
Each of the control cell (FTO / TiO ₂ ), the water-splitting photoelectrochemical cell of Example 1 (FTO / TiO ₂ / BODIPY), and the water-splitting photoelectrochemical cell of Example 2 (FTO / TiO ₂ / D102) The gas (hydrogen, oxygen, and hydrogen peroxide) when irradiated with light was analyzed in the same manner as in the constant potential measurement of photocurrent. The amount of oxygen dissolved in the aqueous solution is measured using a dissolved oxygen meter (dissolved oxygen / thermometer manufactured by Delta Ohm, model number “HD 2109.2”), and the amount of hydrogen gas in the positive electrode chamber is measured as hydrogen gas. Measurement was performed using a detector (high sensitivity combustible gas detector manufactured by Shin Cosmos Electric Co., Ltd., model number “XP-3160”), and the presence of hydrogen peroxide was detected using an acidic solution of potassium permanganate. The obtained results are shown in Table 1.

  In any of the water-splitting photoelectrochemical cells of Example 1 and Example 2, the amount of hydrogen gas shown in Table 1 was detected in the positive electrode chamber. As a result of measuring the amount of oxygen in the aqueous solution, it was confirmed that oxygen gas was not generated. As a result of the presence test of hydrogen peroxide using an acidic solution of potassium permanganate, the generation of hydrogen peroxide was detected in the water-splitting photoelectrochemical cell of Example 2. This suggests that the oxidation of water at the negative electrode proceeds through the production of hydrogen peroxide.

  Thus, in the water-splitting photoelectrochemical cells of Example 1 and Example 2, when the xenon lamp was irradiated at a neutral pH, at a bias voltage of 0 V, and in the absence of a water oxidation catalyst. Hydrogen evolution and the accompanying photocurrent were observed.

で表される化合物（国際公開第２００２／０１１２１３号の化合物（７）；以下、「ＮＫ−００３」と称する）を、Ｎ，Ｎ−ジエチルアミノベンズアルデヒドに代えて４−（Ｎ，Ｎ−ジフェニルアミノ）ベンズアルデヒドを使用したこと以外は国際公開第２００２／０１１２１３号の合成例１と同様にして合成した。 [Synthesis Example 1 of Sensitizing Dye]
As a sensitizing dye, the following structural formula

4- (N, N-diphenylamino) in place of N, N-diethylaminobenzaldehyde instead of the compound represented by the formula (Compound (7) of International Publication No. 2002/011213; hereinafter referred to as “NK-003”) The synthesis was performed in the same manner as in Synthesis Example 1 of WO2002 / 011213 except that benzaldehyde was used.

  That is, 1 part by mass of cyanoacetic acid and 3.1 parts by mass of 4- (N, N-diphenylamino) benzaldehyde were dissolved in 10 parts by mass of ethanol, and 0.6 part by mass of piperazine anhydride was added dropwise thereto. After reacting at reflux for 2 hours, the cooled solid was filtered, washed and dried, then recrystallized with a mixed solvent of ethanol and hexane (ethanol / hexane = 3/1), filtered, washed, And dried to obtain NK003.

で表される化合物（８）（ロダニン含有ジベンゾＢＯＤＩＰＹ；以下、「Ｒｈｏ−ＢＯＤＩＰＹ」と称する）を次に示すスキームで合成した。 [Synthesis Example 2 of Sensitizing Dye]
As a sensitizing dye, the following structural formula

(8) (Rhodanine-containing dibenzo BODIPY; hereinafter referred to as “Rho-BODIPY”) was synthesized according to the following scheme.

[Synthesis of 1- (2-benzoyl-5-bromophenyl) ethane-1-one (compound (2))]
2- [1- (5-Bromo-2-hydroxyphenyl) ethylidene] hydrazide (compound (1); CZ Zheng, L. Wang, J. Liu, Adv. Mater. Res., 2011, 239- 242, p.2153-2157) 16.8 g (37.8 mmol) of lead (IV) acetate (Pb (OAc) ₄ ) was added dropwise to 540 mL of tetrahydrofuran (THF) in which 10.4 g (31.5 mmol) was dissolved. And stirred at room temperature for 2 hours. After removing Pb (OAc) ₄ from the reaction solution, the solvent was distilled off. As a result, 8.97 g of the compound (2) was obtained (yield 93%).

¹Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ₃）：δ（ｐｐｍ）＝２．５０（ｓ，３Ｈ，Ｈ_a），７．３０（ｄ，１Ｈ，Ｊ＝８．１５Ｈｚ，Ｈ_d），７．４３（ｔｔ，２Ｈ，Ｊ＝７．７０ ａｎｄ １．５７ Ｈｚ，Ｈ_f，），７．５６（ｔｔ，１Ｈ，Ｊ＝７．４３ ａｎｄ １．４５ Ｈｚ，Ｈ_g），７．７２（ｄｔ，２Ｈ，Ｊ＝６．８５ ａｎｄ １．５５ Ｈｚ，Ｈ_e），７．７５（ｄｄ，１Ｈ，Ｊ＝８．１０ ａｎｄ １．９０ Ｈｚ，Ｈ_c），７．９６（ｄ，１Ｈ，Ｊ＝１．９０Ｈｚ，Ｈ_b）
ＦＡＢ−ＭＳ：ｍ／ｚ＝３０１［Ｍ］⁺ The measurement results of ¹ H NMR (nuclear magnetic resonance) spectrum and FAB (fast atom bombardment method) -MS (mass spectrometry spectrum) of compound (2) are shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ (ppm) = 2.50 (s, 3H, H _a ), 7.30 (d, 1H, J = 8.15 Hz, H _d ), 7.43 (tt , 2H, J = 7.70 and 1.57 Hz, H f,), 7.56 (tt, 1H, J = 7.43 and 1.45 Hz, H g), 7.72 (dt, 2H, J = 6.85 and 1.55 Hz, H e), 7.75 (dd, 1H, J = 8.10 and 1.90 Hz, H c), 7.96 (d, 1H, J = 1. 90Hz, H _b )
FAB-MS: m / z = 301 [M] ⁺

[Synthesis of (Z) -6-bromo-1-((6-bromo-3-phenyl-2H-isoindol-1-yl) methylene) -3-phenyl-1H-isoindole (compound (3))]
77 mL of acetic acid was added to 385 mL of an ethanol (EtOH) solution of 8.97 g (29.6 mmol) of compound (2) at room temperature. Thereafter, 13.7 g (178 mmol) of ammonium acetate and 1.58 g (29.6 mmol) of ammonium chloride were added at 65 ° C. The mixed solution was stirred at 90 ° C. for 5 hours and poured into a saturated aqueous sodium hydrogen carbonate solution. The resulting precipitate was recrystallized using dichloromethane and methanol to obtain 4.91 g of compound (3) (yield 60%).

¹Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ₃）：δ＝（ｐｐｍ）７．３７（ｄｄ，２Ｈ，Ｊ＝８．５５ ａｎｄ １．７０ Ｈｚ，Ｈ_c），７．４５（ｓ，１Ｈ，Ｈ_a），７．４８（ｔｔ，２Ｈ，Ｊ＝７．４０ ａｎｄ １．４１ Ｈｚ，Ｈ_g），７．５７（ｔ，４Ｈ，Ｊ＝７．６５Ｈｚ，Ｈ_f），７．８６（ｄ，２Ｈ，Ｊ＝８．６５Ｈｚ，Ｈ_d），７．９８（ｄｄ，４Ｈ，Ｊ＝８．１５ ａｎｄ １．０ Ｈｚ，Ｈ_e），８．０４（ｄ，２Ｈ，Ｊ＝１．２５Ｈｚ，Ｈ_b）
ＦＡＢ−ＭＳ：ｍ／ｚ＝５５３［Ｍ］⁺ The measurement results of ¹ H NMR spectrum and FAB-MS of compound (3) are shown below.

_{^{1 H NMR (500MHz, CDCl 3}} ): δ = (ppm) 7.37 (dd, 2H, J = 8.55 and 1.70 Hz, H c), 7.45 (s, 1H, H a), 7.48 (tt, 2H, J = 7.40 and 1.41 Hz, H _g ), 7.57 (t, 4H, J = 7.65 Hz, H _f ), 7.86 (d, 2H, J _{= 8.65Hz, H d), 7.98} (dd, 4H, J = 8.15 and 1.0 Hz, H e), 8.04 (d, 2H, J = 1.25Hz, H b)
FAB-MS: m / z = 553 [M] ⁺

[Difluoro [6-bromo-1-[[6-bromo-3-phenyl-2H-isoindol-1-yl] methylene] -3-phenyl-1H-isoindolate-N ¹ , N ² ] boron (compound Synthesis of (4))
Under a nitrogen atmosphere, 1.91 g (3.45 mmol) of compound (3) was dissolved in 140 mL of dry toluene, and 0.70 mL (0.505 mmol) of triethylamine (NEt ₃ ) was added to the resulting solution. Furthermore, the after solution to the boron trifluoride diethyl ether complex _{(BF 3 · EtO 2) 4.5mL} (35.8mmol) was added at 80 ° C., it was the mixture solution was stirred for 3 hours at 100 ° C.. The reaction solution was poured into water and extracted with methylene chloride. The organic layer was washed with water and dried over sodium sulfate. After the solvent was distilled off, 0.806 g of a solid compound (4) was obtained (yield 39%).

¹Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ₃）：δ（ｐｐｍ）＝７．３４（ｄｄ，２Ｈ，Ｊ＝８．７２ ａｎｄ １．６２ Ｈｚ，Ｈ_c），７．４６-７．５２（ｍ，８Ｈ，Ｈ_d，Ｈ_f，Ｈ_g，ａｎｄ Ｈ_h），７．７７（ｄｄ，４Ｈ，Ｊ＝８．１５ ａｎｄ １．５５ Ｈｚ，Ｈ_e ａｎｄ Ｈ_i）７．７８（ｓ，１Ｈ，Ｈ_a），８．０６（ｄｄ，２Ｈ，Ｊ＝１．５０ ａｎｄ ０．５０ Ｈｚ，Ｈ_b）
¹³Ｃ ＮＭＲ（１２５ＭＨｚ，ＣＤＣｌ₃）：δ（ｐｐｍ）１５２．３，１３５．２，１３０．０，１２９．９，１２９．１，１２８．８，１２８．３，１２６．８，１２５．２，１２４．３，１２１．８，１１５．２，７７．６
ＦＡＢ−ＭＳ：ｍ／ｚ＝６００［Ｍ＋Ｈ］⁺，６０２［Ｍ＋２＋ Ｈ］⁺，６０４［Ｍ＋４＋Ｈ］⁺
ＨＲＭＳ（ＦＡＢ）：ｍ／ｚ［Ｍ］⁺ Ｃ₂₉Ｈ₁₇ＢＢｒ₂Ｆ₂Ｎ₂としての計算値５９９．９８２０；分析値５９９．９８１０ The measurement results of ¹ H NMR spectrum, ¹³ C NMR spectrum, FAB-MS, and HRMS (high resolution mass spectrometry spectrum) (FAB) of compound (4) are shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ (ppm) = 7.34 (dd, 2H, J = 8.72 and 1.62 Hz, H _c ), 7.46-7.52 (m, 8H, _{H d, H f, H g} , and H h), 7.77 (dd, 4H, J = 8.15 and 1.55 Hz, H e and H i) 7.78 (s, 1H, H a) , 8.06 (dd, 2H, J = 1.50 and 0.50 Hz, H _b )
¹³ C NMR (125 MHz, CDCl ₃ ): δ (ppm) 152.3, 135.2, 130.0, 129.9, 129.1, 128.8, 128.3, 126.8, 125.2 124.3, 121.8, 115.2, 77.6
FAB-MS: m / z = 600 [M + H] ⁺ , 602 [M + 2 + H] ⁺ , 604 [M + 4 + H] ⁺
HRMS (FAB): m / z [M] ⁺ calculated for C ₂₉ H ₁₇ BBr ₂ F ₂ N ₂ 599.9820; analytical value 599.9810

[Difluoro [6- (3-hexyl-5- (5,5-dimethyl- [1,3] dioxan-2-yl) thiophen-2-yl) -1-[[6- (3-hexyl-5 (5,5-dimethyl- [1,3] dioxane) thiophen-2-yl) -3-phenyl-2H-isoindol-1-yl] methylene] -3-phenyl-1H-isoindolate-N ¹ , N ² ] Boron (Synthesis of Compound (6))
Compound (4) 1.20 g (1.99 mmol) and 2- (5- (5,5-dimethyl-1,3-dioxan-2-yl) -3-hexylthiophen-2-yl) -4,4 5,5-trimethyl-1,3,2-dioxaborolane (compound (5)); Y. Kubo, D. Eguchi, A. Matsumoto, R. Nishiyabu, H. Yakushiji, K. Shigaki, M. Kaneko, J. Mater Chem. A, 2014, 2, p.5204-5211) 2.50 g (6.12 mmol) was dissolved in 96 mL of THF, and 19.7 mL of 2M aqueous potassium carbonate solution was added thereto. The solution was freeze degassed, and then added with 0.5 g (0.433 mmol) of tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) under a nitrogen atmosphere and stirred overnight at 70 ° C. The reaction solution was poured into water and then dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: dichloromethane (CH ₂ Cl ₂ ) / hexane = 1/1 (v / v)). Thus, 1.34 g of compound (6) was obtained (yield 67%).

¹Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ₃）：δ（ｐｐｍ）＝０．８１（ｓ，１２Ｈ，Ｈ_q），１．２５（ｓｅｘｔｅｔ，４Ｈ，Ｊ＝３．６８Ｈｚ，Ｈ_l），１．２９-１．３２（ｍ，８Ｈ，Ｈ_j ａｎｄ Ｈ_k），１．３１（ｔ，６Ｈ，Ｊ＝６．２２Ｈｚ，Ｈ_m），１．６３（ｑ，４Ｈ，Ｊ＝７．６３Ｈｚ，Ｈ_i），２．７０（ｔ，４Ｈ，Ｊ＝７．８２Ｈｚ，Ｈ_h），３．６７，（ｄ，４Ｈ，Ｊ＝１０．８Ｈｚ，Ｈ_p），３．７９（ｄ，４Ｈ，Ｊ＝１１．３Ｈｚ，Ｈ_p），５．６４（ｓ，２Ｈ，Ｈ_o），７．０８（ｓ，２Ｈ，Ｈ_n）７．３２（ｄｄ，２Ｈ，Ｊ＝８．４７ ａｎｄ １．４８ Ｈｚ，Ｈ_c）７．４５-７．５２（ｍ，６Ｈ，Ｈ_g ａｎｄ Ｈ_f），７．６３（ｄｄ，２Ｈ，Ｊ＝８．４２ ａｎｄ ０．６３ Ｈｚ，Ｈ_d），７．８０（ｓ，１Ｈ，Ｈ_a），７．８３（ｄｄ，４Ｈ，Ｊ＝７．９３ ａｎｄ １．４２ Ｈｚ，Ｈ_e），７．９３-７．９４（ｍ，２Ｈ，Ｈ_b）
¹³Ｃ ＮＭＲ（１２５ＭＨｚ，ＣＤＣｌ₃）：δ（ｐｐｍ）＝１５１．７，１４０．０，１３９．１，１３７．９，１３５．８，１３４．７，１３１．０，１３０．２，１２９．６，１２８．３，１２８．０，１２７．７，１２７．０，１２３．７，１１９．４，１１４．４，９８．４，７７．６，３１．６，３０．９，３０．３，２９．７，２９．２，２９．０，２３．０，２２．６，２１．９，１４．１
ＦＡＢ−ＭＳ：ｍ／ｚ＝１００４［Ｍ］⁺ The measurement results of ¹ H NMR spectrum, ¹³ C NMR spectrum, and FAB-MS of compound (6) are shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ (ppm) = 0.81 (s, 12H, H _q ), 1.25 (sextet, 4H, J = 3.68 Hz, H _l ), 1.29-1. .32 (m, 8H, H _j and H _k ), 1.31 (t, 6H, J = 6.22 Hz, H _m ), 1.63 (q, 4H, J = 7.63 Hz, H _i ), 2.70 (t, 4H, J = 7.82 Hz, H _h ), 3.67, (d, 4H, J = 10.8 Hz, H _p ), 3.79 (d, 4H, J = 11.3 Hz) , H _p ), 5.64 (s, 2H, H _o ), 7.08 (s, 2H, H _n ) 7.32 (dd, 2H, J = 8.47 and 1.48 Hz, H _c ) _{7.45-7.52 (m, 6H, H g} and H f), 7.63 (dd, 2H, J = 8.42 and 0.63 Hz, H d), 7.80 (s, 1H, _{a), 7.83 (dd, 4H} , J = 7.93 and 1.42 Hz, H e), 7.93-7.94 (m, 2H, H b)
¹³ C NMR (125 MHz, CDCl ₃ ): δ (ppm) = 151.7, 140.0, 139.1, 137.9, 135.8, 134.7, 131.0, 130.2, 129.6 , 128.3, 128.0, 127.7, 127.0, 123.7, 119.4, 114.4, 98.4, 77.6, 31.6, 30.9, 30.3, 29 7, 29.2, 29.0, 23.0, 22.6, 21.9, 14.1
FAB-MS: m / z = 1004 [M] ⁺

[Difluoro [6- (3-hexyl-5-formylthiophen-2-yl) -1-[[6- (3-hexyl-5-formylthiophen-2-yl) -3-phenyl-2H-isoindole- 1-yl] methylene] -3-phenyl -1H- isoindolinone rate -N ^1, N ^2] boron (compound (7)) synthesis of] -
1.34 g (1.33 mmol) of compound (6) was dissolved in 172 mL of THF, and 35.5 mL of an aqueous solution of 0.512 g (2.69 mmol) of p-toluenesulfonic acid monohydrate was added to the resulting solution. The mixed solution was stirred at 40 ° C. for 7 hours, poured into water, and extracted with ethyl acetate. The organic layer was washed with water and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (eluent: CH ₂ Cl ₂ / hexane = 3/2 (v / v)). Thus, 0.498 g of compound (7) was obtained (yield 45%).

¹Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ₃）：δ（ｐｐｍ）＝０．８３８（ｔ，６Ｈ，Ｊ＝６．９８Ｈｚ，Ｈ_m），１．２５-１．２７（ｍ，８Ｈ，Ｈ_k ａｎｄ Ｈ_l），１．３３（ｑ，４Ｈ，Ｊ＝７．０６Ｈｚ，Ｈ_j），１．６６（ｑ，４Ｈ，Ｊ＝７．５９Ｈｚ，Ｈ_i），２．７６（ｔ，４Ｈ，Ｊ＝７．８０Ｈｚ，Ｈ_h），７．３２（ｄｄ，２Ｈ，Ｊ＝８．４５ ａｎｄ １．４５ Ｈｚ，Ｈ_c），７．４８-７．５３（ｍ，６Ｈ，Ｈ_f ａｎｄ Ｈ_g），７．７０（ｄ，２Ｈ，Ｊ＝９．７０Ｈｚ，Ｈ_d），７．７０（ｓ，２Ｈ，Ｈ_n），７．８４（ｄｄ，４Ｈ，Ｊ＝７．６７ ａｎｄ １．７７ Ｈｚ，Ｈ_e），７．８９（ｓ，１Ｈ，Ｈ_a），７．９９（ｓ，２Ｈ，Ｈ_b），９．９０（ｓ，２Ｈ，Ｈ_o）
¹³Ｃ ＮＭＲ（１２５ＭＨｚ，ＣＤＣｌ₃）：δ（ｐｐｍ）＝１８２．８，１５２．２，１４８．１，１４１．８，１４１．１，１３８．４，１３４．５，１３４．２，１３０．６，１３０．２，１２９．９，１２８．４，１２８．１，１２６．５，１２４．２，１１９．８，１１４．８，７７．６，３１．６，３０．７，２９．０，２８．８，２２．６，１４．０
ＦＡＢ−ＭＳ：ｍ／ｚ＝８３２［Ｍ］⁺
ＨＲＭＳ（ＦＡＢ）：ｍ／ｚ［Ｍ］⁺ Ｃ₅₁Ｈ₄₇ＢＦ₂Ｎ₂Ｏ₂Ｓ₂としての計算値 ８３２．３１４０；分析値８３２．３１４５ The measurement results of ¹ H NMR spectrum, ¹³ C NMR spectrum, FAB-MS, and HRMS (FAB) of compound (7) are shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ (ppm) = 0.838 (t, 6H, J = 6.98 Hz, H _m ), 1.25-1.27 (m, 8H, H _k and H _l ), 1.33 (q, 4H, J = 7.06 Hz, H _j ), 1.66 (q, 4H, J = 7.59 Hz, H _i ), 2.76 (t, 4H, J = 7. 80 Hz, H _h ), 7.32 (dd, 2 H, J = 8.45 and 1.45 Hz, H _c ), 7.48-7.53 (m, 6 H, H _f and H _g ), 7. 70 (d, 2H, J = 9.70Hz, H d), 7.70 (s, 2H, H n), 7.84 (dd, 4H, J = 7.67 and 1.77 Hz, H e) , 7.89 (s, 1 H, H _a ), 7.99 (s, 2 H, H _b ), 9.90 (s, 2 H, H _o )
¹³ C NMR (125 MHz, CDCl ₃ ): δ (ppm) = 182.8, 152.2, 148.1, 141.8, 141.1, 138.4, 134.5, 134.2, 130.6 130.2, 129.9, 128.4, 128.1, 126.5, 124.2, 119.8, 114.8, 77.6, 31.6, 30.7, 29.0, 28 .8, 22.6, 14.0
FAB-MS: m / z = 832 [M] ⁺
HRMS (FAB): m / z [M] + C 51 H 47 BF 2 N 2 O 2 Calculated as S ₂ 832.3140; analysis 832.3145

[Synthesis of Rho-BODIPY (Compound (8))]
Under a nitrogen atmosphere, 0.288 g (0.346 mmol) of the compound (7), 0.225 g (1.18 mmol) of rhodanine-3-acetic acid, and 0.138 g (1.80 mmol) of ammonium acetate were dissolved in 10 mL of acetic acid. Stir overnight at ° C. The reaction solution was poured into 100 mL of water, and the solid substance was obtained by filtration. The solid was washed with water until pH 7 and the residue was purified by silica gel column chromatography (eluent: CH ₂ Cl ₂ / methanol (MeOH) (0-100%)). Thus, Compound (8) was obtained as 0.130 g of Compound (8) · 2H ₂ O (yield 31%).

¹Ｈ ＮＭＲ（５００ＭＨｚ，ＴＨＦ−ｄ₈）：δ（ｐｐｍ）＝０．８３（ｔ，６Ｈ，Ｊ＝６．８５Ｈｚ，Ｈ_m），１．２７-１．２９（ｍ，１２Ｈ，Ｈ_j，Ｈ_k ａｎｄ Ｈ_l），１．３２-１．３７（ｍ，４Ｈ，Ｈ_i），２．８６（ｔ，４Ｈ，Ｊ＝７．６２Ｈｚ，Ｈ_h），４．７８（ｓ，４Ｈ，Ｈ_p），７．４６-７．５３（ｍ，８Ｈ，Ｈ_c，Ｈ_f，ａｎｄ Ｈ_g），７．５９（ｓ，２Ｈ，Ｈ_n），７．７５（ｄ，２Ｈ，Ｊ＝８．３５Ｈｚ，Ｈ_d），７．８６（ｄ，４Ｈ，Ｊ＝６．７５Ｈｚ，Ｈ_e），７．９８（ｓ，２Ｈ，Ｈ_o），８．２９（ｓ，２Ｈ，Ｈ_b），８．５５（ｓ，１Ｈ，Ｈ_a）．
¹³Ｃ ＮＭＲ（１２５ＭＨｚ，ＴＨＦ−ｄ₈）：δ（ｐｐｍ）＝２０４．８，１９２．９，１６７．３，１５２．７，１４７．２，１４２．８，１３８．７，１３７．６，１３５．６，１３５．４，１３１．９，１３１．１，１３０．４，１２９．４，１２９．０，１２６．９，１２６．１，１２４．８，１２１．５，１２１．１，４５．７，３２．５，３１．５，３０．６，３０．４，３０．０，２９．６，２３．５，１４．４．
¹⁹Ｆ ＮＭＲ（４７０ＭＨｚ，ＴＨＦ−ｄ₈）：δ（ｐｐｍ）＝−１２９．６（ｑｕａｒｔｅｔ，Ｊ_BF＝３１．１Ｈｚ）．
¹¹Ｂ ＮＭＲ（１６０ＭＨｚ，ＴＨＦ−ｄ₈）：δ（ｐｐｍ）＝３．９８（ｔ，Ｊ_FB＝３１．２Ｈｚ）．
ＦＡＢ−ＭＳ：ｍ／ｚ＝１１７９［Ｍ］⁺
元素分析：Ｃ₆₁Ｈ₅₃ＢＦ₂Ｎ₄Ｏ₆Ｓ₆・２Ｈ₂Ｏとしての計算値Ｃ，６０．２８％；Ｈ，４．７３％；Ｎ，４．６１％、分析値Ｃ，６０．１３％；Ｈ，４．４１％；Ｎ，４．６１％ The measurement results of ¹ H NMR spectrum, ¹³ C NMR spectrum, ¹⁹ F NMR spectrum, ¹¹ B NMR spectrum, FAB-MS, and elemental analysis of Rho-BODIPY (compound (8)) are shown below.

¹ H NMR (500 MHz, THF-d ₈ ): δ (ppm) = 0.83 (t, 6H, J = 6.85 Hz, H _m ), 1.27-1.29 (m, 12H, H _j , H _k and H _l ), 1.32-1.37 (m, 4H, H _i ), 2.86 (t, 4H, J = 7.62 Hz, H _h ), 4.78 (s, 4H, H _{p), 7.46-7.53 (m, 8H} , H c, H f, and H g), 7.59 (s, 2H, H n), 7.75 (d, 2H, J = 8. _{35Hz, H d), 7.86 (} d, 4H, J = 6.75Hz, H e), 7.98 (s, 2H, H o), 8.29 (s, 2H, H b), 8. _{55 (s, 1H, H a} ).
¹³ C NMR (125 MHz, THF-d ₈ ): δ (ppm) = 204.8, 192.9, 167.3, 152.7, 147.2, 142.8, 138.7, 137.6, 135 6, 135.4, 131.9, 131.1, 130.4, 129.4, 129.0, 126.9, 126.1, 124.8, 121.5, 121.1, 45.7 32.5, 31.5, 30.6, 30.4, 30.0, 29.6, 23.5, 14.4.
¹⁹ F NMR (470 MHz, THF-d ₈ ): δ (ppm) =-129.6 (quartet, J _BF = 31.1 Hz).
¹¹ B NMR (160 MHz, THF-d ₈ ): δ (ppm) = 3.98 (t, J _FB = 31.2 Hz).
FAB-MS: m / z = 1179 [M] ⁺
Elemental _{analysis: C 61 H 53 BF 2 N} 4 O 6 S 6 · 2H 2 Calculated C as O, 60.28%; H, 4.73 %; N, 4.61%, analysis C, 60. 13%; H, 4.41%; N, 4.61%

Example 3
[Preparation of Photoelectrode 3]
Acetone was used as a solvent, and NK003 was dissolved in acetone to prepare a dye solution. A photoelectrode 3 was prepared in the same manner as in Example 1 except that this dye solution was used in place of the methanol solution of BODIPY.

(Measurement of dye adsorption amount)
The dye adsorption amount on the obtained photoelectrode 3 was calculated from absorption spectrum data before and after the FTO / TiO ₂ electrode was immersed in the dye solution. The dye adsorption amount is shown in Table 2 below.

[Production of Water-Splitting Photoelectrochemical Cell 10A]
The water-resolved photoelectrochemical cell 10A was obtained in the same manner as in Example 1 except that the obtained photoelectrode 3 was used as a working electrode and a phosphate buffer solution having a pH of 7.0 was used instead of an aqueous sodium sulfate solution as an electrolyte. Was made.

Example 4
A water-splitting photoelectrochemical cell 10A was produced in the same manner as in Example 3 except that a phosphate buffer solution having a pH of 5.8 was used instead of the phosphate buffer solution having a pH of 7.0.

Example 5
[Preparation of Photoelectrode 3]
A mixed solvent of THF and acetone (THF / acetone = 1/9 (v / v)) was used as a solvent, and Rho-BODIPY was dissolved in this mixed solvent to prepare a dye solution. A photoelectrode 3 was prepared in the same manner as in Example 1 except that this dye solution was used in place of the methanol solution of BODIPY.

(Measurement of dye adsorption amount)
The dye adsorption amount on the obtained photoelectrode 3 was calculated from absorption spectrum data before and after the FTO / TiO ₂ electrode was immersed in the dye solution. The amount of dye adsorption is shown in Table 2.

[Production of Water-Splitting Photoelectrochemical Cell 10A]
Water-resolved photoelectricity was obtained in the same manner as in Example 1 except that the obtained photoelectrode 3 was used as a working electrode and a sodium fluoride (NaF) aqueous solution having a pH of 7.3 was used as the electrolyte instead of the aqueous sodium sulfate solution. A chemical cell 10A was produced.

Example 6
A water-splitting photoelectrochemical cell 10A was produced in the same manner as in Example 5 except that a phosphate buffer solution having a pH of 5.8 was used instead of the NaF aqueous solution having a pH of 7.3 as the electrolyte.

[Water electrolysis experiment]
For each of the water-splitting photoelectrochemical cells of Examples 3 to 6, a 300 W xenon lamp was used as the light source 6, and light from the xenon lamp was irradiated to the photoelectrode 3 through the 400 nm long pass filter 9 for 2000 seconds. The amount of hydrogen (H ₂ ) generated at this time was quantified by gas chromatography. On the other hand, the amount of hydrogen peroxide (H ₂ O ₂ ) generated at this time was quantified by measuring the change in the absorption spectrum of Fe ³⁺ accompanying the oxidation of Fe ²⁺ . Further, “Faraday coefficient (%)” was measured. These measurement results are summarized in Table 3.

  As described above, in any of the water-splitting photoelectrochemical cells of Examples 3 to 6, generation of photocurrent and generation of hydrogen gas were confirmed during light irradiation, and in the water-splitting photoelectrochemical cell of Example 6 The generation of hydrogen peroxide was confirmed during light irradiation.

  INDUSTRIAL APPLICABILITY The present invention can be used for production of hydrogen using light energy and production of hydrogen peroxide.

DESCRIPTION OF SYMBOLS 1 Electrolyte containing aqueous solution 2 Light-transmitting container 3 Photoelectrode 3a Substrate 3b Compound semiconductor fine particle 3c Sensitizing dye 4 Reduction electrode 5 External circuit 6 Light source 10 Water splitting photoelectrochemical cell

Claims (11)

A water-splitting photoelectrochemical cell provided with a photoelectrode comprising compound semiconductor fine particles and a sensitizing dye supported on the compound semiconductor fine particles,
The water-splitting photoelectrochemical cell, wherein the sensitizing dye is an organic dye compound or a salt thereof comprising at least one metalloid element containing carbon and at least one nonmetal element containing hydrogen.   The organic dye compound or a salt thereof is an aniline dye, dipyrromethene dye, 9-phenylxanthene dye, triphenylmethane dye, acridine dye, coumarin dye, metal-free phthalocyanine dye, oxazine dye, or indigo dye. The water-resolved photoelectrochemical cell according to claim 1, which is a dye, a cyanine dye, a merocyanine dye, a rhodacyanine dye, or a metal-free porphyrin dye. The water-resolved photoelectrochemical cell according to claim 1, wherein the organic dye compound is a compound represented by the following general formula (1) or the following general formula (2) or a salt thereof.

[M1 in the general formula (1) represents an integer of 1 to 4,
M2 in the general formula (2) represents an integer of 2 to 3,
R in the general formulas (1) and (2) represents 0 or 1,
A in the general formulas (1) and (2) may have a carboxy group, a phosphate group, a cyano group, an alkoxycarbonyl group, an acyl group, a nitro group, an alkoxysilyl group, a hydroxy group, or a substituent. A good aromatic hydrocarbon group, a heterocyclic group which may have a substituent, or a substituent represented by any one of the following formulas (A-1) to (A-5);

(In the formulas (A-1) to (A-5), ^* B represents a binding site with B in the general formulas (1) and (2), and X ₁ , X ₂ , Y ₁ , and Y ₂ are Independently, an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, an amino group, Represents a hydroxy group, an alkoxy group, a hydrogen atom, a halogen atom, a carboxy group, a cyano group, a phosphate group, a sulfo group, an alkoxycarbonyl group, an acyl group, or a carbonamido group, and R _{1 to} R ₈ are each independently substituted An aliphatic hydrocarbon group which may have a group, an aromatic hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, an amino group, a hydroxy group, an alkoxy group , Hydrogen atom, halogen atom, cyano group, phosphate group, alkoxycal Group, an acyl group, carbonamido group, an amide group, an aryloxy group, or carboxymethyl group, R ₈ represents 4 radicals on the benzene ring (including a hydrogen atom), be the same or different from each other Z _{1 to} Z ₅ are each independently an oxygen atom, a sulfur atom, a selenium atom, a —CRR′— group, a —CR═CR′— group, or a —NR ″ — group (wherein R, R ′ and R ″ each independently represents a hydrogen atom or a substituent, and R and R ′ may form a bond with each other.)
B in the general formulas (1) and (2) represents a substituent represented by any one of the following formulas (B-1) to (B-4);

(In formulas (B-1) to (B-4), ^* A represents the bonding position with A in formulas (1) and (2), and ^* C represents formulas (1) and (2). Each of R _{101 to} R ₁₀₆ independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, An optionally substituted heterocyclic group, amino group, hydroxy group, phosphoric acid group, cyano group, hydrogen atom, halogen atom, alkoxy group, amide group, carboxy group, carbonamido group, alkoxycarbonyl group, or Represents an acyl group, R ₁₀₅ represents four groups (including hydrogen atoms) on the benzene ring, which may be the same or different from each other, and R ₁₀₆ represents two groups (including hydrogen atoms) on the benzene ring. represents may be the same or different, Z ₁₀₁ or ₁₀₄ are each independently an oxygen atom, a sulfur atom, a selenium atom, -CRR'- group, -CR = CR'- group, or -NR '' - group (wherein, R, R 'and R''are each Independently represents a hydrogen atom or a substituent, and n1 to n4 each independently represents an integer of 1 to 7.)
C in the general formulas (1) and (2) is an aromatic hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or the following formula (C-1 ) Or a substituent represented by the formula (C-2).

(In the formula (C-1), ^* B represents the bonding position with B in the general formulas (1) and (2), R ₂₀₁ represents a hydrogen atom or one or more substituents; The plurality of substituents may be the same or different from each other, and may be bonded to each other or bonded to R ₂₀₂ or R ₂₀₃ to form a ring, and R ₂₀₂ and R ₂₀₃ are each independently A hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent.

(In formula (C-2), ^* B represents the bonding position with B in the general formulas (1) and (2), p1 represents an integer of 1 to 4, M ₁ represents a boron atom, a silicon atom Represents a metalloid atom selected from the group consisting of a germanium atom, an arsenic atom, an antimony atom, and a tellurium atom, and R _{204 to} R ₂₀₆ are each independently a hydrogen atom or an aromatic group optionally having a substituent. A hydrocarbon group or an optionally substituted heterocyclic group, Q ₁ and Q ₂ each independently represent a halogen atom, and Ar 1 and Ar ₂ each independently represent an aromatic ring)] The organic dye compound or a salt thereof is a compound represented by the general formula (1) or a salt thereof,
The combination of r, A, and B is
(A) r is 0 or 1, A is a substituent represented by the formula (A-1), and X ₁ and Y ₁ in the formula (A-1) are each independently a hydrogen atom. , A carboxy group, a cyano group, a phosphoric acid group, or a sulfonic acid group, and R ₁ in the formula (A-1) is a hydrogen atom, an aliphatic hydrocarbon group, a halogen atom, or an alkoxy group, and B is a substituent but represented by the formula (B-1), the formula (B-1) n1 in is an integer of 1 to 5, R ₁₀₁ and R ₁₀₂ in the formula (B-1) Each independently represents a hydrogen atom, an aliphatic hydrocarbon group, a halogen atom, or an alkoxy group,
(B) r is 1, A is a substituent represented by the formula (A-1), and X ₁ and Y ₁ in the formula (A-1) are each independently a hydrogen atom, carboxy A group, a cyano group, a phosphoric acid group, or a sulfonic acid group, R ₁ in the formula (A-1) is a hydrogen atom, an aliphatic hydrocarbon group, a halogen atom, or an alkoxy group; is a substituent represented by formula (B-2), the formula (B-2) n2 is an integer of 1 to 5 in the formula (B-2) R ₁₀₃ and R ₁₀₄ are each in Independently, a hydrogen atom, an aliphatic hydrocarbon group, a halogen atom, or an alkoxy group, and a combination in which Z ₁₀₁ in the formula (B-2) is an oxygen atom, a sulfur atom, or a selenium atom,
(C) r is 0 or 1, A is a formyl group, B is a substituent represented by the formula (B-2), and n2 in the formula (B-2) is 1 to 5 R ₁₀₃ and R ₁₀₄ in the formula (B-2) are each independently a hydrogen atom, an aliphatic hydrocarbon group, a halogen atom, or an alkoxy group, and in the formula (B-2) In which Z ₁₀₁ is an oxygen atom, a sulfur atom, or a selenium atom,
The water-splitting photoelectrochemical cell according to claim 3, which is any one of the above. The organic dye compound or a salt thereof is a compound represented by the general formula (1) or a salt thereof,
m1 is 1,
A is
(A) a substituent represented by the formula (A-1), wherein X ₁ and Y ₁ are carboxy groups,
(B) a substituent represented by the formula (A-1), wherein _one of X ₁ and Y ₁ is a carboxy group and the other is a cyano group;
(C) Substitution represented by the formula (A-3), wherein R ₅ is a carboxymethyl group, R ₆ is a hydrogen atom, Z ₂ is an oxygen atom, and Z ₃ and Z ₄ are sulfur atoms. Group,
(D) Represented by the formula (A-3), R ₅ is an ethyl group, R ₆ is a hydrogen atom, Z ₂ is an oxygen atom, and Z ₃ is

A substituent represented by: Z ₄ is a sulfur atom,
(E) Represented by the formula (A-3), R ₅ is an ethyl group, R ₆ is a hydrogen atom, Z ₂ is an oxygen atom, and Z ₃ is —C (CN) (COOH) — A substituent, wherein Z ₄ is a sulfur atom,
(F) Represented by the formula (A-3), R ₅ is an ethyl group, R ₆ is a hydrogen atom, Z ₂ is an oxygen atom, and Z ₃ is a —C (COOH) ₂ — group. A substituent in which Z ₄ is a sulfur atom,
(G) Represented by the formula (A-3), R ₅ is a carboxymethyl group, R ₆ is a 4- (diphenylamino) phenyl group, Z ₂ and Z ₃ are oxygen atoms, and Z ₄ A substituent in which is a sulfur atom,
(H) Represented by the formula (A-3), R ₅ is a carboxymethyl group, R ₆ is a p-tolyl group, Z ₂ is an oxygen atom, and Z ₃ and Z ₄ are sulfur atoms. A substituent,
Any one of
B is represented by the formula (B-1), R ₁₀₁ and R ₁₀₂ are hydrogen atoms,
C is the following formula (C-1-1)

(In the formula (C-1-1), R ₁₅ represents the following formulas (101) to (105).

Represents an aromatic hydrocarbon group or an aromatic heterocyclic group represented by any one of the following, and the combination of R ₁₆ and R ₁₇ is:
(I) a combination in which R ₁₆ and R ₁₇ are methyl groups;
(Ii) a combination in which R ₁₆ is a hydrogen atom and R ₁₇ is a phenyl group;
(Iii) a combination in which R ₁₆ and R ₁₇ are phenyl groups;
(Iv) a combination in which R ₁₆ and R ₁₇ are p-tolyl groups;
(V) a combination in which R ₁₆ is a 2-thienyl group and R ₁₇ is a hydrogen atom;
(Vi) a combination in which R ₁₆ and R ₁₇ are 2,4-xylyl groups,
(Vii) a combination in which R ₁₆ is a 1-naphthyl group and R ₁₇ is a hydrogen atom;
R ₁₈ represents a hydrogen atom or a phenyl group, R ₁₉ and R ₂₀ represent a hydrogen atom, and X ₃ together with the amino group is represented by the following formulas (106) to (110):

A linking group that forms a cyclic structure represented by any one of the above, n represents 0 or 1; )
The water-resolved photoelectrochemical cell according to claim 3, wherein The organic dye compound or a salt thereof is a compound represented by the general formula (1) or a salt thereof,
m1 is 1, r is 1,
A is a substituent represented by the formula (A-1),
X ₁ and Y ₁ in the formula (A-1) are each independently a hydrogen atom, an aromatic hydrocarbon group, an aromatic heterocyclic group, an aliphatic hydrocarbon group, a carboxy group, a phosphate group, a sulfo group, A cyano group, an acyl group, an amide group, an alkoxycarbonyl group, or a phenylsulfonyl group,
R ₁ in the formula (A-1) is a hydrogen atom, an aromatic hydrocarbon group, an aromatic heterocyclic group, an aliphatic hydrocarbon group, a cyano group, a halogen atom, a carbonamido group, an amide group, an alkoxy group, An aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group, or an acyl group,
B is the following formula (B-11)

(In the formula (B-11), ^* A represents the bonding position with A in the general formula (1), ^* C represents the bonding position with C in the general formula (1),
j represents an integer of 0 to 3, k represents an integer of 1 to 3, q represents an integer of 1 to 5 (where q satisfies j + k + q ≦ 7),
Z _{11 to} Z ₁₃ are each independently an oxygen atom, a sulfur atom, a selenium atom, or a —NR ″ -group (wherein R ″ is independently a hydrogen atom or an aromatic group optionally having a substituent). Represents an aromatic hydrocarbon group, an aromatic heterocyclic group which may have a substituent, or an aliphatic hydrocarbon group which may have a substituent.
A ₄ represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, a cyano group, a halogen atom, a carbonamido group, an alkoxy group, an amide group, an alkoxycarbonyl group, or an acyl group,
A _{7 to} A ₁₀ each independently represent a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, a cyano group, a halogen atom, a carbonamido group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. ,
R ₃₀₁ represents the following formula (302)

(In Formula (302), p represents an integer of 0 to 3, q represents an integer of 0 to 6,
X ₄ and Y ₄ each independently have a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent. Represents an aliphatic hydrocarbon group, a carboxy group, a phosphate group, a sulfo group, a cyano group, an acyl group, an amide group, an alkoxycarbonyl group, or an optionally substituted benzenesulfonyl group,
Z ₁₄ represents an oxygen atom, a sulfur atom, a selenium atom, or a —NR ₁₂ — group (R ₁₂ represents a hydrogen atom, an aromatic hydrocarbon group that may have a substituent, or an aromatic that may have a substituent. Represents a heterocyclic group or an aliphatic hydrocarbon group optionally having substituent (s),
A ₁₁ and A ₁₂ each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, a cyano group, a halogen atom, a carbonamido group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. ,
A _{13 to} A ₁₅ each independently have a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent. And may represent an aliphatic hydrocarbon group, a cyano group, a halogen atom, a carbonamido group, an amide group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group, or an acyl group. )
Represents a substituent represented by
C is a substituent represented by the formula (C-1), and one or more substituents R ₂₀₁ in the formula (C-1) may have a substituent. An aromatic hydrocarbon group that may have a substituent, an aliphatic hydrocarbon group that may have a substituent, a cyano group, an acyl group, an amide group, and a substituent. An optionally substituted alkoxy group, an optionally substituted alkoxycarbonyl group, or an optionally substituted benzenesulfonyl group, wherein R ₂₀₂ and R ₂₀₃ in formula (C-1) are: Independently, the following formula (301)

(In Formula (301), R ₁₂ and R ₁₃ are each independently a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, Or, it represents an aliphatic hydrocarbon group which may have a substituent.)
The water-resolved photoelectrochemical cell according to claim 3, wherein A reduction electrode facing the photoelectrode;
An optical transmission for containing an aqueous solution containing an electrolyte, and capable of transmitting light irradiated to the water-splitting photoelectrochemical cell from the outside of the water-splitting photoelectrochemical cell to the photoelectrode And a sex container,
The photoelectrode and the reduction electrode are disposed in the light transmissive container and are electrically connected to each other,
The water-resolved photoelectrochemical cell according to any one of claims 1 to 6, wherein the photoelectrode includes a compound semiconductor thin film composed of the compound semiconductor fine particles.   A hydrogen production apparatus comprising the water-splitting photoelectrochemical cell according to any one of claims 1 to 7. A hydrogen production apparatus comprising the water-splitting photoelectrochemical cell according to claim 7,
An aqueous solution containing an electrolyte is contained in the light transmissive container, and the photoelectrode and the reduction electrode are immersed in the aqueous solution,
An apparatus for producing hydrogen, characterized in that hydrogen is generated at the reduction electrode when the water-splitting photoelectrochemical cell is irradiated with light from outside the water-splitting photoelectrochemical cell.   A hydrogen peroxide production apparatus comprising the water-splitting photoelectrochemical cell according to any one of claims 1 to 7. A hydrogen peroxide production apparatus comprising the water-splitting photoelectrochemical cell according to claim 7,
An aqueous solution containing an electrolyte is contained in the light transmissive container, and the photoelectrode and the reduction electrode are immersed in the aqueous solution,
An apparatus for producing hydrogen peroxide, wherein hydrogen peroxide is generated at the photoelectrode when the water-splitting photoelectrochemical cell is irradiated with light from the outside of the water-splitting photoelectrochemical cell.

Images