JP2012072228A - Acrylic acid-based compound, and dye-sensitized solar cell using the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound which has absorption maximum in a near infrared region, and which enables high photoelectric conversion efficiency as a sensitizing dye, and to provide a dye-sensitized solar cell using the compound.SOLUTION: The acrylic acid-based compound is expressed by general formula (1) (wherein A denotes an atomic group which has absorption maximum in a near infrared ray region; Y denotes an atomic group which has a π electron conjugated structure; X denotes a hydrogen atom or an electron-withdrawing substituent; and n and m are each an integer of 1 or 2).

Description

The present invention relates to a novel acrylic acid compound having an absorption maximum in the near-infrared region, and a dye-sensitized solar cell using this compound as a sensitizing dye. Specifically, in a dye-sensitized solar cell, the present invention relates to a novel acrylic acid-based compound that efficiently absorbs solar energy over the near-infrared region and a dye-sensitized solar cell having high photoelectric conversion efficiency.

In recent years, interest in energy problems has increased, and research on solar cells that can efficiently convert sunlight into electricity has become active as clean alternative energy. Some have already been put into practical use, and silicon-based solar cells using amorphous silicon or polycrystalline silicon have begun to spread. However, these silicon-based solar cells are expensive to manufacture, and it is difficult to supply high-purity silicon inexpensively and in large quantities. Accordingly, research on a new type of solar cell that replaces a silicon-based solar cell is underway, and one of them is a dye-sensitized solar cell.
Dye-sensitized solar cells are silicon-based solar cells that have a relatively low manufacturing cost, that oxide semiconductors such as titanium oxide can be used as raw materials without being purified with high purity, and that equipment used for manufacturing can be inexpensive. Has many advantages. In addition, dye-sensitized solar cells can be applied to fields with high design that make use of the color tone of dyes, and are expected to be put to practical use in various fields such as exteriors of mobile electronic devices, clothing, and walls of buildings. It is expected to spread as a next-generation solar cell (Patent Document 1).
The dye-sensitized solar cell includes an anode, a cathode, and an electrolyte, as in a normal battery. The cathode is a base material made of transparent conductive glass, and an oxide thin film formed on the surface thereof. And a structure in which a specific sensitizing dye is adsorbed to the oxide thin film electrode.
In the dye-sensitized solar cell, it is known that the photoelectric conversion efficiency largely depends on the sensitizing dye. As the sensitizing dye, for example, a dye called “N719” or a ruthenium complex called “black dye” Is known (Non-Patent Documents 1 and 2).
Although such a dye-sensitized solar cell using a ruthenium complex exhibits high photoelectric conversion efficiency, the photoelectric conversion efficiency is low compared to a silicon-based solar cell, durability is not sufficient, and the ruthenium complex is Since it is an expensive and rare metal, there is a problem to be solved such as an increase in cost.

In order to solve such a problem, a search for a new sensitizing dye that achieves both a photoelectric conversion efficiency higher than that of a ruthenium complex and a low cost has been actively conducted. In particular, new sensitizing dyes such as coumarin dyes and indoline dyes have been actively developed, and photoelectric conversion characteristics comparable to ruthenium complexes have been reported (Patent Document 2 and Non-Patent Document 3). However, the main absorption band of these sensitizing dyes is in the visible light region between 400 and 700 nm, and there is a problem that light in the near infrared region exceeding 700 nm is hardly utilized.
For this problem, for example, a dye-sensitized solar cell using a squarylium-based dye or a dye-sensitized solar cell using a heptamethine-cyanine-based dye has been disclosed in order to more efficiently use light in the long wavelength region. (Non-Patent Documents 4 and 5). Furthermore, from the viewpoint of efficiently using sunlight, a dye-sensitized solar that uses a phthalocyanine dye as a sensitizing dye based on a long conjugated system having absorption in the visible region and a skeleton having an appropriate solubility in a solvent. A battery is also disclosed (Non-patent Document 6 and Patent Document 3). As an example, a phthalocyanine dye is proposed that introduces three tert-butyl groups with large steric hindrance into the phthalocyanine skeleton to improve the solubility and suppress the recombination of charges while suppressing the association and aggregation of the dyes. (Non-Patent Document 6). However, although these sensitizing dyes use light in the near infrared region exceeding 700 nm, they are not sufficient in terms of photoelectric conversion efficiency and durability as a dye-sensitized solar cell.
As described above, various sensitizing dyes as constituent materials of the dye-sensitized solar cell have been studied. However, the sensitizing dye has an effective sensitizing action in the near infrared region of 700 nm or more and also has durability. The pigment has not been developed yet.

U.S. Pat. No. 4,927,721 JP 2007-287694 A JP 9-199744 A

J. et al. Am. Chem. Soc. 115, 1993, 6382 J. et al. Am. Chem. Soc. , 123, 2001, 1613 Angew. Chem. Int. Ed., 47, 1923, 2008 J. et al. Am. Chem. Soc. , 129, 2007, 10320 Chem. Lett. , 2008, 37, 176 Angew. Chem., Int. Ed., 46, 313, 2007.

An object of the present invention is to provide a novel compound that has an absorption maximum in the near-infrared region and enables high photoelectric conversion efficiency as a sensitizing dye, and further provides a dye-sensitized solar cell using this compound There is to do.

〔式中、Ａは近赤外線領域に吸収極大を有する原子団を表し、Ｙはπ電子共役構造を有する原子団を表し、Ｘは水素原子または電子吸引性置換基を表し、ｎおよびｍは１または２の整数を表す。〕

（ii）下記の一般式(２)で表される前記(ｉ)記載のアクリル酸系化合物。

〔式中、Ｍ１は金属原子、金属化合物または２個の水素原子を表し、Ｙはπ電子共役構造を有する原子団、Ｘは水素原子または電子吸引性置換基、ｎおよびｍは１または２の整数、Ｑ１〜Ｑ４は各々独立に環状構造を表す。但し、式中の置換基(１−１)：

は、Ｑ１〜Ｑ４で表される環状構造に置換している。〕
As a result of intensive studies to solve the above problems, the present inventors have described a compound having a substituent having a specific structure having an acrylic acid residue at the terminal and having an absorption maximum in the near infrared region. It has been found that the present invention is very suitable for the purpose, and the present invention has been completed.

That is, the present invention
(I) Regarding an acrylic acid compound represented by the following general formula (1),

[Wherein, A represents an atomic group having an absorption maximum in the near-infrared region, Y represents an atomic group having a π-electron conjugated structure, X represents a hydrogen atom or an electron-withdrawing substituent, and n and m represent 1 Or represents the integer of 2. ]

(Ii) The acrylic acid compound according to the above (i), which is represented by the following general formula (2).

[In the formula, M1 represents a metal atom, a metal compound or two hydrogen atoms, Y represents an atomic group having a π-electron conjugated structure, X represents a hydrogen atom or an electron-withdrawing substituent, and n and m represent 1 or 2. The integers Q1 to Q4 each independently represent a cyclic structure. However, the substituent (1-1) in the formula:

Is substituted with a cyclic structure represented by Q1 to Q4. ]

The present invention also provides:
(Iii) In the formula (2), the cyclic structure of Q1 to Q4 may have a benzene ring or a substituent which may each independently have a substituent other than the substituent (1-1). The acrylic acid-based compound according to (ii), which represents a naphthalene ring or a phenothiazine ring which may have a substituent.

(Iv) The acrylic acid compound according to (ii) or (iii), wherein at least three of the cyclic structures of Q1 to Q4 in the formula (2) are the same.

(V) In the formula (2), a substituent on Q1 to Q4 is a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, substituted or unsubstituted An acrylic acid compound according to any one of (ii) to (iv), which is an aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, or a substituted amino group,

(Vi) The acrylic acid compound according to any one of (i) to (v), wherein Y has at least one arylene group.

(Vii) The acrylic acid compound according to any one of (i) to (vii), wherein X is selected from a hydrogen atom, a cyano group, a carboxyl group, and a trifluoromethyl group,
further,

(Viii) The present invention relates to a dye-sensitized solar cell using the acrylic acid compound according to any one of (i) to (vii) as a sensitizing dye.

When the acrylic acid-based compound of the present invention is used as a sensitizing dye, it is possible to provide a dye-sensitized solar cell having superior photoelectric conversion efficiency and wavelength absorption characteristics as compared with conventional sensitizing dyes.

（式中、Ａは近赤外線領域に吸収極大を有する原子団を表し、Ｙはπ電子共役構造を有する原子団を表し、Ｘは水素原子または電子吸引性置換基を表し、ｎおよびｍは１または２の整数を表す。）

一般式(１)で表されるアクリル酸系化合物において、Ａは近赤外線領域に吸収極大を有する原子団であり、６００ｎｍ〜１１００ｎｍに極大吸収波長を有する化合物を表す。
上記における、近赤外線領域に吸収極大を有する原子団としては、ジイモニウム系化合物、シアニン系化合物、インドシアニン系化合物、ポリメチン系化合物、スクアリリウム系化合物、ポルフィリン系化合物、ジチオール錯体系化合物、アゾ系化合物、ピロメテン系金属錯体化合物が挙げられる。
本発明のアクリル酸系化合物において、近赤外線領域に吸収極大を有する原子団としてはポルフィリン系化合物が好ましい。
The best mode for carrying out the present invention will be described below.

<Acrylic acid compound>
The acrylic acid compound of the present invention is represented by the following general formula (1).

(In the formula, A represents an atomic group having an absorption maximum in the near infrared region, Y represents an atomic group having a π-electron conjugated structure, X represents a hydrogen atom or an electron-withdrawing substituent, and n and m are 1) Or represents an integer of 2.)

In the acrylic acid compound represented by the general formula (1), A is an atomic group having an absorption maximum in the near-infrared region, and represents a compound having a maximum absorption wavelength at 600 nm to 1100 nm.
In the above, as an atomic group having an absorption maximum in the near infrared region, a diimonium compound, a cyanine compound, an indocyanine compound, a polymethine compound, a squarylium compound, a porphyrin compound, a dithiol complex compound, an azo compound, Examples include pyromethene metal complex compounds.
In the acrylic acid compound of the present invention, a porphyrin compound is preferable as the atomic group having an absorption maximum in the near infrared region.

〔式中、Ｍ１は金属原子、金属化合物または２個の水素原子を表し、Ｙはπ電子共役構造を有する原子団、Ｘは水素原子または電子吸引性置換基、ｎおよびｍは１または２の整数、Ｑ１〜Ｑ４は各々独立に環状構造を表す。但し、式中の置換基(１−１)：

は、Ｑ１〜Ｑ４で表される環状構造に置換している。〕

一般式(２)において、Ｑ１〜Ｑ４は、それぞれ独立に置換基を有しても良い環状構造を表す。
上記における環状構造としては、それぞれ独立に、炭素原子、窒素原子、及び水素原子より選ばれる原子で構成される環状構造であり、置換基を有しても良い炭素環式芳香族環、置換基を有しても良い複素環式芳香族基等があげられる。
Hereinafter, the acrylic acid compound represented by the general formula (2) will be described more specifically.

[In the formula, M1 represents a metal atom, a metal compound or two hydrogen atoms, Y represents an atomic group having a π-electron conjugated structure, X represents a hydrogen atom or an electron-withdrawing substituent, and n and m represent 1 or 2. The integers Q1 to Q4 each independently represent a cyclic structure. However, the substituent (1-1) in the formula:

Is substituted with a cyclic structure represented by Q1 to Q4. ]

In General formula (2), Q1-Q4 represents the cyclic structure which may have a substituent each independently.
The cyclic structure in the above is a cyclic structure composed of atoms independently selected from a carbon atom, a nitrogen atom, and a hydrogen atom, and may have a carbocyclic aromatic ring or substituent. A heterocyclic aromatic group which may have

〔式中、Ｙはπ電子共役構造を有する原子団を表し、Ｘは水素原子または電子吸引性置換基を表し、ｍは１または２の整数を表す。〕

特定置換基Ｌにおいて、Ｙはπ電子共役構造を有する原子団を表す。
上記におけるπ電子共役構造を有する原子団としては、π共役平面を有する構造であればよく、例えば、ベンゼン環、ナフタレン環などの芳香族炭化水素環、例えば、ピリジン環、ピラジン環、ピリミジン環、トリアジン環、ピロール環、ピラゾール環、イミダゾール環、トリアゾール環、オキサゾール環、チアゾール環、フラン環、イソチアゾール環、チオフェン環などの芳香族複素環等が挙げられる。
Preferably, each independently a cyclic structure which may have a substituent which forms a 6-membered ring composed of an atom selected from a carbon atom, a nitrogen atom and a hydrogen atom, the carbon atom, nitrogen Examples thereof include a cyclic structure which may have a substituent in which a ring of 5 or more members composed of an atom, a sulfur atom, and an atom selected from a hydrogen atom is further condensed.

Specific examples of the cyclic structure of Q1 to Q4 in the general formula (2) are not particularly limited, but are each independently composed of an atom selected from a carbon atom, a nitrogen atom, and a hydrogen atom. Examples of the cyclic structure forming the member ring include a benzene ring, a pyridine ring, and a pyrazine ring, and a benzene ring is particularly preferable.
Examples of the cyclic structure in which a ring having a 5-membered ring or more composed of an atom selected from a carbon atom, a nitrogen atom, a sulfur atom, and a hydrogen atom is further condensed include, for example, a naphthalene ring, a quinoline ring, Examples thereof include a quinoxaline ring and a phenothiazine ring, and a naphthalene ring and a phenothiazine ring are particularly preferable.

In the general formula (2), one or two substituents substituted on the cyclic structure represented by Q1 to Q4 are groups represented by the substituent (1-1) (hereinafter referred to as “specific substituents” as appropriate). L ”).

[Wherein Y represents an atomic group having a π-electron conjugated structure, X represents a hydrogen atom or an electron-withdrawing substituent, and m represents an integer of 1 or 2. ]

In the specific substituent L, Y represents an atomic group having a π electron conjugated structure.
The atomic group having a π-electron conjugated structure in the above may be a structure having a π-conjugated plane, for example, an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring, for example, a pyridine ring, a pyrazine ring, a pyrimidine ring, Examples include aromatic heterocyclic rings such as triazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, furan ring, isothiazole ring, and thiophene ring.

In the present specification, divalent groups generated by removing one hydrogen atom of each of two ring carbon atoms from an aromatic hydrocarbon ring and an aromatic heterocyclic ring are collectively referred to as an “arylene group”. Represent.
Preferably, a phenylene group, a naphthylene group, a pyridylene group, a pyrazylene group, a pyrimidylene group, a pyrrolylene group, a furylene group, a thienylene group, a thiazolylene group, an imidazolylene group, an oxazolylene group, a triazolylene group, an indoleylene group, a benzoimidazolylene group, a benzofurylene group, Examples thereof include a benzothienylene group, an isoquinolylene group, and an isothiazolylene group.
More preferred are phenylene group, naphthylene group, furylene group, pyrrolylene group and thienylene group.

In the specific substituent L, m represents 1 or 2, and when m is 2, the arylene groups represented by Y may be the same or different.

In the specific substituent L, X represents a hydrogen atom or an electron-withdrawing substituent.
Examples of the electron withdrawing group include a nitro group, a cyano group, a halogen atom, a tosyl group, a mesyl group, an acyl group, a trifluoromethyl group, and a carboxyl group.

Preferably, a cyano group, a halogen atom, a tosyl group, a mesyl group, an acyl group, a trifluoromethyl group, and a carboxyl group are mentioned.
More preferably, a cyano group, a trifluoromethyl group, and a carboxyl group are mentioned.

置換基(１−１)以外の置換基としては、各々独立にハロゲン原子、炭素数１〜２４の置換または未置換のアルキル基、炭素数１〜２４の置換または未置換のアルコキシ基、炭素数６〜３０の置換または未置換のアリール基、炭素数６〜３０の置換または未置換のアリールオキシ基、炭素数１〜２４の置換または未置換のアルキルチオ基、炭素数６〜３０の置換または未置換のアリールチオ基、炭素数１〜２０の置換のアミノ基等が挙げられる。
Hereinafter, specific examples of the specific substituent L are shown by Formula (L-1) to Formula (L-23). However, the present invention is not limited to these. In the formulas (L-1) to (L-23), (+) represents a bonding position, and preferably the formula (L-1), formula (L-4), formula (L-5), Formula (L-6), Formula (L-12), Formula (L-16), or Formula (L-19).

As the substituent other than the substituent (1-1), each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 24 carbon atoms, or a carbon number A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 24 carbon atoms, a substituted or unsubstituted group having 6 to 30 carbon atoms Examples thereof include a substituted arylthio group and a substituted amino group having 1 to 20 carbon atoms.

In the present specification, the aryl group represents a carbocyclic aromatic group such as a phenyl group or a naphthyl group, for example, a heterocyclic aromatic group such as a furyl group, a thienyl group or a pyridyl group.

More preferably, each independently, a fluorine atom, a chlorine atom, a bromine atom, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 16 carbon atoms, or 4 to 26 carbon atoms. Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group having 4 to 26 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 16 carbon atoms, substituted or unsubstituted arylthio group having 4 to 26 carbon atoms And a substituted amino group having 1 to 14 carbon atoms.

More preferably, each independently, a fluorine atom, a chlorine atom, a bromine atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, or 6 to 20 carbon atoms. Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, substituted or unsubstituted arylthio group having 6 to 20 carbon atoms Group, and a substituted amino group having 1 to 12 carbon atoms.

Specific examples of the substituents on Q1 to Q4 in the general formula (2) are not particularly limited, but each of the halogen atoms independently includes, for example, a fluorine atom, a chlorine atom, and a bromine atom. And

Examples of the unsubstituted alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, Neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group, 1 -Methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, 1-ethyloctyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-hexylheptyl group N-tetradecyl group, n-pentadecyl group, 1-heptyloctyl group, n-hexadecyl group, n-heptadecyl group, 1-octylnonyl group, n-octadecyl group, 1-nonyldecyl group, 1-decylundecyl group, n- Examples thereof include linear, branched or cyclic alkyl groups consisting of only carbon atoms and hydrogen atoms such as eicosyl group, n-docosyl group, n-tetracosyl group, 1-adamantyl group, cyclopentyl group, cyclohexyl group and norbornyl group.
Specific examples of the alkyl group having a substituent include, for example, methoxymethyl group, ethoxymethyl group, n-butoxymethyl group, n-hexyloxymethyl group, (2-ethylbutyloxy) methyl group, and n-octyl. Oxymethyl group, n-decyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxyethyl group, 2-n- Pentyloxyethyl group, 2-n-hexyloxyethyl group, 2- (2′-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2- (2 ′ -Ethylhexyloxy) ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group, 2-n-tetradecyloxyethyl group 2-cyclohexyloxyethyl group, 2-methoxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3- (n-butoxy) propyl group, 3- (n-pentyloxy) propyl group, 3- (n-hexyloxy) propyl group, 3- (2′-ethylbutoxy) propyl group, 3- (n-octyloxy) propyl group, 3- (2 ′ -Ethylhexyloxy) propyl group, 3- (n-decyloxy) propyl group, 3- (n-dodecyloxy) propyl group, 3- (n-tetradecyloxy) propyl group, 3-cyclohexyloxypropyl group, 4-methoxy Butyl group, 4-ethoxybutyl group, 4-n-propoxybutyl group, 4-isopropoxybutyl group, 4-n-butoxyb Group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 4-n-decyloxybutyl group, 4-n-dodecyloxybutyl group, 5-methoxypentyl group, 5-ethoxypentyl group 5-n-propoxypentyl group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyloxyhexyl group, 6-n-decyloxyhexyl group, 4- Methoxycyclohexyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group, 10-methoxydecyl group, 10-n-butoxydecyl group, 12-ethoxydodecyl group, 12-isopropoxidedecyl group, An alkyl group having an alkyloxy group, such as a tetrahydrofurfuryl group;
For example, (2-methoxyethoxy) methyl group, (2-ethoxyethoxy) methyl group, (2-n-butyloxyethoxy) methyl group, (2-n-hexyloxyethoxy) methyl group, (3-methoxypropyloxy) ) Methyl group, (3-ethoxypropyloxy) methyl group, (3-n-butyloxypropyloxy) methyl group, (3-n-pentyloxypropyloxy) methyl group, (4-methoxybutyloxy) methyl group, (6-methoxyhexyloxy) methyl group, (10-ethoxydecyloxy) methyl group, 2- (2′-methoxyethoxy) ethyl group, 2- (2′-ethoxyethoxy) ethyl group, 2- (2′-) n-butoxyethoxy) ethyl group, 3- (2′-ethoxyethoxy) propyl group, 3- (2′-methoxypropyloxy) propyl group, Alkyl groups having an alkyloxyalkyloxy group, such as-(2'-isopropyloxypropyloxy) propyl group, 3- (3'-methoxypropyloxy) propyl group, and 3- (3'-ethoxypropyloxy) propyl group .
For example, benzyloxymethyl group, 2-benzyloxyethyl group, 2-phenethyloxyethyl group, 2- (4′-methylbenzyloxy) ethyl group, 2- (2′-methylbenzyloxy) ethyl group, 2- ( 4′-fluorobenzyloxy) ethyl group, 2- (4′-chlorobenzyloxy) ethyl group, 3-benzyloxypropyl group, 3- (4′-methoxybenzyloxy) propyl group, 4-benzyloxybutyl group, Alkyl groups having an aralkyloxy group, such as a 2- (benzyloxymethoxy) ethyl group and a 2- (4′-methylbenzyloxymethoxy) ethyl group;

For example, phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-methoxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 4-chlorophenyl Oxymethyl group, 2-chlorophenyloxymethyl group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′- Methoxyphenyloxy) ethyl group, 2- (4′-chlorophenyloxy) ethyl group, 2- (4′-bromophenyloxy) ethyl group, 2- (1′-naphthyloxy) ethyl group, 2- (2′-) Naphthyloxy) ethyl group, 3-phenyloxypropyl group, 3- (2′-naphthyloxy) propyl group, 4-phenyl Nyloxybutyl group, 4- (2′-ethylphenyloxy) butyl group, 5- (4′-tert-butylphenyloxy) pentyl group, 6- (2′-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl Group, 10-phenyloxydecyl group, 10- (3′-chlorophenyloxy) decyl group, 2- (2′-phenyloxyethoxy) ethyl group, 3- (2′-phenyloxyethoxy) propyl group, 4- ( An alkyl group having an aryloxy group, such as a 2'-phenyloxyethoxy) butyl group;
For example, n-butylthiomethyl group, n-hexylthiomethyl group, 2-methylthioethyl group, 2-ethylthioethyl group, 2-n-butylthioethyl group, 2-n-hexylthioethyl group, 2-n -Octylthioethyl group, 2-n-decylthioethyl group, 3-methylthiopropyl group, 3-ethylthiopropyl group, 3-n-butylthiopropyl group, 4-ethylthiobutyl group, 4-n-propylthio Alkylthio groups such as butyl group, 4-n-butylthiobutyl group, 5-ethylthiopentyl group, 6-methylthiohexyl group, 6-ethylthiohexyl group, 6-n-butylthiohexyl group, and 8-methylthiooctyl group An alkyl group having
For example, fluoromethyl group, 3-fluoropropyl group, 6-fluorohexyl group, 8-fluorooctyl group, trifluoromethyl group, 1,1-dihydro-perfluoroethyl group, 1,1-dihydro-perfluoro-n -Propyl group, 1,1,3-trihydro-perfluoro-n-propyl group, 2-hydro-perfluoro-2-propyl group, 1,1-dihydro-perfluoro-n-butyl group, 1,1- Dihydro-perfluoro-n-pentyl group, 1,1-dihydro-perfluoro-n-hexyl group, 6-fluorohexyl group, 4-fluorocyclohexyl group, 1,1-dihydro-perfluoro-n-octyl group, 1,1-dihydro-perfluoro-n-decyl group, 1,1-dihydro-perfluoro-n-dodecyl group, 1,1-dihydro-perf group O-n-tetradecyl group, 1,1-dihydro-perfluoro-n-hexadecyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, 2 , 2-bis (trifluoromethyl) propyl group, dichloromethyl group, 2-chloroethyl group, 3-chloropropyl group, 4-chlorocyclohexyl group, 7-chloroheptyl group, 8-chlorooctyl group, 2,2,2 An alkyl group having a halogen atom, such as a trichloroethyl group;
For example, fluoromethyloxymethyl group, 3-fluoro-n-propyloxymethyl group, 6-fluoro-n-hexyloxymethyl group, trifluoromethyloxymethyl group, 1,1-dihydro-perfluoroethyloxymethyl group, 1,1-dihydro-perfluoro-n-propyloxymethyl group, 2-hydro-perfluoro-2-propyloxymethyl group, 1,1-dihydro-perfluoro-n-butyloxymethyl group, 1,1- Dihydro-perfluoro-n-pentyloxymethyl group, 1,1-dihydro-perfluoro-n-hexyloxymethyl group, 1,1-dihydro-perfluoro-n-octyloxymethyl group, 1,1-dihydride Rhoperfluoro-n-decyloxymethyl group, 1,1-dihydro-perfluoro-n-tetradecylo Xymethyl group, 2,2-bis (trifluoromethyl) propyloxymethyl group, 3-chloro-n-propyloxymethyl group, 2- (8-fluoro-n-octyloxy) ethyl group, 2- (1,1 -Dihydro-perfluoroethyloxy) ethyl group, 2- (1,1,3-trihydro-perfluoro-n-propyloxy) ethyl group, 2- (1,1-dihydro-perfluoro-n-pentyloxy) An ethyl group, a 2- (6-fluoro-n-hexyloxy) ethyl group, a 2- (1,1-dihydro-perfluoro-n-octyloxy) ethyl group, a 3- (4-fluorocyclohexyloxy) propyl group, 3- (1,1-dihydro-perfluoroethyloxy) propyl group, 3- (1,1-dihydro-perfluoro-n-dodecyloxy) propyl group, -(Perfluoro-n-hexyloxy) butyl group, 4- (1,1-dihydro-perfluoroethyloxy) butyl group, 6- (2-chloroethyloxy) hexyl group, 6- (1,1-dihydro) An alkyl group having a halogenoalkyloxy group, such as a perfluoroethyloxy) hexyl group;

For example, phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-ethylphenyloxymethyl group, 4-n-propylphenyloxymethyl group, 4 -N-butylphenyloxymethyl group, 4-tert-butylphenyloxymethyl group, 4-n-hexylphenyloxymethyl group, 4-n-octylphenyloxymethyl group, 4-n-decylphenyloxymethyl group, 4 -Methoxyphenyloxymethyl group, 4-ethoxyphenyloxymethyl group, 4-butoxyphenyloxymethyl group, 4-n-pentyloxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 3-fluorophenyloxymethyl group, 2-Fluorophenyloxymethyl 3,4-difluorophenyloxymethyl group, 4-chlorophenyloxymethyl group, 2-chlorophenyloxymethyl group, 4-phenylphenyloxymethyl group, 1-naphthyloxymethyl group, 2-naphthyloxymethyl group, 2-furyl Oxymethyl group, 1-phenyloxyethyl group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′- n-hexylphenyloxy) ethyl group, 2- (4′-methoxyphenyloxy) ethyl group, 2- (4′-n-butoxyphenyloxy) ethyl group, 2- (4′-fluorophenyloxy) ethyl group, 2- (4′-chlorophenyloxy) ethyl group, 2- (4′-bromophenyloxy) ethyl group, 2- (1′-naphthylo) Ii) ethyl group, 2- (2'-naphthyloxy) ethyl group, 2-phenyloxypropyl group, 3-phenyloxypropyl group, 3- (4'-methylphenyloxy) propyl group, 3- (2'- Naphthyloxy) propyl group, 4-phenyloxybutyl group, 4- (2′-ethylphenyloxy) butyl group, 4-phenyloxypentyl group, 5-phenyloxypentyl group, 5- (4′-tert-butylphenyl) Oxy) pentyl group, 6-phenyloxyhexyl group, 6- (2′-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 10- (3′-methylphenyloxy) decyl group And an alkyl group having an aryloxy group.

The substituted or unsubstituted alkoxy group is an alkoxy group which may have a substituent similar to the alkyl group listed above, and an alkoxy group derived from the alkyl group shown as a specific example of the alkyl group is Can be mentioned.

Examples of the unsubstituted aryl group include a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 1-pyrenyl group, 2- A pyrenyl group, a 2-perylenyl group, a 3-perylenyl group, a 2-fluoranthenyl group, a 3-fluoranthenyl group, a 7-fluoranthenyl group, and an 8-fluoranthenyl group.
Specific examples of the aryl group having a substituent include, for example, 1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4- (4′-tert-butylcyclohexyl) phenyl group, 3 -An aryl group having an alkyl group such as a cyclohexylphenyl group, a 2-cyclohexylphenyl group, a 4-ethyl-1-naphthyl group, a 6-n-butyl-2-naphthyl group, or a 2,4-dimethylphenyl group.
For example, 4-methoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 3-isopropoxyphenyl group, Such as 2-isopropoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-methyl-5-methoxyphenyl group, 2-phenyloxyphenyl group, etc. An aryl group having an alkoxy group and an aryloxy group;
For example, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 2,6-diphenylphenyl group, 4- (2′-naphthyl) phenyl group, 2-phenyl-1-naphthyl group, 1- Aryl groups having an aryl group such as a phenyl-2-naphthyl group and a 7-phenyl-1-pyrenyl group;
For example, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group Aryl groups having a halogen atom such as 2-methyl-3-chlorophenyl group, 2-methoxy-4-fluorophenyl group, 2-fluoro-4-methoxyphenyl group.
Furthermore, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-perfluoroethylphenyl group, 4-methylthiophenyl Group, 4-ethylthiophenyl group, 4-cyanophenyl group, 3-cyanophenyl group and the like.

The substituted or unsubstituted aryloxy group is an aryloxy group which may have the same substituent as the above-mentioned aryl group, and is shown as a specific example of the above-mentioned substituted aryl group. Examples thereof include a substituted or unsubstituted aryloxy group derived from a substituent.

The substituted or unsubstituted alkylthio group is an alkylthio group which may have a substituent similar to the alkyl group listed above, and an alkylthio group derived from the alkyl group shown as a specific example of the alkyl group is Can be mentioned.

The substituted or unsubstituted arylthio group is an arylthio group which may have the same substituent as the above-mentioned aryl group, and is derived from the substituents shown as specific examples of the substituted aryl groups listed above. Substituted or unsubstituted arylthio groups.

Examples of the substituted amino group include N-methylamino group, N-ethylamino group, Nn-butylamino group, N-cyclohexylamino group, Nn-octylamino group, and Nn-decylamino group. An amino group having an alkyl group.
For example, N-benzylamino group, N-phenylamino group, N- (3-methylphenyl) amino group, N- (4-methylphenyl) amino group, N- (4-n-butylphenyl) amino group, N -(4-methoxyphenyl) amino group, N- (3-fluorophenyl) amino group, N- (4-chlorophenyl) amino group, N- (1-naphthyl) amino group, N- (2-naphthyl) amino group An amino group having an aralkyl group or an aryl group, such as
For example, N, N-dimethylamino group, N, N-diethylamino group, N, N-di-n-butylamino group, N, N-di-n-hexylamino group, N, N-di-n-octyl Amino group, N, N-di-n-decylamino group, N, N-di-n-dodecylamino group, N-methyl-N-ethylamino group, N-ethyl-Nn-butylamino group, N- Alkyl groups or aralkyl groups such as methyl-N-phenylamino group, N-ethyl-N-phenylamino group, Nn-butyl-N-phenylamino group, or disubstituted amino groups;
For example, N, N-diphenylamino group, N, N-di (3-methylphenyl) amino group, N, N-di (4-methylphenyl) amino group, N, N-di (4-ethylphenyl) amino Group, N, N-di (4-tert-butylphenyl) amino group, N, N-di (4-n-hexylphenyl) amino group, N, N-di (4-methoxyphenyl) amino group, N, N-di (4-ethoxyphenyl) amino group, N, N-di (4-n-butoxyphenyl) amino group, N, N-di (4-n-hexyloxyphenyl) amino group, N, N-di (1-naphthyl) amino group, N, N-di (2-naphthyl) amino group, N-phenyl-N- (3-methylphenyl) amino group, N-phenyl-N- (4-methylphenyl) amino group N-phenyl-N- (4-octylphenyl) Mino group, N-phenyl-N- (4-methoxyphenyl) amino group, N-phenyl-N- (4-ethoxyphenyl) amino group, N-phenyl-N- (4-n-hexyloxyphenyl) amino group N-phenyl-N- (4-fluorophenyl) amino group, N-phenyl-N- (1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) amino group, N-phenyl-N— An amino group disubstituted by an aryl group such as (3-phenylphenyl) amino group and N-phenyl-N- (4-phenylphenyl group) can be used.

In the general formula (2), M1 represents a metal atom, a metal compound, or two hydrogen atoms.

The metal atom or metal compound in the above may be any metal atom or metal compound capable of forming a complex, such as a divalent metal atom, metal oxide, metal hydroxide, or metal chloride. And the like.

When M1 represents two hydrogen atoms, the two hydrogen atoms are bonded to two different nitrogen atoms, respectively.
Examples of the divalent metal atom include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, Pb, and Sn.
Examples of the metal oxide include VO and TiO.
Examples of the metal hydroxide include MnOH and Si (OH) ₂ .
Examples of the metal chloride include AlCl, InCl, FeCl, TiCl ₂ ,
SnCl _2, representing a such as SiCl _2, GeCl _2.
Preferred are Mg, AlCl, FeCl, Co, Ni, Cu, Zn, Pd, SnCl ₂ , InCl, VO, MnOH, and TiO.
More preferably Cu, Co, Ni, Pd, MnOH, AlCl, FeCl, InCl, SnCl 2, VO, TiO, Zn and the like.
Particularly preferred are VO, Pd, Cu, and Zn.

上記一般式(２−１）〜（２−８)におけるＭ１１、Ｍ２１、Ｍ３１、Ｍ４１、Ｍ５１、Ｍ６１、Ｍ７１およびＭ８１はいずれも上記一般式(２)のＭ１と同じものを意味する。
Hereinafter, although the preferable form of the acrylic acid type compound represented by General formula (2) is shown by General formula (2-1)-General formula (2-8), in this invention, it is not limited to these Absent.

In the general formulas (2-1) to (2-8), M11, M21, M31, M41, M51, M61, M71, and M81 all mean the same as M1 in the general formula (2).

Z11 and Z12 in general formula (2-1), Z21 and Z22 in general formula (2-2), Z31 and Z32 in general formula (2-3), Z41 in general formula (2-4) and Z42, Z51 and Z52 in general formula (2-5), Z61 and Z62 in general formula (2-6), Z71 and Z72 in general formula (2-7), and in general formula (2-8) Z81 and Z82 each independently represent a hydrogen atom or a specific substituent L. However, it does not become a hydrogen atom at the same time.

R101 to R114, R201 to R216, R301 to R320, R401 to R422, R501 to R520, R601 to R620, R701 to R722 and R801 to R822 in the above general formulas (2-1) to (2-8) It means the same as the substituent on Q1 to Q4 in formula (2).

Next, specific examples of the acrylic acid-based compound represented by the general formula (2) include the following compounds, but the present invention is not limited thereto.

〔式中、Ｙ、およびｍは、一般式(２)中のＹ、およびｍと同じ意味を表す。〕

〔式中、Ｘは、一般式(２)中のＸと同じ意味を表す。〕
<Manufacturing method>
The acrylic acid compound represented by the general formula (2) can be produced with reference to a method known per se. For example, in the general formula (2), a compound having a bromine atom as a substituent on Q1 to Q4 and a boronic acid compound represented by the following general formula (3a) are coupled to the reaction compound by the Suzuki-Miyaura reaction. The compound represented by the following general formula (4a) can be produced by a dehydration condensation reaction.

[In formula, Y and m represent the same meaning as Y and m in general formula (2). ]

[Wherein X represents the same meaning as X in formula (2). ]

は、式（５−Ｐ−１）で表される化合物と式（６−Ｐ−１）で表される化合物、もしくは、式（７−Ｐ−１）で表される化合物と式（８−Ｐ−１）で表される化合物に、ハロゲン化金属として塩化亜鉛を、所望により塩基（例えば、モリブデン酸アンモニウム、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン、１，５−ジアザビシクロ［４．３．０］−５−ノネン、トリアルキルアミン、アンモニア）の存在下で反応させることにより製造することができる［例えば、国際公開第０１／５０１９９号公報に記載の方法に従って製造することができる］。

In addition, about a manufacture example, it describes with reference to the case of the above-mentioned exemplary compound P-1.

Intermediate compound represented by the following formula (2-P-1) in exemplary compound P-1:

Is a compound represented by formula (5-P-1) and a compound represented by formula (6-P-1), or a compound represented by formula (7-P-1) and formula (8- P-1), zinc chloride as a metal halide, and optionally a base (for example, ammonium molybdate, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5- Diazabicyclo [4.3.0] -5-nonene, trialkylamine, ammonia) can be produced by reaction [for example, produced according to the method described in WO 01/50199] be able to].

The intermediate compound represented by the formula (2-P-1) is produced by, for example, reacting a compound represented by the formula (5-P-1) with a boron compound (for example, boron trichloride). The compound represented by the formula (8-P-1) is allowed to act on the halide of the subphthalocyanine boron complex [which can be produced according to the method described in JP-A-2005-289854, for example]. A metal-free body of a compound represented by (2-P-1) is produced [for example, it can be produced according to the method described in JP-A No. 02-9882], and further, a metal-free body and zinc or It can be produced by reacting a metal oxide such as zinc oxide in the presence of a base (for example, triethylamine, sodium hydride) [for example, JP-A-2005-290282. It can be prepared according to the method described.

特定置換基Ｌを構造単位に含む本発明のアクリル酸系化合物においても例外ではなく、本明細書中、例示化合物Ｐ−１〜Ｐ−６８で示した構造式も、あるひとつの構造異性体を示すものであり、この構造に限定はされない。
なお、本発明のアクリル酸系化合物の形態は単一の化合物として用いてもよいし、２種以上の構造異性体からなる混合物として用いることもできる。
構造異性体からなる混合物として用いる場合には、構造異性体の混合比率はいかなるものでもよい。
In addition, the compound represented by the formula (5-P-1), the compound represented by the formula (6-P-1), and zinc chloride are reacted with each other to represent the formula (2-P-1). In general, when an intermediate compound is produced, a plurality of structural isomers having different positions to which substituents are bonded may exist.
For example, the compound represented by the formula (2-P-1) is actually one kind selected from the compounds represented by the formula (2-P-1a) to the formula (2-P-1h). It represents a compound or a mixture of two or more structural isomers. For the description of the structure of such a mixture composed of a plurality of structural isomers, for example, in this specification, for example, one structural formula represented by the formula (2-P-1) is described. is there.

The acrylic acid-based compound of the present invention containing the specific substituent L as a structural unit is not an exception, and in the present specification, the structural formulas represented by Exemplified Compounds P-1 to P-68 are also a certain structural isomer. It is shown and this structure is not limited.
In addition, the form of the acrylic acid compound of the present invention may be used as a single compound, or may be used as a mixture composed of two or more structural isomers.
When used as a mixture of structural isomers, the mixing ratio of the structural isomers may be any.

鈴木−宮浦カップリング反応に用いる前記の溶媒としては、本反応を阻害しないものであれば特に限定されず、例えばベンゼン、トルエン、キシレン等の芳香族炭化水素類、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、クロロホルム、ジクロロメタン等のハロゲン化炭化水素類、酢酸メチル、酢酸エチル等のエステル類、１，２−ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル類、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン、１，３-ジメチル−２−イミダゾリジノン等のアミド類、アセトニトリル、ジメチルスルホキシド、ピリジン等を挙げることができる。
Next, as the intermediate compound represented by the formula (2-P-1) and the boronic acid compound represented by the general formula (3a), 5-formyl-2,2′-bithiophene-5-boric acid is obtained. A precursor compound represented by the general formula (2-P-2) by a Suzuki-Miyaura coupling reaction in the presence or absence of a base and a ligand, in the presence of a transition metal catalyst, preferably using a solvent. To manufacture.

The solvent used in the Suzuki-Miyaura coupling reaction is not particularly limited as long as it does not inhibit this reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketones, halogenated hydrocarbons such as chloroform and dichloromethane, esters such as methyl acetate and ethyl acetate, ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, N, N-dimethylformamide, N, N -Amides such as dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, dimethyl sulfoxide, pyridine and the like.

These solvents are appropriately selected according to the ease of reaction, and can be used singly or in combination of two or more. If necessary, water may be removed with a suitable dehydrating agent or desiccant and used as a non-aqueous solvent.

In the case of using a solvent, generally, when the amount of the solvent increases, the efficiency of the reaction decreases. On the other hand, when the amount of the solvent decreases, it becomes difficult to uniformly heat and stir or a side reaction tends to occur. Therefore, it is desirable that the amount of the solvent is up to 100 times, preferably 5 to 50 times that of the whole intermediate compound by weight ratio.

Examples of the base used in the reaction include alkali metal hydrides such as sodium hydride, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, and carbonate. Examples thereof include alkali metal carbonates such as cesium, and organic bases such as pyridine and triethylamine.
What is necessary is just to select the usage-amount of a base suitably in the range of 1.0-10.0 times mole with respect to the intermediate compound represented by a formula (2-P-1), for example.

Examples of the transition metal catalyst used in the reaction include palladium compounds such as palladium acetate, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and tris (dibenzylacetone) palladium, and bis (triphenylphosphine). ) Nickel compounds such as nickel chloride and tetrakis (triphenylphosphine) nickel.

The amount of the transition metal catalyst used may be appropriately selected, for example, in the range of 0.0001 to 0.2 times moles with respect to the intermediate compound represented by the formula (2-P-1), preferably The range is 0.001 to 0.15 moles.

Examples of the ligand used in the reaction include phosphines such as triphenylphosphine, 1,2-bisdiphenylphosphinoethane, 1,3-bisdiphenylphosphinopropane, 1,4-bisdiphenylphosphinobutane, and the like. Can be mentioned.
The amount of the ligand used may be appropriately selected in the range of 0.5 to 100-fold mol with respect to the transition metal catalyst, but is preferably in the range of 1.0 to 10.0-fold mol, even in the absence. good.

The reaction temperature may be appropriately selected in the range of 0 to 200 ° C., but is preferably in the range of room temperature to solvent reflux temperature.

The reaction time is not constant depending on the reaction scale and reaction temperature, but may be appropriately selected within the range of 1 to 48 hours.

Since this reaction is an equimolar reaction, for example, if the intermediate compound represented by the formula (2-P-1) and the boronic acid compound represented by the general formula (3a) are reacted in an equimolar amount, Although it is good, as the usage-amount of the boronic acid compound represented by General formula (3a), for example with respect to the number of halogen atoms of the intermediate compound represented by Formula (2-P-1), it is set to 0. What is necessary is just to select suitably in the range of 5-5.0 times mole, Preferably it is the range of 1.0-3.0 times mole.

When a solvent that dissolves in water is used after completion of the reaction, the reaction solution is discharged into water, and the precipitate is filtered off and washed with methanol. When a solvent insoluble in water is used, the solvent is distilled off under reduced pressure, water is added, the precipitate is filtered off and washed with methanol. If necessary, the precipitate can be purified by a method such as column chromatography.

Then, as a precursor compound represented by the general formula (2-P-2) produced by the Suzuki-Miyaura coupling reaction described above, and cyanoacetic acid as a compound represented by the general formula (4a), An acrylic acid compound represented by the general formula (2) can be produced by a dehydration condensation reaction in the presence of a base, preferably using a solvent.

The solvent used in the dehydration condensation reaction is not particularly limited as long as it does not inhibit the reaction. For example, hydrocarbons such as pentane, hexane, cyclohexane, octane, benzene, toluene, xylene, carbon tetrachloride, Chloroform, 1,2-dichloroethane, 1,2-dibromoethane, trichloroethylene, tetrachloroethylene, chlorobenzene, bromobenzene, α-dichlorobenzene and other halides, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2 -Butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, phenol, benzyl alcohol, cresol, Alcohols and phenols such as ethylene glycol, triethylene glycol, glycerin, diethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, dicyclohexyl-18-crown -6, ethers such as methyl carbitol and ethyl carbitol, acetic acid, acetic anhydride, trichloroacetic acid, trifluoroacetic acid, propionic anhydride, ethyl acetate, butyl carbonate, ethylene carbonate, propylene carbonate, formamide, N-methylformamide, Acids and acid derivatives such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, hexamethylphosphoric triamide, Examples thereof include nitriles such as tolyl, propionitrile, succinonitrile and benzonitrile, nitro compounds such as nitromethane and nitrobenzene, and sulfur-containing compounds such as dimethyl sulfoxide and sulfolane.

These solvents are appropriately selected according to the ease of reaction, and can be used singly or in combination of two or more. If necessary, water may be removed with a suitable dehydrating agent or desiccant and used as a non-aqueous solvent.

In the case of using a solvent, generally, when the amount of the solvent increases, the efficiency of the reaction decreases. On the other hand, when the amount of the solvent decreases, it becomes difficult to uniformly heat and stir or a side reaction tends to occur. Therefore, the amount of the solvent is, for example, up to 100 times, preferably 5 to 50 times the total amount of the precursor compound represented by the formula (2-P-2) produced by the Suzuki-Miyaura coupling reaction. It is desirable to make it.

Examples of the base used in the reaction include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, ammonia, triethylamine, piperidine, pyridine, pyrrolidine, aniline, N, N-dimethylaniline, N, N-diethylaniline and the like can be mentioned.
What is necessary is just to select the usage-amount of a base suitably in the range of 1-10 times mole with respect to the precursor compound represented by the formula (2-P-2) manufactured by Suzuki-Miyaura coupling reaction, for example. .

The reaction temperature may be appropriately selected in the range of 0 to 200 ° C., but is preferably in the range of room temperature to solvent reflux temperature.

The reaction time is not constant depending on the reaction scale and reaction temperature, but may be appropriately selected within the range of 1 to 48 hours.

Since this reaction is an equimolar reaction, the compound produced by the Suzuki-Miyaura coupling reaction and the compound represented by the general formula (4a) may be reacted in an equimolar amount, but the general formula (4a) The amount of the compound represented is, for example, 0. 0 to the number of -CHO groups of the precursor compound represented by the formula (2-P-2) produced by the Suzuki-Miyaura coupling reaction. What is necessary is just to select suitably in the range of 5-5 times mole, Preferably it is the range of 1-3 times mole.

When a solvent that dissolves in water is used after completion of the reaction, the reaction solution is discharged into water, and the precipitate is filtered off and washed with water. When a solvent insoluble in water is used, the solvent is distilled off under reduced pressure, water is added, the precipitate is filtered off and washed with water. If necessary, the precipitate can be purified by a method such as column chromatography.

The acrylic acid compound of the present invention can be advantageously used in various fields that require an organic compound that absorbs visible light. Further, since it has a carboxyl group, it is extremely useful as a material for a dye-sensitized solar cell, such that a compound can be fixed on the surface of titanium oxide.

In the dye-sensitized solar cell of the present invention, the acrylic acid compound of the present invention may be used alone or in combination. The acrylic acid compound of the present invention includes not only crystals but also amorphous (amorphous).
Considering the required characteristics of the dye-sensitized solar cell of the present invention, the acrylic acid compound of the present invention is preferably a compound having a maximum absorption wavelength at 550 nm to 1200 nm, more preferably 600 nm to 1100 nm. It is a compound having maximum absorption.

<Dye-sensitized solar cell>
Embodiments of the dye-sensitized solar cell of the present invention include, for example, an anode, a cathode, and an electrolyte. The cathode includes a base material made of transparent conductive glass or polymer, and an oxidation formed on the surface thereof. A thin film electrode. The acrylic thin film electrode of the present invention is adsorbed on the oxide thin film electrode. Such a dye-sensitized solar cell exhibits excellent photoelectric conversion efficiency as compared with a conventional dye-sensitized solar cell, and has excellent durability such as weather resistance and heat resistance.

The anode need only be composed of a conductive material, and there are no particular restrictions on the type of constituent material. For example, a material in which a trace amount of platinum or conductive carbon is attached to the surface of a substrate made of transparent conductive glass can be suitably used. As the transparent conductive glass, for example, glass made of tin oxide or indium-tin oxide (ITO) can be used.

The cathode has a substrate made of transparent conductive glass and an oxide thin film electrode formed on the surface thereof, and the acrylic acid compound of the present invention described above is adsorbed to the oxide thin film electrode. Is. As the transparent conductive glass, glass made of the material exemplified in the section of the anode can be used. There is no restriction | limiting in particular about the shape of a base material, For example, a plate-shaped thing etc. can be used.

The oxide thin film electrode is a thin film made of an oxide. Examples of the oxide constituting the oxide thin film electrode include a metal oxide, more specifically, titanium oxide, niobium oxide, zinc oxide, and tin oxide. , Tungsten oxide, indium oxide, and the like. Among these oxides, titanium oxide, niobium oxide and tin oxide are preferable, and titanium oxide is particularly preferable. This oxide thin film electrode is used in a state where the acrylic acid compound of the present invention is adsorbed.

As the electrolyte, a liquid or solid made of an electrolyte, a solution containing the electrolyte, or the like can be used. Among these, it is preferable to use a redox electrolyte. A redox electrolyte is a solution containing a substance (oxidizing agent, reducing agent) that constitutes a redox system. For example, the redox electrolyte forms a redox system (I ⁻ / I ^{3 −} system) represented by the following formula (I). A solution containing iodine and an imidazolium salt of iodine can be preferably used. As the solvent of this solution, an electrochemically inert substance such as acetonitrile or propionitrile can be suitably used.
I ₃ ⁻ + 2e ⁻ ← → 3I ⁻ + I ₂ : (A)

What is necessary is just to comprise a dye-sensitized solar cell so that electrolyte may fill between an anode and a cathode. For example, a configuration in which the container is filled with the electrolyte solution, and the anode and the cathode are disposed so as to face each other in the electrolyte solution.

The acrylic acid-based compound of the present invention is a compound that efficiently absorbs solar energy. Therefore, when the acrylic acid-based compound of the present invention is used as a sensitizing dye, a dye-sensitized solar cell having superior photoelectric conversion efficiency and wavelength absorption characteristics can be provided as compared with conventional sensitizing dyes.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
In the following production examples and examples, the physical properties of each compound were measured by the following methods.
Absorption spectrum: An N, N-dimethylformamide solution having a concentration of 0.01 g / L was measured with an optical path length of 10 mm using a U-3500 self-recording spectroscopic clock manufactured by Hitachi, Ltd. as a measuring instrument.
Mass spectrometry spectrum (MASS): Measured by infusion analysis using a syringe pump by electrospray ionization method using Quattro micro API system Masslynx manufactured by Japan Waters.

Example 1 Synthesis of Exemplary Compound P-1 To 90 ml of N, N-dimethylamino-2-ethanol, 2.0 g of 4-bromophthalonitrile, 8.90 g of 4-tert-butylphthalonitrile, 1.98 g of zinc chloride. And stirred at 120 to 125 ° C. for 6 hours. Thereafter, the reaction solution was cooled to room temperature, 100 ml of water was added, and further stirred for 1.5 hours, and then the precipitate was collected by filtration and washed with 50 ml of methanol four times. After drying at 60 ° C., separation was performed by column chromatography using silica gel (developing solvent: toluene / ethyl acetate = 1/1), and the intermediate compound represented by the formula (2-P-1) was converted to 4 0.21 g (52.8% yield) was obtained as crystals.
MASS spectrum (M + 1) + = 825.1
Subsequently, to 100 ml of 1,3-dimethyl-2-imidazolidinone, 4.0 g of the above intermediate compound, 1.16 g of 5-formyl-2,2′-bithiophene-5-boronic acid, 2.01 g of potassium carbonate, Tetrakis (triphenylphosphine) palladium 0.28g was added, and it stirred at 80-85 degreeC for 8 hours. Thereafter, the reaction solution was cooled to room temperature, 150 ml of water was added, and the mixture was further stirred for 1.5 hours, and then the precipitate was collected by filtration and washed 4 times with 50 ml of methanol to obtain 1.5 g of the precursor compound as crystals. Got as.
Furthermore, 0.75 g of the obtained precursor compound, 0.82 g of cyanoacetic acid, 1.48 g of ammonium acetate were added to 37.5 g of acetic acid, and the mixture was stirred at 90 to 95 ° C. for 8 hours. Thereafter, the reaction solution was cooled to room temperature, 20 ml of water was added, and further stirred for 1.5 hours, and then the precipitate was collected by filtration and washed with 50 ml of water four times. After drying at 60 ° C., the resulting crude product was separated by column chromatography using silica gel (developing solvent: toluene / ethyl acetate = 1/1) to give 153 mg (yield 3.8%) as an example. Compound P-1 was obtained as crystals.
Absorption maximum wavelength in N, N-dimethylformamide solution 676 nm
Gram extinction coefficient in N, N-dimethylformamide solution 1.4 × 10 ⁵ ml / gcm
MASS spectrum (M + 1) + = 1004.2

Example 2 Synthesis of Exemplary Compound P-6 To 135 ml of N, N-dimethylamino-2-ethanol, 4.50 g of 5-bromoisoindolinediimine, 4- (2,4-dimethylpentan-3-yloxy) 15.6 g of isoindoline diimine and 2.74 g of zinc (II) chloride were added, and the mixture was stirred at 120 to 125 ° C. for 11 hours. Thereafter, the reaction solution was cooled to room temperature, 500 ml of water was added, and further stirred for 1.5 hours, and then the precipitate was collected by filtration and washed twice with 200 ml of methanol. After drying at 60 ° C., separation was performed by column chromatography using silica gel (developing solvent: toluene / hexane = 5/1) to obtain 3.21 g (yield 16.0%) of the intermediate compound.
Subsequently, to 200 ml of 1,3-dimethyl-2-imidazolidinone, 2.0 g of the above intermediate compound, 0.95 g of 5-formyl-2,2′-bithiophene-5-boronic acid, 1.66 g of potassium carbonate, Tetrakis (triphenylphosphine) palladium 0.23g was added and it stirred at 80-85 degreeC for 18 hours. Thereafter, the reaction solution was cooled to room temperature, 150 ml of water was added, and the mixture was further stirred for 1.5 hours. The precipitate was collected by filtration, washed twice with 25 ml of methanol, and column chromatography using silica gel (development). Solvent: Toluene / ethyl acetate = 5/1) to obtain 1.15 g of a precursor compound as crystals.
Furthermore, 1.15 g of the obtained precursor compound, 0.92 g of cyanoacetic acid, 1.66 g of ammonium acetate were added to 50 g of acetic acid, and the mixture was stirred at 90 to 95 ° C. for 8 hours. Thereafter, the reaction solution was cooled to room temperature, 20 ml of water was added, and further stirred for 1.5 hours, and then the precipitate was collected by filtration and washed with 50 ml of water four times. After drying at 60 ° C., the obtained crude product is separated by column chromatography using silica gel (developing solvent: toluene / ethyl acetate = 1/1), and 233 mg (yield 19.1%) is exemplified. Compound P-6 was obtained as crystals.
Absorption maximum wavelength in N, N-dimethylformamide solution 704 nm
Gram extinction coefficient in N, N-dimethylformamide solution 1.26 × 10 ⁵ ml / gcm
MASS spectrum (M + 1) + = 1178

Example 3 Synthesis of Exemplary Compound P-7 In Example 2, 3.45 g was used in the same manner as in Example 2 except that 3.66 g of copper (II) acetate was used instead of zinc (II) chloride. The intermediate compound (yield 17.2%) was obtained as crystals.
Subsequently, 255 mg (yield 19.7%) of exemplary compound P-6 was obtained as crystals by the same method as in Example 2 except that 1.0 g of the intermediate compound was used.
Absorption maximum wavelength in N, N-dimethylformamide solution 705 nm
Gram extinction coefficient in N, N-dimethylformamide solution 1.37 × 10 ⁵ ml / gcm
MASS spectrum (M + 1) + = 1177

Example 4 Synthesis of Exemplary Compound P-8 In Example 2, 3.22 g was obtained in the same manner as in Example 2 except that 4.51 g of palladium (II) acetate was used instead of zinc (II) chloride. An intermediate compound (15.4% yield) was obtained as crystals.
Subsequently, 178 mg (yield 15.2%) of exemplary compound P-8 was obtained as crystals by the same method as in Example 2 except that 1.0 g of the intermediate compound was used.
Absorption maximum wavelength in N, N-dimethylformamide solution 695 nm
Gram extinction coefficient in N, N-dimethylformamide solution 1.32 × 10 ⁵ ml / gcm
MASS spectrum (M + 1) + = 1220

(Example 5) Synthesis of Exemplified Compound P-9 In Example 2, an intermediate of 2.22 g (yield 11.8%) was obtained in the same manner as in Example 2 except that zinc (II) chloride was not used. Body compound was obtained as crystals.
Subsequently, 229 mg (yield 19.2%) of Exemplified Compound P-9 was obtained as crystals by the same method as in Example 2 except that 1.0 g of the intermediate compound was used.
Absorption maximum wavelength in N, N-dimethylformamide solution 715 nm
Gram extinction coefficient in N, N-dimethylformamide solution 1.29 × 10 ⁵ ml / gcm
MASS spectrum (M + 1) + = 1116

Example 6 Synthesis of Exemplified Compound P-10 In Example 2, intermediate compound 1 was used instead of intermediate compound 2.0 g and 5-formyl-2,2′-bithiophene-5-boronic acid 0.95 g. In the same manner as in Example 2 except that 0.0 g and 0.31 g of 5-formyl-2-thiophene-5-boronic acid were used, 301 mg (yield 27.4%) of Exemplified Compound P-10 as crystals Obtained.
Absorption maximum wavelength in N, N-dimethylformamide solution 703 nm
Gram extinction coefficient in N, N-dimethylformamide solution 1.36 × 10 ⁵ ml / gcm
MASS spectrum (M + 1) + = 1096

Example 7 Synthesis of Exemplified Compound P-12 In Example 2, instead of 1.15 g of the precursor compound and 0.92 g of cyanoacetic acid, 1.0 g of the precursor compound, 3,3,3, -trifluoropropion Except for using 1.38 g of acid, 321 mg (yield: 32.3%) of Exemplified Compound P-12 was obtained as crystals in the same manner as in Example 2.
Absorption maximum wavelength in N, N-dimethylformamide solution 707 nm
Gram extinction coefficient in N, N-dimethylformamide solution 1.11 × 10 ⁵ ml / gcm
MASS spectrum (M + 1) + = 1221

(Example 8) Synthesis of Exemplified Compound P-13 In Example 2, except that 1.15 g of precursor compound and 0.92 g of cyanoacetic acid were used, 1.0 g of precursor compound and 1.12 g of malonic acid were used. In the same manner as in Example 2, 270 mg (yield 25.1%) of Exemplary Compound P-12 was obtained as crystals.
Absorption maximum wavelength in N, N-dimethylformamide solution 706 nm
Gram extinction coefficient in N, N-dimethylformamide solution 1.24 × 10 ⁵ ml / gcm
MASS spectrum (M + 1) + = 1197

Example 9 Synthesis of Exemplified Compound P-35 50 ml of N, N-dimethylamino-2-ethanol was heated to 134 ° C. and 1,3-diimino-6,7-dibromobenzo [f] isoindoline 70 g of 1,3-diimino-4,9-bis (2-ethoxyethoxy (2-ethoxy) 2-ethoxy) benzo [f] isoindoline and 2.18 g of zinc (II) chloride are added at 125 to 135 ° C. And stirred for 18 hours. Thereafter, the reaction solution was cooled to room temperature, and the resulting solution was concentrated under reduced pressure. After adding 100 ml of water and 300 ml of toluene and stirring for 1.0 hour, the organic layer was taken out and washed twice with 200 ml of water. 30 g of silica gel was added to the obtained organic layer, and the mixture was stirred at 90 ° C. for 30 minutes, and the silica gel adsorbed with the target product was collected by filtration. The obtained silica gel was thoroughly washed with 300 ml of toluene, and then the target product was extracted with 300 ml of ethyl acetate and then with 300 ml of ethanol. The obtained ethyl acetate / ethanol mixed solution was concentrated under reduced pressure, and column chromatography using silica gel (development) (Solvent: ethyl acetate) and 0.70 g of the intermediate compound was obtained as an oil.

Then, 50 ml of 1,3-dimethyl-2-imidazolidinone was added to 0.70 g of the above compound, 0.48 g of 5-formyl-2,2′-bithiophene-5-boronic acid, 0.21 g of potassium carbonate, tetrakis ( Triphenylphosphine) palladium (0.03 g) was added, and the mixture was stirred at 80 to 85 ° C. for 18 hours. Thereafter, the reaction solution was cooled to room temperature, 150 ml of water, 30 ml of acetic acid and 200 ml of toluene were added, and further stirred for 1.5 hours. Then, the organic layer was taken out with a separatory funnel, concentrated under reduced pressure, and then a column using silica gel. Separation was performed by chromatography (developing solvent: ethyl acetate to ethyl acetate / ethanol = 10/1) to obtain 0.50 g of the precursor compound as an oil.
Further, 0.5 g of the obtained precursor compound, 0.60 g of cyanoacetic acid, and 0.54 g of ammonium acetate were added to 25 g of acetic acid, followed by stirring at 90 to 95 ° C. for 24 hours. Thereafter, the reaction solution was cooled to room temperature, 100 ml of toluene and 50 ml of water were added, and further stirred for 1.5 hours, and then the organic layer was taken out and washed twice with 100 ml of water. The obtained organic layer was concentrated under reduced pressure, and the resulting crude product was separated by column chromatography using silica gel (developing solvent: ethyl acetate / ethanol = 10/1) to give 152 mg (yield 3.1%). Example compound P-35 of) was obtained as crystals.
Absorption maximum wavelength in N, N-dimethylformamide solution 808 nm
Gram extinction coefficient in N, N-dimethylformamide solution 1.22 × 10 ⁵ ml / gcm
MASS spectrum (M + 1) ²⁺ = 1177

(Example 10) Production of dye-sensitized solar cell In a mixed medium of 0.4 ml of acetylacetone and 20 ml of ion-exchanged water, 12 g of titanium oxide fine particles and a dispersant (trade name “Triton X-100”, manufactured by Aldrich) 2 g was added to prepare an oxide slurry. This oxide slurry was applied to the surface of a substrate made of transparent conductive glass (having fluorine doped SnO ₂ as a conductive layer) washed with ethanol, and heated in an air atmosphere at 500 ° C. for 0.5 hour. As a result, an oxide thin film electrode made of titanium oxide was formed on the surface of the base material made of transparent conductive glass to obtain a member for cathode.
Next, Exemplified Compound P-1 produced in Example 1 and chenodeoxycholic acid (3.0 × 10 ⁻⁴ M) as a co-adsorbent were dissolved in ethanol, and the concentration of Compound P-1 was 0.5 mmol / L. A solution was prepared. And the cathode by which the compound P-1 was carry | supported by the oxide thin film electrode was manufactured by immersing the said member for cathodes in this solution at 23 degreeC for 24 hours.
Further, a platinum electrode obtained by sintering platinum on the surface of a base material (thickness 4 mm, made of tin oxide, resistance value = 10 Ω / cm ² ) made of transparent conductive glass is used as an anode, and the platinum sintered surface of the anode and the cathode A general ionomer resin spacer was attached to an appropriate position in the cell container so that the oxide thin film electrode formation surface was opposed and the distance between both electrodes was 25 μm.
Thereafter, a redox electrolyte solution (acetonitrile solution containing 0.45 mM iodine and 30 mM lithium iodide) was injected into the cell container to produce a dye-sensitized solar cell.

(Example 11)
In Example 10, in place of Example Compound P-1 produced in Example 1, Example Compound P-6 produced in Example 2 was dissolved so that the concentration was 0.5 mmol / L. A dye-sensitized solar cell was produced in the same manner as in Example 10 except that it was used.

(Example 12)
In Example 10, in place of Example Compound P-1 produced in Example 1, Example Compound P-7 produced in Example 3 was dissolved so that the concentration was 0.5 mmol / L. The same operation as in Example 10 was performed to prepare a dye-sensitized solar cell.

(Example 13)
In Example 10, in place of Example Compound P-1 produced in Example 1, Example Compound P-8 produced in Example 4 was dissolved so that the concentration was 0.5 mmol / L. The same operation as in Example 10 was performed to prepare a dye-sensitized solar cell.

(Example 14)
In Example 10, instead of Exemplified Compound P-1 produced in Example 1, Exemplified Compound P-9 produced in Example 5 was dissolved so as to have a concentration of 0.5 mmol / L. The same operation as in Example 10 was performed to prepare a dye-sensitized solar cell.

(Example 15)
In Example 10, instead of Exemplified Compound P-1 produced in Example 1, Exemplified Compound P-10 produced in Example 6 was dissolved so as to have a concentration of 0.5 mmol / L. The same operation as in Example 10 was performed to prepare a dye-sensitized solar cell.

(Example 16)
In Example 10, instead of Exemplified Compound P-1 produced in Example 1, Exemplified Compound P-12 produced in Example 7 was dissolved so as to have a concentration of 0.5 mmol / L. The same operation as in Example 10 was performed to prepare a dye-sensitized solar cell.

(Example 17)
In Example 10, instead of Exemplified Compound P-1 produced in Example 1, Exemplified Compound P-13 produced in Example 8 was dissolved so that the concentration was 0.5 mmol / L. The same operation as in Example 10 was performed to prepare a dye-sensitized solar cell.

(Example 18)
In Example 10, instead of Exemplified Compound P-1 produced in Example 1, Exemplified Compound P-35 produced in Example 9 was dissolved so that the concentration was 0.5 mmol / L. The same operation as in Example 10 was performed to prepare a dye-sensitized solar cell.

(Comparative Example 1)
In Example 10, instead of Exemplified Compound P-1 produced in Example 1, a ruthenium complex (
A dye-sensitized solar cell was produced in the same manner as in Example 10 except that the product name: N3 (manufactured by Solaronix) was dissolved so as to have a concentration of 0.5 mmol / L.

(Example 19) Photoelectric conversion characteristic evaluation of a dye-sensitized solar cell The photoelectric conversion characteristic of the dye-sensitized solar cell was implemented by the following operation. For this test, an IPCE (Incident Photon to Current Conversion Efficiency) measuring device (manufactured by Nippon Optel) was used, and the photoelectric conversion pole absorption wavelength and wavelength of 800 nm of the dye-sensitized solar cells obtained in Examples 10 to 18 were used. The external quantum yield was determined. The results are shown in Table 1.

表から明らかなように、本発明のアクリル酸系化合物を用いた色素増感太陽電池は近赤外領域において高い光電変換効率を示すことがわかった。
(Comparative Example 2)
The dye-sensitized solar cell produced in Comparative Example 1 was evaluated in the same manner as in Example 19. The results are shown in Table 1.

As is apparent from the table, it was found that the dye-sensitized solar cell using the acrylic acid-based compound of the present invention exhibits high photoelectric conversion efficiency in the near infrared region.

By using the acrylic acid compound of the present invention as a sensitizing dye, it is possible to provide a dye-sensitized solar cell having excellent photoelectric conversion efficiency and wavelength absorption characteristics.

Claims (8)

An acrylic acid compound represented by the following general formula (1).

[Wherein, A represents an atomic group having an absorption maximum in the near-infrared region, Y represents an atomic group having a π-electron conjugated structure, X represents a hydrogen atom or an electron-withdrawing substituent, and n and m represent 1 Or represents the integer of 2. ]
The acrylic acid-based compound according to claim 1, which is represented by the following general formula (2).

[In the formula, M1 represents a metal atom, a metal compound or two hydrogen atoms, Y represents an atomic group having a π-electron conjugated structure, X represents a hydrogen atom or an electron-withdrawing substituent, and n and m represent 1 or 2. The integers Q1 to Q4 each independently represent a cyclic structure. However, the substituent (1-1) in the formula:

Is substituted with a cyclic structure represented by Q1 to Q4. ]
In the formula (2), in addition to the substituent (1-1), the cyclic structures of Q1 to Q4 each independently have a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, The acrylic acid-based compound according to claim 2, which represents a phenothiazine ring which may have a substituent.
The acrylic acid compound according to claim 2 or 3, wherein in the formula (2), at least three of the cyclic structures of Q1 to Q4 are the same.
In the formula (2), the substituent on Q1 to Q4 is a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy The acrylic acid compound according to any one of claims 2 to 4, which is a group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, or a substituted amino group.
The acrylic acid compound according to any one of claims 1 to 5, wherein Y has at least one arylene group.
The acrylic acid compound according to any one of claims 1 to 6, wherein X is selected from a hydrogen atom, a cyano group, a carboxyl group, and a trifluoromethyl group.
A dye-sensitized solar cell, wherein the acrylic acid compound according to any one of claims 1 to 7 is used as a sensitizing dye.