JP2016185911A - New compound and photoelectric conversion element including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound capable of relatively easily converting a wide range of visible light into electricity as a sensitizing dye and to provide a photoelectric conversion element including the same.SOLUTION: There is provided a compound represented bt the following formula. (m is an integer of 1 to 5; l and n each independently is an integer of 0 to 6; j is an integer of 0 to 3; Xand Xare H, a carboxyl group or a salt thereof, a hydroxy group or a salt thereof, a phosphate group or a salt thereof or the like; Qand Qare O, S or the like; Ato Aare H, a substituted or unsubstituted aliphatic hydrocarbon residue, a cyano group, a halogen atom or the like; Ris a group having a boron-pyrromethene structure.)SELECTED DRAWING: None

Description

  The present invention relates to a novel organic compound having a specific structure, a photoelectric conversion element containing the compound as a sensitizing dye, and a solar cell including the photoelectric conversion element.

Solar cells that use sunlight as an energy resource to replace fossil fuels such as oil and coal are drawing attention. Currently, active studies are being made on silicon solar cells using crystalline or amorphous silicon, and compound semiconductor solar cells using gallium, arsenic, or the like. However, since a great amount of energy is required for their production, there is a problem that the production cost is still high as a result. On the other hand, a photoelectric conversion element produced using semiconductor fine particles sensitized with a dye and a solar cell including the same have been developed, and materials such as sensitizing dyes and semiconductor fine particles, as well as element and battery manufacturing technologies Various disclosures have been made (see Patent Document 1, Non-Patent Document 1, and Non-Patent Document 2). Such a dye-sensitized photoelectric conversion element is manufactured using a relatively inexpensive oxide semiconductor such as titanium oxide, and can be obtained at a lower cost than a conventional solar cell using silicon or the like. It is attracting attention because of its ability to produce colorful and colorful solar cells. However, the cost of the ruthenium-based complex itself used as a sensitizing dye for obtaining an element with high conversion efficiency is high, and there is a problem in its stable supply. In response to this, attempts have already been made to use organic dyes that are low in material cost and can be stably supplied as sensitizing dyes. However, photoelectric conversion elements sensitized with an organic dye have problems such as low conversion efficiency, and further improvements in various characteristics such as conversion efficiency are desired (see Patent Document 2).
In order to solve such problems, the present inventors have disclosed several novel organic dyes that can improve the conversion efficiency and the like of photoelectric conversion elements (Patent Documents 3 to 5).

Japanese Patent Laid-Open No. 01-220380 International Patent Publication No. WO2002 / 011213 International Patent Publication No. WO2007 / 100033 International Patent Publication No. WO2013 / 147145 JP 2014-196283 A

B.O'Regan and M.Graetzel Nature, 353, 737 (1991) MKNazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, E. Muller, P. Liska, N. Vlachopoulos, M. Graetzel, J. Am. Chem. Soc., 115, 6382 (1993) Year) Yuji Kubo, Kazuki Watanabe, Ryuhei Nishiyabu, Reiko Hata, Akinori Murakami, Takayuki Shoda, and Hitoshi Ota, Org. Lett., Vol. 13, No. 17, 2011. 4574 W. Kubo, K. Murakoshi, T. Kitamura, K. Hanabusa, H. Shirai, and S. Yanagida, Chem. Lett., 1241 (1998) Norio Miyaura and Akira Suzuki, Chem. Rev., 95, 2457 (1995)

  An object of the present invention is to provide a novel compound capable of converting a wide range of visible light into electricity relatively efficiently as a sensitizing dye, and a photoelectric conversion element including the same, in such a technical level.

As a result of synthesizing various organic semiconductor compounds to achieve the above object and examining the characteristics of semiconductor fine particles as a sensitizing dye, the present inventors have efficiently used a wide range of visible light from short wavelengths to long wavelengths. The present inventors have found an organic compound that can be converted into electricity and completed the present invention.
That is, this invention provides the following compounds, a photoelectric conversion element, and a solar cell:
(1) Compound represented by the following formula (1)

(In Formula (1), m represents an integer of 1 to 5, l and n each independently represents an integer of 0 to 6, and j represents an integer of 0 to 3.
X ₁ and X ₂ are each independently a hydrogen atom, a carboxyl group or a salt thereof, a hydroxyl group or a salt thereof, a phosphate group or a salt thereof, a sulfonic acid group or a salt thereof, a cyano group, a substituted or unsubstituted acyl group, a substituted or non-substituted group. Represents a substituted amide group, a substituted or unsubstituted alkoxycarbonyl group or a phenylsulfonyl group; Alternatively, X ₁ and X ₂ may be connected to each other to form a ring.
Q ₁ and Q ₂ each independently represents an oxygen atom, a sulfur atom, a selenium atom or NR ₁₁ . R ₁₁ represents a hydrogen atom, a substituted or unsubstituted aromatic residue, or a substituted or unsubstituted aliphatic hydrocarbon residue. When m is 2 or more and a plurality of Q ₁ exist, each Q ₁ may be the same as or different from each other. If the j is Q ₂ there are a plurality of two or more, each Q ₂ is may be the same or different from each other.
A ₁ , A ₂ , A ₃ , A ₅ and A ₆ are each independently a hydrogen atom, a substituted or unsubstituted aromatic residue, a substituted or unsubstituted aliphatic hydrocarbon residue, a cyano group, a halogen atom, substituted or non-substituted Substituted carbonamido group, substituted or unsubstituted amide group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted arylcarbonyl group or substituted or unsubstituted acyl group Represent. When l is 2 or more and a plurality of A ₂ and A ₃ are present, each A ₂ and A ₃ may be the same as or different from each other. When n is 2 or more and a plurality of A ₅ and A ₆ are present, each A ₅ and A ₆ may be the same as or different from each other. When l is other than 0, any one of A ₁ , A ₂ and A ₃ may form a ring.
A ₄ represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon residue, a cyano group, a halogen atom, a substituted or unsubstituted carbonamido group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted amide group, a substituted or unsubstituted alkoxy Represents a carbonyl group or a substituted or unsubstituted acyl group. When m is 2 or more and a plurality of A ₄ are present, each A ₄ may be the same as or different from each other.
A ₇ and A ₈ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon residue, a cyano group, a halogen atom, a substituted or unsubstituted carbonamido group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted alkoxycarbonyl Represents a group or a substituted or unsubstituted acyl group. When j is 2 or more and a plurality of A ₇ and A ₈ exist, each A ₇ and A ₈ may be the same as or different from each other.
R ₂ is the following formula (2)

(In Formula (2), M represents a metalloid atom. Y ₁ , Y ₂ and Y ₃ each independently represent a hydrogen atom or a substituted or unsubstituted aromatic residue. Z ₁ and Z ₂ each independently represent Represents a halogen atom, Ar ₁ and Ar ₂ each independently represents a substituted or unsubstituted aromatic ring.) Represents a residue obtained by removing one hydrogen atom from the aromatic ring Ar ₁ or Ar _{2 of the} compound represented by .
R ₁ represents the following formula (3001) or (3003)

(In the formula (3001) or (3003), R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, a substituted or unsubstituted aromatic residue or a substituted or unsubstituted aliphatic hydrocarbon residue. R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently a hydrogen atom, a substituted or unsubstituted aromatic residue, a substituted or unsubstituted aliphatic hydrocarbon residue, a cyano group, a substituted or unsubstituted acyl group Represents a substituted or unsubstituted amide group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted alkoxycarbonyl group, or a phenylsulfonyl group. When m is 2 or more and a plurality of R ₁ are present, each R ₁ may be the same as or different from each other.
When n is other than 0, any one of A ₅ , A ₆ and R ₂ may form a ring. ),
(2) The compound according to item (1), wherein m in formula (1) is 1 to 3,
(3) The compound according to item (2), wherein m in formula (1) is 1.
(4) The compound according to any one of (1) to (3), wherein Q ₁ and Q ₂ in formula (1) are sulfur atoms,
(5) The compound according to any one of (1) to (4), wherein l and n in formula (1) are 0,
(6) The compound according to any one of (1) to (5), wherein one of X ₁ and X ₂ in formula (1) is a carboxyl group and the other is a carboxyl group, a cyano group, or an acyl group,
(7) The compound according to item (6), wherein _one of X ₁ and X ₂ in formula (1) is a carboxyl group and the other is a cyano group,
(8) The compound according to any one of (1) to (5), wherein X ₁ and X ₂ in formula (1) are bonded to form a ring structure,
(9) The compound according to any one of (1) to (8), wherein A _{1 to} A ₈ in formula (1) are hydrogen atoms,
(10) R ₂ in the formula (1) is the following formula (3)

(In formula (3), Z ₃ and Z ₄ each independently represent a halogen atom. A ₂₃ and A ₂₄ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon residue, or a substituted or non-substituted group. The compound according to any one of the above items (1) to (9), which is a residue obtained by removing one hydrogen atom from the benzene ring b ₁ or c ₁ of the compound represented by ,
(11) The compound according to item (10), wherein Z ₃ and Z ₄ in formula (3) are fluorine atoms, and A ₂₃ and A ₂₄ are methoxy groups,
(12) R ₂ in the formula (1) is the following formula (4)

(In Formula (4), Z ₅ and Z ₆ each independently represent a halogen atom. Q ₃ and Q ₄ each independently represent an oxygen atom, a sulfur atom, a selenium atom, or NR ₁₂ , R ₁₂ is a hydrogen atom, A substituted or unsubstituted aromatic residue or a substituted or unsubstituted aliphatic hydrocarbon residue, each of A ₂₅ and A ₂₆ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon residue, The non-substituted alkoxyl group.) According to any one of the above items (1) to (9), which is a residue obtained by removing one hydrogen atom from the benzene ring b ₂ or c _{2 of the} compound represented by Compound,
(13) The compound according to item (12), wherein Z ₅ and Z ₆ in formula (4) are fluorine atoms, and A ₂₅ and A ₂₆ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ,
(14) R ₁ in Formula (1) is a group represented by Formula (3001) or a group represented by Formula (3003), and R ₁₂ and R ₁₃ in Formula (3001) are each independent. Are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ₁₄ and R ₁₅ in formula (3003) are phenyl groups, and R _{16 to} R ₁₉ are each independently a hydrogen atom or an alkoxyl group having 1 to 4 carbon atoms. The compound according to any one of (1) to (13), which is a group,
(15) R ₁ in the formula (1) is represented by the following formulas (3101) to (3108)

The compound according to item (14), which is a group represented by any of the following:
(16) The compound according to item (15), wherein R ₁ in formula (1) is a group represented by formula (3102), (3103) or (3107):
(17) The compound according to item (16), wherein R ₁ in formula (1) is a group represented by formula (3103);
(18) The following formula (902)

The compound according to item (1), which is represented by:
(19) The following formula (909)

The compound according to item (1), which is represented by:
(20) A photoelectric conversion element in which a thin film of oxide semiconductor fine particles on a substrate is loaded with one or more compounds represented by the formula (1) according to any one of (1) to (19) above,
(21) One or more compounds represented by the formula (1) according to any one of the above items (1) to (19) and a compound other than the formula (1) are formed on the thin film of oxide semiconductor fine particles on the substrate. A photoelectric conversion element carrying a sensitizing dye compound having a structure;
(22) The photoelectric conversion element according to (20) or (21) above, wherein the oxide semiconductor fine particles contain titanium dioxide, zinc oxide or tin oxide, and (23) any one of (20) to (22) above A solar cell comprising the photoelectric conversion element according to one item.

  By using the compound of the present invention as a sensitizing dye, a wide range of visible light can be converted into electricity with a relatively high conversion efficiency.

The IPCE spectrum of the solar cell obtained in Examples 2 and 3 and Comparative Example 1 is shown.

The present invention is described in detail below.
The compound of the present invention has a structure represented by the following formula (1).

M in Formula (1) represents an integer of 1 to 5, preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.
L in Formula (1) represents an integer of 0 to 6, and is preferably 0.
N in Formula (1) represents an integer of 0 to 6, and is preferably 0.
J in Formula (1) represents an integer of 0 to 3, preferably 1 to 3, more preferably 1 to 2, and still more preferably 2.

X ₁ and X ₂ in formula (1) are each independently a hydrogen atom, a carboxyl group (—COOH) or a salt thereof, a hydroxyl group (—OH) or a salt thereof, a phosphate group (—PO ₃ H) or a salt thereof, Represents a sulfonic acid group (—SO ₃ H) or a salt thereof, a cyano group (—CN), an acyl group, an amide group, an alkoxycarbonyl group, or a phenylsulfonyl group, or X ₁ and X ₂ are bonded to each other; A ring may be formed.
Examples of the acyl group represented by X ₁ and X _{2 in} the formula (1) include an alkylcarbonyl group having 1 to 10 carbon atoms, an arylcarbonyl group (usually having a monocyclic, bicyclic or tricyclic aryl). And preferably an alkylcarbonyl group having 1 to 4 carbon atoms and a monocyclic or bicyclic arylcarbonyl group. Examples of the alkylcarbonyl group having 1 to 4 carbon atoms include an acetyl group, a propionyl group, a trifluoromethylcarbonyl group, and a pentafluoroethylcarbonyl group. Examples of the monocyclic or bicyclic arylcarbonyl group include a benzoyl group. And a naphthoyl group.

The acyl group represented by X ₁ and X _{2 in} formula (1) may have a substituent. Examples of such a substituent include a sulfonic acid group, a sulfamoyl group, a cyano group, an isocyano group, and a thiocyanato group. , Isothiocyanato group, nitro group, nitrosyl group, halogen atom, hydroxyl group, phosphate group, phosphate ester group, amino group, mercapto group, amide group, alkoxyl group, aryloxy group, carboxyl group, carbamoyl group, acyl group, Examples include aldehyde groups, and substituted carbonyl groups such as alkoxycarbonyl groups and arylcarbonyl groups, and further include aromatic residues and aliphatic hydrocarbon residues.
Examples of the halogen atom as the substituent that the acyl group represented by X ₁ and X _{2 in} Formula (1) may have include fluorine, chlorine, bromine, iodine, and the like. preferable.

Examples of the phosphoric acid ester group as a substituent that the acyl group represented by X ₁ and X _{2 in} the formula (1) may have include a phosphoric acid (C 1 to C 4) alkyl ester group, which is preferable. Specific examples include methyl phosphate group, ethyl phosphate group, n-propyl phosphate group and n-butyl phosphate group.
As the substituted or unsubstituted amino group as the substituent which the acyl group represented by X ₁ and X _{2 in} formula (1) may have, an unsubstituted amino group; a mono or dimethylamino group, a mono or diethylamino group, C1-C4 alkyl-substituted amino groups such as mono- or di-n-propylamino groups; monocyclic, bicyclic or tricyclic aromatic substitutions such as mono- or diphenylamino groups, mono- or dinaphthylamino groups An amino group; an amino group in which an alkyl group such as an alkyl monophenylamino group having 1 to 4 mono carbon atoms and a monocyclic, bicyclic or tricyclic aromatic residue are substituted one by one; a benzylamino group; an acetyl An amino group; and a phenylacetylamino group.

The substituted or unsubstituted mercapto group as a substituent that the acyl group represented by X ₁ and X _{2 in} formula (1) may have is an unsubstituted mercapto group; an alkyl mercapto group, specifically a methyl mercapto group , Ethyl mercapto group, n-propyl mercapto group, isopropyl mercapto group, n-butyl mercapto group, isobutyl mercapto group, sec-butyl mercapto group, t-butyl mercapto group, etc .; A cyclic, bicyclic or tricyclic aromatic substituted mercapto group, specifically a phenyl mercapto group, and the like can be mentioned.
As an amide group as a substituent which the acyl group represented by X ₁ and X _{2 in} Formula (1) may have, an amide group (NH ₂ (CO) H) in a narrow sense, an acetamide group, an alkylamide group, Examples include alkylacetamido group, arylamido group, and arylacetamido group. Preferred are amido group (NH ₂ (CO) H); acetamide group; N-methylamido group, N-ethylamido group, N- (n-propyl) Amide group, N- (n-butyl) amide group, N-isobutylamide group, N- (sec-butylamide) group, N- (t-butyl) amide group, N, N-dimethylamide group, N, N- Mono or di having 1 to 4 carbon atoms such as diethylamide group, N, N-di (n-propyl) amide group, N, N-di (n-butyl) amide group, N, N-diisobutyramide group Alkylamide group; N-methylacetamide group, N-ethylacetamide group, N- (n-propyl) acetamide group, N- (n-butyl) acetamide group, N-isobutylacetamide group, N- (sec-butyl) acetamide group N- (t-butyl) acetamide group, N, N-dimethylacetamide group, N, N-diethylacetamide group, N, N-di (n-propyl) acetamide group, N, N-di (n-butyl) A mono- or dialkylacetamido group having 1 to 4 carbon atoms such as an acetamide group or N, N-diisobutylacetamide group; a monocyclic, bicyclic or tricyclic arylamide group such as a phenylamide group or a naphthylamide group; or Monocyclic, bicyclic or tricyclic arylacetoacetates such as phenylacetamide and naphthylacetamide groups And a mid group.

Examples of the alkoxyl group as a substituent that the acyl group represented by X ₁ and X _{2 in} Formula (1) may have include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, Examples thereof include an alkoxyl group having 1 to 4 carbon atoms such as an isobutoxy group, a sec-butoxy group, and a t-butoxy group.
The aryloxy group as a substituent which the acyl group represented by X ₁ and X _{2 in} the formula (1) may have is monocyclic, bicyclic or tricyclic such as phenoxy group or naphthoxy group. An aryloxy group is mentioned.
As the acyl group as the substituent which the acyl group represented by X ₁ and X _{2 in} the formula (1) may have, those described in the item of the acyl group represented by X ₁ and X _{2 in} the formula (1) The same thing is mentioned.

Examples of the alkoxycarbonyl group as the substituent that the acyl group represented by X ₁ and X _{2 in} Formula (1) may have include, for example, an alkoxycarbonyl group having 1 to 10 carbon atoms, and specific examples thereof are as follows. Methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pentoxycarbonyl group, n -A hexyloxycarbonyl group, an n-heptyloxycarbonyl group, an n-nonyloxycarbonyl group, and an n-decyloxycarbonyl group.
Examples of the arylcarbonyl group as a substituent that the acyl group represented by X ₁ and X _{2 in} formula (1) may have include monocyclic, bicyclic or tricyclic aryl such as benzophenone and naphthophenone. A group in which a group and carbonyl are linked is represented.

The aromatic residue as a substituent that the acyl group represented by X ₁ and X _{2 in} formula (1) may have is one hydrogen atom from an aromatic ring (an aromatic ring and a condensed ring including an aromatic ring). The aromatic residue may have a substituent. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a perylene ring and a terylene ring, and other monocyclic, bicyclic or tricyclic aromatic hydrocarbon rings; , Azulene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrazole ring, pyrazolidine ring, thiazolidine ring, oxazolidine ring, pyran ring, chromene ring, pyrrole ring, pyrrolidine ring, benzimidazole ring, imidazoline ring, imidazolidine ring, imidazole ring , Triazole ring, triazine ring, diazole ring, indoline ring, furan ring, thiophene ring, oxazole ring, oxadiazole ring, thiazine ring, thiazole ring, indole ring, benzothiazole ring, benzothiadiazole ring, naphthothiazole ring, benzoxazole Ring, naphtho Containing a hetero element such as N, O and S such as a xazole ring, an indolenine ring, a benzoindolenine ring, a quinoline ring and a quinazoline ring, and a 4- to 7-membered monocyclic or bicyclic condensed heteroaromatic ring; And a heteroelement such as N, O and S such as a fluorene ring and a carbazole ring, and a 4- to 7-membered tricyclic condensed condensed heteroaromatic ring. The aromatic residue is preferably an aromatic ring having 4 to 20 carbon atoms. Examples of the substituent that the aromatic residue may have include the same substituents that the acyl group represented by X ₁ and X ₂ in Formula (1) may have.

Examples of the aliphatic hydrocarbon residue as a substituent that the acyl group represented by X ₁ and X _{2 in} Formula (1) may have include a saturated or unsaturated linear or branched alkyl group, or cyclic And the aliphatic hydrocarbon residue may have a substituent. The aliphatic hydrocarbon residue is preferably a saturated alkyl group, and more preferably a saturated linear alkyl group. The aliphatic hydrocarbon residue has preferably 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms, and still more preferably 1 to 8 carbon atoms. However, the cyclic alkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms.
Specific examples of these aliphatic hydrocarbon residues include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl. Group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group Group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, cyclohexyl group, vinyl group, propenyl group, pentynyl group, butenyl group, hexenyl group, hexadienyl group, isopropenyl group, isohexenyl group, cyclohexenyl Group, cyclopentadienyl group, ethynyl group, propynyl group, pentynyl group, hexynyl group, isohexynyl group, cyclohexyl group Group, and the like.
Particularly preferred is a linear alkyl group having 1 to 8 carbon atoms. Examples of the substituent that the aliphatic hydrocarbon residue may have include the same substituents that the acyl group represented by X ₁ and X ₂ in Formula (1) may have.

As the amide group represented by X ₁ and X ₂ in the formula (1), those described in the section of the amide group as a substituent which the acyl group represented by X ₁ and X _{2 in} the formula (1) may have The same thing is mentioned. The amide group represented by X ₁ and X _{2 in} formula (1) may have a substituent, and as such a substituent, the acyl group represented by X ₁ and X ₂ in formula (1) has Examples thereof may be the same as those described in the section of the substituent which may be present.
The alkoxycarbonyl group represented by X ₁ and X ₂ in the formula (1) is described in the section of the alkoxycarbonyl group as a substituent which the acyl group represented by X ₁ and X _{2 in} the formula (1) may have. The same thing is mentioned. The alkoxycarbonyl group represented by X ₁ and X _{2 in} formula (1) may have a substituent, and as such a substituent, there is an acyl group represented by X ₁ and X ₂ in formula (1). The same as those described in the section of the substituent which may be used.

Aromatic residue, aliphatic hydrocarbon residue, amide group, acyl group as a substituent that the acyl group, amide group and alkoxycarbonyl group represented by X ₁ and X _{2 in} formula (1) may have, The alkoxyl group, aryloxy group, arylcarbonyl group and alkoxycarbonyl group may have a substituent, and such a substituent has an acyl group represented by X ₁ and X _{2 in} the formula (1). And the same as those described in the section of the substituent which may be used.

Examples of the ring formed by combining X ₁ and X ₂ with each other include an aromatic ring and a heterocyclic ring, and these rings may have a substituent.
Specific examples of the aromatic ring formed by combining X ₁ and X ₂ with each other include a specific description in the explanation of the aromatic residue as a substituent that the acyl group represented by X ₁ and X ₂ may have. The thing similar to the aromatic ring described as an example is mentioned. As the X ₁ and X ₂ and a bond to substituent which may be ring have to be formed with each other, may have acyl group represented by X ₁ and X ₂ in the formula (1) substituted Examples are the same as those described in the group section.
Examples of the heterocyclic ring formed by combining X ₁ and X ₂ with each other include, for example, a heterocyclic ring containing a 4- to 7-membered hetero atom such as S, O, and N, and the following formulas (2001) to (2017) Is preferably a ring represented by formula (2007) or formula (2012), more preferably a ring represented by formula (2007). .

Incidentally, mark * in the formula (2001) to in (2017) represents a carbon atom to which both of X ₁ and X ₂ in the formula (1) is attached.

X ₁ and X ₂ in Formula (1) are each preferably independently a carboxyl group, a phosphate group, a cyano group, or an acyl group, and more preferably each independently a carboxyl group, a cyano group, or an acyl group. It is more preferable that one is a carboxyl group and the other is a carboxyl group, a cyano group or an acyl group, and it is particularly preferable that one is a carboxyl group and the other is a cyano group.

Q ₁ and Q ₂ in formula (1) each independently represent an oxygen atom, a sulfur atom, a selenium atom or NR ₁₁ , and R ₁₁ represents a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue.
The aromatic residue represented by R ₁₁ is the same as that described in the section of the aromatic residue as a substituent that the acyl group represented by X ₁ and X _{2 in} the formula (1) may have. Can be mentioned.
As the aliphatic hydrocarbon residue represented by R ₁₁ , those described in the paragraph of the aliphatic hydrocarbon residue as a substituent that the acyl group represented by X ₁ and X _{2 in} the formula (1) may have The same thing is mentioned.
The aromatic residue and aliphatic hydrocarbon residue represented by R ₁₁ may have a substituent, and the substituent that may be present is represented by X ₁ and X _{2 in} the formula (1). The same thing as what was mentioned in the term of the substituent which the acyl group may have is mentioned.

When m in the formula (1) is 2 or more and a plurality of Q ₁ are present, each Q ₁ may be the same as or different from each other. Similarly, when j is 2 or more and a plurality of Q ₂ exist, each Q ₂ may be the same as or different from each other.
Q ₁ and Q ₂ in Formula (1) are each independently preferably an oxygen atom, a sulfur atom or a selenium atom, and more preferably a sulfur atom.

A ₁ , A ₂ , A ₃ , A ₅ and A ₆ in formula (1) are each independently a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an amide Represents a group, an alkoxyl group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or an acyl group.
As aromatic residues, aliphatic hydrocarbon residues, halogen atoms, amide groups, alkoxyl groups, aryloxy groups, alkoxycarbonyl groups and arylcarbonyl groups represented by A ₁ , A ₂ , A ₃ , A ₅ and A ₆ , An aromatic residue, aliphatic hydrocarbon residue, halogen atom, amide group, alkoxyl group, aryloxy group as a substituent that the acyl group represented by X ₁ and X ₂ in formula (1) may have , The same as those described in the section of alkoxycarbonyl group and arylcarbonyl group.
Examples of the acyl group represented by A ₁ , A ₂ , A ₃ , A ₅ and A ₆ include the same as those described in the section of the acyl group represented by X ₁ and X _{2 in} the formula (1).
The aromatic residue, aliphatic hydrocarbon residue, amide group, alkoxyl group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group and acyl group represented by A ₁ , A ₂ , A ₃ , A ₅ and A ₆ are substituted. The substituent may be the same as those described in the section of the substituent that the acyl group represented by X ₁ and X _{2 in} the formula (1) may have. Can be mentioned.

When l in Formula (1) is 2 or more and a plurality of A ₂ and A ₃ are present, each A ₂ and A ₃ may be the same as or different from each other. Alternatively, when l is other than 0, any one of A ₁ , A ₂ and A ₃ may form a ring.
Examples of the ring formed by any one of A ₁ , A ₂ and A ₃ include an unsaturated hydrocarbon ring or a heterocyclic ring.
Examples of the unsaturated hydrocarbon ring formed by any one of A ₁ , A ₂ and A ₃ include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, indene ring, azulene ring, fluorene ring, Examples include a cyclobutene ring, a cyclohexene ring, a cyclopentene ring, a cyclohexadiene ring, a cyclopentadiene ring, and examples of the heterocyclic ring include a pyran ring, a pyridine ring, a pyrazine ring, a piperidine ring, an indoline ring, an oxazole ring, a thiazole ring, and a thiadiazole. Ring, oxadiazole ring, indole ring, benzothiazole ring, benzoxazole ring, quinoline ring, carbazole ring, benzopyran ring and the like. Among these, a benzene ring, a cyclobutene ring, a cyclopentene ring, and a cyclohexene ring are preferable.
These unsaturated hydrocarbon rings and heterocyclic rings may have a substituent, and as such a substituent, an acyl group represented by X ₁ and X ₂ in formula (1) may have. The same thing as what was mentioned in the term of the substituent is mentioned.

When the heterocyclic ring formed by any one of A ₁ , A ₂ and A ₃ has a substituent such as a carbonyl group or a thiocarbonyl group, it may form a cyclic ketone or a cyclic thioketone. The ring may further have a substituent. Such substituents may be the same as those described in the section of X ₁ and X ₂ substituents which may be the acyl group have represented the formula (1).

Similarly, when n in the formula (1) is 2 or more and a plurality of A ₅ and A ₆ are present, each A ₅ and A ₆ may be the same as or different from each other. Alternatively, when n is other than 0, any one of A ₅ , A ₆ and R ₂ may form a ring. Examples of the ring formed of any one of A ₅ , A ₆ and R ₂ include the same ring as the unsaturated hydrocarbon ring or heterocyclic ring formed of any one of A ₁ , A ₂ and A _3. .
The ring formed by any one of A ₅ , A ₆ and R ₂ may have a substituent, and examples of the substituent which may have include X ₁ and X _{2 in the} formula (1). The same thing as what was mentioned in the term of the substituent which the acyl group which this represents may have is mentioned.

A ₁ , A ₂ , A ₃ , A ₅ and A ₆ in the formula (1) are preferably each independently a hydrogen atom or an aliphatic hydrocarbon residue, and each independently a hydrogen atom or a carbon number of 1 to 8 The linear alkyl group is more preferably a hydrogen atom.

A ₄ in Formula (1) represents a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an alkoxyl group, an amide group, an alkoxycarbonyl group, or an acyl group.
As the aliphatic hydrocarbon residue, halogen atom, alkoxyl group, amide group and alkoxycarbonyl group represented by A _{4, the} substituent which the acyl group represented by X ₁ and X _{2 in} the formula (1) may have And the same as those described in the section of the aliphatic hydrocarbon residue, halogen atom, alkoxyl group, amide group and alkoxycarbonyl group.
Examples of the acyl group represented by A ₄ include the same groups as those described in the section of the acyl group represented by X ₁ and X _{2 in} the formula (1).

The aliphatic hydrocarbon residue represented by A ₄ , the alkoxyl group, the amide group, the alkoxycarbonyl group, and the acyl group may have a substituent. Examples of such a substituent include X _{1 in the} formula (1) and acyl group X ₂ is represented by may be the same as those described in the section of the substituent which may have.
When m is 2 or more and a plurality of A ₄ are present, each A ₄ may be the same as or different from each other.
A ₄ in Formula (1) is preferably a hydrogen atom or an aliphatic hydrocarbon residue, more preferably a hydrogen atom or a linear alkyl group having 1 to 8 carbon atoms, and preferably a hydrogen atom. Further preferred.

A ₇ and A ₈ in Formula (1) each independently represent a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an alkoxyl group, an alkoxycarbonyl group, or an acyl group.
As the aliphatic hydrocarbon residue, halogen atom, alkoxyl group and alkoxycarbonyl group represented by A ₇ and A _8, as the substituent that the acyl group represented by X ₁ and X ₂ in formula (1) may have The same as those described in the section of the aliphatic hydrocarbon residue, halogen atom, alkoxyl group and alkoxycarbonyl group.
Examples of the acyl group represented by A ₇ and A ₈ include the same groups as those described in the section of the acyl group represented by X ₁ and X _{2 in} the formula (1).
The aliphatic hydrocarbon residue, alkoxyl group, alkoxycarbonyl group and acyl group represented by A ₇ and A ₈ may have a substituent. Examples of such a substituent include X _{1 in} formula (1) and acyl group X ₂ is represented by may be the same as those described in the section of the substituent which may have.
When j is 2 or more and a plurality of A ₇ and A ₈ exist, each A ₇ and A ₈ may be the same as or different from each other.
A ₇ and A ₈ in formula (1) are each independently preferably a hydrogen atom or an aliphatic hydrocarbon residue, each independently a hydrogen atom or a linear alkyl group having 1 to 8 carbon atoms. Is more preferable, and a hydrogen atom is still more preferable. Thus, in a preferred embodiment of the invention, all of A _{1 to} A ₈ are hydrogen.

R ₂ in the formula (1) represents a residue obtained by removing one hydrogen atom from the aromatic ring Ar ₁ or Ar _{2 of the} compound represented by the following formula (2). The position at which one hydrogen atom on the aromatic ring Ar ₁ or Ar ₂ is removed is not particularly limited.

In formula (2), M represents a metalloid atom. The metalloid in the present invention refers to a substance that exhibits an intermediate property between a metal and a nonmetal, and specifically includes a boron atom, a silicon atom, a germanium atom, and an antimony atom, and is preferably a boron atom.
In the formula (2), Y ₁ , Y ₂ and Y ₃ each independently represent a hydrogen atom or an aromatic residue, and the aromatic residue represented by Y ₁ , Y ₂ and Y ₃ is represented by the formula (1) it may be the same as those acyl groups represented by X ₁ and X ₂ are described in the section of an aromatic residue as the substituent which may have.
The aromatic residue represented by Y ₁ , Y ₂ and Y ₃ may have a substituent, and examples of the substituent which may be present include acyl represented by X ₁ and X ₂ in formula (1). The same thing as what was mentioned in the term of the substituent which group may have is mentioned.
As the substituent that the aromatic residue represented by Y ₁ , Y _2, and Y ₃ may have, an alkoxyl group or an alkyl group is preferable.
Y ₁ and Y ₂ in Formula (2) are preferably each independently an aromatic residue, more preferably each independently a phenyl group, a thienyl group, or a naphthyl group, and a phenyl group or a thienyl group. More preferably it is. Y ₃ in formula (1) is preferably a hydrogen atom.

In formula (2), Z ₁ and Z ₂ each independently represent a halogen atom. Examples of the halogen atom represented by Z ₁ and Z ₂ include the same as those described in the section of the substituent which the acyl group represented by X ₁ and X ₂ in formula (1) may have, and a fluorine atom It is preferable that

In formula (2), Ar ₁ and Ar ₂ each independently represent an aromatic ring. Specific examples of the aromatic ring represented by Ar ₁ and Ar ₂ include specific examples in the explanation part of the aromatic residue as a substituent which the acyl group represented by X ₁ and X ₂ in formula (1) may have. Are the same as the aromatic rings described as above, each independently preferably a benzene ring or a naphthalene ring, more preferably a benzene ring.

That is, R ₂ in the formula (1) is a residue obtained by removing one hydrogen atom from the benzene ring b ₁ or c _{1 of the} compound represented by the following formula (3), or represented by the following formula (4). It is preferably a residue obtained by removing one hydrogen atom from the benzene ring b ₂ or c _{2 of the} compound. The position at which one hydrogen atom on the benzene ring b ₁ or c ₁ or b ₂ or c ₂ is removed is not particularly limited, but the indole ring comprising the benzene ring b ₁ or c ₁ in the formula (3) Or the 6-position of the indole ring comprising the benzene ring b ₂ or c ₂ in formula (4).

Z ₃ and Z _{4 in} formula (3) and Z ₅ and Z _{6 in} formula (4) each independently represent a halogen atom. As the halogen atom represented by Z ₃ , Z ₄ , Z ₅ and Z ₆ , the halogen atom as a substituent which the acyl group represented by X ₁ and X _{2 in} the formula (1) may have is described. The same thing is mentioned, It is preferable that it is a fluorine atom.
A ₂₃ and A ₂₄ in the formula (3) and A ₂₅ and A ₂₆ in the formula (4) each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon residue or an alkoxyl group.
As the halogen atom, aliphatic hydrocarbon residue and alkoxyl group represented by A ₂₃ , A ₂₄ , A ₂₅ and A _{26, the} acyl group represented by X ₁ and X ₂ in formula (1) may have a substituent Examples are the same as those described in the section of the halogen atom, aliphatic hydrocarbon residue and alkoxyl group as the group.
As A ₂₃ and A ₂₄ in Formula (3), an alkoxyl group is preferable, an alkoxyl group having 1 to 4 carbon atoms is more preferable, and a methoxy group is further preferable.
A ₂₅ and A ₂₆ in Formula (4) are preferably alkyl groups, more preferably alkyl groups having 1 to 8 carbon atoms, and still more preferably alkyl groups having 4 to 6 carbon atoms. Particularly preferred is a hexyl group.
Q ₃ and Q ₄ in Formula (4) are each independently preferably an oxygen atom, a sulfur atom or a selenium atom, and more preferably a sulfur atom.

R ₁ in the formula (1) is a group represented by the following formula (3001) or (3003).

In formula (3001), R ₁₂ and R ₁₃ each independently represents a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue.
R ₁₂ and R ₁₃ in Formula (3001) are each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably each independently an alkyl group having 1 to 8 carbon atoms. More preferably, they are each independently a linear alkyl group having 1 to 8 carbon atoms, more preferably both are the same linear alkyl group having 1 to 8 carbon atoms, and both are n-butyl groups. It is particularly preferred.

In formula (3003), R ₁₄ and R ₁₅ each independently represent a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue.
As the aromatic residue and aliphatic hydrocarbon residue represented by R ₁₄ and R ₁₅ , an aromatic residue as a substituent which the acyl group represented by X ₁ and X ₂ in formula (1) may have And the same group as described in the section of the aliphatic hydrocarbon residue and the group represented by the formula (3001).
The aromatic residue and aliphatic hydrocarbon residue represented by R ₁₄ and R ₁₅ may have a substituent, and examples of the substituent that may be present include X ₁ and X in the formula (1) _The same thing as what was mentioned in the term of the substituent which the acyl group which ₂ represents may have is mentioned.
R ₁₄ and R ₁₅ in formula (3003) are preferably each independently an aromatic residue, more preferably independently a group represented by formula (3001) or a phenyl group, More preferably, it is a phenyl group.

In the formula (3003), R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, acyl group, amide group, alkoxyl group, alkoxycarbonyl Represents a group or a phenylsulfonyl group.
As the aromatic residue, aliphatic hydrocarbon residue, amide group, alkoxyl group and alkoxycarbonyl group represented by R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ , acyl represented by X ₁ and X _{2 in} the formula (1) Examples are the same as those described in the paragraphs of the aromatic residue, aliphatic hydrocarbon residue, amide group, alkoxyl group and alkoxycarbonyl group as the substituent that the group may have.
Examples of the acyl group represented by R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ include the same as those described in the section of the acyl group represented by X ₁ and X ₂ in formula (1).

R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ in the formula (3003) are preferably each independently a hydrogen atom or an alkoxyl group, and each independently a hydrogen atom or an alkoxyl group having 1 to 4 carbon atoms. Are more preferable, and all of them are more preferably hydrogen atoms.

More specifically, R ₁ in the formula (1) is particularly preferably a group represented by any of the following formulas (3101) to (3108).

Among these groups, R ₂ in Formula (1) is preferably a group represented by Formula (3103) or (3107), and most preferably a group represented by Formula (3103). .

  When the compound represented by the formula (1) has an acidic group such as a carboxyl group, a phosphoric acid group, a hydroxyl group and a sulfonic acid group as a substituent, a salt may be formed respectively. Examples of such salts include salts with alkali metals such as lithium, sodium and potassium, salts with alkaline earth metals such as magnesium and calcium, or tetramethylammonium, tetrabutylammonium, pyridinium, imidazolium, piperazinium, Mention may be made of salts with organic bases such as quaternary ammonium such as piperidinium.

  The compound represented by the formula (1) can take structural isomers such as a cis isomer, a trans isomer, and a racemate, but is not particularly limited, and any isomer is preferable as a photosensitizing dye in the present invention. It can be used.

Preferred combinations of options that are preferred in each of m, l, n, j, X _{1 to} X ₂ , Q _{1 to} Q ₂ , A _{1 to} A ₈ , and R _{1 to} R ₂ in formula (1) are preferred, A more preferable combination of these is as follows.
That is, in the formula (1), l and n are 0, m and j are 1 to 3 (more preferably, m is 1 and j is 1 to 3), and X ₁ and X ₂ are respectively Independently a carboxyl group, a phosphate group, a cyano group or an acyl group, Q ₁ and Q ₂ are each independently an oxygen atom, a sulfur atom or a selenium atom, and A _{1 to} A ₈ are each independently a hydrogen atom or a fat Is a group hydrocarbon residue, wherein R ₂ is a residue obtained by removing one hydrogen atom from the aromatic ring Ar ₁ of the compound represented by formula (2), and Y ₁ and Y ₂ are each independently phenyl A group, a thienyl group or a naphthyl group, Y ₃ is a hydrogen atom, Ar ₁ and Ar ₂ are each independently a benzene ring or a naphthalene ring, and R ₁ is any of the above formulas (3101) to (3108) A group represented by the formula (1) Compounds are preferred.

More preferably, in the formula (1), l and n are 0, m and j are 1 to 2 (more preferably, m is 1 and j is 1 to 2), and X ₁ and X ₂ Are each independently a carboxyl group, a cyano group or an acyl group, Q ₁ and Q ₂ are each independently an oxygen atom, a sulfur atom or a selenium atom, and A _{1 to} A ₈ are each independently a hydrogen atom or a carbon number of 1 A linear alkyl group of 1 to 8, R ₂ is a residue obtained by removing one hydrogen atom from the aromatic ring b ₁ or b _{2 of the} compound represented by formula (3) or formula (4), and R ₁ is a compound represented by the formula (1), which is a group represented by the above formula (3103) or (3107).
Particularly preferably, in the formula (1), l and n are 0, m and j are 1 to 2 (more preferably m is 1 and j is 1 to 2), and X ₁ and X ₂ One of them is a carboxyl group, the other is a carboxyl group, a cyano group or an acyl group, Q ₁ and Q ₂ are sulfur atoms, A _{1 to} A ₈ are hydrogen atoms, and R ₁ is represented by formula (3103). R ₂ is a residue obtained by removing one hydrogen atom from the aromatic ring b ₁ or b _{2 of the} compound represented by formula (3) or formula (4), wherein R ₂ is a group represented by formula (3) Z ₃ and Z _{4 in} the formula are fluorine atoms, A ₂₃ and A ₂₄ are each independently an alkoxyl group having 1 to 4 carbon atoms, Z ₅ and Z ₆ in the formula (4) are fluorine atoms, and Q ₃ And Q ₄ is a sulfur atom, and A ₂₅ and A ₂₆ are each independently an alkyl group having 4 to 6 carbon atoms. ).

The compound represented by the formula (1) can be produced, for example, according to the following reaction formula, but the present invention is not limited to these synthesis methods.
First, a method for synthesizing a compound represented by the formula (m), which is an intermediate material, will be described. The compound represented by the formula (a) as a raw material and the compound represented by the formula (b) are reacted in an appropriate solvent such as alcohol to obtain a compound represented by the formula (c). Next, the compound represented by the formula (c) is treated with lead tetraacetate in an appropriate solvent such as tetrahydrofuran to obtain the compound represented by the formula (d). On the other hand, from the compound represented by formula (g) obtained by the reaction of the compound represented by formula (e) and the compound represented by formula (f) by the same procedure as described above, The compound represented by h) is obtained. Next, the compound represented by the formula (d) and the compound represented by the formula (h) are reacted with each other at room temperature by adding ammonia water in an appropriate alcohol and acetic acid mixed solvent, and then separated and purified. Thus, a compound represented by formula (i) is obtained. Next, the compound represented by the formula (i) is reacted with a halide of the semimetal M (boron trihalide or antimony, silicon tetrahalide or germanium, etc.), and the compound represented by the formula (j) Get. Further, the compound represented by the formula (m) is obtained by bonding the compound represented by the formula (j) and the compound represented by the formula (k) by cross coupling or the like. Y ₃ can be substituted with a substituent other than a hydrogen atom by a Grignard reaction or the like as necessary.

  Further, a compound represented by formula (n) and a compound represented by formula (o) synthesized in advance by a known method, or a compound and formula represented by formula (p) synthesized in advance by a known method The compound represented by formula (i) obtained by reacting the compound represented by (q) with a solvent such as ethanol or tetrahydrofuran in the presence of an acid catalyst such as hydrobromic acid or hydrogen chloride. The compound represented by the formula (m) can also be obtained by performing the same treatment as above.

  The compound represented by the formula (t) is obtained by the reaction of the compound represented by the formula (r) with the boronic acid represented by the formula (s). The compound represented by the formula (t) is treated with N-iodosuccinimide to obtain the compound represented by the formula (u). This is reacted with a boronic acid represented by the formula (v) to derive a compound represented by the formula (w), and then reacted with the compound represented by the formula (m) obtained above to formula ( A carbonyl compound represented by x) is obtained. If necessary, this compound represented by the formula (x) and the compound having an active methylene represented by the formula (y) are converted into caustic soda, sodium methylate, sodium acetate, diethylamine, triethylamine, piperidine, piperazine, diazabicyclo. Usually in alcohols such as methanol, ethanol, isopropanol and butanol, aprotic polar solvents such as dimethylformamide and N-methylpyrrolidone, and solvents such as toluene, acetic anhydride and acetonitrile in the presence of basic catalysts such as undecene By condensing at 20 ° C. to 180 ° C., preferably 50 ° C. to 150 ° C., the compound (dye) represented by the formula (1) of the present invention is obtained. In the above reaction, when the compound having active methylene represented by the formula (y) has an ester group, it is also possible to obtain a carboxylic acid form by performing hydrolysis or the like after the condensation reaction.

  In particular, when l in the formula (1) is 0, the reaction between the compound represented by the formula (r) and the boronic acid represented by the formula (s) is not performed, and the formula (t) It can synthesize | combine similarly by using the compound represented by a formula (t ') instead of the represented compound.

A more detailed description of the cross-coupling reaction in the above process is described in Non-Patent Document 5, and the entire contents thereof are incorporated herein by reference.

Specific examples of compounds represented by the following formula (1-1) (compounds in which R ₂ in the formula (1) is a residue of the compound represented by the formula (3)) are shown in Tables 1 to 19. In each table, Ph means a phenyl group. Those expressed as (2001) to (2017) represent a ring formed by combining X ₁ and X ₂ , and correspond to the above formulas (2001) to (2017). The notations (3101) to (3108) correspond to the above formulas (3101) to (3108).

Specific examples of the compound represented by the following formula (1-2) (the compound in which R ₂ in the formula (1) is a residue of the compound represented by the formula (4)) are shown in Table 20 to Table 38. In each table, Ph means a phenyl group. Those expressed as (2001) to (2017) represent a ring formed by combining X ₁ and X ₂ , and correspond to the above formulas (2001) to (2017). The notations (3101) to (3108) correspond to the above formulas (3101) to (3108).

In the photoelectric conversion element of the present invention, for example, a thin film of oxide semiconductor fine particles is provided on a substrate using oxide semiconductor fine particles, and then a compound (pigment) represented by formula (1) is supported on the thin film. It is.
As a substrate on which a thin film of oxide semiconductor fine particles is provided, a substrate having a conductive surface is preferable, but such a substrate is easily available in the market. For example, conductive metal oxides such as tin oxide doped with indium, fluorine and antimony on the surface of transparent polymer materials such as glass or polyethylene terephthalate or polyether sulfone, and metals such as copper, silver and gold A substrate provided with a thin film can be used as the substrate. The conductivity of such a substrate is usually 1000Ω or less, preferably 100Ω or less.
The oxide semiconductor fine particles are preferably made of a metal oxide. Examples of such metal oxides include titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, and vanadium. And the like. Among these, oxides such as titanium, tin, zinc, niobium, and indium are preferable, and titanium oxide, zinc oxide, and tin oxide are most preferable. These oxide semiconductors may be used alone or in combination of two or more. These oxide semiconductors may be coated on the surface of the semiconductor. The average particle size of the oxide semiconductor fine particles is usually 1 to 500 nm, preferably 1 to 100 nm. Further, oxide semiconductor fine particles having a large particle diameter and oxide semiconductor fine particles having a small particle diameter may be combined, and a plurality of layers containing oxide semiconductor fine particles having different types or particle diameters may be provided.

  A thin film of oxide semiconductor fine particles is formed by spraying oxide semiconductor fine particles directly onto a substrate by spraying or the like, a method of forming a thin film of semiconductor fine particles, a method of electrically depositing semiconductor fine particles into a thin film using a substrate as an electrode, or a semiconductor The paste containing fine particles obtained by hydrolyzing a fine particle slurry or a precursor of fine semiconductor particles such as semiconductor alkoxide may be applied on a substrate, followed by drying, curing or baking. Among these, a method using a slurry is preferable in terms of the performance of an electrode including an oxide semiconductor. In this method, the slurry is obtained by dispersing the secondary agglomerated oxide semiconductor fine particles in a dispersion medium by an ordinary method so that the average primary particle diameter is 1 to 200 nm.

  The dispersion medium for dispersing the slurry may be anything as long as it can disperse the semiconductor fine particles, and water, alcohol such as ethanol, ketone such as acetone and acetylacetone, hydrocarbon such as hexane, and the like can be used. These may be used as a mixture, but it is preferable to use water in order to reduce the viscosity change of the slurry. A dispersion stabilizer can be used for the purpose of stabilizing the dispersion state of the oxide semiconductor fine particles. Examples of the dispersion stabilizer that can be used include acids such as acetic acid, hydrochloric acid, and nitric acid, and organic solvents such as acetylacetone, acrylic acid, polyethylene glycol, and polyvinyl alcohol.

  The substrate coated with the slurry may be fired, and the firing temperature is usually 100 ° C. or higher, preferably 200 ° C. or higher, while the upper limit is generally below the melting point (softening point) of the substrate material, usually 900 ° C. It is below, Preferably it is 600 degrees C or less. The firing time is not particularly limited, but is preferably within 4 hours. The thickness of the thin film on the substrate is usually 1 to 200 μm, preferably 1 to 50 μm.

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

Next, a method for supporting the compound represented by the formula (1) on the thin film of oxide semiconductor fine particles will be described.
As a method of supporting the compound represented by the formula (1), a solution obtained by dissolving the compound in a solvent capable of dissolving the compound or a compound having low solubility may be obtained by dispersing the compound. And a method in which the substrate provided with the thin film of oxide semiconductor fine particles is immersed in the dispersion. The concentration in the solution or dispersion may be appropriately determined depending on the compound. A thin film of semiconductor fine particles formed on the substrate is immersed in the solution. The immersion temperature is generally from room temperature to the boiling point of the solvent, and the immersion time is about 1 minute to 48 hours. Solvents that can be used to dissolve the compound include, for example, methanol, ethanol, isopropanol, tetrahydrofuran (THF), acetonitrile, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), acetone, n-butanol, t-butanol, water. , N-hexane, chloroform, dichloromethane, toluene and the like, and may be used alone or in combination according to the solubility of the compound. The compound concentration of the solution is usually 1 × 10 ⁻⁶ M to 1M, and preferably 1 × 10 ⁻⁵ M to 1 × 10 ⁻¹ M.
After the immersion, the solvent is removed by air drying or heating if necessary. Thus, the photoelectric conversion element of the present invention having a thin film of oxide semiconductor fine particles sensitized with the compound (pigment) represented by the formula (1) is obtained.

  The dye to be supported may be one of the compounds represented by the formula (1) or a combination of two or more compounds. When combining a plurality of compounds, two or more of the compounds represented by formula (1) may be combined, or other organic dyes and / or metal complex dyes may be combined. In particular, by combining pigments having different absorption wavelengths, a wide range of absorption wavelengths can be used, and a solar cell with high conversion efficiency can be obtained. The metal complex dyes that can be combined are not particularly limited, but ruthenium complexes shown in Non-Patent Document 2 or quaternary ammonium salts thereof, phthalocyanines, porphyrins, and the like are preferable. Examples of organic dyes that can be combined include metal-free phthalocyanine, porphyrin, cyanine, merocyanine, oxonol, triphenylmethane, methine dyes such as acrylic acid dyes disclosed in Patent Document 2, xanthene, azo, and anthraquinone And perylene-based pigments. Preferred examples include ruthenium complexes, merocyanines, and methine dyes such as acrylic acid. When two or more dyes are used, the dyes may be sequentially adsorbed on the thin film of semiconductor fine particles, or a mixed solution may be prepared, and the liquid may be applied and adsorbed simultaneously.

  The ratio of the dye to be mixed is not particularly limited, and the optimization condition may be appropriately selected for each dye. Generally, from the mixing of equimolar amounts to about 10% mol or more per dye. preferable. When a dye is adsorbed to a thin film of oxide semiconductor fine particles using a solution in which two or more kinds of dyes are dissolved or dispersed, the total concentration of the dyes in the solution may be the same as when only one kind is supported. As the solvent in the case of using a mixture of dyes, the above-mentioned solvents can be used, and the solvents for the respective dyes to be used may be the same or different.

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

  The solar cell uses, as a first electrode, a photoelectric conversion element in which the compound (dye) of the present invention is supported on a thin film of the oxide semiconductor fine particles, a second electrode having a counter electrode, and a third redox electrolyte or hole. It is composed of three elements comprising a transport material or a p-type semiconductor. The forms of the third component redox electrolyte, hole transport material, p-type semiconductor, and the like include liquids, solidified bodies (gels and gels), solids, and the like, and known ones can be used. Examples of liquid materials include redox electrolytes, molten salts, hole transport materials, p-type semiconductors and the like dissolved in solvents, and room temperature molten salts. As the solidified body (gel and gel), there are those in which these are contained in a polymer matrix or a low molecular gelling agent. Examples of solid materials include those using redox electrolytes, molten salts, hole transport materials, p-type semiconductors, and the like as they are. Examples of the hole transport material include amine derivatives; conductive polymers such as polyacetylene, polyaniline, and polythiophene; triphenylene compounds. Examples of the p-type semiconductor include CuI and CuSCN. The counter electrode is preferably one that has conductivity and catalyzes the reduction reaction of the redox electrolyte. For example, a glass or polymer film deposited with platinum, carbon, rhodium, ruthenium or the like, or a film coated with conductive fine particles is used.

The redox electrolyte used in the solar cell of the present invention includes a halogen redox electrolyte comprising a halogen compound having a halogen ion as a counter ion and a halogen molecule; ferrocyanate-ferricyanate or ferrocene-ferricinium ion, cobalt complex Metal redox electrolytes such as metal complexes, etc .; or organic redox electrolytes such as alkyl thiol-alkyl disulfides, viologen dyes, hydroquinone-quinones, etc., and halogen redox electrolytes are preferred. Examples of the halogen molecule in the halogen redox electrolyte comprising a halogen compound and a halogen molecule include an iodine molecule and a bromine molecule, and an iodine molecule is preferable. As the halogen compound having a halogen ion as a counter ion, for example LiBr, NaBr, KBr, LiI, NaI, KI, CsI, CaI 2, MgI 2, CuI and halogenated metal salt or tetraalkylammonium iodide, and imidazolium Examples include halogen organic quaternary ammonium salts such as rhodium iodide and pyridinium iodide, and salts having iodine ions as counter ions are preferred. Moreover, you may use the electrolyte which uses imide ions, such as a bis (trifluoromethanesulfonyl) imide ion and a dicyano imide ion, as a counter ion other than the said iodine ion.

  When the redox electrolyte is formed in the form of a solution containing the redox electrolyte, an electrochemically inert solvent is used as the solvent. For example, acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, γ-butyrolactone, dimethoxyethane, diethyl carbonate, diethyl ether, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, dimethylformamide, dimethyl sulfoxide, 1,3-dioxolane, methyl formate, 2-methyltetrahydrofuran, 3-methyl-oxazolidin-2-one, sulfolane, tetrahydrofuran, water and the like. Among these, acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionate Le, methoxy acetonitrile, ethylene glycol, 3-methyl - oxazolidin-2-one, .gamma.-butyrolactone are particularly preferred. You may use these individually or in combination of 2 or more types. In the case of a gel electrolyte, examples include those in which an electrolyte or an electrolyte solution is contained in a matrix such as an oligomer and a polymer, and those in which a low-molecular gelling agent or the like is similarly contained in an electrolyte or an electrolyte solution. The concentration of the redox electrolyte is usually 0.01 to 99% by mass, preferably about 0.1 to 90% by mass.

  The solar cell of the present invention has a counter electrode so that a thin film of oxide semiconductor fine particles on a substrate is sandwiched between electrodes of a photoelectric conversion element carrying a compound (pigment) represented by the formula (1) of the present invention. Deploy. In the meantime, it is obtained by filling a solution containing a redox electrolyte.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the examples, parts represent parts by mass unless otherwise specified. M representing the concentration of the solution represents mol / L. The maximum absorption wavelength was measured with an ultraviolet-visible spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation). Nuclear magnetic resonance was measured by JNM-ECS400 (manufactured by JEOL Ltd.).

Synthesis example 1
26 parts of 9,9-dibutyl-2-iodofluorene, 10 parts of 3-thiopheneboronic acid, 2.3 parts of tetrakis (triphenylphosphine) palladium (0) and 180 parts of 20% aqueous sodium carbonate solution were added to 1,2-dimethoxyethane. The mixture was added to 340 parts and reacted under reflux for 5 hours. The reaction mixture was extracted with toluene-water, the toluene phase was concentrated, separated and purified by column chromatography (toluene-hexane), and 15 parts of the following compound (700) was obtained as a colorless oil.

Synthesis example 2
15 parts of Compound (700) was dissolved in a mixed solution of 40 parts of acetic acid and 60 parts of chloroform, 5 parts of N-bromosuccinimide was added, and the mixture was stirred under reflux. After 1 hour, 2.5 parts of N-bromosuccinimide was added, and the mixture was further stirred for 1 hour under reflux. The reaction mixture was extracted with chloroform-water, the chloroform phase was concentrated, separated and purified by column chromatography (hexane), and 17 parts of the following compound (701) was obtained as a colorless oil.

Synthesis example 3
Compound (701) 2.8 parts, 5-formyl-5 ′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2,2′-bithiophene 3 parts, Tetrakis (triphenylphosphine) palladium (0) 0.22 part and 20% aqueous sodium carbonate solution 17 parts were added to 63 parts of 1,2-dimethoxyethane and reacted under reflux for 5 hours. The reaction mixture was extracted with chloroform-water, the chloroform phase was concentrated, separated and purified by column chromatography (chloroform-hexane), and 0.66 parts of the following compound (709) was obtained as a brown solid.

Synthesis example 4
1.7 parts of compound (709) was dissolved in a mixed solution of 34 parts of acetic acid and 47 parts of chloroform, 0.70 part of N-iodosuccinimide was added, and the mixture was stirred at 50 ° C. After 1 hour, 0.36 part of N-iodosuccinimide was added, and the mixture was further stirred at 50 ° C. for 3 hours. The reaction mixture was extracted with chloroform-water, the chloroform phase was concentrated, separated and purified by column chromatography (chloroform-hexane), and 1.6 parts of the following compound (900) was obtained as a yellow solid.

Synthesis example 5
A compound represented by the following formula (805) was obtained using 4-bromo-2-hydroxyacetophenone and 2-methoxybenzoylhydrazine according to the synthesis method described in Non-Patent Document 3.

Synthesis Example 6
2.3 parts of 2-hydroxyacetophenone and 2.4 parts of 2-methoxybenzoylhydrazine were added to 24 parts of absolute ethanol and reacted at 85 ° C. for 2 days in a nitrogen atmosphere. After completion of the reaction, the precipitated solid was washed with a small amount of ethanol and dried under reduced pressure to obtain 4.1 parts of a compound represented by the following formula (806) as a pale yellow solid.

Synthesis example 7
In 230 parts of tetrahydrofuran, 4.1 parts of the compound represented by the formula (806) obtained in Synthesis Example 6 was dissolved and ice-cooled. After adding 8.0 parts of lead tetraacetate little by little, it stirred at room temperature for about 5 hours. After completion of the reaction, the mixture was filtered through a Kiriyama funnel containing silica gel, and the filtrate was distilled off under reduced pressure to obtain 4.4 parts of a compound represented by the following formula (807) as an ocherous solid.

Synthesis Example 8
In a mixed solution of 37 parts of methanol and 28 parts of acetic acid, 1.6 parts of the compound represented by the formula (805) obtained in Synthesis Example 5 and the compound 1 represented by the formula (807) obtained in Synthesis Example 7 2 parts were dissolved with stirring to obtain a homogeneous solution. This solution was ice-cooled, 19 parts of aqueous ammonia was added, and the mixture was stirred overnight at 45 ° C. Quenched with saturated aqueous sodium hydrogen carbonate solution, the precipitated solid was filtered off. The obtained solid was separated and purified by column chromatography (hexane-benzene) to obtain 0.31 part of a compound represented by the following formula (808) as a dark blue solid.

Synthesis Example 9
After 1.2 parts of the compound represented by the formula (808) obtained in Synthesis Example 8 was dissolved in 72 parts of anhydrous toluene under a nitrogen atmosphere, 0.58 parts of triethylamine was added and heated to 80 ° C. After slowly adding dropwise 3.4 parts of diethyl ether complex of trifluoroboron, the mixture was stirred at 100 ° C. overnight. The reaction mixture was quenched by adding 40 parts of water, extracted with 110 parts of ethyl acetate, washed with 300 parts of water, and the organic layer was concentrated. The obtained solid was separated and purified by column chromatography (hexane-benzene) to obtain 1.1 parts of a compound represented by the following formula (809) as a dark blue solid.

Synthesis Example 10
Under a nitrogen atmosphere, 1.1 parts of the compound represented by the formula (809) obtained in Synthesis Example 9 and 1.9 parts of potassium acetate were dissolved in 29 parts of anhydrous dimethoxyethane, and freeze degassing was performed three times. 1.3 parts of bis (pinacolato) diboron was added to the solution in the glove box. 29 parts of anhydrous dimethoxyethane was put in another container and freeze deaeration was performed three times. Then, 0.38 part of [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) was added in the glove box. It was. This solution was added to the previous solution and stirred at 80 ° C. for 10 hours under a nitrogen atmosphere. The reaction mixture was quenched with 10 parts of water, extracted with 90 parts of ethyl acetate, washed with 200 parts of water, and the organic layer was concentrated. The obtained solid was separated and purified by column chromatography (hexane-dichloromethane) to obtain 1.0 part of a compound represented by the following formula (810) as a dark blue solid.

Synthesis Example 11
0.12 part of the compound represented by the formula (900) obtained in Synthesis Example 4; 0.17 part of the compound represented by the formula (810) obtained in Synthesis Example 10; tetrakis (triphenylphosphine) palladium ( 0) 0.0062 part and 1 part of a 20% sodium carbonate aqueous solution were added to 12 parts of 1,2-dimethoxyethane and reacted for 3 hours under reflux. The reaction mixture was extracted with chloroform-water, the chloroform phase was concentrated, separated and purified by column chromatography (chloroform-hexane), and 0.19 part of the following compound (901) was obtained as a green solid.

Example 1
0.19 part of the compound represented by the formula (901) obtained in Synthesis Example 11 and 0.094 part of cyanoacetic acid are dissolved in 35 parts of a mixed solution of ethanol-toluene (2: 1) to obtain 0.005 part of anhydrous piperazine. Was added and reacted under reflux for 1 hour. 0.094 parts of cyanoacetic acid was added, and the mixture was further reacted for 3 hours under reflux. Further, 0.094 part of cyanoacetic acid and 0.005 part of anhydrous piperazine were added and reacted under reflux for 3 hours. The reaction mixture is extracted with dichloromethane-water, the dichloromethane phase is concentrated, separated and purified by column chromatography (dichloromethane-ethanol), and the compound of the present invention represented by the following formula (902) (compound 1 in Table 1). 0.028 parts were obtained as a black-green solid.

The maximum absorption wavelength of the compound represented by the formula (902) and the measured values in the nuclear magnetic resonance apparatus are as follows.
Maximum absorption wavelength; λmax = 645 nm (1.6 × 10 ⁻⁵ M, tetrahydrofuran solution)
Measurement value of nuclear magnetic resonance: ¹ H-NMR (PPM: DMSO-d6): 0.52 (m, 4H), 0.53 (m, 6H), 0.90 (m, 4H), 1.88 (m, 4H), 3.72 (m , 6H), 7.06 (m, 3H), 7.23 (m, 3H), 7.32 (m, 5H), 7.42 (m, 3H), 7.51 (m, 5H), 7.59 (m, 2H), 7.74 (d, 1H), 7.85 (m, 1H), 7.91 (d, 1H), 8.02 (m, 2H), 8.17 (m, 1H), 8.24 (m, 1H), 8.71 (s, 1H)

Synthesis Example 12
1.6 parts of 1- (4-bromo-2-hydroxyphenyl) ethanone and 1.1 parts of 5-hexylthiophene-2-carboxylic acid hydrazide are added to 6 parts of absolute ethanol and reacted at 85 ° C. for 2 days in a nitrogen atmosphere. It was. After completion of the reaction, the precipitated solid was washed with a small amount of ethanol and dried under reduced pressure to obtain 1.6 parts of a compound represented by the following formula (903).

Synthesis Example 13
In 11 parts of tetrahydrofuran, 0.28 part of the compound represented by the formula (903) obtained in Synthesis Example 12 was dissolved and ice-cooled. After adding 0.35 part of lead tetraacetate little by little, it stirred at room temperature for about 5 hours. After completion of the reaction, the mixture was filtered through a Kiriyama funnel containing silica gel, and the filtrate was distilled off under reduced pressure to obtain 0.26 parts of a compound represented by the following formula (904).

Synthesis Example 14
0.84 part of 2-hydroxyacetophenone and 1.4 part of 5-hexylthiophene-2-carboxylic acid hydrazide were added to 12 parts of absolute ethanol, and stirred overnight at 85 ° C. under a nitrogen atmosphere. After completion of the reaction, the precipitated solid was washed with a small amount of ethanol, and then separated and purified by column chromatography (hexane-dichloromethane) to obtain 1.2 parts of a compound represented by the following formula (905).

Synthesis Example 15
In 53 parts of tetrahydrofuran, 1.1 parts of the compound represented by the formula (905) obtained in Synthesis Example 14 was dissolved and ice-cooled. After adding 1.8 parts of lead tetraacetate little by little, it stirred at room temperature for about 5 hours. After completion of the reaction, the mixture was filtered through a Kiriyama funnel containing silica gel, and the filtrate was distilled off under reduced pressure, followed by liquid separation with water and ethyl acetate. This organic phase was distilled off under reduced pressure and dried under reduced pressure to obtain 1.0 part of a compound represented by the following formula (906).

Synthesis Example 16
In 43 parts of ethanol, 1.0 part of the compound represented by the formula (904) obtained in Synthesis Example 13 and 0.81 part of the compound represented by the formula (906) obtained in Synthesis Example 15 were dissolved. 12 parts were added and heated to 65 ° C. To this solution, 2.4 parts of ammonium acetate and 0.28 part of ammonium chloride were added little by little, and then stirred at 90 ° C. overnight. After cooling, the solvent was distilled off under reduced pressure, and then a liquid separation operation was performed with chloroform and saturated aqueous sodium chloride. The chloroform phase was distilled off under reduced pressure, and column chromatography (hexane-chloroform, 1: 1) was performed to obtain a mixture from which the origin component was removed.

  This mixture was dissolved in 30 parts of anhydrous toluene under a nitrogen atmosphere, 0.36 part of triethylamine was added, and the mixture was heated to 80 ° C. After slowly dropwise adding 1.7 parts of a diethyl ether complex of trifluoroboron, the mixture was stirred at 100 ° C. overnight. The reaction mixture was quenched by adding 45 parts of water, extracted with ethyl acetate, washed with water, and then the organic layer was concentrated to obtain a purple solid.

  This solid and 0.79 part of potassium acetate were dissolved in 16 parts of dehydrated 1,2-dimethoxyethane in a nitrogen atmosphere, and then [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) 0. .16 parts were added and freeze deaeration was performed 3 times. This solution was dissolved in 16 parts of dehydrated 1,2-dimethoxyethane in a glove box, added to the solution that had been subjected to freeze degassing three times, and then heated and stirred at 80 ° C. overnight. The reaction mixture was quenched by adding 15 parts of water, extracted with ethyl acetate, the organic phase was concentrated, separated and purified by column chromatography (hexane-ethyl acetate) and reprecipitation (methanol-water), and represented by the following formula (907). 0.092 parts of the compound was obtained as a dark blue solid.

Synthesis Example 17
0.09 part of the compound represented by Formula (900) obtained in Synthesis Example 4; 0.12 part of the compound represented by Formula (907) obtained in Synthesis Example 16; tetrakis (triphenylphosphine) palladium ( 0) 0.0042 part and 0.5 part of 20% sodium carbonate aqueous solution were added to 7 parts of 1,2-dimethoxyethane and reacted for 3 hours under reflux. The reaction mixture was extracted with chloroform-water, the chloroform phase was concentrated, separated and purified by column chromatography (chloroform-hexane), and 0.14 parts of the following compound (908) was obtained as a dark green solid.

Example 2
0.14 part of the compound represented by the formula (908) obtained in Synthesis Example 17 and 0.061 part of cyanoacetic acid are dissolved in 23 parts of ethanol-toluene (2: 1) mixed solution, and 0.005 part of anhydrous piperazine is dissolved. Was added and reacted under reflux for 1 hour. 0.061 part of cyanoacetic acid was added, and the mixture was further reacted for 5 hours under reflux. The reaction mixture was extracted with dichloromethane-water, the dichloromethane phase was concentrated, separated and purified by column chromatography (dichloromethane-ethanol), and the compound of the present invention represented by the following formula (909) (Compound 705 in Table 20) 0 0.040 part was obtained as a dark green solid.

The maximum absorption wavelength of the compound represented by the formula (909) and the measured values in the nuclear magnetic resonance apparatus are as follows.
Maximum absorption wavelength; λmax = 712 nm (1.6 × 10 ⁻⁵ M, tetrahydrofuran solution)
Measurement value of nuclear magnetic resonance: ¹ H-NMR (PPM: DMSO-d6): 0.44 (m, 4H), 0.54 (m, 6H), 0.89 (m, 8H), 1.33 (m, 14H), 1.73 (m , 4H), 1.92 (m, 4H), 2.95 (m, 4H), 7.10 (d, 1H), 7.14 (m, 2H), 7.22 (d, 1H), 7.30 (d, 1H), 7.35 (m, 2H), 7.42 (m, 3H), 7.58 (m, 3H), 7.75 (s, 1H), 7.85 (m, 3H), 7.98 (m, 4H), 8.18 (m, 3H), 8.52 (s, 1H )

Examples 3 and 4
The compound of the present invention represented by the formula (902) obtained in Example 1 (compound 1 of Table 1) and the cholic acid represented by the following formula (d) were 3.2 × 10 ⁻⁴ M and 1 respectively. The compound of the present invention represented by the formula (909) obtained in Example 2 (compound 705 in Table 20) and cholic acid represented by the following formula (a) were used so as to be × 10 ^-2 M. It melt | dissolved in the 1: 1 mixed solvent (v / v) of t-butanol and acetonitrile so that it might become 3.2 * 10 < ^-4 > M and 1 * 10 ^<-2 > M, respectively. A porous substrate (semiconductor thin film electrode obtained by sintering porous titanium oxide for 30 minutes at 450 ° C. on a transparent conductive glass electrode) in this solution is immersed overnight at room temperature, and then washed with a solvent and dried. A photoelectric conversion element was obtained. The semiconductor thin film layer of the photoelectric conversion element obtained above and the platinum layer of conductive glass with platinum sputtered on the surface are arranged oppositely and fixed, and a solution containing an electrolyte is injected into and sealed in the gap. An inventive solar cell was obtained. The electrolyte solution was iodine / lithium iodide / 1,2-dimethyl-3-n-propylimidazolium iodide dissolved in 3-methoxypropionitrile to 0.1M / 0.1M / 0.6M, respectively. We used what we did.

Comparative Example 1
Except that the compound of the present invention represented by the formula (902) obtained in Example 1 was changed to a comparative compound represented by the following formula (A) (compound (190) described in Patent Document 4). In accordance with Example 3, a comparative solar cell was obtained.

(IPCE measurement of solar cells)
The IPCE at 300 to 800 nm of the solar cells obtained in Example 2 and Comparative Example 1 was measured by the DC method using SM-25YD manufactured by Spectrometer Co., Ltd., and the obtained IPCE spectrum is shown in FIG. In FIG. 1, “1” is the measurement result of the solar cell of the present invention obtained in Example 2, and “A” is the comparison solar cell obtained using the compound represented by the above formula (A). Each measurement result is shown.

(Evaluation of photoelectric conversion characteristics of solar cells)
The photoelectric conversion characteristics of the solar cells obtained in Example 2 and Comparative Example 1 were evaluated. The size of the battery to be measured was an effective part of 0.25 cm ² . A 500 W xenon lamp was used as the light source, and it was set to 100 mW / cm ² through an AM (air passing through the atmosphere) 1.5 filter. Measurements were made using a potentio galvanostat. The results are shown in Table 39.

  From the results of Table 39 and FIG. 1, it is clear that the solar cell using the compound of the present invention as the sensitizing dye can effectively convert the visible light region having a longer wavelength into electricity than the comparative solar cell.

  By using the compound of the present invention having a specific partial structure as a sensitizing dye, a photoelectric conversion element and a solar cell capable of effectively converting a wide range of visible light into electricity could be provided.

Claims (23)

Compound represented by the following formula (1)

(In the formula (1), m is an integer of 1 to 5, l and n are each independently an integer of 0 to 6, and j is an integer of 0 to 3. X ₁ and X ₂ are each independently hydrogen. Atom, carboxyl group or salt thereof, hydroxyl group or salt thereof, phosphoric acid group or salt thereof, sulfonic acid group or salt thereof, cyano group, substituted or unsubstituted acyl group, substituted or unsubstituted amide group, substituted or unsubstituted alkoxycarbonyl X ₁ and X ₂ may be linked to each other to form a ring, and Q ₁ and Q ₂ each independently represents an oxygen atom, a sulfur atom, a selenium atom or NR ₁₁ R ₁₁ represents a hydrogen atom, a substituted or unsubstituted aromatic residue, or a substituted or unsubstituted aliphatic hydrocarbon residue, and when m is 2 or more and a plurality of Q ₁ are present, each Q ₁ is same Flip or different and have well, if j is Q ₂ there are a plurality of two or more, each Q ₂ is optionally the same or different from each other _{.A 1, A 2, A 3} , A 5 And A ₆ are each independently a hydrogen atom, a substituted or unsubstituted aromatic residue, a substituted or unsubstituted aliphatic hydrocarbon residue, a cyano group, a halogen atom, a substituted or unsubstituted carbonamido group, a substituted or unsubstituted amide group Represents a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted arylcarbonyl group, or a substituted or unsubstituted acyl group, wherein l is 2 or more and A ₂ and A If _{the 3} there are a plurality, each of a ₂ and a ₃ may be the same or different from one another, if n is a ₅ and a ₆ are a plurality exist in two or more , Each of A ₅ and A ₆ may be the same or different from each other. Also, if l is other than 0, may form a ring with any plurality of A _1, A ₂ and A ₃ A ₄ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon residue, a cyano group, a halogen atom, a substituted or unsubstituted carbonamido group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted amide group, substituted or unsubstituted when the .m to an alkoxycarbonyl group or a substituted or unsubstituted acyl group a ₄ is more present in 2 or more, each a ₄ are each the same or different optionally .A ₇ and a ₈ be each independently A hydrogen atom, substituted or unsubstituted aliphatic hydrocarbon residue, cyano group, halogen atom, substituted or unsubstituted carbonamido group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted An alkoxycarbonyl group or a substituted or unsubstituted acyl group is represented. When j is 2 or more and a plurality of A ₇ and A ₈ exist, each A ₇ and A ₈ may be the same as or different from each other. R ₂ is the following formula (2)

(In Formula (2), M represents a metalloid atom. Y ₁ , Y ₂ and Y ₃ each independently represent a hydrogen atom or a substituted or unsubstituted aromatic residue. Z ₁ and Z ₂ each independently represent Represents a halogen atom, Ar ₁ and Ar ₂ each independently represents a substituted or unsubstituted aromatic ring.) Represents a residue obtained by removing one hydrogen atom from the aromatic ring Ar ₁ or Ar _{2 of the} compound represented by . R ₁ represents the following formula (3001) or (3003)

(In the formula (3001) or (3003), R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, a substituted or unsubstituted aromatic residue or a substituted or unsubstituted aliphatic hydrocarbon residue. R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, substituted or unsubstituted acyl group, substituted or unsubstituted amide group, A substituted or unsubstituted alkoxyl group, a substituted or unsubstituted alkoxycarbonyl group or a phenylsulfonyl group). When m is 2 or more and a plurality of R ₁ are present, each R ₁ may be the same as or different from each other. When n is other than 0, any one of A ₅ , A ₆ and R ₂ may form a ring. ). The compound according to claim 1, wherein m in the formula (1) is 1 to 3. The compound according to claim 2, wherein m in the formula (1) is 1. The compound according to any one of claims 1 to 3, wherein Q ₁ and Q ₂ in the formula (1) are sulfur atoms. L and n in Formula (1) are 0, The compound of any one of Claims 1-4. The compound according to any one of claims 1 to 5, wherein one of X ₁ and X ₂ in formula (1) is a carboxyl group and the other is a carboxyl group, a cyano group, or an acyl group. The compound according to claim 6, wherein one of X ₁ and X ₂ in formula (1) is a carboxyl group and the other is a cyano group. The compound according to any one of claims 1 to 7, wherein X ₁ and X ₂ in formula (1) are bonded to form a ring structure. A compound according to any one of claims 1 to 8 A ₁ to A ₈ in formula (1) is a hydrogen atom. R ₂ in the formula (1) is the following formula (3)

(In formula (3), Z ₃ and Z ₄ each independently represent a halogen atom. A ₂₃ and A ₂₄ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon residue, or a substituted or non-substituted group. a compound according to any one of a substituted alkoxyl group.) is a residue obtained by removing one hydrogen atom from the top benzene ring b ₁ or c ₁ of the compound represented by the claims 1-9. The compound according to claim 10, wherein Z ₃ and Z ₄ in formula (3) are fluorine atoms, and A ₂₃ and A ₂₄ are methoxy groups. R ₂ in the formula (1) is the following formula (4)

(In Formula (4), Z ₅ and Z ₆ each independently represent a halogen atom. Q ₃ and Q ₄ each independently represent an oxygen atom, a sulfur atom, a selenium atom, or NR ₁₂ , R ₁₂ is a hydrogen atom, A substituted or unsubstituted aromatic residue or a substituted or unsubstituted aliphatic hydrocarbon residue, each of A ₂₅ and A ₂₆ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon residue, a compound according to any one of claims 1 to 9 is a residue obtained by removing one hydrogen atom from the top benzene ring b ₂ or c ₂ of the compound represented by the representative.) an unsubstituted alkoxyl group. The compound according to claim 12, wherein Z ₅ and Z ₆ in formula (4) are fluorine atoms, and A ₂₅ and A ₂₆ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ₁ in Formula (1) is a group represented by Formula (3001) or a group represented by Formula (3003), and R ₁₂ and R ₁₃ in Formula (3001) are each independently hydrogen. An atom or an alkyl group having 1 to 8 carbon atoms, R ₁₄ and R ₁₅ in formula (3003) are phenyl groups, and R _{16 to} R ₁₉ are each independently a hydrogen atom or an alkoxyl group having 1 to 4 carbon atoms. The compound according to any one of claims 1 to 13. R ₁ in the formula (1) is represented by the following formulas (3101) to (3108)

The compound of Claim 14 which is group represented by either of these. The compound according to claim 15, wherein R ₁ in the formula (1) is a group represented by the formula (3102), (3103) or (3107). The compound according to claim 16, wherein R ₁ in formula (1) is a group represented by formula (3103). The following formula (902)

The compound of Claim 1 represented by these. Following formula (909)

The compound of Claim 1 represented by these. The photoelectric conversion element which carry | supported the 1 or more types of compound represented by Formula (1) of Claim 1 in the thin film of the oxide semiconductor fine particle provided on the board | substrate. One or more compounds represented by formula (1) according to claim 1 and a sensitizing dye compound having a structure other than formula (1) are supported on a thin film of oxide semiconductor fine particles provided on a substrate. Photoelectric conversion element. The photoelectric conversion element according to claim 20 or 21, wherein the oxide semiconductor fine particles contain titanium dioxide, zinc oxide, or tin oxide. A solar cell provided with the photoelectric conversion element as described in any one of Claims 20 thru | or 22.