WO2012096134A1

WO2012096134A1 - Alkyne derivative and use thereof

Info

Publication number: WO2012096134A1
Application number: PCT/JP2011/080403
Authority: WO
Inventors: 前田　勝美; 中村　新; 中原　謙太郎; 輝昌下山; 須黒　雅博
Original assignee: 日本電気株式会社
Priority date: 2011-01-12
Filing date: 2011-12-28
Publication date: 2012-07-19
Also published as: JP2014088323A

Abstract

The present invention provides a compound which has excellent photoelectric conversion properties and is useful as a photoelectric conversion dye. This compound is an alkyne derivative characterized by being represented by general formula (1), a tautomer or stereoisomer of the alkyne derivative, or a salt of the alkyne derivative or the tautomer or stereoisomer. In general formula (1), D represents an organic group containing an electron-donating substituent; X represents a group having an acidic group; and Z represents a linking group having at least one heterocyclic ring selected from the group consisting of a thiophene ring, a furan ring and a pyrrole ring.

Description

Alkyne derivatives and uses thereof

The present invention relates to an alkyne derivative and its use.

Due to the large amount of fossil fuels represented by petroleum so far, global warming has become a serious problem due to the increase in CO ₂ concentration, and there is a concern about the depletion of fossil fuels. Therefore, how to meet future demand for large amounts of energy has become a very important issue on a global scale. Under such circumstances, the use of light energy that is infinite and clean with respect to nuclear power generation is being actively studied. Solar cells that convert light energy into electrical energy include inorganic solar cells that use inorganic materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and organic solar cells that use organic dyes and conductive polymer materials. Solar cells have been proposed.

Under such circumstances, a dye-sensitized solar cell (Gretzel solar cell) proposed by Dr. Gretzell of Switzerland in 1991 (for example, see Patent Document 1 and Non-Patent Document 1) is a simple manufacturing process. In addition, it is expected to be a next-generation solar cell because it can achieve the same conversion efficiency as amorphous silicon. A Gretzel type solar cell includes a semiconductor layer having a dye adsorbed thereon, a semiconductor electrode formed on a conductive substrate, a counter electrode made of a conductive substrate opposite to the semiconductor electrode, and an electrolyte held between the electrodes. With layers.

In this Gretzel type solar cell, the adsorbed dye absorbs light and enters an excited state, and electrons are injected from the excited dye into the semiconductor layer. The dye that has been oxidized by the emission of electrons is reduced by the transfer of electrons to the dye by the oxidation reaction of the redox agent in the electrolyte layer, and returns to the original dye. Then, the redox agent that has donated electrons to the dye is reduced again on the counter electrode side. The Gretzel type solar cell functions as a solar cell that converts light energy into electric energy by this series of reactions.

In this Gretzel-type solar cell, the surface area on which the dye is adsorbed, that is, the effective reaction surface area is increased by about 1000 times by using porous titanium oxide obtained by sintering fine particles in the semiconductor layer. . Compared with the case of using a titanium oxide film produced by a vapor phase growth method, the use of porous titanium oxide has a great feature that a larger photocurrent can be taken out.

In a Gretzel type solar cell, a metal complex such as a ruthenium complex is used as a sensitizing dye. Specifically, for example, cis-bis (isothiocyanato) -bis- (2,2′-bipyridyl-4,4′-dicarboxylic acid) is used. Acid) ruthenium (II) ditetrabutylammonium complexes, cis-bis (isothiocyanato) -bis- (2,2′-bipyridyl-4,4′-dicarboxylic acid) ruthenium (II) and other ruthenium bipyridine complexes, ruthenium Tris (isothiocyanato) (2,2 ′: 6 ′, 2 ″ -terpyridyl-4,4 ′, 4 ″ -tricarboxylic acid) ruthenium (II) tritetrabutylammonium complex is used.

Japanese Patent No. 2664194

As described above, in the dye-sensitized solar cell described in the background art, a metal complex containing a noble metal such as a ruthenium complex is used as a sensitizing dye. For example, when mass-producing dye-sensitized solar cells using a ruthenium complex, ruthenium has many uses such as a catalyst, and thus there is a possibility that a problem may arise in terms of “resource constraints”. Further, since noble metals are used, the dye-sensitized solar cell becomes expensive and hinders its spread. For this reason, development of the organic dye which does not contain noble metals, such as ruthenium, is calculated | required as a sensitizing dye used for a dye-sensitized solar cell. In general, compared to metal complexes such as ruthenium complexes, organic dyes have a large molar extinction coefficient and also have a high degree of freedom in molecular design, and therefore, development of organic dyes with high photoelectric conversion efficiency is expected.

The present invention has been made to solve the above-described problems, and has excellent photoelectric conversion characteristics, an alkyne derivative compound that can be used as a dye for photoelectric conversion, and a photoelectric conversion characteristic that includes the alkyne derivative compound. It is in providing the pigment | dye for conversion, the semiconductor electrode for photoelectrochemical cells using the same, the photoelectric conversion element for photoelectrochemical cells, and a photoelectrochemical cell.

The alkyne derivative compound of the present invention
An alkyne derivative represented by the following general formula (1), a tautomer or stereoisomer thereof, or a salt thereof.

In the formula (1),
D represents an organic group containing an electron-donating substituent,
X represents a group having an acidic group,
Z represents a linking group having at least one heterocyclic ring selected from the group consisting of a thiophene ring, a furan ring and a pyrrole ring.

The dye for photoelectric conversion of the present invention is
The alkyne derivative represented by the general formula (1), a tautomer or stereoisomer thereof, or a salt thereof according to the present invention is included.

The semiconductor electrode for a photoelectrochemical cell of the present invention is characterized by having a semiconductor layer containing the dye for photoelectric conversion of the present invention.

The photoelectric conversion element for photoelectrochemical cells of the present invention is characterized by having the semiconductor electrode for photoelectrochemical cells of the present invention.

The photoelectrochemical cell of the present invention is characterized by having the photoelectric conversion element for a photoelectrochemical cell of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, the alkyne derivative compound which can be used for the photoelectric conversion pigment | dye etc. which were excellent in the photoelectric conversion characteristic, the photoelectric conversion pigment | dye excellent in the photoelectric conversion characteristic containing the said alkyne derivative compound, and a photoelectrochemical cell using the same Semiconductor electrodes, photoelectric conversion elements for photoelectrochemical cells, and photoelectrochemical cells can be provided.

FIG. 1 is a cross-sectional view schematically showing a configuration of an example of a photoelectric conversion element for a photoelectrochemical cell of the present invention. FIG. 2 is a graph showing an absorption spectrum of the alkyne derivative (TA-1) of the first embodiment. FIG. 3 shows the absorption spectrum of the alkyne derivative (TA-2) of the second embodiment. FIG. 4 shows the evaluation results of the photoelectric conversion characteristics of the cell (photoelectric conversion element) described in the fifth embodiment, which was produced using the alkyne derivative (TA-1) of the first embodiment, that is, the current − It is a figure which shows a voltage curve.

In addition, the code | symbol attached | subjected in FIG. 1 means the following, respectively.

DESCRIPTION OF SYMBOLS 1 Semiconductor layer 2 Transparent conductive layer 3 Light transmissive substrate 4 Semiconductor electrode for photoelectrochemical cells 5 Electrolyte layer (charge transport layer)
6 Catalyst layer 7 Substrate 8 Counter electrode

Hereinafter, the present invention will be described in detail with examples.

<Alkyne derivatives>
As described above, the alkyne derivative compound of the present invention is an alkyne derivative represented by the following general formula (1), a tautomer or stereoisomer thereof, or a salt thereof.

In the general formula (1),
D represents an organic group containing an electron-donating substituent,
X represents a group having an acidic group,
Z represents a linking group having at least one heterocyclic ring selected from the group consisting of a thiophene ring, a furan ring and a pyrrole ring.

In addition, the pyrrole ring used for the structure of Z preferably has a 1H-pyrrole structure among the three isomers of 1H-pyrrole, 2H-pyrrole, and 3H-pyrrole.

When the alkyne derivative compound of the present invention has isomers such as tautomers or stereoisomers (eg, geometric isomers, conformers and optical isomers), any isomers of the present invention Can be used. The salt of the alkyne derivative compound of the present invention may be an acid addition salt or a base addition salt. Furthermore, the acid forming the acid addition salt may be an inorganic acid or an organic acid, and the base forming the base addition salt may be an inorganic base or an organic base. The inorganic acid is not particularly limited. For example, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hypofluorite, hypochlorous acid, hypobromite, Hypoiodous acid, fluorinated acid, chlorous acid, bromic acid, iodic acid, fluoric acid, chloric acid, bromic acid, iodic acid, perfluoric acid, perchloric acid, perbromic acid, periodic acid, etc. Can be mentioned. The organic acid is not particularly limited, and examples thereof include p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, p-bromobenzenesulfonic acid, succinic acid, citric acid, benzoic acid, and acetic acid. Examples of the inorganic base include, but are not limited to, ammonium hydroxide, alkali metal hydroxide, alkaline earth metal hydroxide, carbonate, bicarbonate, and the like. More specifically, for example, Examples thereof include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydroxide and calcium carbonate. The organic base is not particularly limited, and examples thereof include alcohol amine, trialkylamine, tetraalkylammonium, and tris (hydroxymethyl) aminomethane. Examples of the alcohol amine include ethanolamine. Examples of the trialkylamine include trimethylamine, triethylamine, tripropylamine, tributylamine, and trioctylamine. Examples of the tetraalkylammonium include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetraoctylammonium and the like. The method for producing these salts is not particularly limited, and for example, the salts can be produced by a method such as appropriately adding the above acid or base to the alkyne derivative compound by a known method.

In the present invention, the alkyl group has, for example, 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and the aryl group has, for example, 5 to 24 carbon atoms, preferably 6 to 12 carbon atoms. In the case of a substituted alkyl group or a substituted aryl group, the number of carbon atoms does not include the number of carbon atoms of the substituent. In the present invention, the alkyl group specifically includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, Examples include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like. The same applies to a group containing an alkyl group in the structure (alkylamino group, alkoxy group, alkanoyl group, etc.). In the present invention, the substituted alkyl group may be a substituted alkyl group in which the alkyl group (unsubstituted alkyl group) is substituted with an arbitrary substituent. One or a plurality of substituents of the substituted alkyl group may be used, and when there are a plurality of substituents, they may be the same or different. As for the substituent of the said substituted alkyl group, a hydroxyl group, an alkoxy group, an aryl group (for example, phenyl group) etc. are mentioned, for example. Specific examples of the substituted alkyl group include araalkyl groups such as a benzyl group.

In the present invention, the aryl group includes a heteroaryl group unless specifically limited, and specifically includes, for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a pyridyl group, a quinolyl group, and an acridyl group. Pyrrolyl group (1H-pyrrolyl group), furanyl group (furyl group), thienyl group, carbazoyl group, fluorenyl group and the like. In the present invention, the substituted aryl group may be a substituted aryl group in which the aryl group (unsubstituted aryl group) is substituted with an arbitrary substituent. One or a plurality of substituents of the substituted aryl group may be used, and when there are a plurality of substituents, they may be the same or different. Examples of the substituent of the substituted aryl group include an alkyl group, a hydroxy group, an alkoxy group, an amino group, an alkylamino group, and a dialkylamino group. Specific examples of the substituted or unsubstituted aryl group in the present invention include, for example, a phenyl group, a tolyl group, a 4-t-butylphenyl group, a 3,5-di-t-butylphenyl group, and 4-methoxyphenyl. Group, 4- (N, N-dimethylamino) phenyl group, 4-hexyloxyphenyl group, 4-octyloxyphenyl group, 4- (α, α-dimethylbenzyl) phenyl group, and 9,9-dimethylfluorene And -2-yl group.

In general, an aryl group means a monovalent group (Ar—) derived from “aromatic hydrocarbon (ArH)”, and “aromatic hydrocarbon (ArH)” includes benzene-based aromatic carbonization. Hydrogen and non-benzene aromatic hydrocarbons are included.

In the present invention, the alkenyl group may have a structure in which any carbon-carbon bond of the alkyl group is converted to a double bond by dehydrogenation. In the present invention, the acyl group is not particularly limited. (C ₂ H ₅ —O—CO—) and the like, and the same applies to groups containing an acyl group in the structure (acyloxy group, alkanoyloxy group, etc.). In the present invention, the carbon number of the acyl group includes carbonyl carbon. For example, an alkanoyl group having 1 carbon atom (acyl group) refers to a formyl group. In the present invention, “halogen” refers to any halogen element, and examples thereof include fluorine, chlorine, bromine and iodine.

In the present invention, a chain group such as an alkyl group, an alkoxy group, an alkenyl group, and an alkanoyl group may be linear or branched unless otherwise specified. In the present invention, when there is an isomer due to the configuration of substituents, etc., any isomer may be used unless otherwise limited. For example, when simply referring to a “propyl group”, either an n-propyl group or an isopropyl group may be used. When simply referred to as “butyl group”, any of n-butyl group, isobutyl group, sec-butyl group and tert-butyl group may be used. When simply referred to as “naphthyl group”, either a 1-naphthyl group or a 2-naphthyl group may be used.

D in the general formula (1) represents an organic group containing an electron-donating substituent as described above. The organic group D containing an electron donating substituent is preferably a group represented by the following general formula (5).

In the general formula (5), Ar ¹ and Ar ² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group. Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, etc., an alkyl group having 1 to 8 carbon atoms, a benzyl group, etc. Examples of the substituent bonded to the alkyl group include a hydroxy group, an alkoxy group (for example, an alkoxy group having 1 to 4 carbon atoms), a phenyl group, and the like. Examples of the substituted or unsubstituted aryl group include phenyl group, tolyl group, 4-t-butylphenyl group, 3,5-di-t-butylphenyl group, 4-methoxyphenyl group, 4-hexyloxyphenyl group, 4 -Octyloxyphenyl group, 4- (N, N-dimethylamino) phenyl group, 4- (N, N-diphenylamino) phenyl group, 4- (α, α-dimethylbenzyl) phenyl group, 9,9-dimethyl Examples thereof include substituted or unsubstituted aryl groups having 6 to 22 carbon atoms such as a fluoren-2-yl group. Examples of the substituent bonded to the aryl group include an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms), A hydroxy group, an alkoxy group (for example, an alkoxy group having 1 to 8 carbon atoms), an N, N-dialkylamino group (the alkyl group portion is, for example, an alkyl group having 1 to 8 carbon atoms), N, N-diphenylamino group and the like can be mentioned. Examples of the substituted or unsubstituted heterocyclic group include a thienyl group, a furyl group, a pyrrolyl group (1H-pyrrolyl group), an indolyl group, a carbazoyl group, and the like, and examples of the substituent bonded to the heterocyclic group include an alkyl group ( Examples thereof include alkyl groups having 1 to 8 carbon atoms, hydroxy groups, alkoxy groups (for example, alkoxy groups having 1 to 8 carbon atoms), and the like. Ar ³ represents a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group. Examples of the substituted or unsubstituted arylene group include a phenylene group (for example, benzene-1,4-diyl group), a naphthylene group, and the like, and examples of the substituent bonded to the arylene group include an alkyl group (for example, having 1 carbon atom). ˜8 alkyl group), hydroxy group, alkoxy group (for example, alkoxy group having 1 to 8 carbon atoms) and the like. Examples of the substituted or unsubstituted divalent heterocyclic group include a thiophene diyl group, a furandiyl group, and a pyrrole diyl group (1H-pyrrole diyl group). Examples of the substituent bonded to the divalent heterocyclic group include an alkyl group. A group (for example, an alkyl group having 1 to 8 carbon atoms), a hydroxy group, an alkoxy group (for example, an alkoxy group having 1 to 8 carbon atoms) and the like.

In general, an arylene group means a divalent group (—Ar—) derived from “aromatic hydrocarbon (HArH)” and having a bond on different carbon atoms constituting the aromatic ring, “Aromatic hydrocarbon (HArH)” includes benzene-based aromatic hydrocarbons and non-benzene-based aromatic hydrocarbons.

Specific examples of the organic group D containing the electron donating substituent other than the group represented by the general formula (5) are shown in the following chemical formulas (D1) to (D9), but are not limited thereto. Absent. In the following chemical formulas (D3) to (D6), (D9), R represents a carbon number of 1 such as methyl, ethyl, propyl, n-butyl, pentyl, hexyl, heptyl, octyl, etc. Represents an alkyl group of ˜8.

X in the general formula (1) represents a group having an acidic group as described above. X may consist of only an acidic group, or may be a group in which an acidic group is bonded to another group. X is preferably an organic group having an acidic group. For example, the other group to which the acidic group is bonded may be an organic group. The organic group is not particularly limited, but is preferably a group that can be conjugated with Z. The group capable of conjugating with Z is more preferably a group having a carbon-carbon double bond. Examples of the acidic group include a carboxy group, a sulfonic acid group, a phosphonic acid group, or a salt thereof, and a carboxy group or a salt thereof is particularly preferable. When the acidic group is a salt, a monovalent or divalent metal salt, ammonium salt or organic ammonium salt is preferable. Examples of the monovalent or divalent metal salt include alkali metal salts such as Li, Na, K, and Cs, and alkaline earth metal salts such as Mg, Ca, and Sr. Examples of the organic group of the organic ammonium salt include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

The alkyne derivative compound represented by the general formula (1) can be adsorbed on a semiconductor layer used in a semiconductor electrode for a photoelectrochemical cell described later because X has an acidic group.

Specific examples of the organic group X having an acidic group are shown in the following chemical formulas (Xa) to (Xm). These organic groups X have an intercarbon (carbon-carbon) double bond in addition to an acidic group, and one bond of the linking group Z is bonded to one carbon of the carbon-carbon double bond. The other carbon is bonded to any of a cyano group, a carbonyl group, another carbon-carbon double bond carbon, and a carbon-nitrogen double bond carbon. However, the organic group X is not limited to these. Further, the organic group X represented by the chemical formulas (Xa) to (Xm) may be either Z-form or E-form. That is, these organic groups X may have structures as represented by chemical formulas (Xa) to (Xm) or geometric isomers thereof.

In the formulas (Xa) to (Xm),
M represents a hydrogen atom or a salt-forming cation,
B ⁻ represents a hydroxide ion or a salt-forming anion.

M and B ⁻ may be monovalent ions, but may be multivalent ions. When M or B ⁻ is a multivalent ion, the number in the chemical formulas (Xa) to (Xm) may be a fraction of the valence. For example, M may be 1 / 2Mg ²⁺ and B ⁻ may be 1 / 2SO ₄ ^2- , but is not limited thereto.

Examples of the salt-forming cation M include various cations capable of forming a salt (—COOM) with a carboxy group (—COO ⁻ ). Examples of such a cation include an ammonium cation (NH ⁴⁺ ); an organic ammonium cation derived from an amine (A ¹ A ² A ³ A ⁴ N ⁺ , A ¹ to A ⁴ represent a hydrogen atom or an organic group. At least one of which is an organic group); alkali metal ions such as Li ⁺ , Na ⁺ , K ⁺ and Cs ⁺ ; alkaline earth metal ions such as Mg ²⁺ , Ca ²⁺ and Sr ²⁺ . Examples of the organic group (A ¹ to A ⁴ ) of the organic ammonium cation (A ¹ A ² A ³ A ⁴ N ⁺ ) include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and a carbon number Examples include 6 to 12 aryl groups.

The organic group X having an acidic group is more preferably represented by the following chemical formulas (X1) to (X16). Further, the organic group X represented by the chemical formulas (X1) to (X16) may be either Z-form or E-form. That is, these organic groups X may have structures as represented by chemical formulas (X1) to (X16) or geometric isomers thereof.

The organic group X is more preferably a group represented by the following general formula (2).

In the general formula (2), M represents a hydrogen atom or a salt-forming cation, and is the same as M in the formulas (Xa) to (Xm).

Z in the general formula (1) represents a linking group having at least one heteroaromatic ring or aromatic ring selected from a thiophene ring, a furan ring, a pyrrole ring and an aromatic ring (aromatic hydrocarbon ring). The pyrrole ring used for the constitution of Z preferably has a 1H-pyrrole structure among the three isomers of 1H-pyrrole, 2H-pyrrole, and 3H-pyrrole. The linking group Z is not particularly limited, but is preferably an atomic group that can be conjugated with a carbon-carbon triple bond to which Z is bonded (that is, —C≡C— shown in the general formula (1)). . For example, from the carbon-carbon triple bond (> C—C≡C—C <) bonded to Z due to “conjugation”, “cumulene” that can be expressed as> C = C = C = C < This means that it can be converted to a structure. The linking group Z is preferably a linking group having a structure represented by at least the following general formula (3).

In the general formula (3), R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group, or a substituted or unsubstituted linear or branched alkoxy group, R ¹ and R ² may be connected to each other to form a ring. In addition, when R < ¹ >, R < ² > is mutually connected and forms a ring, it is preferable that the ring formed is a 5-membered ring or more. For example, when R ¹ and R ² are connected to each other to form a ring, the formed ring can be a six-membered ring or more. Examples of the substituted or unsubstituted alkyl group include an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of the substituent bonded to the group include a hydroxy group and an alkoxy group. Examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

In the general formula (3), Y represents an oxygen atom, a sulfur atom or NRa, and Ra represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group, or a substituted or unsubstituted aryl group. Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, etc., an alkyl group having 1 to 8 carbon atoms, a benzyl group, etc. Examples of the substituent bonded to the alkyl group include a hydroxy group, an alkoxy group (for example, an alkoxy group having 1 to 4 carbon atoms), a phenyl group, and the like. Examples of the substituted or unsubstituted aryl group include phenyl group, tolyl group, 4-t-butylphenyl group, 3,5-di-t-butylphenyl group, 4-methoxyphenyl group, 4- (N, N-dimethyl group). Examples thereof include substituted or unsubstituted aryl groups having 6 to 22 carbon atoms such as (amino) phenyl group. Examples of the substituent bonded to the aryl group include an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms), a hydroxy group, an alkoxy group (for example, an alkoxy group having 1 to 4 carbon atoms), and an N, N-dialkylamino group. (The alkyl group moiety is, for example, an alkyl group having 1 to 8 carbon atoms).

Specific examples of the linking group Z are shown in the chemical formulas (Z1) to (Z26), but are not limited thereto. Examples of these are heteroaromatic rings or divalent groups having a bond to the aromatic ring. When there are multiple heteroaromatic rings or aromatic rings, are the carbons that make up the heteroaromatic ring or aromatic rings directly bonded to each other? Or a condensed ring to form a bond. Further, a group in which a plurality of these linking groups are linked may be used.

Examples of the alkyne derivative compound represented by the general formula (1), tautomers or stereoisomers thereof, or combinations of X and Z in the salts thereof include the following (am)-(1 To 26). In Tables 1-a to 1-m below, Xa may be replaced with X1 to X4, Xb may be replaced with X5, Xc may be replaced with X6, and Xd may be replaced with X7. Xe may be replaced with X8, Xf may be replaced with X9, Xg may be replaced with X10, Xh may be replaced with X11, Xi may be replaced with X12, and Xj may be replaced with X13 Xk may be replaced with X14, Xl may be replaced with X15, and Xm may be replaced with X16.

Examples of combinations of Ar ¹ to Ar ^{3 in} the alkyne derivative compound represented by the general formula (1), a tautomer or stereoisomer thereof, or a salt thereof include, for example, Ar 2 -1 to Ar-16. Ar-1 to Ar-16 exemplified in Table 2 below are combinations in which Ar ¹ and Ar ² are the same atomic group, but are not limited thereto, and Ar ¹ and Ar ² are the same as described above. A combination of different atomic groups each independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a heterocyclic group may be adopted. For example, in Table 2 below, among the eight atomic groups employed as Ar ¹ and Ar ² , combinations of different atomic groups may be employed.

The alkyne derivative of the present invention is more preferably an alkyne derivative represented by the following general formula (4).

In the general formula (4), Ar ¹ and Ar ² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, etc., an alkyl group having 1 to 8 carbon atoms, a benzyl group, etc. Examples of the substituent bonded to the alkyl group include a hydroxy group, an alkoxy group (for example, an alkoxy group having 1 to 4 carbon atoms), a phenyl group, and the like. Examples of the substituted or unsubstituted aryl group include phenyl group, tolyl group, 4-t-butylphenyl group, 3,5-di-t-butylphenyl group, 4-methoxyphenyl group, 4-hexyloxyphenyl group, 4 -Octyloxyphenyl group, 4- (N, N-dimethylamino) phenyl group, 4- (N, N-diphenylamino) phenyl group, 4- (α, α-dimethylbenzyl) phenyl group, 9,9-dimethyl Examples thereof include substituted or unsubstituted aryl groups having 6 to 22 carbon atoms such as a fluoren-2-yl group. Examples of the substituent bonded to the aryl group include an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms), hydroxy A group, an alkoxy group (for example, an alkoxy group having 1 to 8 carbon atoms), an N, N-dialkylamino group (the alkyl group portion is, for example, an alkyl group having 1 to 8 carbon atoms), N , N-diphenylamino group and the like. Examples of the substituted or unsubstituted heterocyclic group include a thienyl group, a furyl group, a pyrrolyl group, an indolyl group, a carbazoyl group, and the like. Examples of the substituent bonded to the heterocyclic group include an alkyl group (for example, 1 to 8 alkyl group), a hydroxy group, an alkoxy group (for example, an alkoxy group having 1 to 8 carbon atoms), and the like. Ar ³ represents a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group. Examples of the substituted or unsubstituted arylene group include a phenylene group and a naphthylene group. Examples of the substituent bonded to the arylene group include an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms), a hydroxy group, and an alkoxy group. (For example, an alkoxy group having 1 to 8 carbon atoms) and the like. Examples of the substituted or unsubstituted divalent heterocyclic group include a thiophene diyl group, a furandiyl group, and a pyrrole diyl group. Examples of the substituent bonded to the divalent heterocyclic group include an alkyl group (for example, having 1 carbon atom). ˜8 alkyl group), hydroxy group, alkoxy group (for example, alkoxy group having 1 to 8 carbon atoms) and the like.

M in the general formula (4) represents a hydrogen atom or a salt-forming cation, and is the same as M in the formulas (Xa) to (Xm).

Further, Z in the general formula (4) is the same as Z in the general formula (1), and preferably represents a linking group including a structure represented by the general formula (3).

The alkyne derivative compound of the present invention is particularly preferably an alkyne derivative represented by the following formula TA-1, a tautomer or stereoisomer thereof, or a salt thereof.

The alkyne derivative compound of the present invention is also particularly preferably an alkyne derivative represented by the following formula TA-2, a tautomer or stereoisomer thereof, or a salt thereof.

In addition to the compounds TA-1 and TA-2, for example, compounds TA-3 to TA-6 shown in Table 3 below are particularly preferred. Table 3 below shows the structures of the compounds TA-3 to TA-6 in combinations of D, X and Z in the general formula (1). In addition, these compounds TA-3 to TA-6 can be obtained by referring to the production methods and examples described below, and by those skilled in the art, without undue trial and error and complicated advanced experiments. It can be easily produced and used according to 1 or TA-2. The combination of X and Z in each of compounds TA-1 to TA-6 in Table 3 below is replaced with, for example, any of the combinations of X and Z shown in Tables 1-a to 1-m above. May be. Further, the alkyne derivative compound of the present invention is not limited to these examples, and any combination of D, X and Z can be used. For example, combinations of X and Z shown in Table 1-a to Table 1-m above And an organic group D containing an electron donating substituent represented by the chemical formulas (D1) to (D9) can be combined. Further, for example, when the organic group D containing an electron donating substituent is represented by the general formula (5), combinations of X and Z shown in Table 1-a to Table 1-m, and shown in Table 2 above, , Ar ¹ to Ar ³ can be combined.

In the alkyne derivative of the present invention, a tautomer or stereoisomer thereof, or a salt thereof, the organic group D containing an electron-donating substituent and the linking group Z are carbon-carbon triple bonds (—C≡C— ). The dissociation energy of the carbon-carbon triple bond (—C≡C—) is 956.6 kJ / mol, and the dissociation energy of the carbon-carbon double bond (—CH═CH—) is 719 kJ / mol (Basics of Chemical Handbook II, (described in p317). Therefore, the organic group D containing an electron-donating substituent and the linking group Z are linked by a carbon-carbon triple bond (—C≡C—) rather than by a carbon-carbon double bond (—CH═CH—). It can be expected that the dye is excellent in thermal stability. Furthermore, compounds having a carbon-carbon double bond (—CH═CH—) are generally known to undergo cis-trans isomerization by light, and the carbon-carbon double bond (—CH═CH—) is known. ) Is considered to have a problem in light resistance. However, in the carbon-carbon triple bond (—CH═CH—) such as the alkyne derivative of the present invention, the isomerization reaction at the carbon-carbon triple bond (—CH═CH—) moiety induced by light irradiation is not possible. Since it does not occur, it can be a dye having more excellent light resistance.

The alkyne derivative of the present invention, its tautomer or stereoisomer, or a salt thereof is useful for, for example, a photoelectric conversion dye excellent in photoelectric conversion characteristics, but is not limited thereto, and any use is possible. You may use for.

<Method for producing alkyne derivative>
The production method of the alkyne derivative represented by the general formula (1), a tautomer or stereoisomer thereof, or a salt thereof is not particularly limited, and is arbitrary. For example, the production method shown in the following scheme But you can. Specifically, the following scheme:
The 1st coupling process which manufactures the compound represented by the following general formula (III) by the coupling reaction of the compound represented by the following general formula (I), and the compound represented by the following general formula (II) ,
A deprotection step for producing a compound represented by the following general formula (IV) by deprotecting the compound represented by the following general formula (III);
A second coupling step in which a compound represented by the following general formula (IV) and a compound represented by the following general formula (V) are subjected to a coupling reaction to produce a compound represented by the following general formula (VI); and,
It includes an acidic group introduction step of converting Q ² in the following general formula (VI) to introduce an acidic group X to produce an alkyne derivative compound represented by the general formula (1).

In the general formula (I), general formula (III), general formula (IV) and general formula (VI),
D is the same as D in the general formula (1),
In the general formula (II) and general formula (III),
Q ¹ is a protecting group,
In the general formula (I),
Hal ¹ is halogen,
In the general formula (V),
Hal ² is halogen,
Hal ¹ and Hal ² may be the same or different,
In the general formula (V) and the general formula (VI),
Z is the same as Z in the general formula (1),
Q ² is an arbitrary substituent that can be converted to the acidic group X.

Note that Hal ¹ is a halogen selected from Cl, Br, and I; Hal ² is preferably a halogen selected from Cl, Br, and I.

In the first coupling step, the deprotection step, the second coupling step, and the acidic group introduction step, the reaction time, the reaction temperature, the amount of each reactant used, etc. are not particularly limited. You may set suitably with reference to a similar reaction etc. In each of the steps, a solvent, a catalyst, or the like may be appropriately used in addition to the reactants, or may not be used.

Hal ¹ and Hal ² are not particularly limited, but chlorine, bromine or iodine are preferable, and bromine or iodine is more preferable from the viewpoint of reactivity. The first coupling step and the second coupling step are each performed in the presence of a palladium catalyst and a base that activate the halide of the general formula (I) and the halide of the general formula (V), respectively. Preferably, the copper catalyst further converts the terminal alkyne (—C≡C—H) of the general formula (II) and the terminal alkyne (—C≡C—H) of the general formula (IV) into —C≡C—Cu. May be performed together. A coupling reaction between a terminal alkyne and an aryl halide using a palladium catalyst and a copper catalyst in the presence of such a base may be called, for example, Sonogashira coupling.

In the general formula (V) and the general formula (VI),
Q ² is an acyl group represented by the following general formula (VII),
In the general formula (I),
X is an acidic group represented by the following general formula (VIII),
In the acidic group introduction step, Q ² is preferably converted to X by reacting Q ² with cyanoacetic acid.

In the general formula (VII) and general formula (VIII),
R ¹⁰ is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,
In the general formula (VIII),
For example, H in —COOH may be substituted with the same M as in the general formula (2).

<Dye for photoelectric conversion>
The photoelectric conversion dye of the present invention contains at least one of the alkyne derivative of the present invention, a tautomer or stereoisomer thereof, or a salt thereof. The alkyne derivative compound or the like is useful as a photoelectric conversion dye having excellent photoelectric conversion characteristics.

<Photoelectric conversion element for photoelectrochemical cell>
FIG. 1 schematically shows a cross-sectional structure of an example of the photoelectric conversion element for a photoelectrochemical cell of the present invention. The photoelectric conversion element shown in FIG. 1 includes a semiconductor electrode 4 for a photoelectrochemical cell, a counter electrode 8, and an electrolyte layer (charge transport layer) 5 held between both electrodes. The semiconductor electrode 4 for photoelectrochemical cells includes a conductive substrate including a light transmissive substrate 3 and a transparent conductive layer 2, and a semiconductor layer 1. The counter electrode 8 includes a catalyst layer 6 and a substrate 7. The semiconductor layer 1 is adsorbed with the photoelectric conversion dye.

When light is incident on the photoelectric conversion element for a photoelectrochemical cell, the photoelectric conversion dye adsorbed on the semiconductor layer 1 is excited and emits electrons. The electrons move to the conduction band of the semiconductor, and further move to the transparent conductive layer 2 by diffusion. The electrons in the transparent conductive layer 2 move to the counter electrode 8 via an external circuit (not shown). The photoelectric conversion dye (oxidized dye) that has released the electrons receives (reduced) electrons from the electrolyte layer 5 and returns to the original state, so that the photoelectric conversion dye is regenerated. On the other hand, the electrons moved to the counter electrode are given to the electrolyte layer 5 and the electrolyte is reduced. Thus, the photoelectric conversion element is configured to function as a battery (for example, a dye-sensitized solar cell). Hereinafter, each component will be described by taking the photoelectric conversion element for a photoelectrochemical cell shown in FIG. 1 as an example.

<Semiconductor electrode for photoelectrochemical cell>
The semiconductor electrode 4 for photoelectrochemical cells includes the conductive substrate including the light-transmitting substrate 3 and the transparent conductive layer 2 and the semiconductor layer 1 as described above. As shown in FIG. 1, a light transmissive substrate 3, a transparent conductive layer 2, and a semiconductor layer 1 are laminated in this order from the outside to the inside of the element. The semiconductor layer 1 is adsorbed with a dye for photoelectric conversion (not shown).

<Conductive substrate>
The conductive substrate constituting the semiconductor electrode 4 for photoelectrochemical cells may have a single-layer structure in which the substrate itself has conductivity, or a two-layer structure in which a conductive layer is formed on the substrate. Also good. The conductive substrate of the photoelectric conversion element for a photoelectrochemical cell shown in FIG. 1 has a two-layer structure in which a transparent conductive layer 2 is formed on a light transmissive substrate 3.

Examples of the substrate used for the conductive substrate include a glass substrate, a plastic substrate, and a metal plate. Among them, a substrate having high light transmittance, for example, a transparent plastic substrate is particularly preferable. Examples of the material for the transparent plastic substrate include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polycycloolefin, and polyphenylene sulfide.

Further, the conductive layer (for example, the transparent conductive layer 2) formed on the substrate (for example, the light transmissive substrate 3) is not particularly limited, but for example, indium tin oxide (Indium-Tin-Oxide: A transparent conductive layer made of a transparent material such as ITO, fluorine-doped tin oxide (FTO), indium-zinc oxide (IZO), tin oxide (SnO ₂ ), or the like is preferable. The conductive layer formed over the substrate can be formed into a film shape over the entire surface or a part of the surface of the substrate. The thickness of the conductive layer can be selected as appropriate, but is preferably about 0.02 μm or more and 10 μm or less. Such a conductive layer can be formed using a normal film formation technique.

Note that the conductive substrate in this embodiment can be provided with a metal lead wire for the purpose of reducing the resistance of the conductive substrate. Examples of the material of the metal lead wire include metals such as aluminum, copper, gold, silver, platinum, and nickel. The metal lead wire can be produced by vapor deposition, sputtering, or the like. After a metal lead wire is formed on the substrate (for example, the light transmissive substrate 3), a conductive layer (for example, a transparent conductive layer 2 such as ITO or FTO) can be provided on the metal lead wire. Alternatively, after providing a conductive layer (for example, transparent conductive layer 2) on a substrate (for example, light transmissive substrate 3), a metal lead wire may be formed on this conductive layer.

The description of the following embodiment is based on an example in which a conductive substrate having a two-layer structure in which a transparent conductive layer 2 is formed on a light transmissive substrate 3 is used as the conductive substrate in the semiconductor electrode 4 for a photoelectrochemical cell. The operation principle of the photoelectrochemical cell (for example, dye-sensitized solar cell) according to the present invention will be described. However, the technical scope of the present invention is not limited to the illustrated embodiment.

<Semiconductor layer>
As a material constituting the semiconductor layer 1, a single semiconductor such as silicon or germanium, a compound semiconductor such as a metal chalcogenide, a semiconductor compound having a perovskite structure, or the like can be used.

Metal chalcogenides include oxides such as titanium, tin, zinc, iron, tungsten, indium, zirconium, vanadium, niobium, tantalum, strontium, hafnium, cerium, lanthanum; cadmium, zinc, lead, silver, antimony, bismuth, etc. Sulfides; selenides such as cadmium and lead; tellurides of cadmium and the like. Examples of other compound semiconductors include phosphides such as zinc, gallium, indium, and cadmium; gallium arsenide; copper-indium-selenide; copper-indium-sulfide, and the like. Examples of the semiconductor compound having a perovskite structure include commonly known semiconductor compounds such as barium titanate, strontium titanate, and potassium niobate. These semiconductor materials can be used alone or in combination of two or more.

Among these semiconductor materials, from the viewpoint of conversion efficiency, stability, and safety, a semiconductor material containing titanium oxide or zinc oxide is preferable, and a semiconductor material containing titanium oxide is more preferable.
Examples of titanium oxide include various types of titanium oxide such as anatase type titanium oxide, rutile type titanium oxide, amorphous titanium oxide, metatitanic acid, orthotitanic acid, and a titanium oxide-containing complex can be used. . Among these, anatase type titanium oxide is preferable from the viewpoint of further improving the stability of photoelectric conversion.

Examples of the form of the semiconductor layer include a porous semiconductor layer obtained by sintering semiconductor fine particles, a thin film semiconductor layer obtained by a sol-gel method, a sputtering method, a spray pyrolysis method, and the like. Moreover, it is good also as a semiconductor layer which consists of a fibrous semiconductor layer or an acicular crystal | crystallization. The form of these semiconductor layers can be appropriately selected according to the purpose of use of the photoelectric conversion element. Among these, a semiconductor layer having a large specific surface area such as a porous semiconductor layer and a needle-like semiconductor layer is preferable from the viewpoint of the amount of dye adsorbed. Furthermore, a porous semiconductor layer formed from semiconductor fine particles is preferable from the viewpoint that the utilization factor of incident light and the like can be adjusted by the particle size of the semiconductor fine particles. Further, the semiconductor layer may be a single layer or a multilayer. By forming a multilayer, a sufficiently thick semiconductor layer can be more easily formed. Moreover, when the porous semiconductor layer formed from semiconductor fine particles is a multilayer, you may form several semiconductor layers from which the average particle diameter of semiconductor fine particles differs. For example, the average particle diameter of the semiconductor fine particles of the semiconductor layer closer to the light incident side (first semiconductor layer) may be smaller than that of the semiconductor layer farther from the light incident side (second semiconductor layer). In this way, the first semiconductor layer absorbs a lot of light, and the light that has passed through the first semiconductor layer is efficiently scattered by the second semiconductor layer and returned to the first semiconductor layer, and the returned light is returned to the first semiconductor layer. By making it absorb with 1 semiconductor layer, the whole optical absorptance can be improved further.

Although the film thickness of a semiconductor layer is not specifically limited, From viewpoints, such as permeability | transmittance and conversion efficiency, it can be 0.5 micrometer or more and 45 micrometers or less, for example. More preferably, they are 1 micrometer or more and 30 micrometers or less. The specific surface area of the semiconductor layer can be set to, for example, 10 m ² / g or more and 200 m ² / g or less from the viewpoint of adsorbing a large amount of dye.

Further, in the case where the dye is adsorbed on the porous semiconductor layer, the porosity of the porous semiconductor layer is, for example, 40% or more from the viewpoint that ions in the electrolyte are further sufficiently diffused and charge transport is performed. 80% or less is preferable. Here, the porosity is a percentage of the volume of the semiconductor layer occupied by the pores in the semiconductor layer.

<Method for forming semiconductor layer>
Next, a method for forming the semiconductor layer 1 will be described by taking the case of a porous semiconductor layer as an example. The porous semiconductor layer can be formed, for example, as follows. First, a suspension is prepared by adding semiconductor fine particles together with an organic compound such as a resin and a dispersant to a dispersion medium such as an organic solvent or water. And this suspension is apply | coated on a conductive substrate (transparent conductive layer 2 in FIG. 1), a semiconductor layer is obtained by drying and baking this. When an organic compound is added to the dispersion medium together with the semiconductor fine particles, the organic compound is combusted at the time of firing, so that a sufficient gap (void) can be secured in the porous semiconductor layer. Moreover, the porosity can be changed by controlling the molecular weight and the addition amount of the organic compound combusted at the time of baking.

The organic compound is not particularly limited as long as it can be dissolved in a suspension and burned and removed when fired. For example, polyethylene glycol, cellulose ester resin, cellulose ether resin, epoxy resin, urethane resin, phenol resin, polycarbonate resin, polyarylate resin, polyvinyl butyral resin, polyester resin, polyvinyl formal resin, silicone resin, styrene, Examples thereof include polymers and copolymers of vinyl compounds such as vinyl acetate, acrylic acid esters, and methacrylic acid esters. The type and amount of the organic compound can be appropriately selected according to the type and state of the fine particles used, the composition ratio of the suspension, the total weight, and the like. The ratio of the semiconductor fine particles is preferably 10% by mass or more and 40% by mass or less with respect to the total weight of the entire suspension. When the ratio of the semiconductor fine particles is 10% by mass or more based on the total weight of the entire suspension, the strength of the produced film can be further sufficiently increased. Further, when the proportion of the semiconductor fine particles is 40% by mass or less with respect to the total weight of the whole suspension, a porous semiconductor layer having a large porosity can be obtained more stably.

As the semiconductor fine particles, single or plural compound semiconductor particles having an appropriate average particle diameter, for example, an average particle diameter of about 1 nm to about 500 nm, for example, compound semiconductor particles such as metal chalcogenide are used. it can. Among these, from the viewpoint of increasing the specific surface area, those having an average particle diameter of about 1 nm to 50 nm are desirable. In order to increase the utilization rate of incident light, semiconductor particles having a relatively large average particle diameter of about 200 nm to 400 nm may be added.

Further, examples of the method for producing the semiconductor fine particles include a sol-gel method such as a hydrothermal synthesis method, a sulfuric acid method, a chlorine method, and the like. The method is not limited as long as the method can produce the desired fine particles. Is preferably synthesized by a hydrothermal synthesis method.

Examples of the dispersion medium used in the suspension include glyme solvents such as ethylene glycol monomethyl ether; alcohols such as isopropyl alcohol; mixed solvents such as isopropyl alcohol / toluene; water and the like.

The suspension can be applied by a usual application method such as a doctor blade method, a squeegee method, a spin coating method, or a screen printing method. The conditions of drying and baking of the coating film performed after application of the suspension are, for example, about 10 seconds to 12 hours in the range of about 50 ° C. to 800 ° C. in the air or in an inert gas atmosphere. it can. This drying and baking may be performed once or a plurality of times at a single temperature, or may be performed a plurality of times by changing the temperature.

Other types of semiconductor layers other than the porous semiconductor layer can be formed using a normal method for forming a semiconductor layer used in a photoelectric conversion element for a photoelectrochemical cell.

<Adsorption method of photoelectric conversion dye>
The photoelectric conversion dye is as described above. As a method for adsorbing the dye on the semiconductor layer 1, for example, a method of immersing a semiconductor substrate (that is, a conductive substrate including the semiconductor layer 1) in a solution in which the dye is dissolved, or a solution of the dye in a semiconductor is used. The method of apply | coating to the layer 1 and making it adsorb | suck is mentioned.

Solvents for this dye solution include nitrile solvents such as acetonitrile, propionitrile, methoxyacetonitrile; alcohol solvents such as methanol, ethanol, isopropyl alcohol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; acetic acid Ester solvents such as ethyl and butyl acetate; ether solvents such as tetrahydrofuran and dioxane; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; dichloromethane, chloroform, And halogen solvents such as dichloroethane, trichloroethane, and chlorobenzene; hydrocarbon solvents such as toluene, xylene, and cyclohexane; and water. These may be used alone or in combination of two or more.

When the method of immersing the semiconductor substrate in the dye solution is employed, the solution may be stirred, heated to reflux, or ultrasonic waves may be applied when the semiconductor substrate is immersed in the dye solution. it can.

After performing the dye adsorption treatment, it is desirable to wash with a solvent such as alcohol in order to remove the dye remaining without being adsorbed.

The amount of the dye supported can be set, for example, in the range of 1 × 10 ⁻¹⁰ mol / cm ² or more and 1 × 10 ⁻⁴ mol / cm ² or less, and 1 × 10 ⁻⁹ mol / cm ² or more and 9.0 × 10. A range of ⁻⁶ mol / cm ² or less is preferable. Within this range, the effect of improving the photoelectric conversion efficiency can be obtained economically and sufficiently.

Further, in order to make the wavelength range capable of photoelectric conversion as wide as possible and increase the conversion efficiency, two or more types of photoelectric conversion dyes may be used in combination, in which case the absorption wavelength range and intensity of the dye are taken into consideration. Thus, it is preferable to appropriately select the type and ratio of the pigment. In addition, an additive may be used in combination when adsorbing the dye in order to suppress a decrease in conversion efficiency due to the association between the dyes. Examples of such additives include steroidal compounds having a carboxy group (for example, deoxycholic acid, cholic acid, chenodeoxycholic acid, etc.).

<Counter electrode>
The counter electrode 8 in this example has a catalyst layer 6 on a substrate 7. In this photoelectric conversion element for a photoelectrochemical cell, holes generated from the dye adsorbed on the semiconductor layer 1 due to the incidence of light are carried to the counter electrode 8 through the electrolyte layer 5. There is no limit to the material as long as it can perform the function of effectively eliminating the pair.

The catalyst layer 6 can be formed, for example, as a metal vapor deposition film on the substrate 7 by a vapor deposition method or the like. The catalyst layer 6 may be, for example, a Pt layer formed on the substrate 7. Further, the catalyst layer 6 may contain a nanocarbon material. For example, the catalyst layer 6 may be formed by sintering a paste containing carbon nanotubes, carbon nanohorns, or carbon fibers on the porous insulating film. Nanocarbon materials have a large specific surface area and can improve the probability of annihilation of electrons and holes.

Examples of the substrate 7 include transparent substrates such as glass and polymer films, and metal plates (foil). When the light-transmissive counter electrode 8 is produced, glass with a transparent conductive film is selected as the substrate 7, and platinum or carbon (for example, a nanocarbon material) is used as a catalyst layer by vapor deposition or sputtering. 6 can be formed.

<Electrolyte layer (charge transport layer)>
The electrolyte layer (charge transport layer) 5 has a function of transporting holes generated from the dye adsorbed on the semiconductor layer 1 due to incidence of light to the counter electrode 8. The electrolyte layer 5 contains a charge transport material. The electrolyte layer 5 includes an electrolytic solution in which a redox couple is dissolved in an organic solvent, a gel electrolyte in which a liquid in which the redox couple is dissolved in an organic solvent is impregnated in a polymer matrix, a molten salt containing the redox couple, a solid electrolyte, an organic A hole transport material or the like can be used.

The electrolyte layer can be composed of an electrolyte, a solvent, and an additive. As the electrolyte, LiI, NaI, KI, CsI , CaI 2 , etc. of the metal iodides, tetraalkylammonium iodide, pyridinium iodide, imidazolium iodide iodide and _{I 2,} such as iodine salts of quaternary ammonium compounds such as id A combination of a bromide such as a bromide of a quaternary ammonium compound such as a metal bromide such as LiBr, NaBr, KBr, CsBr or CaBr ₂ or a tetraalkylammonium bromide or pyridinium bromide with Br ₂ ; Metal complexes such as ferricyanate and ferrocene-ferricinium ions; sulfur compounds such as sodium polysulfide and alkylthiol-alkyl disulfides; viologen dyes; hydroquinone-quinone and the like. Among these, a combination of LiI and pyridinium iodide, or a combination of imidazolium iodide and I ₂ is preferable. Moreover, said electrolyte may be used independently or may be used in mixture of 2 or more types. In addition, a molten salt that is in a molten state at room temperature can be used as the electrolyte. In this case, a solvent need not be used.

Examples of the solvent include carbonate solvents such as ethylene carbonate, diethyl carbonate, dimethyl carbonate, and propylene carbonate; amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide; methoxypropionitrile, pro Nitrile solvents such as pionitrile, methoxyacetonitrile, acetonitrile; lactone solvents such as γ-butyrolactone and valerolactone; ether solvents such as tetrahydrofuran, dioxane, diethyl ether, ethylene glycol dialkyl ether; methanol, ethanol, isopropyl alcohol, etc. Alcohol solvents; aprotic polar solvents such as dimethyl sulfoxide and sulfolane; 2-methyl-3-oxazolidinone, 2-methyl-1,3-dioxo Heterocyclic compounds such as emissions and the like. These solvents may be used alone or in combination of two or more.

A basic compound may be added to the electrolyte layer in order to suppress dark current. The type of basic compound is not particularly limited, and examples thereof include t-butylpyridine, 2-picoline (2-methylpyridine), 2,6-lutidine and the like. The addition concentration in the case of adding a basic compound can be, for example, about 0.05 mol / L or more and 2 mol / L or less.

A solid electrolyte can also be used as the electrolyte layer. As this solid electrolyte, a gel electrolyte or a completely solid electrolyte can be used. As gel electrolyte, what added electrolyte or normal temperature molten salt in the gelatinizer can be used. As a gelation method, gelation can be performed by a technique such as addition of a polymer or an oil gelling agent, polymerization of coexisting polyfunctional monomers, or a crosslinking reaction of the polymer. Examples of the polymer for gelation by adding a polymer include polyacrylonitrile and polyvinylidene fluoride. Oil gelling agents include dibenzylden-D-sorbitol, cholesterol derivatives, amino acid derivatives, alkylamide derivatives of trans- (1R, 2R) -1,2-cyclohexanediamine, alkylurea derivatives, N-octyl-D-gluconamide benzoate Double-headed amino acid derivatives, quaternary ammonium salt derivatives, and the like.

When gelation is performed by polymerization of a polyfunctional monomer, the monomer used is preferably a compound having two or more ethylenically unsaturated groups, such as divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, Examples include diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, and trimethylolpropane triacrylate. In the gelation, a monofunctional monomer may be included in addition to the polyfunctional monomer. Monofunctional monomers include esters derived from acrylic acid and α-alkyl acrylic acids such as acrylamide, N-isopropylacrylamide, methyl acrylate, and hydroxyethyl acrylate; amides; dimethyl maleate, diethyl fumarate, dibutyl maleate Esters derived from maleic acid and fumaric acid such as: Dienes such as butadiene, isoprene and cyclopentadiene; Aromatic vinyl compounds such as styrene, p-chlorostyrene and sodium styrenesulfonate; Vinyl esters such as vinyl acetate Nitriles such as acrylonitrile and methacrylonitrile; vinyl compounds having a nitrogen-containing heterocycle such as vinyl carbazole; vinyl compounds having a quaternary ammonium salt; other N-vinylformamide, vinyl sulfone , Vinylidene fluoride, vinyl alkyl ethers, N- phenylmaleimide, and the like. 0.5 mass% or more and 70 mass% or less are preferable, and the polyfunctional monomer which occupies for the monomer whole quantity has more preferable 1.0 mass% or more and 50 mass% or less.

Polymerization of the monomer for gelation can be performed by a radical polymerization method or the like. This radical polymerization can be carried out by heating, light, ultraviolet light or electron beam, or electrochemically. Examples of the polymerization initiator used when forming a crosslinked polymer by heating include azo initiators such as 2,2′-azobis (isobutyronitrile) and 2,2′-azobis (dimethylvaleronitrile), Examples thereof include peroxide initiators such as benzoyl peroxide. The addition amount of the polymerization initiator is preferably 0.01% by mass or more and 15% by mass or less, and more preferably 0.05% by mass or more and 10% by mass or less with respect to the total amount of monomers.

When gelation is performed by a polymer crosslinking reaction, it is desirable to use a polymer having a reactive group necessary for the crosslinking reaction and a crosslinking agent in combination. Preferred crosslinkable reactive groups are nitrogen-containing heterocycles such as pyridine ring, imidazole ring, thiazole ring, oxazole ring, triazole ring, morpholine ring, piperidine ring, piperazine ring, and preferred crosslinkers are alkyl halides, halogenated alkyls. Bifunctional or higher functional compounds capable of electrophilic substitution reaction with nitrogen atoms such as aralkyl, sulfonic acid ester, acid anhydride, acid chloride, isocyanate and the like can be mentioned.

As the complete solid electrolyte, for example, a mixture of an electrolyte and an ion conductive polymer compound can be used. Examples of the ion conductive polymer compound include polar polymer compounds such as polyethers, polyesters, polyamines, and polysulfides.

As the charge transport material, for example, an inorganic hole transport material such as copper iodide or copper thiocyanide can be used. The inorganic hole transport material can be introduced into the electrode by a method such as a casting method, a coating method, a spin coating method, a dipping method, or electrolytic plating.

In the photoelectric conversion element for a photoelectrochemical cell of this example, an organic hole transport material can also be used as the charge transport material. Examples of the organic hole transport material include 2,2 ′, 7,7′-tetrakis (N, N-di-p-methoxyphenylamine) -9,9′-spirobifluorene (for example, Adv. Mater. 2005, 17, 813), aromatic compounds such as N, N′-diphenyl-N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine Diamines (for example, compounds described in U.S. Pat. No. 4,764,625), triphenylamine derivatives (for example, compounds described in JP-A-4-129271), stilbene derivatives (for example, JP-A-2-74271) And compounds described in JP-A-5-226160) and hydrazone derivatives (for example, compounds described in JP-A-2-226160). The organic hole transport material can be introduced into the electrode by a method such as a vacuum deposition method, a cast method, a spin coating method, a dipping method, or an electrolytic polymerization method.

The production of the electrolyte layer 5 can be performed, for example, by the following two methods. One is a method in which the counter electrode 8 is first bonded onto the semiconductor layer 1 on which the photoelectric conversion dye is adsorbed, and the liquid electrolyte layer 5 is introduced into the gap. The other is a method of forming the electrolyte layer 5 directly on the semiconductor layer 1. In the latter case, after the electrolyte layer 5 is formed, the counter electrode 8 is formed thereon.

A photoelectrochemical cell can be provided using the photoelectric conversion element for a photoelectrochemical cell described above. This photoelectrochemical cell can be suitably used as a solar cell (for example, a dye-sensitized solar cell).

Hereinafter, the present invention will be described in more detail with reference to embodiments. Each embodiment illustrated below is an example of the best embodiment of the present invention, but the technical scope of the present invention is not limited to the form shown in the embodiment.

(First embodiment)
<Synthesis of Alkyne Derivative TA-1>
According to the following reaction formula, alkyne derivative TA-1 was synthesized as follows.

30 g of 4-iodo-4 ′, 4 ″ -dimethoxytriphenylamine was dissolved in 630 mL of diethylamine, and 317 mg of copper iodide (CuI) and 2.22 g of bis (triphenylphosphine) palladium (II) dichloride were added thereto, Further, 11.4 mL of trimethylsilylacetylene was added and stirred at 60 ° C. for 1.5 hours. After returning to room temperature, the solvent was distilled off under reduced pressure, 100 mL of water was added to the residue, extracted with diethyl ether, washed with 100 mL of water, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column (eluent: hexane / chloroform = 3/1) to obtain 31 g of Compound A1.

Next, 15.5 g of A1 was dissolved in 100 mL of methanol, and 6.92 g of potassium carbonate was added thereto, followed by stirring at room temperature for 1 hour. Celite filtration was performed, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column (eluent: hexane / chloroform = 3/1) to obtain 7.7 g of A2.

Next, to a mixed solution of 1 g of A2, 0.912 g of 5-bromo-5′-formyl-2,2′-bithiophene and 60 mL of diisopropylamine, 95.4 mg of triphenylphosphine and bis (triphenylphosphine) palladium (II ) 128 mg of dichloride was added and heated to reflux for 1 hour. The temperature was returned to room temperature, the solvent was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted with chloroform. The organic layer was washed with water and dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by a silica gel column (eluent: hexane / toluene = 2/8) to obtain 0.285 g of Compound A3 (yield 12%).

Next, 1 g of A3 is dissolved in 50 mL of chloroform, 0.245 g of cyanoacetic acid and 0.41 g of piperidine are added thereto, and the mixture is heated to reflux for 9.5 hours. After allowing to cool, 200 mL of chloroform was added, washed with 0.04N hydrochloric acid and further washed with water, and then the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was dissolved in tetrahydrofuran (THF) and reprecipitated in 360 mL of hexane / ethyl acetate (5/1) to obtain 0.297 g of the target alkyne derivative TA-1. Yield 26%).

The measurement results of ¹ H-NMR (THF-d8) of the obtained alkyne derivative TA-1 were as follows: δ was 8.44 (1H, s), 8.01 (1H, s), 7 .95 (1H, d), 7.53-7.55 (2H, m), 7.33 (2H, d), 7.29 (1H, d), 7.12 (4H, d), 6. 95 (4H, d), 6.77 (2H, d)
Further, FIG. 2 shows an absorption spectrum of the obtained alkyne derivative TA-1 (dye) in THF. Λ _max of the alkyne derivative TA-1 was 462 nm.

(Second embodiment)
<Synthesis of Alkyne Derivative TA-2>
According to the following reaction formula, alkyne derivative TA-2 was synthesized as follows.

A solution obtained by dissolving 21.1 g of N-bromosuccinimide (NBS) in 280 mL of DMF in a solution of 39.5 g of 3,4′-dihexyl-2,2′-bithiophene in N, N-dimethylformamide (DMF) at 0 ° C. Was dripped. After stirring for 1 hour, the mixture was extracted with diethyl ether at 500 mL, and the organic layer was washed with water, saturated aqueous sodium carbonate solution and brine in that order, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column (elution solvent: hexane) to obtain 49.3 g of B1.

Next, 585 mL of 2M aqueous sodium carbonate solution and tetrakis (triphenylphosphine) palladium (0) were added to a toluene solution of 49.3 g of B1 and 4-hexylthiophene-2-boranoic acid pinacol ester 38.2 g, and heated for 48 hours. Refluxed. It returned to room temperature, the organic layer was wash | cleaned in order of water and salt solution, and it dried with magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column (elution solvent: hexane) to obtain 58.3 g of B2.

Next, 77.7 mL of n-butyllithium (1.64 M hexane solution) was dropped into 58.3 g of B2 in 700 mL of THF at −78 ° C. and stirred for 2 hours. At the same temperature, 13.5 mL of DMF was added and stirred for 1 hour. The mixture was returned to room temperature and further stirred for 1 hour. Water was added and extracted with diethyl ether. The organic layer was washed with brine and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column (elution solvent: hexane / ethyl acetate = 20/1) to obtain 39.84 g of B3.

Next, 39.84 g of B3 was dissolved in 480 mL of DMF, and 13.41 g of NBS was added to the solution at −20 ° C., followed by stirring for 1 hour. It returned to room temperature and stirred for 2 hours. The mixture was extracted with diethyl ether, washed successively with water, a saturated aqueous sodium carbonate solution and brine, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column (elution solvent: hexane / ethyl acetate = 20/1) to obtain 44.59 g of B4.

Next, 19.5 g of A2 synthesized in the first embodiment and 30 g of B4 were dissolved in 1150 mL of diisopropylamine, and 1.55 g of triphenylphosphine and bis (triphenylphosphine) palladium (II) dichloride were added to the solution. 2.08 g and 564 mg of copper iodide (CuI) were added, and the mixture was stirred at room temperature for 1 hour and then stirred at 50 ° C. for 30 minutes. Then, it heated and refluxed for 30 minutes. The temperature was returned to room temperature, and the solvent was distilled off under reduced pressure. The residue was purified by a silica gel column (elution solvent: hexane / ethyl acetate = 20/1) to obtain 35.3 g of B5.

Next, 2 g of B5, 0.298 g of cyanoacetic acid, and 0.497 g of piperidine were dissolved in 60 mL of chloroform and heated to reflux for 9 hours. The temperature was returned to room temperature, the solvent was distilled off under reduced pressure, 200 mL of chloroform was added, washed with 0.04N hydrochloric acid, further washed with water, and then the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was dissolved in a small amount of THF and reprecipitated in 400 mL of hexane to obtain 1.251 g of the desired alkyne derivative TA-2 (yield 57%).

The measurement results of ¹ H-NMR (THF-d8) of the obtained alkyne derivative TA-2 were as follows: δ was 8.22 (1H, s), 7.68 (1H, s), 7 .24-7.27 (3H, m), 7.05-7.08 (5H, m), 6.87 (4H, d), 6.81 (2H, d), 3.76 (6H, s) ), 2.7-2.9 (6H, m), 1.3-1.9 (24H, m), 0.89-0.93 (9H, m).

Further, FIG. 3 shows an absorption spectrum of the obtained alkyne derivative TA-2 (dye) in THF. Λ _max of the alkyne derivative TA-2 was 453 nm.

(Third embodiment)
<Production of photoelectric conversion element for photoelectrochemical cell>
A photoelectric conversion element for a photoelectrochemical cell was produced as follows.

(A) Production of Photoelectrochemical Battery Semiconductor Electrode and Counter Electrode First, a photoelectrochemical battery semiconductor electrode was produced in the following order.

A glass with FTO (10 Ωcm ₂ ) having a size of 15 mm × 15 mm and a thickness of 1.1 mm was prepared as a conductive substrate (light transmissive substrate with a transparent conductive layer).

Also, a titanium oxide paste (semiconductor layer material) was prepared as follows. Commercially available titanium oxide powder (trade name: P25, manufactured by Nippon Aerosil Co., Ltd., average primary particle size: 21 nm) 5 g, 15 vol% acetic acid aqueous solution 20 mL, surfactant 0.1 mL (trade name: Triton (registered trademark) X- 100, Sigma-Aldrich Co., Ltd.) and polyethylene glycol (molecular weight 20000) (manufactured by Wako Pure Chemical Industries, Ltd., product code: 168-11285) 0.3 g were mixed, and this mixture was stirred with a stirring mixer for about 1 hour to oxidize. A titanium paste was obtained.

Next, this titanium oxide paste was applied onto a glass with FTO by a doctor blade method so that the film thickness was about 50 μm (application area: 10 mm × 10 mm). Thereafter, the glass with FTO coated with the titanium oxide paste was put in an electric furnace, baked at 450 ° C. for about 30 minutes in an air atmosphere, and naturally cooled to obtain a porous titanium oxide film on the glass with FTO. .

Further, a light scattering layer was formed on the titanium oxide film as follows. A titanium oxide paste having an average particle size of 400 nm (trade name: PST-400C, manufactured by JGC Catalysts & Chemicals Co., Ltd.) was applied to the above-described titanium oxide film at a thickness of 20 μm by screen printing. Then, the light-scattering layer on the titanium oxide film was obtained by baking for about 30 minutes at 450 degreeC in air | atmosphere, and making it cool naturally. As described above, a semiconductor electrode before the dye was adsorbed was obtained.

On the other hand, a platinum layer having an average film thickness of 1 μm was deposited as a catalyst layer on a soda lime glass plate (thickness 1.1 mm) by a vacuum deposition method to obtain a counter electrode.

(B) Adsorption of dye Next, the dye for photoelectric conversion was adsorbed on the semiconductor layer composed of the above-described titanium oxide film and the light scattering layer. For adsorption of the photoelectric conversion dye, a solution in which the alkyne derivative TA-1 described in the first embodiment was dissolved in THF at a concentration of about 2 × 10 ⁻⁴ M was used. The above-mentioned semiconductor electrode was immersed in this dye solution and stored overnight. Thereafter, the semiconductor electrode was taken out from the dye solution, rinsed with acetonitrile to remove excess dye, and dried in air to obtain a semiconductor electrode on which the photoelectric conversion dye was adsorbed.

(C) Cell assembly The semiconductor electrode for photoelectrochemical cell after the above-mentioned dye conversion treatment for photoelectric conversion and the above-mentioned counter electrode are arranged so that the semiconductor layer and the catalyst layer face each other to form a cell before electrolyte injection did. Next, a thermosetting resin film in which the electrolyte was allowed to penetrate into the gap between the semiconductor electrode and the counter electrode was thermocompression bonded to the outer periphery of the cell.

(D) Injection of electrolyte An iodine-based electrolyte was injected into the above-described cell from the above-mentioned cut and allowed to penetrate between the semiconductor electrode and the counter electrode. The iodine-based electrolyte uses acetonitrile as a solvent, the concentration of iodine (I ₂ ) is 0.5 mol / L, the concentration of lithium iodide is 0.1 mol / L, and the concentration of 4-tert-butylpyridine is 0.05 mol / L. A solution having a concentration of L, 1,2-dimethyl-3-propylimidazolium iodide of 0.6 mol / L was used.

(E) Photocurrent measurement The photoelectric conversion element for a photoelectrochemical cell produced as described above is irradiated with light having an intensity of 100 mW / cm ² under AM1.5 conditions with a solar simulator, and the generated electricity is converted into a current. It measured with the voltage measuring device and evaluated the photoelectric conversion characteristic. As a result, the photoelectric conversion efficiency was 3.3%.

(Fourth embodiment)
A photoelectric conversion device was produced in the same manner as in the third embodiment except that the alkyne derivative TA-2 was used instead of the alkyne derivative TA-1. As a result of evaluating the photoelectric conversion characteristics of the obtained photoelectric conversion element, a photoelectric conversion efficiency of 3.5% was obtained with the element using the alkyne derivative TA-2.

(Fifth embodiment)
According to the procedure described in the third embodiment, a photoelectric conversion element was produced under the following conditions. First, when adsorbing the dye, a solution in which alkyne derivative TA-1 was dissolved in ethanol at a concentration of 0.3 mM and deoxycholic acid at 150 mM was used. The iodine-based electrolyte uses acetonitrile as the solvent, the iodine concentration is 0.05 mol / L, the lithium iodide concentration is 0.1 mol / L, the 4-tert-butylpyridine concentration is 0.5 mol / L, A solution having a concentration of 1,2-dimethyl-3-propylimidazolium iodide of 0.6 mol / L was used. The photoelectric conversion characteristics of the obtained photoelectric conversion element were evaluated. FIG. 4 shows a current-voltage curve of the obtained photoelectric conversion element. As a result, a photoelectric conversion efficiency of 5.0% was obtained.

Although the present invention has been described with reference to the embodiments (and examples), the present invention is not limited to the above embodiments (and examples). Various changes that can be understood by those skilled in the art can be made to the configuration and details of the present invention within the scope of the present invention.

This application claims priority based on Japanese Patent Application No. 2011-004427 filed on January 12, 2011, the entire disclosure of which is incorporated herein.

As described above, the alkyne derivative of the present invention, its tautomer or stereoisomer, or a salt thereof is useful for a photoelectric conversion dye. The photoelectric conversion dye containing the alkyne derivative of the present invention is excellent in photoelectric conversion characteristics. Further, since no noble metal such as ruthenium is essential, the problem of resource limitation is solved, and a solar cell (for example, a dye-sensitized solar cell) can be supplied at a lower cost. Therefore, it is possible to use solar cells (for example, dye-sensitized solar cells) for a wide range of applications. The use of the alkyne derivative of the present invention is not limited to this, and can be used in various fields.

Some or all of the above embodiments may be described as in the following supplementary notes, but are not limited to the following.

(Appendix 1)
An alkyne derivative represented by the following general formula (1), a tautomer or stereoisomer thereof, or a salt thereof.

(Appendix 2)
The alkyne derivative according to appendix 1, the tautomer or stereoisomer thereof, or the organic group D containing the electron-donating substituent is a group represented by the following general formula (5): Salt.

In the general formula (5),
Ar ¹ and Ar ² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group;
Ar ³ represents a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group.

(Appendix 3)
The alkyne derivative according to appendix 1, wherein the organic group D containing the electron donating substituent is a group represented by any of the following formulas (D1) to (D9), and tautomers thereof Or a stereoisomer or a salt thereof.

R in the formulas (D3) to (D6) and (D9) represents an alkyl group having 1 to 8 carbon atoms.

(Appendix 4)
4. The alkyne derivative according to any one of supplementary notes 1 to 3, wherein t is an organic group having an acidic group, a tautomer or stereoisomer thereof, or a salt thereof.

(Appendix 5)
6. The alkyne derivative according to appendix 4, a tautomer or stereoisomer thereof, or a salt thereof, wherein X is a group in which an acidic group is bonded to a group that can be conjugated with Z.

(Appendix 6)
6. The alkyne derivative according to appendix 5, a tautomer or stereoisomer thereof, or a salt thereof, wherein the group capable of conjugating with Z is a group having a carbon-carbon double bond.

(Appendix 7)
The alkyne derivative, the tautomer or stereoisomer thereof according to any one of appendix 1 to appendix 6, wherein X is a group represented by any of the following formulas (Xa) to (Xm) Or their salts.

In the formulas (Xa) to (Xm),
M represents a hydrogen atom or a salt-forming cation;
B ⁻ represents a hydroxide ion or a salt-forming anion.

(Appendix 8)
The alkyne derivative according to any one of appendix 1 to appendix 6, the tautomer or stereoisomer thereof, wherein X is a group represented by any one of the following formulas (X1) to (X16) Or their salts.

(Appendix 9)
7. The alkyne derivative according to any one of appendix 1 to appendix 6, the tautomer or stereoisomer thereof, or a salt thereof, wherein X is a group represented by the following general formula (2):

In the general formula (2), M represents a hydrogen atom or a salt-forming cation.

(Appendix 10)
Z is an atomic group including a structure represented by the following general formula (3), the alkyne derivative according to any one of appendix 1 to appendix 9, a tautomer or stereoisomer thereof, or Their salt.

In the general formula (3),
R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group, or a substituted or unsubstituted linear or branched alkoxy group,
R ¹ and R ² may be connected to each other to form a ring;
Y represents an oxygen atom, a sulfur atom or NRa;
Ra represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group, or a substituted or unsubstituted aryl group.

(Appendix 11)
The alkyne derivative according to any one of appendix 1 to appendix 10, which is represented by the following general formula (4), a tautomer or stereoisomer thereof, or a salt thereof.

In the general formula (4),
Ar ¹ and Ar ² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group;
Ar ³ represents a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group,
M represents a hydrogen atom or a salt-forming cation,
Z represents a linking group including a structure represented by the following general formula (3).

In the general formula (3),
R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group, or a substituted or unsubstituted linear or branched alkoxy group,
R ¹ and R ² may be connected to each other to form a ring;
Y represents an oxygen atom, a sulfur atom, or NRa;
Ra represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group, or a substituted or unsubstituted aryl group.

(Appendix 12)
In R ¹ and R ²
The alkyne derivative according to appendix 11, a tautomer or stereoisomer thereof, wherein the alkyl group has 1 to 12 carbon atoms and the aryl group has 5 to 24 carbon atoms, or Salt.

(Appendix 13)
Z is represented by any one of the following formulas (Z1) to (Z26), the alkyne derivative according to any one of appendix 1 to appendix 12, the tautomer or stereoisomer thereof, or those Salt.

(Appendix 14)
The alkyne derivative according to Supplementary Note 1, represented by the following formula TA-1, a tautomer or stereoisomer thereof, or a salt thereof.

(Appendix 15)
The alkyne derivative according to Supplementary Note 1, represented by the following formula TA-2, a tautomer or stereoisomer thereof, or a salt thereof.

(Appendix 16)
A dye for photoelectric conversion, comprising at least one of the alkyne derivative according to any one of appendix 1 to appendix 15, a tautomer or stereoisomer thereof, or a salt thereof.

(Appendix 17)
A semiconductor electrode for a photoelectrochemical cell, comprising a semiconductor layer containing the photoelectric conversion dye according to appendix 16.

(Appendix 18)
The semiconductor electrode for a photoelectrochemical cell according to appendix 17, wherein the semiconductor layer is at least one selected from the group consisting of a single semiconductor, a compound semiconductor, a metal chalcogenide, and a semiconductor compound having a perovskite structure. .

(Appendix 19)
Item 19. The semiconductor electrode for a photoelectrochemical cell according to appendix 18, wherein the single semiconductor is at least one of silicon and germanium.

(Appendix 20)
The metal chalcogenide is
Oxides of titanium, tin, zinc, iron, tungsten, indium, zirconium, vanadium, niobium, tantalum, strontium, hafnium, cerium, or lanthanum;
Cadmium, zinc, lead, silver, antimony, or bismuth sulfide;
The semiconductor electrode for a photoelectrochemical cell according to appendix 18 or appendix 19, wherein the semiconductor electrode is at least one selected from the group consisting of cadmium, lead selenide; and cadmium telluride.

(Appendix 21)
The compound semiconductor is
Metal chalcogenide according to appendix 20;
Zinc, gallium, indium, or cadmium phosphide;
Gallium arsenide;
21. The semiconductor electrode for a photoelectrochemical cell according to any one of appendix 18 to appendix 20, wherein the semiconductor electrode is at least one selected from the group consisting of copper-indium-selenide; and copper-indium-sulfide.

(Appendix 22)
The semiconductor compound having the perovskite structure is
The semiconductor electrode for a photoelectrochemical cell according to any one of appendix 18 to appendix 21, wherein the semiconductor electrode is any one selected from the group consisting of barium titanate, strontium titanate, and potassium niobate.

(Appendix 23)
23. The semiconductor electrode for a photoelectrochemical cell according to any one of appendix 17 to appendix 22, wherein the semiconductor layer contains titanium oxide or zinc oxide.

(Appendix 24)
A photoelectric conversion element for a photoelectrochemical cell comprising the semiconductor electrode for a photoelectrochemical cell according to any one of appendix 17 to appendix 23.

(Appendix 25)
Furthermore, it has a counter electrode facing the semiconductor electrode for photoelectrochemical cells,
The photoelectric conversion element for a photoelectrochemical cell according to appendix 24, wherein a charge transport material is included between the semiconductor electrode for the photoelectrochemical cell and the counter electrode.

(Appendix 26)
A photoelectrochemical cell comprising the photoelectric conversion element for a photoelectrochemical cell according to appendix 24 or appendix 25.

(Appendix 27)
The 1st coupling process which manufactures the compound represented by the following general formula (III) by the coupling reaction of the compound represented by the following general formula (I), and the compound represented by the following general formula (II) ;
A deprotection step for producing a compound represented by the following general formula (IV) by deprotecting the compound represented by the following general formula (III);
A second coupling step of producing a compound represented by the following general formula (VI) by subjecting a compound represented by the following general formula (IV) and a compound represented by the following general formula (V) to a coupling reaction ;and,
Supplementary note 1 including an acidic group introduction step of converting Q ² in the following general formula (VI) to introduce an acidic group X to produce an alkyne derivative compound represented by the general formula (1) A process for producing an alkyne derivative, a tautomer or stereoisomer thereof, or a salt thereof according to any one of to Supplementary Note 15.

In the general formula (I), general formula (III), general formula (IV) and general formula (VI),
D is the same as D in the general formula (1),
In the general formula (II) and general formula (III),
Q ¹ is a protecting group,
In the general formula (I),
Hal ¹ is halogen,
In the general formula (V),
Hal ² is halogen,
Hal ¹ and Hal ² may be the same or different,
In the general formulas (V) and (VI),
Z is the same as Z in the general formula (1),
Q ² is an arbitrary substituent that can be converted to the acidic group X.

(Appendix 28)
At least one of the first coupling step and the second coupling step,
The production method according to appendix 27, which is performed in the presence of a palladium catalyst and a base.

(Appendix 29)
At least one of the first coupling step and the second coupling step,
The production method according to appendix 27, which is performed in the presence of a palladium catalyst, a copper catalyst, and a base.

(Appendix 30)
In the general formula (V) and the general formula (VI),
Q ² is an acyl group represented by the following general formula (VII),
In the general formula (I),
X is an acidic group represented by the following general formula (VIII),
30. The production method according to any one of supplementary notes 27 to 29, wherein in the acidic group introduction step, Q ² is reacted with cyanoacetic acid to convert to X.

Claims

An alkyne derivative represented by the following general formula (1), a tautomer or stereoisomer thereof, or a salt thereof.

In the general formula (1),
D represents an organic group containing an electron-donating substituent,
X represents a group having an acidic group,
Z represents a linking group having at least one heterocyclic ring selected from the group consisting of a thiophene ring, a furan ring and a pyrrole ring.
2. The alkyne derivative, its tautomer or stereoisomer, or a salt thereof according to claim 1, wherein X is a group represented by any of the following formulas (Xa) to (Xm): .

In the formulas (Xa) to (Xm),
M represents a hydrogen atom or a salt-forming cation,
B − represents a hydroxide ion or a salt-forming anion.
Z is an atomic group including a structure represented by the following general formula (3), the alkyne derivative, a tautomer or stereoisomer thereof, or a salt thereof according to claim 1 or 2 .

In the general formula (3),
R 1 and R 2 each independently represent a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group, or a substituted or unsubstituted linear or branched alkoxy group,
R 1 and R 2 may be connected to each other to form a ring;
Y represents an oxygen atom, a sulfur atom or NRa;
Ra represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group, or a substituted or unsubstituted aryl group.
The alkyne derivative, its tautomer or stereoisomer, or a salt thereof according to any one of claims 1 to 3, which is represented by the following general formula (4).

In the general formula (4),
Ar 1 and Ar 2 each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group;
Ar 3 represents a substituted or unsubstituted arylene group, or a substituted or unsubstituted divalent heterocyclic group,
M represents a hydrogen atom or a salt-forming cation,
Z represents a linking group including a structure represented by the following general formula (3).

In the general formula (3),
R 1 and R 2 each independently represent a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group, or a substituted or unsubstituted linear or branched alkoxy group,
R 1 and R 2 may be connected to each other to form a ring;
Y represents an oxygen atom, a sulfur atom, or NRa;
Ra represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group, or a substituted or unsubstituted aryl group.
A photoelectric conversion dye comprising at least one of the alkyne derivative according to any one of claims 1 to 4, a tautomer or stereoisomer thereof, or a salt thereof.
A semiconductor electrode for a photoelectrochemical cell, comprising a semiconductor layer containing the photoelectric conversion dye according to claim 5.
The semiconductor electrode for a photoelectrochemical cell according to claim 6, wherein the semiconductor layer contains titanium oxide or zinc oxide.
A photoelectric conversion element for a photoelectrochemical cell, comprising the semiconductor electrode for a photoelectrochemical cell according to claim 6.
Furthermore, it has a counter electrode facing the semiconductor electrode for photoelectrochemical cells,
The photoelectric conversion element for a photoelectrochemical cell according to claim 8, further comprising a charge transport material between the semiconductor electrode for the photoelectrochemical cell and the counter electrode.
A photoelectrochemical cell comprising the photoelectric conversion element for a photoelectrochemical cell according to claim 8 or 9.