TWI611621B - Photoelectric conversion element, dye-sensitized solar cell, metal complex, metal complex dye, dye solution, dye-adsorbed electrode and production method of dye-sensitized solar cell - Google Patents

Abstract

The present invention provides a photoelectric conversion element, a dye-sensitized solar cell, a metal complex compound and a metal complex dye, a dye solution, a dye adsorption electrode, and a dye-sensitized solar cell, which are excellent in photoelectric conversion efficiency and durability. Production method. The photoelectric conversion element has the following formula (I): M(LD)(LA)(LX). (Y) Semiconductor fine particle of the metal complex dye represented by n. [wherein, M represents a metal ion, and LD represents a bidentate ligand grouped on an M with an anion and an isolated electron pair. LA represents a tridentate ligand represented by the following formula. LX represents a chlorine atom, a bromine atom or an iodine atom, and Y represents a counter ion necessary for neutralizing the charge. n represents an integer from 0 to 4]

Description

Photoelectric conversion elements, dye-sensitized solar cells, metal complexes, Metal complex dye, dye solution, dye adsorption electrode, and method for producing dye-sensitized solar cell

The present invention relates to a method for producing a photoelectric conversion element, a dye-sensitized solar cell, a metal complex, a metal complex dye, a dye solution, a dye adsorption electrode, and a dye-sensitized solar cell.

The photoelectric conversion element is used in various photo sensors, copying machines, solar cells, and the like. In the photoelectric conversion element, a photoelectric conversion element using a metal, a photoelectric conversion element using a semiconductor, a photoelectric conversion element using an organic pigment or a dye, or a photoelectric conversion element in which these photoelectric conversion elements are combined have been used in various forms. Practical application. In particular, solar cells using non-exhaustive solar energy do not require fuel, and it is expected to be a practical application as an inexhaustible clean energy source. Among them, the lanthanide solar cells have been researched and developed since ancient times, and are also being popularized due to policy considerations of various countries. However, 矽 is an inorganic material, in production (through put) and cost (cost) and other improvements have their own boundaries.

Therefore, research on dye-sensitized solar cells is being concentrated. In particular, the results of research by Graetzel of Lausanne University of Technology in Switzerland (see Patent Document 1) have become a turning point in the above research. Graetzel et al. used a structure in which a pigment containing a ruthenium complex was immobilized on the surface of a porous titanium oxide film to achieve conversion efficiency equivalent to that of amorphous ruthenium. Thereby, the dye-sensitized solar cell which can be manufactured without using an expensive vacuum device is attracting the attention of researchers all over the world.

Heretofore, dyes commonly referred to as "N3", "N719", "Z907", and "J2" have been developed as metal complex dyes used in photoelectric conversion elements.

A black dye (Black Dye) having a terpyridine ligand is known as a long-wave ruthenium complex (Patent Document 1). Recently, in order to improve the spectral sensitivity characteristics in the long wavelength range of visible light, it has been proposed. A large number of base metal complex dyes having a terpyridine ligand (see Patent Document 2 or Patent Document 3).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent No. 4298799

[Patent Document 2] US Patent Application Publication No. 2010/0258175

[Patent Document 3] International Publication No. 12/121236 Manual

Each of the dyes described in Patent Literatures 1 to 3 has no spectral sensitivity characteristics or photoelectric conversion efficiency in a long wavelength range of 800 nm to 900 nm. It must meet the requirements and it is expected to improve durability.

In view of the above circumstances, an object of the present invention is to provide a photoelectric conversion element, a dye-sensitized solar cell, a metal complex compound, a metal complex dye, a dye solution, a dye adsorption electrode, and a dye-sensitized solar cell. In the absorption characteristics of the metal complex dye, the photoelectric conversion element increases light absorption in a long wavelength range, and improves spectral sensitivity characteristics in the long wavelength range, thereby improving photoelectric conversion efficiency and durability. Also excellent.

Since the spectroscopic sensitivity characteristics of the conventional metal complex dye in the long wavelength range are not necessarily sufficient, the inventors of the present invention have spectral sensitivity characteristics in a long wavelength range, particularly sensitivity characteristics in 800 nm to 900 nm, that is, quantum yield. (Incremental Photon-to-electron Conversion Efficiency (IPCE)) has been studied in various ways.

As a result, it has been found that when a tridentate ligand having a function of adsorbing on the surface of the semiconductor fine particles and a so-called donor ligand of the second tooth are used and a monodentate ligand is used, the photoelectric conversion element is improved. In terms of the spectral sensitivity characteristics in the long wavelength range, it is important to increase the π supply of the monodentate ligand to the coordinated central metal. Further, it has been found that the durability of the photoelectric conversion element can be improved by using a monodentate ligand having improved π supply in combination with the above ligand.

The present inventors have further studied in accordance with these findings, and have achieved the present invention.

That is, the problem of the present invention is achieved by the following means.

(1) A photoelectric conversion element comprising a conductive support, a photoreceptor layer containing an electrolyte, a charge transporting body layer containing an electrolyte, and a counter electrode, and the photoreceptor layer contains a metal complex represented by the following formula (I) Pigment semiconductor microparticles, M(LD)(LA)(LX). (Y)n formula (I)

[wherein, M represents a metal ion; LD represents a bidentate ligand coordinated to M with an anion and an isolated electron pair; LA represents a tridentate ligand represented by the following formula (LA); LX represents chlorine An atom, a bromine atom, an iodine atom, or -S(Rz1), -O(Rz1), -N(Rz1) ₂ or any one of the following formulas (Z1-1) to (Z1-3) Monodentate ligand, Rz1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a decyl group, an alkylsulfonyl group or an arylsulfonyl group; Y represents a neutralization charge Counter ion; n represents an integer from 0 to 4]; [Chemical 1]

[Wherein, ring A, ring B and ring C each independently represent a nitrogen-containing aromatic heterocyclic ring; the bond between the bond between Here, Z ¹ and the N atom, Z ² is a single bond with the N atom can also It may be a double bond; Z ¹ and Z ² each independently represent a carbon atom or a nitrogen atom; Anc1 to Anc3 each independently represent an acidic group; and X ¹ , X ² and X ³ each independently represent a single bond or a linking group; L3 independently represents an integer from 1 to 5; m1 and m3 independently represent integers from 0 to 4, and m2 represents an integer from 0 to 3; wherein the sum of m1 to m3 is 1 or more; and R ¹ to R ³ are independent The ground represents a substituent other than Anc1~Anc3; n1 and n3 each independently represent an integer of 0~4, and n2 represents an integer of 0~3]; [Chemical 2]

[wherein, Xz1 represents -ORz1, -SRz1, -N(Rz1) ₂ or -Rz1, and Zz1 and Zz2 each independently represent a group of non-metal atoms necessary for forming a 5-membered ring to a 7-membered ring].

(2) The photoelectric conversion element according to the above aspect, wherein the semiconductor fine particles are adsorbed by the metal complex dye represented by the above formula (I).

(3) The photoelectric conversion element according to (1), wherein the M is Fe ²⁺ , Ru ²⁺ or Os ²⁺ .

The photoelectric conversion element according to any one of (1) to (3) wherein the LX is an iodine atom.

(5) The photoelectric conversion element according to any one of (1), wherein the LX is -S(Rz1), -O(Rz1) or -N(Rz1) ₂ or the above formula (Z1- 1) a monodentate ligand represented by any one of formula (Z1-3), wherein Rz1 is an aryl group, a heterocyclic group or a decyl group, and Xz1 is an aryl group, and Zz1 and Zz2 are independently It is a nitrogen-containing heterocyclic group.

(6) The photoelectric conversion element according to any one of (1) to (3), wherein the LX is represented by any one of the following formulas (Z1-4) to (Z1-18). [Chemical 3]

[wherein, Xz2 represents O, S, N or NRz1, Xz3 represents N or CRz1, Xz4~Xz7 independently represents O, S, NRz1 or C(Rz1) ₂ ; when Xz2 is N, nz1 represents 2, in Xz2 When O, S and NRz1, nz1 represents 1. Rz1 has the same meaning as Rz1 of (1), and Rz2~Rz12 and Rz16~Rz45 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkenyl group, an alkynyl group, a halogen atom, an aryl group or a heterocyclic ring. A group, an amine group, a cyano group or a nitro group, and Rz13 to Rz15 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group].

The photoelectric conversion element according to any one of (1) to (6), wherein the LD is a bidentate ligand represented by the following formula (2L-1) or (2L-2),

[wherein, * represents a bonding position with the above metal ion M; ring D represents an aromatic ring; A ¹¹¹ represents a nitrogen anion or a carbon anion; and A ¹²¹ represents any one of a nitrogen anion, an oxyanion or a sulfur anion; R ¹¹¹ ~ R ¹²⁴ represents a hydrogen atom or a substituent having no Anc1, Anc2 and Anc3].

The photoelectric conversion element according to any one of (1) to (5), wherein in the above formula (LA), Anc1 to Anc3 represent -CO ₂ H, -SO ₃ H, -PO ₃ H ₂ , -OH, -SH or such salts.

The photoelectric conversion element according to any one of the above aspects, wherein the ring A, the ring B and the ring C of the above formula (LA) are each a pyridine ring.

The photoelectric conversion element according to any one of the above formulas (LA), wherein the formula (LA) is any one of the following formulas (AL-1) to (AL-4),

[wherein, Anc1 to Anc3 each independently represent -CO ₂ H, -SO ₃ H, -PO ₃ H ₂ , -SH or the like; R ^AL represents a substituent other than Anc1 to Anc3, and b1 represents 0~ An integer of 4; X ^2a represents -O-, -S-, -NR'-, a saturated aliphatic group, an aromatic hydrocarbon ring group, a non-aromatic hydrocarbon ring group, an aromatic heterocyclic group, a non-aromatic heterocyclic group the linking group or a combination of these groups to be formed; here, R 'represents a hydrogen atom or a substituent group; X ^1a represents a linking group, X ³ represents a single bond or a linking group; M4 represents 0 or 1].

The photoelectric conversion element according to any one of (1), wherein the semiconductor fine particles further carry one or more acids. A co-adsorbent based on the base.

(12) The photoelectric conversion element according to (11), wherein the co-adsorbent is represented by the following formula (CA),

[wherein R ^A1 represents a substituent having an acidic group; R ^A2 represents a substituent; and nA represents an integer of 0 or more].

(13) A dye-sensitized solar cell, comprising the photoelectric conversion element according to any one of (1) to (12).

(14) A metal complex dye which is represented by the following formula (I), M(LD)(LA)(LX). (Y)n formula (I)

[wherein, M represents a metal ion; LD represents a bidentate ligand coordinated to M with an anion and an isolated electron pair; LA represents a tridentate ligand represented by the following formula (LA); LX represents chlorine An atom, a bromine atom, an iodine atom, or -S(Rz1), -O(Rz1), -N(Rz1) ₂ or any one of the following formulas (Z1-1) to (Z1-3) Monodentate ligand, Rz1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a decyl group, an alkylsulfonyl group or an arylsulfonyl group; Y represents a neutralization charge Counter ion; n represents an integer from 0 to 4];

[wherein, ring A, ring B and ring C each independently represent a nitrogen-containing aromatic heterocyclic ring; here, the bond between Z ¹ and the N atom, and the bond between Z ² and the N atom may be a single bond. It may be a double bond; Z ¹ and Z ² each independently represent a carbon atom or a nitrogen atom; Anc1 to Anc3 each independently represent an acidic group; and X ¹ , X ² and X ³ each independently represent a single bond or a linking group; L3 independently represents an integer from 1 to 5; m1 and m3 independently represent integers from 0 to 4, and m2 represents an integer from 0 to 3; wherein the sum of m1 to m3 is 1 or more; and R ¹ to R ³ are independent The ground represents a substituent other than Anc1~Anc3; n1 and n3 each independently represent an integer of 0-4, and n2 represents an integer of 0~3];

In the formula, Xz1 represents -ORz1, -SRz1, -N(Rz1) ₂ or -Rz1, and Zz1 and Zz2 each independently represent a group of non-metal atoms necessary for forming a 5-membered ring to a 7-membered ring.

(15) The metal complex dye according to (14), wherein the LX is an iodine atom.

(16) The metal complex dye according to (14), wherein the LX is represented by any one of the following formulas (Z1-4) to (Z1-18), [Chemical 9]

[wherein, Xz2 represents O, S, N or NRz1, Xz3 represents N or CRz1, Xz4~Xz7 represents O, S, NRz1 or C(Rz1) ₂ ; when Xz2 is N, nz1 represents 2, and Xz2 is O, When S and NRz1, nz1 represents 1; Rz1 and R1 of (1) have the same meaning, and Rz2 to Rz12 and Rz16 to Rz45 independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkenyl group, an alkynyl group, A halogen atom, an aryl group, a heterocyclic group, an amine group, a cyano group or a nitro group, and Rz13 to Rz15 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group].

(17) A dye solution containing the metal complex dye according to any one of (14) to (16).

(18) The dye solution according to the above (17), which contains 0.001% by mass to 0.1% by mass of the metal complex dye and 0.1% by mass or less of water in the organic solvent.

(19) The dye solution according to (17) or (18), wherein the dye solution further contains a co-adsorbent.

(20) The dye solution according to (19), wherein the co-adsorbent is represented by the following formula (CA),

[wherein R ^A1 represents a substituent having an acidic group; R ^A2 represents a substituent; and nA represents an integer of 0 or more].

(21) A dye-adsorbing electrode for a dye-sensitized solar cell, which is obtained by coating a composition obtained by the dye solution according to any one of (17) to (20) on a conductive support. The composition after the cloth is hardened to form a photoreceptor layer Made.

(22) A method for producing a dye-sensitized solar cell, comprising the dye-adsorbing electrode, the electrolyte, and the counter electrode according to (21), and assembling the member using the member.

(23) A metal complex represented by the following formula (III), M(LD)(LA')(LX). (Y)n formula (III)

Wherein M represents a metal ion; LD represents a bidentate ligand coordinated to M with an anion and an isolated electron pair; LA' represents a tridentate ligand represented by the following formula (LA'); a chlorine atom, a bromine atom, an iodine atom, or -S(Rz1), -O(Rz1), -N(Rz1) ₂ or any one of the following formulas (Z1-1) to (Z1-3) a monodentate ligand represented, Rz1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a decyl group, an alkylsulfonyl group or an arylsulfonyl group; Y represents a neutralizing charge The necessary counter ion; n represents an integer from 0 to 4; [Chem. 11]

[wherein, ring A, ring B and ring C each independently represent a nitrogen-containing aromatic heterocyclic ring; here, the bond between Z ¹ and the N atom, and the bond between Z ² and the N atom may be a single bond. It may be a double bond; Z ¹ and Z ² each independently represent a carbon atom or a nitrogen atom; and G represents an alkoxycarbonyl group, an aryloxycarbonyl group, a decyl group or a group which may have a substituent represented by any of the following structures X ¹⁰ , X ²⁰ and X ³⁰ each independently represent a single bond or a linking group; p1 and p3 each independently represent an integer of 0 to 4, and p2 represents an integer of 0 to 3; wherein, the sum of p1 to p3 is 1 Above; R ¹ to R ³ each independently represent a substituent; n1 and n3 each independently represent an integer of 0 to 4, and n2 represents an integer of 0 to 3];

Wherein R ^G each independently represents an alkyl group; * represents a bonding position with X ¹⁰ , X ²⁰ and X ³⁰ or ring A, ring B or ring C];

[wherein, Xz1 represents -ORz1, -SRz1, -N(Rz1) ₂ or -Rz1, and Zz1 and Zz2 each independently represent a group of non-metal atoms necessary for forming a 5-membered ring to a 7-membered ring].

In the present specification, the carbon-carbon double bond may be either E-type or Z-form in the molecule unless otherwise specified, and may be any of these. When a plurality of substituents, a linking group, a ligand, and the like (hereinafter referred to as a substituent, etc.) represented by a specific symbol are present, or a plurality of substituents or the like are simultaneously or alternatively specified, unless otherwise specified, Each substituent or the like may be the same or different from each other. In this case, the same applies to the regulation of the number of substituents and the like. Further, when a plurality of substituents or the like are close to each other (particularly in the case of adjacent), the groups may be bonded to each other to form a ring unless otherwise specified. Further, a ring (for example, an alicyclic ring, an aromatic ring or a heterocyclic ring) may be further condensed to form a condensed ring.

In the present invention, each substituent may be further substituted with a substituent unless otherwise specified.

According to the present invention, there is provided a photoelectric conversion element, a dye-sensitized solar cell, a metal complex compound and a metal complex dye, a dye solution, a dye adsorption electrode, and a method for producing a dye-sensitized solar cell, wherein the photoelectric conversion device In the absorption characteristics of the metal complex dye, the conversion element increases light absorption in a long wavelength range, and improves spectral sensitivity characteristics in the long wavelength range, thereby improving photoelectric conversion efficiency and also excellent in durability.

1‧‧‧Electrical support

2‧‧‧Photoreceptor layer

3‧‧‧Charge mobile body layer

4‧‧‧relative electrode (opposite electrode)

5‧‧‧Photoelectrode

6‧‧‧ Circuitry

10‧‧‧ photoelectric conversion components

20‧‧‧Pigment sensitized solar cells (photoelectrochemical cells)

21‧‧‧ pigment

22‧‧‧Semiconductor particles

40‧‧‧Photoelectrode

41‧‧‧Transparent electrode

42‧‧‧Semiconductor electrodes

43‧‧‧Transparent conductive film

44‧‧‧Substrate

45‧‧‧Semiconductor layer

46‧‧‧Light scattering layer

100‧‧‧Systems using photoelectrochemical cells (systems using dye-sensitized solar cells)

CE‧‧‧relative electrode

E‧‧‧ Electrolytes

M‧‧‧Electric motor (fan)

S‧‧‧ spacers

Fig. 1 is a cross-sectional view schematically showing an embodiment (also including an enlarged view of a circular portion in a layer) of a photoelectric conversion element of the present invention.

Fig. 2 is a cross-sectional view schematically showing a dye-sensitized solar cell according to another embodiment of the photoelectric conversion element of the present invention.

Fig. 3 is a chart showing the visible absorption spectrum of the metal complex dye Dye-1 synthesized in the examples in tetrabutylammonium hydroxide (TBAOH)/methanol solvent.

Figure 4 is a metal complex dye Dye-28 synthesized in the examples in TBAOH / A Visible absorption spectrum in an alcohol solvent.

Fig. 5 is a chart showing the visible absorption spectrum of the metal complex dye Dye-201 synthesized in the examples in TBAOH/methanol solvent.

Fig. 6 is a chart showing the visible absorption spectrum of the metal complex dye Dye-202 synthesized in the examples in TBAOH/methanol solvent.

The photoelectric conversion element of the present invention has an electroconductive support, a photoreceptor layer containing an electrolyte, a charge transporting body layer containing an electrolyte, and a counter electrode. The photoreceptor layer contains semiconductor fine particles carrying a metal complex dye represented by the following formula (I).

<<Metal complex pigment>>

The metal complex dye of the present invention is represented by the following formula (I), M(LD)(LA)(LX). (Y)n formula (I)

[wherein, M represents a metal ion.

LD represents a bidentate ligand coordinated to M with an anion and an isolated electron pair.

LA represents a tridentate ligand represented by the following formula (LA).

LX represents a chlorine atom, a bromine atom, an iodine atom, or -S(Rz1), -O(Rz1), -N(Rz1) ₂ or any one of the following formulas (Z1-1) to (Z1-3). The monodentate ligand represented by a sub, Rz1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a decyl group, an alkylsulfonyl group or an arylsulfonyl group.

Y represents the counter ion necessary to neutralize the charge; n represents an integer from 0 to 4]

[wherein, Ring A, Ring B, and Ring C each independently represent a nitrogen-containing aromatic heterocyclic ring. Here, the bond between Z ¹ and the N atom, and the bond between the Z ² and the N atom may be a single bond or a double bond. Z ¹ and Z ² each independently represent a carbon atom or a nitrogen atom.

Anc1~Anc3 independently represent an acidic group. X ¹ , X ² and X ³ each independently represent a single bond or a linking group. L1~l3 independently represent integers from 1 to 5. M1 and m3 each independently represent an integer of 0 to 4, and m2 represents an integer of 0 to 3. Among them, the sum of m1 to m3 is 1 or more.

R ¹ to R ³ each independently represent a substituent other than Anc1 to Anc3. N1 and n3 each independently represent an integer of 0 to 4, and n2 represents an integer of 0 to 3]

[wherein, Xz1 represents -ORz1, -SRz1, -N(Rz1) ₂ or -Rz1, and Zz1 and Zz2 each independently represent a group of non-metal atoms necessary for forming a 5-membered ring to a 7-membered ring].

- metal ion M-

M is a central metal ion of a metal complex dye, and examples of the metal include elements of Groups 8 to 10 of the long-period periodic table.

Specific examples of such an element include ruthenium (Ru), iron (Fe), osmium (Os), copper (Cu), tungsten (W), chromium (Cr), molybdenum (Mo), nickel (Ni), and palladium (Pd). ), platinum (Pt), cobalt (Co), iridium (Ir), ruthenium (Rh), ruthenium (Re), manganese (Mn), and zinc (Zn).

M is preferably an Os ²⁺ ion, a Ru ²⁺ ion or a Fe ²⁺ ion, of which a Ru ²⁺ ion is preferred.

Further, in a state of being incorporated into the photoelectric conversion element, the valence of M sometimes changes due to the redox reaction with the surrounding material.

- ligand LD-

The ligand LD represents a ligand bonded to the metal ion M by a second tooth, and is classified into a donor ligand. The ligand LD preferably has no adsorption to the semiconductor microparticle table. The ligand of the adsorbing group on the surface.

That is, the ligand LD is allowed to contain a group corresponding to an adsorption group, and the group is also contained in the form of a group bonded to a metal ion, and is not a group adsorbed on the surface of the semiconductor fine particle.

Further, the adsorbing group adsorbed on the surface of the semiconductor fine particle is a group represented by Anc1 to Anc3 in the ligand LA described later or a group containing the group.

When such a ligand LD is used in combination with the ligand LA and the ligand LX, the photoelectric conversion efficiency in the long wavelength range is greatly increased.

The ligand LD is a bidentate ligand. In the ligand LD, one coordinating atom has an isolated electron pair, and the isolated electron pair is coordinated. The other coordinating atom is an anion.

Here, the so-called isolated electron pair refers to an electron pair (a group of two electrons) that does not participate in a covalent bond in the outermost electron pair of the atom. The isolated electron pair has, for example, 1 pair in >N-, 2 pairs in -O- or -S-, and 3 pairs in -Cl. Further, in the case of a nitrogen atom, there are one pair of =N-, >N-, and >N-H.

Further, in the case where the atoms are anions, >N ^- , -O ^- , -S ^{- each} become an anion in a state having an isolated pair of electrons. However, with regard to the atoms assigned to the metal ions M, the anions are preferred over the isolated electrons. Therefore, in the case of such a state, in the present invention, a coordinating atom is regarded as an anion.

On the other hand, for example, in >NH, -OH, -SH, etc., in the state where the hydrogen atom does not dissociate, that is, in the state where no anion is formed, there may be a pair of isolated electron pairs with N atoms, O atoms, and S atoms. . Also in this case, in the present invention, an anion having a coordinating atom is regarded as a stable coordination structure. That is, in the case of >NH, -OH, -SH, the anions regarded as >N ^- , -O ^- , -S ^- are coordinated. However, in the case of an anion of a carbon atom, there is no isolated electron pair. Therefore, as a complex which can be present in a stable state, it is not coordinated in the state of CH, but it is necessary to forcibly form an anion of a carbon atom and then coordinate. Therefore, even if CH is present, it is not considered to result in the formation of carbon anions and is coordinated to the metal ions M. Further, in the case of an atomic group or a ring in which a carbon anion and an isolated electron pair coexist, since the carbon anion is preferentially coordinated, the coordinating atom becomes a carbon anion.

According to the above, an atom coordinated with an isolated electron pair is an atom having no hydrogen atom. The atom to which the isolated electron pair is coordinated may be a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a trivalent phosphorus atom or the like. In the present invention, a nitrogen atom, an oxygen atom or a sulfur atom is preferred, and a nitrogen atom or an oxygen atom is more preferred, and a nitrogen atom is particularly preferred. Furthermore, in the case of a sulfur atom, -S(O)-, -S(=O) ₂ - exists due to the difference in oxidation state, and only the former has a pair of isolated electron pairs, and the latter has no isolation. Electronic pair.

With respect to atoms that coordinate with an isolated pair of electrons, the atoms may be ring-forming atoms or may be atoms contained in a group (a substituent, preferably an atom substituted in a substituent on the ring structure). . In particular, in the case of a nitrogen atom, it may be an atom constituting a ring of a heteroaromatic ring, and such an atom is preferred.

The atom in which the coordinating atom is an anion may typically be a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a trivalent phosphorus atom or the like. In the present invention, preferred are carbon anions, nitrogen anions, oxyanions, sulfur anions, and more preferably carbon cations. Ions, nitrogen anions, and more preferably nitrogen anions.

The atoms may be ring-forming atoms or may be atoms contained in a group (a substituent, preferably an atom substituted in a substituent on the ring structure). In particular, in the case of a nitrogen atom, it may be an atom constituting a ring of a heteroaromatic ring, and such an atom is preferred.

Further, a carbon atom or a nitrogen atom may form an aromatic ring or a heteroaromatic ring. In the present invention, a carbanion or a nitrogen anion which is a ring-forming atom constituting an aromatic ring or a heteroaromatic ring is preferred.

In the present invention, it is preferred to have an atom and an anion of an isolated electron pair. The subunits are each an atom constituting a ring or a substituent on a ring. The rings are preferably aromatic or heteroaromatic rings, and the heteroaromatic rings are more preferably nitrogen-containing heteroaromatic rings (also known as nitrogen-containing aromatic rings).

Hereinafter, in the present invention, a more preferred bidentate ligand will be described.

In the present invention, it is preferred that the same or different species of the following coordination skeleton (La) to coordination skeleton (Lf) are linked by an anion and an isolated electron pair to form a bidentate ligand.

1) Coordination framework for coordination with isolated electron pairs

(La): a nitrogen-containing aromatic ring group having an isolated electron pair and an anion atom (including >NH) bonded to a metal ion M,

2) Coordination framework coordinated by anions

(Lb): a nitrogen-containing aromatic ring group having a nitrogen anion (including NH) as a ring-forming atom bonded to the metal ion M, (Lc): having a carbon anion as a ring-forming atom bonded to the metal ion M An aromatic ring group other than the nitrogen-containing aromatic ring group (Lb), (Ld): an aromatic hydrocarbon ring group substituted with a functional group having a nitrogen anion (including NH), an oxyanion or a sulfur anion, (Le): a nitrogen-containing aromatic ring group substituted with a functional group of a nitrogen anion (including NH), an oxyanion or a sulfur anion, and

3) A coordination skeleton that coordinates any of an isolated electron pair or an anion

(Lf): coordination skeleton other than (La)~(Le)

Further, the coordination skeleton may have a substituent which does not impair the properties of each coordination skeleton. Examples of such a substituent include a substituent other than the adsorbing group adsorbed on the surface of the semiconductor fine particle, and examples thereof include a substituent T which will be described later. Specifically, the nitrogen-containing aromatic ring group (La) may contain a substituent T which does not have an anion atom (also including >NH). Preferred substituents in the substituent T are, for example, an alkyl group, an alkenyl group, a perfluoroalkyl group, an alkoxy group, an aryl group, a heterocyclic group, a cyano group, a nitro group, a halogen atom, or a combination of a plurality of groups. Mission and so on. The substituents T may also be bonded to the adjacent two rings and to the condensed rings, respectively.

Regarding "a nitrogen-containing aromatic ring group (La) having an isolated electron pair bonded to a metal ion M and having no anion", at least one of the ring-forming atoms contains a nitrogen atom having an isolated electron pair as the ring-forming atom In addition to the nitrogen atom, an oxygen atom, a sulfur atom (-S-, -SO-, -SO ₂ -), a selenium atom, or the like may be contained. Here, the isolated electron pair in the nitrogen-containing aromatic ring group (La) having an isolated electron pair is not a π-electron on the aromatic ring but an isolated electron pair that does not participate in the bonding.

The nitrogen-containing aromatic ring group (La) has a carbon atom having no anion or a nitrogen atom of an anion as a functional group bonded to a ring-forming atom of the metal ion M and having no anion. Further, the carbon atom of the anion, the nitrogen atom of the anion, and the functional group of the anion will be described later. The ring in the nitrogen-containing aromatic ring group (La) is preferably a 5-membered ring to a 7-membered ring, and may also be condensed. When the ring containing the nitrogen-containing aromatic ring group (La) is a 5-membered ring, an oxazole ring, a thiazole ring, a pyrazole ring having a substituent at the 1-position, and a substituent at the 1-position may be mentioned. An imidazole ring, a triazole ring having a substituent at the 1-position, a tetrazole ring having a substituent at the 1-position, or a ring in which benzene is condensed on the rings, in the case of a 6-membered ring, A pyridine ring, a quinoline ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring or a ring in which benzene is condensed on the rings is exemplified. In the present invention, a pyridine ring is preferred. The nitrogen-containing aromatic ring group (La) may have a substituent T, and when the ligand L ² is selected from a nitrogen-containing aromatic ring group (La), it preferably has a substituent T. The substituent T of the nitrogen-containing aromatic ring group (La) is preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an aryl group substituted with one or two or more alkoxy groups, and has one or two. An aryl group or a heterocyclic group of one or more alkyl groups or an alkenyl group substituted with an aryl group or a heterocyclic group having one or two or more alkyl groups.

When a nitrogen atom having an anion is used as a nitrogen-containing aromatic ring group (Lb) bonded to a ring atom of a metal ion M, it is a nitrogen-containing aroma when it is incorporated as a ligand of a metal complex dye. At least one nitrogen atom of the family ring group -NH- moiety becomes an anion-N ^- carbocyclic aromatic group. Further, the nitrogen-containing aromatic ring group (Lb) is preferably such that the -NH- moiety becomes an anion-N ^- - and is bonded to the metal ion M or may be bonded to the metal ion M. That is, in the nitrogen-containing aromatic ring group (Lb), the nitrogen atom which is a ring-forming atom bonded to the metal ion M has an active hydrogen. The ring in the nitrogen-containing aromatic ring group (Lb) is preferably a 5-membered ring to a 7-membered ring, and may also be condensed. The ring containing a nitrogen-containing aromatic ring group (Lb) has a NH in a ring-forming atom, and in the case of a 5-membered ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, and a benzene are mentioned. The imidazole ring, the 1H-carbazole ring, the anthracene ring and the like are preferably a pyrazole ring, an imidazole ring, a triazole ring or a pyrrole ring.

Wherein, the nitrogen-containing aromatic ring group (Lb) is preferably a group represented by the following formula (a-1) to formula (a-5) derived from an imidazole ring, a pyrazole ring, a triazole ring or a pyrrole ring; The group is more preferably a group represented by (a-1), (a-2) or (a-5), and particularly preferably a group represented by (a-2).

In the formula, Rd represents a substituent. B1 represents an integer from 0 to 2, b2 represents an integer from 0 to 3, and b3 represents 0 or 1. When b1 is 2 or b2 is 2 or more, a plurality of Rds may be bonded to each other to form a ring. Rd may, for example, be the above-mentioned substituent T.

Here, in the formula (a-1) to the formula (a-5), when a ring in which adjacent rads are formed is also formed, a group having the following structure may be mentioned.

[化17]

Wherein Rd, b1 to b3 are in the above formula (a-1) to formula (a-5) Rd, b1~b3 have the same meaning, and the preferred range is also the same. B4 represents 0~4, and b5 represents each integer of 0~5. Further, in the formula (a-1a) and the formula (a-1b), the benzene ring may have Rd, and the benzene ring and the pyrrole ring may have Rd.

Rd is preferably a linear or branched alkyl group, a cycloalkyl group, an alkenyl group, a fluoroalkyl group, An aryl group, a halogen atom, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, and a group in which the groups are combined, more preferably a linear or branched alkyl group, a cycloalkyl group, an alkenyl group or a fluoroalkyl group. The aryl group and a group in which the groups are combined are preferably a linear or branched alkyl group, a cycloalkyl group, an alkenyl group, a fluoroalkyl group, and a group in which the groups are combined.

"A carbon atom having an anion as an aromatic ring group (Lc) other than a nitrogen-containing aromatic ring group (Lb) bonded to a ring atom of a metal ion M" is incorporated as a ligand of a metal complex dye when the case is part of an aromatic ring carbon atom -CH- an anionic group -C ^{- -} aromatic ring group. The aromatic ring group (Lc) may be a ring having a carbon atom as a ring-forming atom bonded to the metal ion M and exhibiting aromaticity, and examples thereof include an aromatic hydrocarbon ring group and a heterocyclic group. There is no nitrogen atom as a nitrogen-containing aromatic ring group or the like bonded to a ring-forming atom of the metal ion M. Examples of the aromatic hydrocarbon ring group include a carbon atom having an anion in the aryl group of the substituent T as a ring-forming atom, and particularly, an m-difluorobenzene ring, an o-, a p-difluorobenzene ring, and a p-group. A fluorobenzene ring, a p-cyanobenzene ring, a p-nitrobenzene ring, a cyclopentadiene ring, a naphthalene ring, an unsubstituted benzene ring, and the like. Further, the substitution position of the benzene ring is adjacent, interposed and paired with respect to the position of the carbon atom bonded to the metal ion M. Further, examples of the heterocyclic group include those in which a carbon atom as a ring-constituting atom in the heterocyclic group of the substituent T is an anion such as furan or thiophene. Further, the nitrogen-containing aromatic ring group bonded to the ring-forming atom of the metal ion M other than the nitrogen atom may be a pyrazole ring group bonded to a carbon atom of a 5-position atom of the metal ion M, and bonded to the metal ion. The atom of M is a pyridine ring group of a carbon atom at the 4-position.

When the "aromatic hydrocarbon ring group (Ld) substituted with a functional group having an anionic nitrogen atom, an oxygen atom or a sulfur atom is incorporated as a ligand of the metal complex dye, it is a functional nitrogen. The -XH- moiety (X represents N, O or S) of at least one of an atom, an oxygen atom or a sulfur atom becomes an anionic-X ^-- aromatic hydrocarbon ring group. Further, the aromatic hydrocarbon ring group (Ld) is preferably one in which the -XH- moiety is anion-X ^- - and is bonded to the metal ion M or may be bonded to the metal ion M. That is, in the aromatic hydrocarbon ring group (Ld), at least one nitrogen atom, oxygen atom or sulfur atom constituting the functional group has an active hydrogen. The ring in the aromatic hydrocarbon ring group (Ld) may, for example, be a ring containing an aryl group of the substituent T. Further, the aromatic hydrocarbon ring group (Ld) may have a substituent T.

Examples of the functional group of the aromatic hydrocarbon ring group (Ld) include a hydroxyl group. A thiol group, an amine group, a substituted amino group, a hydroxyalkyl group, a mercaptoalkyl group, an aminoalkyl group or the like is preferably a hydroxyl group, a thiol group, an amine group or a substituted amino group. Specific examples of the aromatic hydrocarbon ring group (Ld) having such a functional group include a phenol ring group, a thiophenol ring group, an aniline ring group, a substituted anilino ring group, a hydroxyalkylbenzene group, and a mercaptoalkylbenzene ring. Alkyl, aminoalkylbenzene group, and the like.

In the functional group, the substituted amino group is an amine group in which one or two hydrogen atoms are substituted, and examples thereof include -NHSO ₂ Ry (Ry represents a substituent). Ry may be exemplified by the substituent T described later, and among them, an alkyl group is preferred. Specific examples of -NHSO ₂ Ry include -NHSO ₂ CH ₃ , -NHSO ₂ C ₂ H ₅ , -NHSO ₂ C ₃ H ₇ and the like. The hydroxyalkyl group is an alkyl group in which at least one hydrogen atom is substituted with a hydroxyl group, and examples thereof include a hydroxymethyl group and a hydroxyethyl group. The mercaptoalkyl group is an alkyl group in which at least one hydrogen atom is substituted with a thiol group, and examples thereof include a mercaptomethyl group, a mercaptoethyl group and the like. The aminoalkyl group is an alkyl group in which at least one hydrogen atom is substituted with an amine group, and examples thereof include an aminomethyl group, an aminoethyl group and the like. Here, in the hydroxyalkyl group, the mercaptoalkyl group and the aminoalkyl group, the carbon atom of the alkyl group bonded to the hydroxyl group, the mercapto group or the amine group is not particularly limited, and in consideration of the ease of coordination with the metal ion M, It is preferred to use a terminal carbon atom of the alkyl group.

When a nitrogen-containing aromatic ring group (Le) substituted with a functional group having an anionic nitrogen atom, an oxygen atom or a sulfur atom is incorporated as a ligand of a metal complex dye, it is a functional group. The -XH- moiety (X represents N, O or S) of at least one of a nitrogen atom, an oxygen atom or a sulfur atom is a nitrogen-containing aromatic ring group of an anion-X ^- . Further, the nitrogen-containing aromatic ring group (Le) is preferably one in which the -XH- moiety is anion-X ^- - and is bonded to the metal ion M or may be bonded to the metal ion M. That is, in the nitrogen-containing aromatic ring group (Le), at least one nitrogen atom, oxygen atom or sulfur atom constituting the functional group has an active hydrogen. The nitrogen-containing aromatic ring group (Le) has the same meaning as the aromatic hydrocarbon ring group (Ld) except that it has a nitrogen-containing aromatic ring group instead of the aromatic hydrocarbon ring group. That is, the functional group of the nitrogen-containing aromatic ring group (Le) has the same meaning as the functional group of the aromatic hydrocarbon ring group (Ld), and preferably the same. The nitrogen-containing aromatic ring group of the nitrogen-containing aromatic ring group (Le) may be the same ring as the ring of the nitrogen-containing aromatic ring group (La) or the ring containing the nitrogen-containing aromatic ring group (Lb), preferably. It is the same ring as the ring of the nitrogen-containing aromatic ring group (La) having no active hydrogen. The nitrogen-containing aromatic ring group (Le) may have, for example, a substituent T.

The "coordination skeleton (Lf)" may be a coordination skeleton other than (La) to (Le), and examples thereof include an inorganic coordination skeleton. In addition, the "coordination skeleton (Lf)" may be an organic coordination skeleton having no nitrogen-containing aromatic ring group or an organic coordination group having no coordination skeleton (Ld) and a coordination skeleton (Le). Skeleton and so on. In the present invention, an inorganic compound or an anion, an atom or a compound derived from an inorganic compound is referred to as an "inorganic coordination skeleton". Further, in the present invention, an organic compound in which a group other than the nitrogen-containing aromatic ring group or the above functional group is bonded to the metal ion M or an anion derived from the organic compound is referred to as an "organic coordination skeleton". Such a coordination skeleton can be exemplified by a known coordination skeleton. Such a coordination skeleton is, for example, represented by a group selected from the group consisting of a ruthenium anion, a sulfonium anion, a thioanthracene anion, and a thio group. Anthracene thio anion, mercaptoamine oxy anion, carbamate anion, dithiocarbamate anion, thiocarbonate anion, dithiocarbonate anion, trithiocarbonate An anion in a group consisting of an ester anion, a sulfhydryl anion, an alkylthio anion, an alkoxy anion, an alkylguanamine anion or a monodentate coordination skeleton bonded to the group, or selected from the group consisting of ethers Group of anions, atoms or compounds of a thioether, anthracene, carbonyl, dialkyl ketone, carbonamide, thiobenzamide and thiourea (compounds containing a hydrogen atom in an anion) Single tooth coordination skeleton in the group. Further, when the coordination skeleton (Lf) contains an alkyl group, an alkenyl group, an alkynyl group or an alkylene group, the groups may be linear or branched or cyclic. Substituted or unsubstituted. Further, when the coordination skeleton (Lf) contains an aryl group, a heterocyclic group, a cycloalkyl group or the like, the groups may be substituted or unsubstituted, and may be monocyclic or condensed.

The ligand LD is a coordination skeleton selected from (La)~(Lf) which is straight to each other Bonding to form a bidentate ligand. Among these coordination skeletons, (La) is a coordination skeleton coordinated by an isolated electron pair, and (Lb)~(Le) is a coordination skeleton coordinated by an anion coordination atom, and (Lf) is isolated A coordination skeleton in which an electron pair or an anion coordination atom is coordinated. The ligand LD is a bidentate ligand coordinated by an isolated electron pair and an anion coordinating atom. That is, the ligand LD is a coordination skeleton coordinated to an anion coordinating atom selected from (Lb) to (Lf), and a coordination group of (La) or (Lf) coordinated with an isolated electron pair A bidentate ligand in which the skeletons are directly bonded to each other. By using such a ligand LD, the following effect can be expected: the highest occupied molecular orbital of the metal complex pigment The level of the Lowest Unoccupied Molecular Orbital is appropriately changed to exhibit an effect of better absorption characteristics and/or an effect of increasing the voltage. As a result, the photoelectric conversion efficiency of the photoelectric conversion element is improved.

The ligand LD is preferably a bidentate ligand represented by the following formula (2L-1) or formula (2L-2).

Where * represents the bonding position with the metal ion M. Ring D represents an aromatic ring. A ¹¹¹ represents a nitrogen anion or a carbon anion, and A ¹²¹ represents any one of a nitrogen anion, an oxyanion or a sulfur anion. R ¹¹¹ to R ¹²⁴ represent a hydrogen atom, or R ¹¹¹ to R ¹²⁴ represent a substituent having no Anc1, Anc2 and Anc3.

A ¹¹¹ is a carbanion or a nitrogen anion formed by detaching a nitrogen atom or a hydrogen atom bonded to a carbon atom of the ring D. And A ¹²¹ (Le) a functional group in an aromatic hydrocarbon ring group (Ld) and the nitrogen-containing aromatic ring group (substituted) from amine, hydroxyl or thiol group of the resultant active hydrogen removing residues same meaning. In the formula (2L-1), the ring D is an aromatic ring containing A ¹¹¹ and a carbon atom or an aromatic ring containing two carbon atoms. Examples of the aromatic ring include a nitrogen-containing aromatic ring composed of a nitrogen-containing aromatic ring group (Lb) or an aromatic hydrocarbon ring composed of an (Ac) aromatic hydrocarbon ring group, and (Lc). A heterocyclic ring composed of a heterocyclic group or a nitrogen-containing aromatic ring composed of (Lc) a nitrogen-containing aromatic ring group having no nitrogen atom as a ring-forming atom bonded to the metal ion M is preferably used. They are also the same. Of formula (2L-1) A ¹¹¹ is formed in the ring D and the formula (2L-2) A ¹²¹ before the anion substituted ring D include for example: benzene, Room, - a ring-difluorophenyl, o, p - Difluorobenzene ring, p-fluorobenzene ring, p-cyanobenzene ring, p-nitrobenzene ring or thiophene ring, furan ring, or containing formula (a-1)~ formula (a-5), formula (a-1a) The ring of the group represented by the formula (a-2a), the formula (a-1b) and the formula (a-4a) is preferably a pyrazole ring, a triazole ring or a benzene ring.

The substituent of R ¹¹¹ to R ¹²⁴ is, for example, a substituent T, and particularly preferably a substituent of the nitrogen-containing aromatic ring group (La), a halogen atom or a nitro group.

In particular, it is preferable that the substituent of R ¹¹¹ to R ¹²⁴ is improved in durability of the photoelectric conversion element as follows: "LD No. LD-6-15 to LD No. LD-6-18" will be described later. a ring-forming atom at the 2-position (ortho) or the 3-position (meta) in relation to a ring-forming atom bonded to an aromatic ring of a nitrogen-containing aromatic ring group (La) directly or via another group. The substituent has a substituent, particularly an alkyl group having 4 or more carbon atoms.

Specific examples of the ligand LD are shown below, but the present invention is not limited to these specific examples.

[Chemistry 19]

[Chemistry 20]

[Chem. 21]

[化23]

[Chem. 24]

[化25]

[化27]

The monocyclic ligand LD other than the above may be exemplified by the following ligand LD-8-1 to ligand LD-8-4.

The ligands LD can be disclosed, for example, by US Patent Application Publication No. The method described in the specification No. 2010/0258175, Japanese Patent No. 4298799, "Angew. Chem. Int. Ed.", (2011, Vol. 50, pp. 2054-2058), The methods described in the references cited in the literature or the methods according to the methods are synthesized.

- Ligand LA-

In the present invention, the ligand LA is a tridentate ligand represented by the above formula (LA).

The ligand LA is a ligand having an adsorption group adsorbed on the surface of the semiconductor fine particles.

The aromatic heterocyclic ring of the ring A to the ring C may be any ring as long as it is an aromatic ring having a nitrogen atom in the ring-constituting hetero atom.

The aromatic heterocyclic ring of Ring A to Ring C is preferably a 5-membered ring or a 6-membered ring, and these aromatic heterocyclic rings may also be bonded to an aromatic hydrocarbon ring, an aromatic heterocyclic ring, a non-aromatic heterocyclic ring or an alicyclic ring. Shrink ring. Further, the aromatic heterocyclic ring-forming hetero atom is two to four nitrogen atoms, and may contain other hetero atoms (for example, an oxygen atom or a sulfur atom) in addition to the nitrogen atom.

In the present invention, the aromatic heterocyclic ring is preferably a 5-membered ring which is a non-condensed ring of 6-membered ring or a ring-condensed ring on a benzene ring.

Examples of the aromatic heterocyclic ring include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, a quinoline ring, an isoquinoline ring, and a quinazoline ring, and the 5-membered ring may be a pyrrole ring. Ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, porphyrin ring, indazole ring, triazole ring, tetrazole ring, different Oxazole ring, isothiazole ring, furazane ring, anthracene ring, benzopyrrole ring, isoindole ring, benzotriazole ring, oxadiazole ring, thiadiazole ring.

The ring A and the ring C are preferably a non-condensed 5-membered ring or a 6-membered ring, a 5-membered ring which is condensed (preferably a benzo ring), and is preferably a ring exemplified in the above aromatic heterocyclic ring.

Ring B is preferably a non-condensed 6-membered ring, more preferably a pyridine ring, a pyrazine ring, a pyrimidine ring or a triazole ring, and among them, a pyridine ring is preferred.

In the combination of the rings A to C, in the present invention, the ring B is preferably pyridine. Ring, and Ring A and Ring C are a pyridine ring, a quinoline ring or a pyrimidine ring, and particularly preferably a ring A to a ring C are pyridine rings.

Z ¹ and Z ^{2 are} preferably those in which at least one is a carbon atom, and more preferably both are carbon atoms.

Anc1~Anc3 is an adsorption group adsorbed on the surface of the semiconductor fine particles, At least one of the adsorbing groups is adsorbed on the surface of the semiconductor fine particles.

Anc1~Anc3 independently represent an acidic group. The acidic group herein refers to a substituent having a dissociated proton and has a pKa of 11 or less. The acidic group may be in a form in which protons are released and dissociated, and may also be a salt. The acidic group is preferably -CO ₂ H, -SO ₃ H, -PO ₃ H ₂ , -OH, -SH or the like, and more preferably -CO ₂ H, -OH or the like.

X ¹ , X ² and X ³ each independently represent a single bond or a linking group.

The linking group is preferably a linking group which is bonded to the bonded nitrogen-containing aromatic heterocyclic ring to form a π conjugate. Examples of such a linking group include a group in which the substituent T is adjusted to be divalent.

For example, a vinyl group, an ethynyl group, an aryl group, a heteroaromatic ring group, and a group in which the groups are combined are preferable. These groups may have a substituent, and examples of the substituent include a substituent T described later.

If X ¹ , X ² and X ³ are groups containing an unsaturated bond (for example, a vinyl group) bonded to the ring in a manner conjugated to ring A, ring B or ring C, photoelectric conversion can be improved. The photoelectric conversion efficiency of the component.

Here, in the case of the formula (LA), when Anc1 to Anc3 are -OH, it is preferably Anc1-X ¹ -, Anc2-X ² -, Anc3-X ³ - or a linker X ¹ - link The partial structure of a part of the group X ³ is represented by the following formula (AncX).

In the formula (AncX), Zx represents a single bond or -[C(=W ³ )]nx-. Here, nx represents an integer from 1 to 3. =W ¹ , =W ² and =W ³ respectively represent =O or =C(Ra1)(Ra2). Ra1 and Ra2 each independently represent a substituent. Further, -OH in the above formula may also form a salt.

In the formula (AncX), the substituent of Ra1 and Ra2 in =C(Ra1)(Ra2) of W ¹ to W ³ may be a substituent T to be described later. More preferably, Ra1 and Ra2 are an alkyl group, an aryl group, a heterocyclic group, a cyano group, a decyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, an amine sulfonyl group, and more preferably an alkane. Base, aryl, cyano.

The group or partial structure represented by the formula (AncX) is preferably the following formula A group or partial structure represented by any one of (Anc-1)~(Anc-5).

In the formula, R ^a1 to R ^a4 each independently represent a substituent. The -OH in the above formula may also form a salt.

The substituent of R ^a1 to R ^a4 is more preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, a decyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group or an amine sulfonyl group. Further preferred are alkyl groups, aryl groups, and cyano groups.

Among the groups represented by the formula (Anc-1) to the formula (Anc-5), a group represented by the formula (Anc-1) or the formula (Anc-5) is preferred, and a formula (Anc-1) is preferred. ) the group indicated.

Further, in the case of the formula (LA), when Anc1 to Anc3 are -OH, it is preferably Anc1-X ¹ -, Anc2-X ² -, Anc3-X ³ - or the linking group X ¹ - linking group. The partial structure of a part of X ³ is represented by the following formula (AncY).

[化31]

In the formula (AncY), W ⁴ in the above formula (AncX) W ¹ ~ W ³ have the same meaning, the preferred range is also the same.

In the formula (LA), when Anc1 to Anc3 are -CO ₂ H, Anc1-X ¹ -, Anc2-X ² -, Anc3-X ³ - or the linking group X ¹ - linking group is preferably contained. The partial structure of a part of X ³ is represented by the following formula (AncZ).

In the formula (AncZ), Rz represents a substituent having a σp value of 0.30 or more in Hammett's rule.

Examples of such a group include a cyano group, a decyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, an amine sulfonyl group, a perfluoroalkyl group, and a nitro group.

Rz is preferably a cyano group, a fluorenyl group (preferably an ethylene group), a perfluoroalkyl group (preferably a trifluoromethyl group), and particularly preferably a cyano group.

In the formula (LA), l1 to l3 represent integers of 1 to 5. L1~l3 is preferably 1 Or 2, more preferably 1.

M1 and m3 represent integers of 0 to 4, m2 represents an integer of 0 to 3, and the sum of m1 to m3 is 1 or more. The sum of m1 to m3 is preferably from 1 to 3, more preferably 2 or 3, and particularly preferably 3. Among them, it is preferable that any two or three of m1 to m3 are 1, and it is particularly preferable that m1 to m3 are both 1.

In the formula (LA), R ¹ to R ³ represent a substituent. The substituent T which will be described later is exemplified as the substituent. R ¹ to R ^{3 are} preferably an alkyl group, an aryl group, a heterocyclic group, an amine group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and a halogen atom, a cyano group or a sulfonyl group. The specific σp value is a positive electron withdrawing group, and more preferably an alkyl group, an aryl group, a heterocyclic group, an amine group, a halogen atom or a cyano group.

N1 and n3 are preferably 0 or 1, and n2 is preferably 0. More preferably, n1~n3 are 0.

The ligand represented by the formula (LA) is preferably a ligand represented by the following formula (AL-1) to the formula (AL-4).

[化33]

In the formula (AL-1) to the formula (AL-4), Anc1 to Anc3 each independently represent -CO ₂ H, -SO ₃ H, -PO ₃ H ₂ , -SH or the like. R ^AL represents a substituent other than Anc1 to Anc3, and b1 represents an integer of 0 to 4.

X ^2a represents -O-, -S-, -NR'-, a saturated aliphatic group, an aromatic hydrocarbon ring group, a non-aromatic hydrocarbon ring group, an aromatic heterocyclic group, a non-aromatic heterocyclic group, or the like The linkage formed by the combination. R' represents a hydrogen atom or a substituent. X ^1a represents a linking group, and X ³ represents a single bond or a linking group. M4 represents 0 or 1.

Anc1~Anc3 is preferably -CO ₂ H or a salt thereof.

The substituent of R ^AL is exemplified by the substituent T described later. The substituent of R ^AL is preferably an alkyl group, an alkenyl group, an aryl group or a heterocyclic group (preferably a heteroaromatic ring group, preferably a thiophene ring group or a furanyl ring group).

B1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and further preferably 0 or 1.

In X ^2a , the substituent of R' includes a substituent T which will be described later. R' is preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

Further, the saturated aliphatic group, the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group, and the non-aromatic heterocyclic group are divalent groups, and the groups may have a substituent, and the substituent may have a substituent. The substituent T mentioned later is mentioned.

The saturated aliphatic group of X ^2a may be either a straight chain or a branched chain. More preferably, the saturated aliphatic group is an alkylene group, and specific examples thereof include a methylene group having a carbon number of 1 to 6 such as a methylene group, an ethyl group, a propenylene group, and a butyl group.

The aromatic hydrocarbon ring group may, for example, be a group corresponding to the aryl group of the substituent T, and specific examples thereof include a benzene ring group and a naphthalene ring group.

The non-aromatic hydrocarbon ring group is a saturated hydrocarbon group (cycloalkyl group) or an unsaturated hydrocarbon group. For example, a hydrocarbon ring group having one or two or more carbon-carbon double bonds or carbon-carbon triple bonds in a manner that does not satisfy Huckel's rule can be cited. Further, when the ring-forming atom contains a pendant oxy group (>C=O), an enol structure can be obtained as a tautomer, so that, for example, a 6π conjugate is formed in the form, and the class is classified into a non-aromatic group. In the hydrocarbon ring group.

The aromatic heterocyclic group may include nitrogen of the ring A to ring C in the formula (LA). A divalent group of the ring exemplified in the aromatic hetero ring. Examples of the aromatic heterocyclic ring of the aromatic heterocyclic group include a pyridine ring, a pyrimidine ring, a triazine ring, a triazole ring, a pyrazole ring, a thiophene ring, a benzothiophene ring, and a furan ring.

Examples of the non-aromatic heterocyclic group include a saturated heterocyclic group (for example, pyrrolidine ring group, morpholine ring group, piperidinyl group), a carbon-carbon double bond which is unsaturated and does not satisfy the Heckel's law and/or a heterocyclic group of a carbon-hetero double bond (for example, 2H-pyrrole group, pyrroline ring group, imidazolidinyl group, pyrazolidine ring group), -SO-, -SO ₂ -, -C in a ring-forming atom (=O)-heterocyclyl (e.g., thiophene-1-oxide ring, thiophene-1,1-dioxide ring, pyrrolidone ring).

The non-aromatic heterocyclic group may be exemplified by a vinyl group or an ethynyl group. A benzene ring group or a group having a thiophene ring structure, a group obtained by combining two or more groups having a thiophene ring structure, and the like.

In terms of the higher photoelectric conversion efficiency (η) of the metal complex dye, X ^{2a is} preferably a linear or branched aliphatic hydrocarbon group, an aromatic hydrocarbon ring group, or an aromatic heterocyclic group. Preferably, it is an aromatic hydrocarbon ring group, and particularly preferably a benzene ring group.

X ^1a represents a linking group. The linker does not contain a single bond.

The linking group of X ^1a and X ³ preferably contains a linking group of X ^2a or an unsaturated hydrocarbon group such as a vinyl group or an ethynyl group.

The linking group of X ^1a and X ³ is preferably a linking group in which an atom bonded to Anc1 to Anc3 is conjugated to a pyridine ring by π. Thereby, the effect of improving the absorption characteristics obtained by the elongation of the π-conjugated system can be expected. Examples of such a linking group include a vinyl group, an ethynyl group, an aryl group, a divalent aromatic heterocyclic group, or a linking group obtained by combining the groups.

Further, among the non-aromatic hydrocarbon ring groups or non-aromatic heterocyclic groups, it is also preferred An extension of the π conjugate system can be performed. For example, among the non-aromatic heterocyclic groups, an unsaturated heterocyclic group (a group in which a ring-forming atom is a pendant oxy group (>C=O) and a carbon-carbon double bond) is preferred. The carbon-carbon double bond participating in the π-conjugated ring may be a carbon-monogen The sub-double bond (for example, C=N) may also be a hetero atom-hetero atom double bond (for example, N=N).

Wherein * and ** indicate the bonding position to the pyridine ring or Anc1 or Anc3. R ¹¹ and R ¹² each independently represent a substituent. The substituent of R ¹¹ is exemplified by the substituent T described later. The substituent of R ¹² may, for example, be an electron withdrawing group in the substituent T described later, and for example, a cyano group or the like is preferable.

X ^1a, X ³ is linking group containing X ^2a, is preferably formed as aforesaid group π conjugated. More preferably, such a group is a vinyl group, an ethynyl group, an aryl group (preferably a phenyl group), a divalent thiophene ring, and a combination of the groups, and examples thereof include: -vinyl group - benzene Base-, -exetylene-phenylene-,-vinyl-divalent thiophene-, ethynyl-divalent thiophene-,-divalent thiophene-divalent thiophene-.

Further, the substituent T described later in the linking group may be substituted, and it is preferably substituted with an electron-donating substituent. By substituting an electron-donating substituent, the molar absorption coefficient of the metal complex dye is increased, the photoelectric conversion efficiency is improved, and the unevenness in performance can be reduced. Such an electron-donating group is, for example, preferably a fluoroalkyl group, a halogen atom, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a substituted or unsubstituted aminosulfonyl group, Nitro, substituted or unsubstituted guanamine and cyano.

In terms of the higher photoelectric conversion efficiency (η) of the metal complex dye, X ^1a and X ^{3 are} preferably an exoacetylene group which may have a substituent, a divalent thiophene ring group, and an unsaturated group having a thiophene skeleton. A heterocyclic group or a linking group obtained by combining the groups.

X ^1a and X ^{3 are} preferably a ethynyl group which may have a substituent or a conjugated group of 2 to 5 linked, and particularly preferably a group represented by the following formula (3) to formula (6) or The unsaturated heterocyclic group of the divalent thiophene ring group or the divalent thiophene ring skeleton is particularly preferably a group represented by the following formula (3) and formula (7) to formula (9).

Wherein * represents the bonding position with the pyridine ring, and ** represents the bonding position with Anc1 or Anc3. s represents an integer from 0 to 2. R ³¹ to R ¹⁰² each independently represent a hydrogen atom or a substituent, and a plurality of substituents may be bonded to each other directly or via a linking group to form a ring. Here, R ³¹ to R ¹⁰² may, for example, be a substituent T to be described later, and among them, an electron-donating group is preferred.

In the formula (AL-3) to the formula (AL-4), m4 represents 0 or 1. From the viewpoint of durability, m4 is preferably 1.

Further, the ligand represented by the formula (LA) is preferably a ligand represented by the following formula (AL-5).

In the formula, X ¹ ~X ³ , l1~l3, m1~m3, R ¹ ~R ³ , n1~n3 and X ¹ ~X ³ , l1~l3, m1~m3, R ¹ ~ in formula (LA) R ^3, n1 ~ n3 have the same meaning, the preferred range is also the same. The -OH in the formula can also form a salt. Where m4 represents 0 or 1. From the viewpoint of durability, m4 is preferably 1

Specific examples of the ligand LA are shown below, but the present invention is not limited thereto. These specific examples are set.

Series 1 of ligands LA [Chem. 37]

Ligand LA Series 2

Anc1~Anc3 in any of the three rings is -OH, and the -OH is a ligand bonded to -OH of the following formula (AncX)

[39]

Ligand LA Series 3

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The ligand LA can be synthesized by a metal-halogen exchange reaction, a cross-coupling reaction, a Knoevenagel condensation reaction, or the like.

- Ligand LX-

The ligand LX represents a chlorine atom, a bromine atom or an iodine atom. The ligands can interact with the above ligand LD and the ligand LA to absorb not only the maximum wavelength (λmax) The length is increased and the long wavelength end is made longer, thereby improving the spectral sensitivity characteristics in the long wavelength range and improving the durability. In particular, the chlorine atom has a high effect of improving the spectral sensitivity characteristics in the long wavelength range, and the iodine atom has a high durability improvement effect in addition to the spectral sensitivity characteristics in the long wavelength range. Therefore, it is preferred to select a halogen atom for the purpose of improving the spectral sensitivity characteristics and durability in a long wavelength range. Although the detailed mechanism for exerting this effect is not certain, it is considered that the effect is exhibited by the fact that a halogen atom having a strong π supply is used as a ligand and is combined with a ligand LD and a ligand LA. When used, the highest occupied molecular orbital (HOMO) of the metal M is made shallow.

Further, the ligand LX represents a monodentate ligand. The ligand LX represents a single tooth coordination represented by any one of -S(Rz1), -O(Rz1) or -N(Rz1) ₂ or (Z1-1) to (Z1-3). base.

These ligands LX interact with the ligand LD and the ligand LA to contribute to improvement in spectral sensitivity characteristics and durability in a long wavelength range. Although the detailed mechanism for exerting this effect is not certain, the spectral sensitivity characteristic in the long wavelength range is improved by not only absorbing the maximum wavelength (λmax) but also absorbing the long wavelength end. The reason why the above effect is exerted is that the highest occupied molecular orbital (HOMO) of the metal ion M is made shallow if the ligand Zn having a strong π supply is used together with the ligand LD and the ligand LA. . Further, it is presumed that the ligand LX has a large volume due to the presence of Rz1, and the center metal can be three-dimensionally protected to improve durability.

The ligand LX may be -S(Rz1), -O(Rz1) or -N(Rz1) ₂ .

Here, Rz1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a decyl group, an alkylsulfonyl group or an arylsulfonyl group. Among these, Rz1 is preferably an aryl group, a heterocyclic group, a decyl group, an alkylsulfonyl group or an arylsulfonyl group in terms of three-dimensionally protecting the central metal to improve durability. Particularly, Rz1 is preferably an aryl group, a heterocyclic group or a decyl group in -S(Rz1), preferably an aryl group in -O(Rz1), and an aryl group or a decane in -N(Rz1) ₂ . Base, alkyl sulfonyl group.

Further, in the case where the ligand LX is -N(Rz1) ₂ , the two Rz1 are not bonded to each other and do not form a ring structure.

Alkyl, alkenyl, alkynyl, aryl, heterocyclic, decyl, alkane of Rz1 The sulfonyl group and the arylsulfonyl group have the same meanings as the substituent T, respectively, and preferably the same. Particularly in -S(Rz1), Rz1 is preferably a benzene ring group, a thiophene ring group, a 4,5-dehydrothiazole ring group and a benzothiazole ring group.

The ligand LX may be exemplified by the formula (Z1-1) in addition to the above ligand. A monodentate ligand represented by any one of the formulae (Z1-3).

Wherein Xz1 represents -ORz1, -SRz1, -N(Rz1) ₂ or -Rz1. Zz1 and Zz2 independently represent the non-metallic atomic groups necessary for forming a 5-membered ring to a 7-membered ring.

-ORz1, -SRz1, -N(Rz1) ₂ and -Rz1 represented by Xz1 in the formula (Z1-1) have the same meanings as the above -ORz1, -SRz1, -N(Rz1) ₂ and -Rz1, respectively. The same is true for the best. Further, when Xz1 is -Rz1, two Rz1 are not bonded to each other, and a ring structure is not formed.

Xz1 is preferably an alkyl group, an aryl group and a heterocyclic group, and more preferably an aryl group, in terms of enhancing the durability of the center metal in a three-dimensional manner.

Zz1 in the formula (Z1-2) is necessary for forming a 5-membered ring to a 7-membered ring. Group of metal atoms. The atom constituting the non-metal atom group is preferably a carbon atom or a hetero atom (a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a boron atom, a germanium atom, a selenium atom or the like).

The ligand LX represented by the formula (Z1-2) has a ring structure of 5 to 7 members containing a carbon atom, and the above carbon atom is bonded to a nitrogen atom coordinated to the metal ion M. The ring structure is, for example, a ring structure of the following formula (Z2-2).

Zz2 in formula (Z1-3) is a nitrogen source containing a metal ion M It forms a non-metallic atomic group necessary for a 5-membered ring to a 7-membered ring. The atom constituting the non-metal atom group is preferably a carbon atom or a hetero atom (a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a boron atom, a germanium atom, a selenium atom or the like).

The ligand LX represented by the formula (Z1-3) has a nitrogen-containing heterocyclic group of 5 to 7 members containing a nitrogen atom coordinated to the metal ion M (saturated and unsaturated (including aromatic and non-aromatic) ). The nitrogen-containing heterocyclic group is, for example, a ring structure of the following formula (Z2-3).

The monodentate ligand LX is preferably exemplified by the following formula (Z2-1) to (Z2-3) A single-dentate ligand represented by any of the formulas.

In the formula (Z2-1), Xz2 represents O, S or NRz1. Xz2 is preferably S in terms of the spectral sensitivity characteristics or photoelectric conversion efficiency in the long wavelength range. X ³ represents a carbon atom or a nitrogen atom. W represents a non-metallic atomic group necessary to form a 5-membered ring to a 7-membered ring containing a carbon atom bonded to Xz2. The atom constituting the non-metal atom group is preferably a carbon atom or a hetero atom (a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a boron atom, a ruthenium atom, a selenium atom or the like).

The ring structure in the formula (Z2-1) may be a hydrocarbon ring or a heterocyclic ring, and may be an aromatic ring or a non-aromatic unsaturated hetero ring. The aromatic carbocyclic ring may, for example, be a benzene ring, and may include a benzene ring condensed by another ring, for example, a naphthalene ring. Examples of the aromatic heterocyclic ring include a thiophene ring group, a furan ring group, a pyrrole ring group, a thiazole ring group, and a pyridine ring group. The aromatic heterocyclic ring includes a ring obtained by condensation of a benzene ring or the like, and examples thereof include a benzothiazole ring and the like. Among these, a thiophene ring group, a thiazole ring group, and a benzothiazole ring group are more preferable. The non-aromatic unsaturated heterocyclic ring may, for example, be a pyrroline ring group or a 4,5-dehydrothiazole ring group, and is preferably a 4,5-dehydrothiazole ring group.

In the formula (Z2-2) and the formula (Z2-3), X ¹ , X ² and Y each independently represent O, S, NRz1, >C=O, >C=S, and C(Rz1) ₂ . Rz1 is as described above. Both X ¹ and X ² are preferably O or >C=O. Y is preferably >C=S.

The ring structure in the formula (Z2-2) may be a saturated ring or an unsaturated ring, and Further, the hydrocarbon ring group may be a heterocyclic group. Preferred examples of the saturated ring include a hydrocarbon ring group such as a cyclopentane ring group and a cyclopentanedione ring group, and a heterocyclic group such as a dioxolane ring group. Among these, a cyclopentanedione ring group and a dioxolane ring group are preferable. On the other hand, examples of the preferred unsaturated ring include an unsaturated hydrocarbon ring group such as a cyclopentene ring group and a cyclopentenedione ring group, and an unsaturated heterocyclic group such as a dehydrodioxolane group. These groups also include those obtained by condensation of a benzene ring or the like. Among these, a cyclopentenedione ring group, a dehydrodioxolane group, a cyclopentenedione ring group condensed by a benzene ring, and a dehydrogenated dioxane condensed by a benzene ring are preferred. Pentane ring group.

The nitrogen-containing heterocyclic group in the formula (Z2-3) may be a saturated ring or an unsaturated ring. Preferred saturated rings include a pyrrolidine ring group, a pyrrolidin-2-thione ring group and the like. Among these, a pyrrolidin-2-thione ring group is preferred. On the other hand, a preferred unsaturated ring may, for example, be a dihydropyrrolidine ring group or a dihydropyrrolidinium-2-thione ring group, and the like may be one obtained by condensation of a benzene ring or the like. Among these, a dihydropyrrolidinium-2-thione ring group and a dihydropyrrolidinium-2-thione ring group condensed by a benzene ring are preferred.

In the formula (Z2-1)~(Z2-3), R represents a hydrogen atom, an alkyl group, or an alkane Oxyl, alkylthio, alkenyl, alkynyl, halogen atom, aryl, heterocyclic, amine, cyano or nitro. Among these, an alkyl group, an alkoxy group, an alkylthio group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group and a substituent T have the same meanings, and preferably the same.

In the formula (Z2-1)~(Z2-3), n is an integer of 0 or more, which is the root. It is suitably determined according to the ring structure in each formula, and is preferably 0, 1, or 2. When n is 2 or more, that is, when a plurality of Rs are present, the Rs may be connected to each other to form a ring.

Specifically, the monodentate ligand LX is preferably a monodentate ligand represented by any one of the following formulae (Z1-4) to (Z1-18).

Wherein Xz2 represents O, S, N or NRz1. Xz3 represents N or CRz1. Xz4~Xz7 independently represent O, S, NRz1 or C(Rz1) ₂ . When Xz2 is N, nz1 represents "2", and when Xz2 is O, S, and NRz1, nz1 represents "1". Rz1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a decyl group, an alkylsulfonyl group or an arylsulfonyl group. Rz2 to Rz12 and Rz16 to Rz45 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkenyl group, an alkynyl group, a halogen atom, an aryl group, a heterocyclic group, an amine group, a cyano group or a nitro group. Rz13 to Rz15 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

Rz2 to Rz45 are preferably a hydrogen atom and an alkyl group, more preferably a hydrogen atom. Rz2 to Rz45 may also be bonded to each other to form a ring, which has the same meaning as the substituent T, and preferably the same.

In the formula (Z1-4) to the formula (Z1-8), Xz2 is preferably S and N, and more preferably S, in terms of spectral sensitivity characteristics and durability in a long wavelength range. Similarly, in formula (Z1-5) ~ formula (Z1-7), Xz3 preferably N and C (Rz1) ₂ (Rz1 is particularly preferably a hydrogen atom), Xz4 preferred is S.

In the formula (Z1-9), the center metal is three-dimensionally protected to improve durability. In terms of aspect, both Rz14 and Rz15 are preferably an aryl group, and particularly preferably a phenyl group.

In the formula (Z1-10) to the formula (Z1-12), Xz5 is preferably all O.

In the formula (Z1-13) to the formula (Z1-15), Xz6 is preferably all O.

Formula (Z1-16) ~ Formula (Z1-18) in, Xz6 preferably S, Xz7 preferably C (Rz1) ₂ (Rz1 is particularly preferably a hydrogen atom).

Specific examples of the ligand LX are shown below, but the present invention is not limited thereto. These specific examples are set.

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- Charge neutralization counterion Y-

Y represents the counter ion in the case where the counter ion is necessary to neutralize the charge. Usually, whether the dye is a cation or an anion or whether it has a net ionic charge is a metal, a ligand, and a substituent depending on the metal complex dye.

The metal complex dye can also be dissociated to have a negative charge by the substituent having a dissociable group or the like. In this case, the charge of the entire metal complex dye is adjusted to be electrically neutral by Y.

When the counter ion Y is a positive counter ion, such as counter ion Y It is an inorganic or organic ammonium ion (for example, a tetraalkylammonium ion such as a tetrabutylammonium ion, a triethylbenzylammonium ion, a pyridinium ion or the like), a phosphonium ion (for example, a tetraalkylphosphonium ion such as a tetrabutylphosphonium ion). , an alkyltriphenylphosphonium ion, a triethylphenylphosphonium ion, etc.), an alkali metal ion, a metal complex ion or a proton. The positive counter ion is preferably an inorganic or organic ammonium ion (triethylammonium, tetrabutylammonium ion, etc.) or a proton.

In the case where the counter ion Y is a negative counter ion, such as counter ion Y The inorganic anion may also be an organic anion. Examples of the counter ion Y include hydroxide ions, halogen anions (for example, fluoride ions, chloride ions, bromide ions, iodide ions, etc.), substituted or unsubstituted alkyl carboxylate ions (acetate ions). , trifluoroacetate ion, etc.), substituted or unsubstituted aryl carboxylate ion (benzoate ion, etc.), substituted or unsubstituted alkylsulfonate ion (methanesulfonate ion, trifluoromethyl a sulfonate ion, etc., a substituted or unsubstituted arylsulfonate ion (eg, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion, etc.), an aryldisulfonate ion (eg, 1,3-benzenedisulfonate) Acid ion, 1,5-naphthalene disulfonate ion, 2,6-naphthalene disulfonate ion, etc.), alkyl sulfate ion (such as methyl sulfate ion, etc.), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate Salt ion, picrate ion. Further, the charge-balancing counter ion may also use an ionic polymer or other pigment having an opposite charge to the pigments, or a metal complex ion (for example, bisphenyl-1,2-dithiol nickel). (III), etc.). The negative counterion is preferably a halogen anion, a substituted or unsubstituted alkyl carboxylate ion, a substituted or unsubstituted alkylsulfonate ion, a substituted or unsubstituted arylsulfonate ion, an aryl group. The disulfonate ion, the perchlorate ion, and the hexafluorophosphate ion are more preferably a halogen anion or a hexafluorophosphate ion.

-n-

n in the formula (I) represents an integer of 0 to 4, preferably 0 or 1, more preferably 0.

<Substituent T>

The expression of the compound (including the complex compound and the coloring matter) in the present specification is intended to include the salt and the ion thereof in addition to the compound itself. Further, the unsubstituted or unsubstituted substituent (the same applies to the linking group and the ligand) is not specifically described in the present specification, and means that any substituent may be present on the group. This case also has the same meaning for compounds which are not clearly described as substituted or unsubstituted. Preferred substituents include the following substituents T.

Further, in the present specification, when only a substituent is described, the substituent T is referred to, and when only a group, for example, an alkyl group is described, a preferred range and a specific range of the corresponding group of the substituent T are applied. example.

The substituent T can be exemplified by the following groups.

The above group is an alkyl group (preferably having a carbon number of 1 to 20, such as methyl, ethyl, isopropyl, tert-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2- Ethoxyethyl, 1-carboxymethyl, trifluoromethyl, etc.), alkenyl (preferably having a carbon number of 2 to 20, such as a vinyl group, an allyl group, an oleyl group, etc.), an alkynyl group (preferably a carbon number of 2 to 20, such as ethynyl, butadiynyl, phenylethynyl, etc., a cycloalkyl group (preferably having a carbon number of 3 to 20, such as cyclopropyl, cyclopentyl, cyclohexyl, 4- a methylcyclohexyl group or the like, a cycloalkenyl group (preferably having a carbon number of 5 to 20, such as a cyclopentenyl group or a cyclohexenyl group), or an aryl group (preferably having a carbon number of 6 to 26, for example, a phenyl group, 1) -naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), heterocyclic group (preferably having a carbon number of 2 to 20, preferably having at least one oxygen atom, sulfur) a 5-membered ring or a 6-membered ring heterocyclic group of an atom, a nitrogen atom, such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl , a thienyl group, a 4,5-dehydrothiazole ring group, a benzothiazole ring group, etc.), an alkoxy group (preferably a carbon number of 1 to 20, such as a methoxy group, an ethoxy group, an isopropoxy group, a benzyl group) a group or the like, an alkenyloxy group (preferably having a carbon number of 2 to 20, for example, a vinyloxy group or an allyloxy group), an alkynyloxy group (preferably having a carbon number of 2 to 20, for example, 2-propynyloxy group, 4-butynyloxy or the like), cycloalkoxy (preferably having a carbon number of 3 to 20, such as a cyclopropoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a 4-methylcyclohexyloxy group, etc.), An aryloxy group (preferably having a carbon number of 6 to 26, such as a phenoxy group, a 1-naphthyloxy group, a 3-methylphenoxy group, a 4-methoxyphenoxy group, etc.) or a heterocyclic oxy group (such as an imidazole) Oxyl, benzimidazolyloxy, thiazolyloxy, benzothiazolyloxy, triazinyloxy, decyloxy), alkoxycarbonyl (preferably having a carbon number of 2 to 20, such as ethoxycarbonyl, 2 -ethylhexyloxycarbonyl or the like), cycloalkoxycarbonyl (preferably having a carbon number of 4 to 20, such as a ring) a propyloxycarbonyl group, a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group, etc.), an aryloxycarbonyl group (preferably having a carbon number of 6 to 20, such as a phenoxycarbonyl group, a naphthyloxycarbonyl group, etc.), an amine group (more Preferably, the carbon number is from 0 to 20, and includes an alkylamino group, an alkenylamino group, an alkynylamino group, a cycloalkylamino group, a cycloalkenylamino group, an arylamino group, a heterocyclic amino group, for example, an amine group, N,N-Dimethylamino, N,N-diethylamino, N-ethylamino, N-allylamino, N-(2-propynyl)amine, N-ring Hexylamino, N-cyclohexenylamino, anilino, pyridylamino, imidazolylamino, benzimidazolylamino, thiazolylamino, benzothiazolylamino, triazinylamino And the sulfonyl group (preferably a sulfonyl group having a carbon number of 0 to 20, preferably an alkyl group, a cycloalkyl group or an aryl group, such as N,N-dimethylamine sulfonyl, N- a cyclohexylamine sulfonyl group, an N-phenylamine sulfonyl group, etc., a fluorenyl group (preferably having a carbon number of 1 to 20, such as an ethylidene group, a cyclohexylcarbonyl group, a benzhydryl group, etc.), a decyloxy group ( Preferably, it has a carbon number of 1 to 20, such as an ethoxylated group, a cyclohexylcarbonyloxy group, a benzhydryloxy group or the like, an amine methyl sulfonyl group (preferably having a carbon number of 1 to 20, preferably an alkyl group). Aminoalkyl group of a cycloalkyl or aryl group, such as N,N-dimethylaminecarbamyl, N-cyclohexylaminecarbamyl, N-phenylaminecarbamyl, etc.), mercaptoamine group ( Preferably, it is a mercaptoamine group having 1 to 20 carbon atoms, such as an ethylamino group, a cyclohexylcarbonylamino group, a benzhydrylamino group, or the like, and a sulfonylamino group (preferably having a carbon number of 0 to 20). Preferred is a sulfonylamino group of an alkyl group, a cycloalkyl group or an aryl group, such as a methylsulfonylamino group, a benzenesulfonylamino group, an N-methylmethanesulfonylamino group, an N-cyclohexylsulfonylamino group, N-ethylbenzenesulfonylamino group, etc., alkylthio (preferably having a carbon number of 1 to 20, such as methylthio, ethylthio, isopropylthio, benzylthio, etc.), cycloalkylthio ( Preferably, the carbon number is 3 to 20, such as a cyclopropylthio group, a cyclopentylthio group, a cyclohexylthio group, a 4-methylcyclohexylthio group or the like, and an arylthio group (preferably having a carbon number of 6 to 26, for example, Phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio or the like, a sulfonyl group of an alkyl group, a cycloalkyl group or an aryl group (preferably having a carbon number of 1 to 20, such as methylsulfonyl, ethylsulfonyl, cyclohexylsulfonate) Anthracenyl, phenylsulfonyl, etc.), a decyl group (preferably a carbon number of 1 to 20, preferably an alkyl group substituted with an alkyl group, an aryl group, an alkoxy group, and an aryloxy group, such as a trimethyl decyl group , triethyl decyl, triphenyl decyl, diethyl benzyl decyl, dimethyl phenyl decyl, etc., decyloxy (preferably having a carbon number of 1 to 20, preferably an alkyl group) , aryl, alkoxy and aryloxy substituted decyloxy, such as triethyl decyloxy, triphenyl decyloxy, diethylbenzyl decyloxy, dimethylphenyl decyloxy, etc. ), hydroxy, cyano, nitro, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), carboxyl group, sulfonic acid group, phosphonyl group, phosphoryl group, boric acid group .

When the compound or the substituent or the like contains an alkyl group, an alkenyl group or the like, the groups may be linear or branched, and may be substituted or unsubstituted. Further, when an aryl group, a heterocyclic group or the like is contained, the groups may be a monocyclic ring or a condensed ring, and may be substituted or unsubstituted.

Specific examples of the metal complex dye represented by the formula (I) of the present invention are shown in Dye-1 to Dye-29, but the present invention is not limited to these specific examples.

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[化53]

In addition, Dye-201 to Dye-238 which will be described later are shown as specific examples of the metal complex dye represented by the formula (I) of the present invention, but the present invention is not limited to these specific examples.

The maximum absorption wavelength of the metal complex dye of the present invention in the solution is preferably in the range of 300 nm to 1000 nm, more preferably in the range of 350 nm to 950 nm, and still more preferably in the range of 370 nm to 900 nm.

The metal complex dye represented by the formula (I) of the present invention can be synthesized by a method according to the methods described in Patent Document 1 and Patent Document 2.

An example of this will be briefly explained. First, a nitrogen-containing aromatic heterocyclic compound having a halogen atom at the 2-position and a halogen atom or an alkyl group at a position where an acidic group is introduced or directly or via a substituent is used as a starting material. An oxycarbonyl group, an aryloxycarbonyl group, a formazan group or a group represented by the following formula. Then, for example, a precursor represented by the formula (LA') is synthesized. The precursor is a precursor of a tridentate acceptor ligand having at least one alkoxycarbonyl group, aryloxycarbonyl group, formyl group or a group represented by the following formula in the ring A to ring C.

[54]

In the formula, Ring A, Ring B and Ring C each independently represent a nitrogen-containing aromatic heterocyclic ring. Z ¹ and Z ² each independently represent a carbon atom or a nitrogen atom. Here, the bond between Z ¹ and the N atom and the bond between the Z ² and N atom may be a single bond or a double bond.

R ¹ to R ³ each independently represent a substituent. N1 and n3 each independently represent an integer of 0 to 4, and n2 represents an integer of 0 to 3.

X ¹⁰ to X ³⁰ each independently represent a single bond or a linking group. G represents an alkoxycarbonyl group, an aryloxycarbonyl group, a decyl group or the following group which may have a substituent.

P1 and p3 represent integers from 0 to 4, and p2 represents an integer from 0 to 3. Among them, the sum of p1 to p3 is 1 or more.

Ring A, Ring B and Ring C have the same meanings as Ring A, Ring B and Ring C in formula (I), respectively, and preferably the same. Z ¹ and Z ² have the same meanings as Z ¹ and Z ² in the formula (I), respectively.

R ¹ to R ³ have the same meanings as R ¹ to R ³ in the formula (I), and preferably the same. N1 to n3 have the same meanings as n1 to n3 in the formula (I), and preferably the same.

X ¹⁰ to X ³⁰ have the same meanings as X ¹ to X ³ in the formula (I), and preferably the same, and particularly preferably an aromatic hydrocarbon ring group, an aromatic heterocyclic group or a single bond.

G represents an alkoxycarbonyl group, an aryloxycarbonyl group, a decyl group or a group which may have a substituent represented by any of the following structures. The alkoxycarbonyl group and the aryloxycarbonyl group are not particularly limited, and the alkoxy group of the alkoxy group and the aryloxy group and the substituent T are high in terms of the stability of the compound and the fact that it is not easily hydrolyzed in the reaction. The carbonyl group and the aryloxycarbonyl group have the same meaning, and preferably the same.

In the formula, R ^G each independently represents an alkyl group. * indicates the bonding position with ring A, ring B or ring C.

R ^G each independently represents an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 or 2 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group.

The substituent which the above group may have may be a substituent T.

In the formula (LA'), p1 to p3 have the same meanings as m1 to m3 in the formula (I), and preferably the same.

The precursor is placed on the compound of the metal ion M, and if necessary, the separately synthesized bidentate ligand LD and the monodentate ligand LX are coordinated to the metal ion M, and the following formula (III) is synthesized as a synthetic intermediate. The metal complex represented.

M(LD)(LA')(LX). (Y)n formula (III)

[wherein, M represents a metal ion. LD represents a bidentate ligand coordinated to M with an anion and an isolated electron pair. LA represents a tridentate ligand represented by the above formula (LA'). LX represents a chlorine atom, a bromine atom, an iodine atom, or -S(Rz1), -O(Rz1), -N(Rz1) ₂ or any one of the following formulas (Z1-1) to (Z1-3). The monodentate ligand represented by a sub, Rz1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a decyl group, an alkylsulfonyl group or an arylsulfonyl group. Y represents the counter ion necessary to neutralize the charge. n represents an integer from 0 to 4]

[Wherein, Xz1 represents -ORz1, -SRz1, -N (Rz1) 2 or -Rz1, Zz1 Zz2 and each independently represent a non-metallic atomic group forming 5-membered ring to 7-membered ring Required] This formula (III The metal complex represented by the above is specifically represented by the following formula (III').

[Wherein, LD, LX, Ring A ~ ring ^{C, Z 1, Z 2,} R 1 ~ R 3, n1 ~ n3, X 10 ~ X 30, G, p1 ~ p3, Y and n of formula (LA ' The same meaning is used, and M has the same meaning as the formula (I), and preferably the same is true. The compound of the metal ion M is not particularly limited, and examples thereof include a halide of the metal ion M and the like.

Specific examples of the metal complex represented by the formula (III) include the following description Ru-III-1 to Ru-III-29c and the metal complexes shown below, but the present invention is not limited to these specific examples.

Further, specific examples of the metal complex represented by the formula (III) include Although Ru-III-201-Ru-III-238 and the following metal complexes are described, the present invention is not limited to these specific examples.

[化59]

Then, by reacting the metal complex with a compound corresponding to the linking group X ¹ to the linking group X ³ and the acidic group Anc1 to the acidic group Anc3, the metal complex dye represented by the formula (I) can be synthesized. For example, when the moiety to which the acidic group Anc is bonded in the linking group is a vinyl group (including a bonding group), the metal complex represented by the formula (III') is active with, for example, cyanoacetic acid. e.g. methylene compound described Gail g brain (the Knoevenagel) condensation reaction, can be synthesized X ¹ ~ X ³ is a linking group metal complex dye of formula (I) represents. In the case where the G of the metal complex represented by the formula (III') is a group represented by the above formula, it is preferred to set it to a formazan group by deprotection by hydrolysis or the like.

Further, when X ¹ to X ³ are a single bond, G which is an alkoxycarbonyl group, an aryloxycarbonyl group, a formazan group or the above group can be hydrolyzed by a usual method, and is represented by the formula (I). Metal complex pigment.

<<Photoelectric conversion element and dye-sensitized solar cell>>

As shown in FIG. 1, the photoelectric conversion element 10 according to an embodiment of the present invention includes, for example, a conductive support 1 including a dye (metal complex dye) 21 The photoreceptor layer 2 of the semiconductor fine particles, the charge transport layer 3 as the hole transport layer, and the counter electrode 4. It is preferable that a pigment (metal complex dye) 21 is adsorbed on the semiconductor fine particles 22, and a co-adsorbent is adsorbed. The conductive support 1 provided with the photoreceptor layer 2 functions as a working electrode in the photoelectric conversion element 10. In the present embodiment, the photoelectric conversion element 10 is shown in the form of a system 100 using a dye-sensitized solar cell. The system 100 using a dye-sensitized solar cell can use the photoelectric conversion element 10 as a battery for operating the electric motor M as an operating mechanism by the external circuit 6.

In the embodiment, the light receiving electrode 5 includes the conductive support 1 and The photoreceptor layer 2 having semiconductor fine particles to which a pigment (metal complex dye) 21 is adsorbed. The photoreceptor layer 2 is designed according to the purpose, and may be a single layer or a multilayer. The pigment (metal complex pigment) 21 in the photoreceptor layer of one layer may be one or a mixture of a plurality of types, at least one of which uses the above-described metal complex dye of the present invention. The light incident on the photoreceptor layer 2 excites the dye (metal complex dye) 21. The excited dye has electrons having high energy, and the electrons are transferred from the dye (metal complex dye) 21 to the conduction band of the semiconductor fine particles 22, and further reach the conductive support 1 by diffusion. At this time, the dye (metal complex dye) 21 becomes an oxidized body. The electrons on the electrode are operated by the external circuit 6, and return to the photoreceptor layer 2 in which the oxidized body of the dye (metal complex dye) 21 and the electrolyte are present via the counter electrode 4, thereby functioning as a solar cell. effect.

In the present invention, as for the material used in the photoelectric conversion element or the dye-sensitized solar cell and the method for producing each member, it is only necessary to use a usual material and each member. For example, U.S. Patent No. 4,927,721, U.S. Patent No. 4,684,537, U.S. Patent No. 5,084,,,,, U.S. Patent No. 5,350,644, U.S. Patent No. 5,350,644, U.S. Patent No. 5,463,057, U.S. Patent No. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

Hereinafter, the main components will be briefly described.

- Conductive support -

The conductive support is preferably a metal or the support of a glass or plastic having a conductive film layer on its surface as a metal. In addition to the glass and the plastic, a ceramic (Japanese Patent Laid-Open Publication No. 2005-135902) and a conductive resin (Japanese Patent Laid-Open Publication No. 2001-160425) can be used. The surface of the support may be subjected to an optical management function, and an anti-reflection method in which a high refractive film and a low refractive index oxide film are alternately laminated as described in Japanese Laid-Open Patent Publication No. 2003-123859, for example, may be mentioned. The light guide function described in Japanese Laid-Open Patent Publication No. 2002-260746.

The thickness of the conductive film layer is preferably from 0.01 μm to 30 μm, more preferably 0.03. Mm~25μm, especially preferably 0.05μm~20μm.

The conductive support is preferably substantially transparent. The term "substantially transparent" means that the transmittance of light is 10% or more, preferably 50% or more, and particularly preferably 80% or more. The transparent conductive support is preferably one in which a conductive metal oxide is coated on glass or plastic. The metal oxide is preferably a tin oxide, more preferably an indium-tin oxide or a fluorine-doped oxide. At this time, the coating amount of the conductive metal oxide is preferably from 0.1 g to 100 g per 1 m ² of the glass or plastic support. In the case of using a transparent conductive support, it is preferred that light is incident from the side of the support.

-Semiconductor microparticles -

The semiconductor fine particles are preferably metal chalcogenides (e.g., oxides, sulfides, selenides, etc.) or perovskite fine particles. The chalcogenide of the metal is preferably an oxide of titanium, tin, zinc, tungsten, zirconium, hafnium, tantalum, indium, lanthanum, cerium, lanthanum, vanadium, niobium or tantalum, cadmium sulfide, cadmium selenide or the like. The perovskite preferably includes barium titanate or calcium titanate. Among these, titanium oxide (titanium dioxide), zinc oxide, tin oxide, and tungsten oxide are particularly preferable.

The crystal structure of titanium dioxide may be anatase type, brookite type or gold red. The stone type is preferably an anatase type or a brookite type. Titanium dioxide nanotubes, nanowires, and nanorods may also be mixed into the titanium dioxide microparticles or used as a semiconductor electrode.

Regarding the particle size of the semiconductor fine particles, the projected area is converted into a circle by using The average particle diameter of the diameter is preferably 0.001 μm to 1 μm, and the average particle diameter of the dispersion is 0.01 μm to 100 μm. Examples of the method of coating the semiconductor fine particles on the conductive support include a wet method, a dry method, and other methods.

Between the transparent conductive film and the semiconductor layer (photoreceptor layer), in order to prevent The reverse current caused by the direct contact between the electrolyte and the electrode is preferably a short-circuit proof layer. In order to prevent contact between the photoelectrode and the counter electrode, it is preferred to use a spacer or a separator. The semiconductor fine particles preferably have a large surface area so that a large amount of pigment can be adsorbed. For example, it is preferable to apply semiconductor fine particles to the support. In the state, the surface area is 10 times or more, more preferably 100 times or more, with respect to the projected area. The upper limit is not particularly limited and is usually about 5,000 times. Generally, the larger the thickness of the layer containing the semiconductor fine particles, the more the amount of the dye that can be carried per unit area is increased, so that the light absorption efficiency is increased, and on the other hand, the diffusion distance of the generated electrons is increased, so that the charge is recombined. The resulting loss also increases. The preferred thickness of the photoreceptor layer as the semiconductor layer varies depending on the use of the element, and is typically 0.1 μm to 100 μm. In the case of use as a dye-sensitized solar cell, it is preferably 1 μm to 50 μm, more preferably 3 μm to 30 μm. The semiconductor fine particles may be calcined at a temperature of from 100 ° C to 800 ° C for 10 minutes to 10 hours in order to adhere the particles to each other after application to the support. In the case where glass is used as the support, the film formation temperature is preferably from 400 ° C to 600 ° C.

Further, the amount of the semiconductor fine particles applied per 1 m ^{2 of the} support is preferably from 0.5 g to 500 g, more preferably from 5 g to 100 g. The amount of the pigment used is preferably 0.01 millimolar to 100 millimolar per 1 m ^{2 of the} support, more preferably 0.1 millimolar to 50 millimolar, and particularly preferably 0.1 millimolar to 10 millimolar. ear. In this case, the amount of the metal complex dye used in the present invention is preferably set to 5 mol% or more. Further, the amount of adsorption of the pigment to the semiconductor fine particles is preferably from 0.001 mmol to 1 mmol, more preferably from 0.1 mmol to 0.5 mmol, relative to 1 g of the semiconductor fine particles. By setting the amount of such a pigment, the sensitizing effect of the semiconductor fine particles can be sufficiently obtained.

In the case where the dye is a salt, the counter ion of the specific metal complex dye is not particularly limited, and examples thereof include an alkali metal ion or a quaternary ammonium ion.

Thus, the semiconductor fine particles are adsorbed by the added metal complex dye represented by the above formula (I). Adding a metal complex color to semiconductor microparticles The metal complex dye is adsorbed onto the semiconductor fine particles. Thus, the metal complex pigment is carried on the semiconductor fine particles. The adsorption method will be described later. After the dye is adsorbed, the surface of the semiconductor fine particles may be treated with an amine. Preferred examples of the amines include pyridines (for example, 4-tert-butylpyridine and polyvinylpyridine). These amines can be used as they are in the case of a liquid, or can be used by dissolving in an organic solvent.

Photoelectric conversion element (for example, photoelectric conversion element 10) and pigment of the present invention In the sensitized solar cell (for example, photoelectrochemical cell 20), at least the above-described metal complex dye of the present invention is used.

In the present invention, the metal complex dye of the present invention and other pigments may also be used. And use it.

The pigment to be used together is exemplified by Japanese Patent No. 3,731, 752, Japanese Patent Publication No. 2002-512729, Japanese Patent Laid-Open No. 2001-59062, Japanese Patent Laid-Open No. Hei No. Hei No. Hei. a Ru complex dye disclosed in each of the publications or the specification of Japanese Patent Laid-Open Publication No. 2001-291534 Squarylium cyanine pigment described in each of the publications of Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. 2005-123033, Japanese Patent Laid-Open No. Hei. No. 2007-287694, Japanese Patent Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. The organic pigment described in the book, "Angew. Chem. Int. Ed.", (vol. 49, pp. 1-5 (2010)), porphyrin pigments, "Germany A phthalocyanine dye described in International Journal of Applied Chemistry (Angew. Chem. Int. Ed.), (Vol. 46, p. 8358 (2007)). The pigment to be used in combination is preferably a Ru complex dye, a squaraine phthalocyanine dye or an organic dye.

In the case where the metal complex dye of the present invention is used in combination with other pigments When the quality of the metal complex dye of the present invention/the quality of other pigments is preferably 95/5 to 10/90, more preferably 95/5 to 50/50, and further preferably 95/5 to 60/40. , especially for 95/5~65/35, the best is 95/5~70/30.

- Charge moving body layer -

The charge transporting body layer used in the photoelectric conversion element of the present invention is a layer having a function of supplementing electrons to the oxidant of the dye, and is provided between the light receiving electrode and the counter electrode (opposing electrode). Representative examples include a liquid electrolyte in which a redox pair is dissolved in an organic solvent, a so-called gel electrolyte in which a liquid in which a redox pair is dissolved in an organic solvent is impregnated into a polymer matrix, a molten salt containing a redox pair, and the like. . In order to improve efficiency, a liquid electrolyte is preferred. As the organic solvent of the liquid electrolyte, a nitrile compound, an ether compound, an ester compound or the like can be used, and a nitrile compound is preferable, and acetonitrile or methoxypropionitrile is particularly preferable.

Examples of the redox pair include iodine and iodide (preferably iodide). a salt, an iodinated ionic liquid, preferably a combination of lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, methylpropylimidazolium iodide, or a violin (eg, Methyl viologen chloride, hexyl violet bromide, benzyl viologen tetrafluoroborate and its reduction Combination of body, polyhydroxybenzene (such as hydroquinone, naphthalenediol, etc.) and its oxidant combination, combination of divalent iron complex and trivalent iron complex (such as red blood salt and yellow blood salt a combination), a combination of a divalent cobalt complex and a trivalent cobalt complex, and the like. Among these, a combination of iodine and iodide, a combination of a divalent cobalt complex and a trivalent cobalt complex is preferred.

Among them, the cobalt complex is preferably a complex represented by the following formula (CC).

Co(LL)ma(X)mb. CI type (CC)

In the formula (CC), LL represents a bidentate ligand or a tridentate ligand. X represents a single tooth ligand. Ma represents an integer from 0 to 3. Mb represents an integer from 0 to 6. CI represents a counter ion that is necessary to counter ions in order to neutralize the charge.

CI can be enumerated as Y in the formula (I).

LL is preferably a ligand represented by the following formula (LC).

In the formula (LC), Z ^LC1 , Z ^LC2 and Z ^LC3 each independently represent a group of non-metal atoms necessary for forming a 5-membered ring or a 6-membered ring. Z ^LC1 , Z ^LC2 and Z ^LC3 may have a substituent or may be ring-closed to an adjacent ring via a substituent. X ^LC1 and X ^LC3 represent a carbon atom or a nitrogen atom. q means 0 or 1. The substituent T can be mentioned as this substituent.

X is preferably a halogen ion.

The ligand represented by the above formula (LC) is more preferably a ligand represented by the following formula (LC-1) to formula (LC-3).

R ^LC1 to R ^LC9 represent a substituent. Q1, q2, q6, and q7 each independently represent an integer of 0-4. Q3 and q5 each independently represent an integer of 0~3. Q4 represents an integer from 0 to 2.

In the formula (LC-1) to the formula (LC-3), ^examples of the substituent of R ^LC1 to R ^LC9 include an aliphatic group, an aromatic group, and a heterocyclic group. Specific examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, and a heterocyclic ring. Preferred examples thereof include an alkyl group (e.g., methyl, ethyl, n-butyl, n-hexyl, isobutyl, t-butyl, t-butyl, n-dodecyl, cyclohexyl, benzyl, etc.) , aryl (eg phenyl, tolyl, naphthyl, etc.), alkoxy (eg methoxy, ethoxy, isopropoxy, butoxy, etc.), alkylthio (eg methylthio, positive) Butylthio, n-hexylthio, 2-ethylhexylthio, etc.), aryloxy (eg phenoxy, naphthyloxy, etc.), arylthio (eg phenylthio, naphthylthio, etc.), heterocycle A group (for example, 2-thienyl, 2-furyl, etc.).

Specific examples of the cobalt complex represented by the formula (LC) include the following complexes.

In the case where a combination of iodine and iodide is used as the electrolyte, it is preferred to further use an iodide salt of a nitrogen-containing aromatic cation having a 5-membered ring or a 6-membered ring.

The organic solvent for dissolving the redox couples is preferably an aprotic polar solvent (for example, acetonitrile, propyl carbonate, ethyl carbonate, dimethylformamide, dimethyl hydrazine, cyclobutyl hydrazine, 1 , 3-dimethylimidazolidinone, 3-methyloxazolidinone, etc.). The polymer used for the matrix of the gel electrolyte may, for example, be polyacrylonitrile, polyvinylidene fluoride or the like. The molten salt may, for example, be a mixture of lithium iodide and at least one other lithium salt (for example, lithium acetate, lithium perchlorate, etc.) in a polyethylene oxide, thereby imparting room temperature. Liquidity, etc. The amount of the polymer added in this case is from 1% by mass to 50% by mass. Further, γ-butyrolactone may be contained in the electrolytic solution, whereby the diffusion efficiency of the iodide ions is increased and the conversion efficiency is improved.

The addition to the electrolyte can be added in addition to the above 4-tert-butylpyridine An aminopyridine-based compound, a benzimidazole-based compound, an aminotriazole-based compound, an aminothiazole-based compound, an imidazole-based compound, an aminotriazine-based compound, a urea derivative, a guanamine compound, a pyrimidine compound, and Nitrogen-containing heterocycle.

In order to improve the efficiency, a method of controlling the moisture of the electrolyte may also be employed. control A preferred method of producing moisture may be a method of controlling the concentration or a method of allowing the dehydrating agent to coexist. In order to reduce the toxicity of iodine, a crystal cage compound of iodine and cyclodextrin may be used, and a method of replenishing water from time to time may be used. Alternatively, a cyclic ruthenium may be used, and an antioxidant, a hydrolysis inhibitor, an anti-decomposition agent, and zinc iodide may be added.

A molten salt can also be used as the electrolyte, and preferred molten salts can be enumerated: An ionic liquid having an imidazolium or triazolium type cation, an oxazolidine system, a pyridinium system, a guanidinium system, and combinations thereof. It is also possible to combine specific anions with these cations. Additives may also be added to the molten salts. It may also have a liquid crystal substituent. Further, a molten salt of a quaternary ammonium salt system can also be used.

Examples of the molten salt other than the above may be exemplified by lithium iodide and at least one other A lithium salt (for example, lithium acetate, lithium perchlorate, or the like) is mixed with polyethylene oxide to impart fluidity at room temperature or the like.

By adding a gelling agent to an electrolyte containing an electrolyte and a solvent By gelling it, the electrolyte can also be made into a solid-solid. Gelling agent Examples thereof include an organic compound having a molecular weight of 1,000 or less, an Si-containing compound having a molecular weight of 500 to 5,000, an organic salt formed from a specific acidic compound and a basic compound, a sorbitol derivative, and polyvinylpyridine.

Further, a method of blocking a matrix polymer, a crosslinked polymer compound or a monomer, a crosslinking agent, an electrolyte, and a solvent in a polymer may be employed.

The matrix polymer preferably includes a polymer having a nitrogen-containing hetero ring in a repeating unit of a main chain or a side chain, a crosslinked body obtained by reacting the electron-retarding compound, and a polymer having a triazine structure. a polymer having a urea-based structure, a liquid crystal-containing compound, a polymer having an ether bond, a polyvinylidene fluoride-based compound, a methacrylate-acrylate type, a thermosetting resin, a crosslinked polyoxyalkylene, A crystal cage compound such as polyvinyl alcohol (PVA), polyalkylene glycol or dextrin, a system in which an oxygen-containing or sulfur-containing polymer is added, or a natural polymer. Further, a base swelling polymer, a polymer having a compound capable of forming a charge transfer complex of a cation moiety and iodine in one polymer, or the like may be added thereto.

As the matrix polymer, a system containing a difunctional or higher isocyanate as a component and a functional group such as a hydroxyl group, an amine group or a carboxyl group may be used. Further, a crosslinking method in which a crosslinked polymer obtained from a hydroquinone group and a double bond compound, a polysulfonic acid or a polycarboxylic acid, or the like is reacted with a divalent or higher metal ion compound can be used.

Examples of the solvent which can be preferably used in combination with the above solid-like electrolyte include a specific phosphate ester, a mixed solvent containing ethylene carbonate, a solvent having a specific relative dielectric constant, and the like. Solid electrolyte membrane or pore-holding liquid The method of the bulk electrolyte solution is preferably a cloth-like solid such as a conductive polymer film, a fibrous solid, or a filter.

Instead of the above liquid electrolyte and solid-like electrolyte, a solid charge transport layer such as a p-type semiconductor or a hole transport material, such as CuI, CuNCS or the like can be used. Further, an electrolyte described in "Nature" (Vol. 486, p. 487, 2012) or the like can also be used. An organic hole transport material can also be used as the solid charge transport layer. The hole transport layer is preferably a conductive polymer such as polythiophene, polyaniline, polypyrrole or polydecane, or a spiro compound having a tetrahedral central element such as C or Si, and a triarylamine. An aromatic amine derivative, a triphenylene derivative, a nitrogen-containing heterocyclic derivative, a liquid crystalline cyano derivative.

The redox pair acts as a carrier for electrons. The preferred concentration is 0.01 mol/l or more, more preferably 0.1 mol/l, and particularly preferably 0.3 mol/l or more. The upper limit of the case is not particularly limited and is usually about 5 m/l.

-Co-adsorbent -

In the photoelectric conversion element of the present invention, it is preferred to use a co-adsorbent together with the metal complex dye of the present invention or a dye which is used in combination as needed. Such a co-adsorbent is preferably a co-adsorbent having one or more acidic groups (preferably a carboxyl group or a salt thereof), and examples thereof include a fatty acid or a compound having a steroid skeleton. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid, and examples thereof include butyric acid, caproic acid, caprylic acid, capric acid, palmitic acid, dodecanoic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid. , linoleic acid and so on.

Examples of compounds having a steroid skeleton include: cholic acid, glycocholic acid (glycocholic) Acid), chenodeoxycholic acid, hyocholic acid, deoxycholic acid, lithocholic acid, ursodeoxycholic acid, and the like. Preferred is cholic acid, deoxycholic acid, chenodeoxycholic acid, and more preferably chenodeoxycholic acid.

A preferred co-adsorbent is a compound represented by the following formula (CA).

In the formula, R ^A1 represents a substituent having an acidic group. R ^A2 represents a substituent. nA represents an integer of 0 or more.

The acidic group has the same meaning as the group shown above.

nA is preferably 2 to 4.

Specific examples of such a compound include compounds exemplified as the above-described compound having a steroid skeleton.

By adsorbing on the semiconductor fine particles, the co-adsorbent has the following effects: suppressing the effect of inefficient association of the dye, and preventing the surface from the semiconductor fine particles The effect of reverse electron transfer of a redox system in an electrolyte. The amount of the co-adsorbent used is not particularly limited, and from the viewpoint of effectively exhibiting the above effects, it is preferably from 1 mol to 200 mol, more preferably 10 mol, per mol of the dye. Ears ~150 m, especially good 20 m ~ 50 m.

The counter electrode (also referred to as a counter electrode) preferably functions as a positive electrode of a dye-sensitized solar cell (photoelectrochemical cell). The counter electrode generally has the same meaning as the above-described conductive support. If the structure is sufficiently maintained, the support is not necessarily required. The structure of the opposite electrode is preferably a structure having a high current collecting effect. In order to allow light to reach the photoreceptor layer, at least one of the above-described conductive support and counter electrode must be substantially transparent. In the dye-sensitized solar cell, it is preferred that the conductive support is transparent and that sunlight is incident from the support side. In this case, it is more preferable that the counter electrode has a property of reflecting light. The counter electrode of the dye-sensitized solar cell is preferably a glass or a plastic which is vapor-deposited with a metal or a conductive oxide, and more preferably a glass in which platinum is vapor-deposited. In the dye-sensitized solar cell, in order to prevent evapotranspiration of the constituent, it is preferred to seal the side surface of the battery with a polymer or an adhesive. The characteristics of the dye-sensitized solar cell obtained in this way are preferably such that when the air mass (Air Mass, AM) is 1.5 G and 100 mW/cm ² , the open circuit voltage is 0.01 V to 1.5 V, and the short-circuit current density is 0.001 mA/cm ² ~ 20 mA/cm ² , the shape factor is 0.1 to 0.9, and the conversion efficiency is 0.001% to 25%.

The present invention is applicable to Japanese Patent No. 4260494, Japanese Patent JP-A-2004-146425, JP-A-2000-340269, JP-A-2002-289274, and JP-A-2004-152613 A photoelectric conversion element and a dye-sensitized solar cell described in Japanese Laid-Open Patent Publication No. Hei 9-27352. In addition, it is applicable to Japanese Patent Laid-Open Publication No. 2004-152613, Japanese Patent Laid-Open No. 2000-90989, Japanese Patent Laid-Open No. 2003-217688, Japanese Patent Laid-Open Publication No. 2002-367686, and Japanese Patent Publication No. 2003 Japanese Laid-Open Patent Publication No. 2001-43907, Japanese Patent Laid-Open No. 2000-340269, Japanese Patent Laid-Open No. Hei No. Hei No. Hei. No. Hei. No. 2005-85500, Japanese Patent Laid-Open No. 2004-273272, Japanese Patent Laid-Open No. 2000 Japanese Laid-Open Patent Publication No. 2000-228234, Japanese Patent Laid-Open Publication No. 2001-266963, Japanese Patent Laid-Open No. 2001-185244, Japanese Patent Laid-Open Publication No. 2001-525108, Japanese Patent Laid-Open No. 2001 Japanese Laid-Open Patent Publication No. 2000-100483, Japanese Patent Laid-Open Publication No. 2001-210390, Japanese Patent Laid-Open Publication No. JP-A-2002-280587, Japanese Patent Laid-Open No. 2001-273937, and Japanese Patent Laid-Open No. 2000 A photoelectric conversion element and a dye-sensitized solar cell described in Japanese Laid-Open Patent Publication No. 2001-320068, and the like.

<<Pigment solution, semiconductor electrode using the same, and dye-sensitized solar power Pool manufacturing method>>

It is preferred to use a dye solution containing the metal complex dye of the present invention to produce a semiconductor electrode (also referred to as a dye adsorption electrode).

Such a dye solution is obtained by dissolving the metal complex dye of the present invention in a solvent, and may contain a co-adsorbent or other components as necessary.

The solvent to be used is exemplified in Japanese Patent Laid-Open Publication No. 2001-291534. The solvent to be carried is not particularly limited. In the present embodiment, an organic solvent is preferable, and an alcohol, a guanamine, a nitrile, a hydrocarbon, and a mixed solvent of two or more of these are more preferable. The mixed solvent is preferably a mixed solvent of an alcohol and a solvent selected from the group consisting of guanamines, nitriles or hydrocarbons. Further, it is preferably a mixed solvent of an alcohol and a guanamine, an alcohol and a hydrocarbon, and more preferably a mixed solvent of an alcohol and a guanamine. Specifically, methanol, ethanol, propanol, butanol, dimethylformamide, and dimethylacetamide are preferred.

The dye solution preferably contains a co-adsorbent. The co-adsorbent is preferably the above The adsorbent is preferably a compound represented by the formula (CA).

Here, it is preferable that the dye solution adjusts the concentration of the metal complex dye or the co-adsorbent so that the solution can be directly used in the production of the photoelectric conversion element or the dye-sensitized solar cell. It is preferable to contain 0.001% by mass to 0.1% by mass of a metal complex dye.

The pigment solution is particularly preferably used to adjust the moisture content, and therefore, it is preferred to include the water. The amount (content ratio) is adjusted to 0% by mass to 0.1% by mass.

Similarly, the adjustment of the moisture content of the electrolytic solution in the photoelectric conversion element or the dye-sensitized solar cell is also effective, and therefore it is preferable. The water content (content ratio) of the electrolytic solution is preferably adjusted to 0% by mass to 0.1% by mass. The adjustment of the electrolytic solution is particularly preferably carried out using a dye solution.

It is preferable to use a dye-sensitized solar cell semiconductor electrode in which the dye solution is used to carry the metal complex dye on the surface of the semiconductor fine particles provided on the semiconductor electrode.

Further, it is preferable to use the dye solution to cause the metal complex dye to be supported on the surface of the semiconductor fine particles provided in the semiconductor electrode, thereby producing a dye sensitization too. Yang battery.

[Examples]

Hereinafter, the present invention will be described in more detail based on the examples, but the invention is not limited by the examples.

<<The case where the ligand LX is a chlorine atom, a bromine atom or an iodine atom>>

Example 1 [Synthesis of Metal Complex Pigment]

The following metal complex dye Dye-1 to metal complex dye Dye-6, metal complex dye Dye-8, metal complex dye Dye-9, metal complex dye Dye-11 were synthesized as follows. ~ Metal complex dye Dye-25, metal complex dye Dye-28 and metal complex dye Dye-29. The obtained compound was confirmed by Electrospray ionization-Mass spectrometry (ESI-MS). The MS measurement results of the respective metal complex dyes are shown in Table 1.

[化64]

[化65]

1. Synthesis of Dye-28

First, the bidentate ligand LD-6-9 of the metal complex dye Dye-28 was synthesized according to the following scheme.

Compound LD-6-9A (2-ethylindenyl-4-methylpyrene) under nitrogen atmosphere 25 g of pyridine was dissolved in 200 mL of THF (tetrahydrofuran), and while stirring at 0 ° C, 18.9 g of sodium ethoxide was added and stirred for 15 minutes. Then, 28.9 g of ethyl trifluoroacetate was added dropwise, and the mixture was stirred at an external temperature of 70 ° C for 20 hours. After returning to room temperature, an aqueous solution of ammonium chloride was added dropwise to carry out liquid separation, and the organic layer was concentrated to obtain 72.6 g of crude product LD-6-9B. This was dissolved in 220 mL of ethanol under a nitrogen atmosphere, and 5.6 mL of hydrazine monohydrate was added thereto while stirring at room temperature, and the mixture was heated at an external temperature of 90 ° C for 12 hours. Thereafter, 5 mL of concentrated hydrochloric acid was added, and the mixture was stirred for 1 hour. After concentration, the mixture was extracted with 150 mL of an aqueous solution of sodium hydrogencarbonate and 150 mL of ethyl acetate. The machine layer is concentrated. After recrystallization from acetonitrile, 31.5 g of the compound LD-6-9C was obtained.

4.1 g of diisopropylamine and 30 mL of tetrahydrofuran under nitrogen atmosphere After stirring at -40 ° C, 23.1 mL of a 1.6 M n-butyllithium hexane solution was added dropwise, followed by stirring for 2 hours. Thereafter, 4.0 g of the compound LD-6-9C was added, and the mixture was stirred at 0 ° C for 80 minutes, and then 15 mL of a solution of 3-hexylthiophene-1-carbaldehyde (d-1-4), 3.45 g, in tetrahydrofuran was added dropwise. Thereafter, the mixture was stirred at 0 ° C for 80 minutes and at room temperature for 5 hours. Thereafter, an ammonium chloride solution was added, and extraction and separation were carried out using ethyl acetate. The organic layer was concentrated and purified by a silica gel column chromatography to yield 5.7 g of Compound LD-6-9D.

5.0 g of the compound LD-6-9D and p-toluene were used under a nitrogen atmosphere. 5.9 g of pyridinium p-toluene sulfonate (PPTS) was dissolved in 50 mL of toluene, and heated under reflux for 5 hours. After concentration, the mixture was separated with a saturated aqueous solution of sodium hydrogen carbonate and dichloromethane, and the organic layer was concentrated. The obtained crystal was recrystallized with methanol and dichloromethane, whereby 4.3 g of a ligand LD-6-9 was obtained.

Using the ligand LD-6-9, the metal complex dye Dye-28 was synthesized according to the following procedure.

[67]

Introducing 152 mg of the compound into a 50 mL flask under a nitrogen atmosphere 1. 101 mg of the ligand LD-6-9 was added with 10 mL of a mixed solvent of ethanol/water (5:1) as a solvent, and then 67 mg of N-methylmorpholine was added thereto, followed by heating under reflux for 3 hours. After cooling to room temperature and distilling off the solvent under reduced pressure, the obtained black solid was purified by an alumina column chromatography to thereby obtain 150 mg of Compound 2. 150 mg of this compound 2 was dissolved in 4 mL of a mixed solvent (1:1) of tetrahydrofuran/methanol, and while stirring at room temperature, 0.5 mL of a 3N aqueous sodium hydroxide solution was added dropwise. While maintaining this state, the mixture was stirred at room temperature for 1 hour, and a 1 N solution of trifluoromethanesulfonic acid in methanol was gradually added dropwise until the pH became 3.0. The crystals were gradually precipitated, filtered, washed with methanol, and dried to obtain 87 mg of the target metal complex dye Dye-28.

In the synthesis of Dye-28, Compound 2 (Ru-III-28) which is a metal complex represented by the above formula (III) was confirmed by ESI-MS.

2. Synthesis of Dye-1

The metal complex dye Dye-1 was synthesized according to the following scheme.

Add 228mg to diethylene glycol dimethyl ether 10mL under nitrogen atmosphere Compound 2, 2.13 g of potassium iodide, was stirred at 110 ° C for 1.5 hours. After cooling to room temperature and distilling off the solvent under reduced pressure, the obtained black solid was purified by a silica gel column chromatography to obtain 164 mg of Compound 3. The ester moiety was hydrolyzed to the obtained Compound 3 by the same method as Dye-28 to obtain the target metal complex dye Dye-1.

In the synthesis of Dye-1, the compound 3 (Ru-III-1) which is a metal complex represented by the above formula (III) was confirmed by ESI-MS. The MS measurement results of the respective metal complexes are shown in Table 2.

3. Synthesis of Dye-6

The metal complex dye Dye-6 was synthesized according to the following procedure.

[化69]

Confirmation of the metal error represented by the above formula (III) by ESI-MS Metal complex III-6 of the complex. The MS measurement results of the respective metal complexes are shown in Table 2.

5.Dye-2~Dye-5, Dye-8, Dye-9, Dye-11~Dye-25 and Synthesis of Dye-29

Metal complex dye Dye-2~ metal complex dye Dye-5, metal complex dye Dye-8, metal complex dye Dye-9, metal complex dye Dye-11~ metal complex pigment Dye-25 and metal complex dye Dye-29 are made with the above gold It is synthesized by the same method as the synthesis method of the complex dye Dye-1, the metal complex dye Dye-6 and the metal complex dye Dye-28.

In the synthesis of the metal complex dyes, the metal complex Ru-III-1 to the metal complex Ru-III-29c represented by the above formula (III) was confirmed by ESI-MS. The MS measurement results of the respective metal complexes are shown in Table 3.

Example 2 [Pigment sensitized solar cell]

A dye-sensitized solar cell was produced by the following procedure.

A photoelectrode having the same configuration as that of the photoelectrode 12 shown in FIG. 5 described in Japanese Laid-Open Patent Publication No. 2002-289274 was produced. Further, a dye-sensitized solar cell having a scale of 10 mm × 10 mm having the same configuration as that of the dye-sensitized solar cell 20 other than the photoelectrode shown in Fig. 3 of the above-mentioned publication was produced. The specific configuration is shown in Fig. 2 attached to the drawings of the present application. As shown in FIG. 2 of the present application, the dye-sensitized solar cell 20 has a transparent electrode 41, a semiconductor electrode 42, a transparent conductive film 43, a substrate 44, a semiconductor layer 45, a light scattering layer 46, a photoelectrode 40, and a counter electrode CE. , electrolyte E and spacer S.

(Preparation of paste)

(Paste A) A spherical titanium oxide slurry was prepared by putting spherical TiO ₂ particles (anatase, average particle diameter: 25 nm, hereinafter referred to as "spherical TiO ₂ particles A") into a nitric acid solution and stirring. Then, a cellulose-based binder was added as a thickener to the titanium dioxide slurry, and kneading was carried out to prepare a paste.

(Paste 1) The spherical TiO ₂ particles A and spherical TiO ₂ particles (anatase having an average particle diameter of 200 nm, hereinafter referred to as "spherical TiO ₂ particles B") are placed in a nitric acid solution and stirred. A titanium dioxide slurry was prepared. Then, a cellulose-based binder was added as a thickener to the titanium dioxide slurry, and kneading was carried out to prepare a paste (mass of TiO ₂ particles A: mass of TiO ₂ particles B = 30:70).

(Paste 2) In a paste A, rod-shaped TiO ₂ particles (anatase, diameter: 100 nm, aspect ratio: 5, hereinafter referred to as "rod TiO ₂ particles C") were mixed to prepare rod-shaped TiO ₂ particles C. Quality: paste A quality = 30:70 paste.

(production of photoelectrode)

A transparent electrode in which a fluorine-doped SnO ₂ conductive film (film thickness: 500 nm) was formed on a glass substrate was prepared. Then, the paste 1 was screen-printed on the SnO ₂ conductive film, followed by drying. Thereafter, calcination was carried out in the air at 450 °C. Further, by repeating the screen printing and firing using the paste 2, a semiconductor electrode (light receiving surface) having the same configuration as that of the semiconductor electrode 42 shown in FIG. 2 of the drawings of the present application is formed on the SnO ₂ conductive film. Area: 10 mm × 10 mm, layer thickness: 16 μm, layer thickness of the dye adsorption layer: 12 μm, layer thickness of the light scattering layer: 4 μm, content of the rod-shaped TiO ₂ particles C contained in the light scattering layer: 30% by mass ), making a photoelectrode without a pigment.

(pigment adsorption)

Then, the dye was adsorbed onto the semiconductor electrode containing no dye as follows. First, anhydrous ethanol dehydrated with MgSO4 was used as a solvent, and the metal complex dye described in Table 3 below was dissolved at a concentration of 3 × 10 ^-4 mol/L. Further, 20 mol of a molar mixture of chenodeoxycholic acid and cholic acid as a co-adsorbent was added to 1 mol of the metal complex dye to prepare each dye solution. The water content of the dye solution was measured by Karl Fischer titration, and as a result, the water was less than 0.01% by mass. Then, the semiconductor electrode was immersed in the solution, and after being lifted up, it was dried at 50 ° C to prepare a photoelectrode 10 having a dye of about 1.5 × 10 ^-7 mol/cm ² adsorbed on the semiconductor electrode.

(assembly of solar cells)

Then, a platinum electrode having the same shape and size as the above photoelectrode is prepared (Pt The thickness of the film: 100 nm) was used as the counter electrode CE, and an iodine-based redox solution containing iodine and lithium iodide was prepared as the electrolyte E. Further, a spacer S (trade name: "Surlyn") manufactured by DuPont Co., Ltd. having a shape that matches the size of the semiconductor electrode is prepared, as described in Japanese Laid-Open Patent Publication No. 2002-289274. As shown in Fig. 3, the photoelectrode 40 and the counter electrode CE are opposed to each other via a spacer S, and the electrolyte is filled thereinto to form a dye-sensitized solar cell using a photoelectrode (sample No. 1 to sample No.). 25 and sample No. c1 to sample No. c3).

The performance of each of the dye-sensitized solar cells produced in this manner was evaluated.

<Absorption coefficient at wavelength 750 nm>

The absorption spectrum at a wavelength of 300 nm to 900 nm was measured using UV-3600 manufactured by Shimadzu Corporation. The measurement was carried out by adding 20 equivalents of tetrabutylammonium hydroxide (TBAOH) to the metal complex dye using methanol as a solvent. Among them, the absorption coefficient ε at 750 nm was evaluated according to the following criteria.

Further, the absorption spectra of Dye-1 and Dye-28 are shown in Fig. 3 and Fig. 4.

Evaluation basis

AA: 2 times or more relative to the comparative compound (2)

A: 1.8 times or more and less than 2 times with respect to the comparative compound (2)

B: 1.5 times or more and less than 1.8 times with respect to the comparative compound (2)

C: 1 time or more and less than 1.5 times with respect to the comparative compound (2)

D: less than 1 time relative to the comparative compound (2)

<Spectrum sensitivity characteristics at wavelengths of 800 nm, 850 nm, and 900 nm>

Using an IPCE measuring device manufactured by Peccell Corporation for wavelength 300 The IPCE (quantum yield) at nm to 1000 nm was measured. Among them, IPCE at 800 nm, 850 nm, and 900 nm was evaluated according to the following criteria.

Evaluation criteria at 800 nm

AA: 1.5 times or more relative to the comparative compound (2)

A: 1.2 times or more and less than 1.5 times with respect to the comparative compound (2)

B: 1.1 times or more and less than 1.2 times with respect to the comparative compound (2)

C: 1 time or more and less than 1.1 times with respect to the comparative compound (2)

D: less than 1 time relative to the comparative compound (2)

Evaluation standard at 850 nm

AA: 2 times or more relative to the comparative compound (2)

A: 1.5 times or more and less than 2 times with respect to the comparative compound (2)

B: 1.4 times or more and less than 1.5 times with respect to the comparative compound (2)

C: 1 time or more and less than 1.4 times with respect to the comparative compound (2)

D: less than 1 time relative to the comparative compound (2)

Evaluation criteria at 900 nm

AA: 10 times or more relative to the comparative compound (2)

A: 3 times or more and less than 10 times with respect to the comparative compound (2)

B: 2 times or more and less than 3 times with respect to the comparative compound (2)

C: 1 time or more and less than 2 times with respect to the comparative compound (2)

D: less than 1 time relative to the comparative compound (2)

<Evaluation of thermal deterioration>

Put each dye-sensitized solar cell into a thermostat at 40 ° C for heat resistance test Test. The dye-sensitized solar cell before the heat resistance test and the dye-sensitized solar cell after 12 hours of the heat resistance test were evaluated for the current. The value obtained by dividing the decrease value of the current value after the heat resistance test by the current value before the heat resistance test was determined as the heat deterioration rate. The thermal deterioration rate was evaluated in accordance with the following criteria.

Evaluation basis

AA: 1.2 times or more relative to the comparative compound (2)

A: 1.1 times or more and less than 1.2 times with respect to the comparative compound (2)

B: 1.05 times or more and less than 1.1 times with respect to the comparative compound (2)

C: 1 time or more and less than 1.05 times with respect to the comparative compound (2)

D: less than 1 time relative to the comparative compound (2)

Further, it is shown in Table 3 as durability.

The above comparative compound (1) to comparative compound (3) are as described below. Metal complex pigment.

Comparative Compound (1): Patent Document 1 above

Comparative Compound (2): Patent Document 2 above

Comparative Compound (3): "Journal of the American Chemical Society (J. Am. Chem. Soc.)" (2001, Vol. 123, p. 1613)

As is clear from the above Table 3, each of the dye-sensitized solar cells using the comparative compound has a π-providing halogen atom as a monodentate ligand LX and has a ligand LD and a ligand LA. Each of the dye-sensitized solar cells of the present invention in Sample No. 1 to Sample No. 25 was excellent in sensitivity characteristics and durability in a long wavelength range.

Specifically, each dye-sensitized solar cell of the present invention is excellent in the light absorption coefficient ε at 750 nm of each dye-sensitized solar cell of the present invention, and exhibits excellent photoelectricity at 800 nm, 850 nm, and 900 nm. Conversion efficiency. In particular, when the ligand LX is an iodine atom, the photoelectric conversion efficiency of 850 nm or less is greatly improved with respect to each of the dye-sensitized solar cells using the comparative compound, and the durability is also excellent. As described above, the iodine atom can simultaneously improve the sensitivity characteristics and the durability in the long wavelength range at a high level. On the other hand, when the ligand LX is a chlorine atom, the photoelectric conversion efficiency of 900 nm or less is greatly improved with respect to each of the dye-sensitized solar cells using the comparative compound. Thus, it is known that the chlorine atom can greatly improve the sensitivity characteristics in the long wavelength range.

Further, as shown in FIG. 3 and FIG. 4, the sag of the absorption peak of each dye-sensitized solar cell of sample No. 8 (Dye-1) and sample No. 24 (Dye-28) was confirmed. It is not only broadened to wavelengths of around 400 nm and 500 nm, but also broadened to a long wavelength range of wavelengths exceeding 700 nm.

<<The case where the ligand LX is represented by any one of -S(Rz1), -O(Rz1), -N(Rz1) ₂ or (Z1-1)~(Z1-3)>>

Example 3 [Synthesis of Metal Complex Pigment]

The metal complex dye Dye-201~metal complex dye Dye-238 was synthesized as follows. The obtained compound was confirmed by ESI-MS. The MS measurement results of the respective metal complex dyes are shown in Table 4.

1. Synthesis of Dye-201

First, the bidentate ligand LD-6-9 of the metal complex dye Dye-201 was synthesized in accordance with the procedure described in Example 1.

The following compound 2 was synthesized by the following procedure using a ligand LD-6-9.

[化75]

Introducing 152 mg of the compound into a 50 mL flask under a nitrogen atmosphere 1. 101 mg of the ligand LD-6-9 was added with 10 mL of a mixed solvent of ethanol/water (5:1) as a solvent, and then 67 mg of N-methylmorpholine was added thereto, followed by heating under reflux for 3 hours. After cooling to room temperature and distilling off the solvent under reduced pressure, the obtained black solid was purified by an alumina column chromatography, whereby 150 mg of Compound 2 was obtained.

The metal complex dye Dye-201 is hydrolyzed by the following compound 4 to make. Compound 4 was synthesized according to the following scheme.

Add 237 mg of chlorination to 10 mL of dichloromethane under nitrogen atmosphere. The compound 2 and silver trifluoromethanesulfonate (84 mg) were heated under reflux for 3 hours. After cooling to room temperature, the precipitate of the formed silver chloride was removed by filtration through diatomaceous earth. The filtrate was introduced into 244 mg of sodium 2-mercaptobenzothiazole under a nitrogen atmosphere, and heated under reflux for 5 hours. cool down After the solvent was distilled off under reduced pressure at room temperature, the obtained black oil was purified using a silica gel column chromatography, whereby 132 mg of Compound 4 was obtained.

42 mg of this compound 4 was dissolved in 4 mL of a mixed solvent (1:1) of tetrahydrofuran/methanol, and while stirring at room temperature, 0.5 mL of a 3N aqueous sodium hydroxide solution was added dropwise. While maintaining this state, the mixture was stirred at room temperature for 1 hour, and a 1 N solution of trifluoromethanesulfonic acid in methanol was gradually added dropwise until the pH became 3.0. The crystals were gradually precipitated, filtered, washed with methanol, and dried to obtain 40 mg of the target metal complex dye Dye-201.

In the synthesis of Dye-201, the compound 4 (Ru-III-201) which is a metal complex represented by the above formula (III) (hereinafter referred to as Ru-III) was confirmed by ESI-MS. The MS measurement results of the respective metal complexes are shown in Table 5.

2. Synthesis of Dye-202~Dye-238

The metal complex dye Dye-202~metal complex dye Dye-238 was synthesized by the same method as the above-mentioned metal complex dye Dye-201.

In the synthesis of the metal complex dye Dye-202~ metal complex dye Dye-238, ESI-MS or matrix-assisted laser desorption Ionization-Mass Spectrometry (MALDI) -MS) The metal complex Ru-III-201 to metal complex Ru-III-238 represented by the above formula (III) was confirmed. The MS measurement results of the respective metal complexes are shown in Table 5.

[化78]

Example 4 [Pigment sensitized solar cell]

A dye-sensitized solar cell was produced by the procedure described in Example 2.

Preparation of a paste, preparation of a photoelectrode, dye adsorption, and assembly of a solar cell were carried out as described in Example 2, and a dye-sensitized solar cell using a photoelectrode was prepared (sample No. 201 to sample No. 238). And sample No. c1 to sample No. c2).

The performance of each of the dye-sensitized solar cells thus produced was evaluated.

<Absorption coefficient at wavelength 750 nm>

The absorption spectrum at a wavelength of 300 nm to 900 nm was measured using UV-3600 manufactured by Shimadzu Corporation. The measurement was carried out by adding 20 equivalents of tetrabutylammonium hydroxide (TBAOH) to the metal complex dye using methanol as a solvent. Among them, the absorption coefficient ε at 750 nm was evaluated according to the following criteria.

Further, the absorption spectra of Dye-201 and Dye-202 are shown in Fig. 5 and Fig. 6, respectively.

Evaluation basis

AA: 3 times or more relative to the comparative compound (1)

A: 2 times or more and less than 3 times with respect to the comparative compound (1)

B: 1.5 times or more and less than 2 times with respect to the comparative compound (1)

C: 1 time or more and less than 1.5 times with respect to the comparative compound (1)

D: less than 1 time relative to the comparative compound (1)

<Spectrum sensitivity characteristics at a wavelength of 900 nm>

The IPCE (quantum yield) at a wavelength of 300 nm to 1000 nm was measured using an IPCE measuring apparatus manufactured by Peccell. Among them, IPCE at a wavelength of 900 nm was evaluated according to the following criteria.

Evaluation criteria at 900 nm

AA: 2 times or more relative to the comparative compound (1)

A: 1.7 times or more and less than 2 times with respect to the comparative compound (1)

B: 1.5 times or more and less than 1.7 times with respect to the comparative compound (1)

C: 1 time or more and less than 1.5 times with respect to the comparative compound (1)

D: less than 1 time relative to the comparative compound (1)

<Evaluation of thermal deterioration>

Each dye-sensitized solar cell was placed in a thermostat at 40 ° C for heat resistance test. The dye-sensitized solar cell before the heat resistance test and the dye-sensitized solar cell after 12 hours of the heat resistance test were evaluated for the current. The value obtained by dividing the decrease value of the current value after the heat resistance test by the current value before the heat resistance test was determined as the heat deterioration rate. The thermal deterioration rate was evaluated on the basis of the following criteria.

Evaluation basis

AA: 1.5 times or more relative to the comparative compound (1)

A: 1.3 times or more and less than 1.5 times with respect to the comparative compound (1)

B: 1.2 times or more and 1.3 times or less relative to the comparative compound (1)

C: 1 time or more and less than 1.2 times with respect to the comparative compound (1)

D: less than 1 time relative to the comparative compound (1)

Further, it is shown in Table 6 as durability.

[化79]

The comparative compound (1) and the comparative compound (2) are metal complex dyes described below.

Comparative Compound (1): Patent Document 1 above

Comparative Compound (2): Patent Document 2 above

As is clear from the above Table 6, each of the dye-sensitized solar cells using the comparative compound has the above-mentioned ligand having a high π supply as the monodentate ligand LX and has a ligand LD and a ligand. Each of the dye-sensitized solar cells of the present invention in Sample No. 201 to Sample No. 238 of LA is excellent in sensitivity characteristics and durability in a long wavelength range. Specifically, the dye absorption coefficient ε at 750 nm of each dye-sensitized solar cell of the present invention is of course excellent with respect to each of the dye-sensitized solar cells using the comparative compound, and also exhibits good photoelectric conversion efficiency especially at a wavelength of 900 nm. .

In particular, if the coordination atom of the ligand LX is a sulfur atom as in sample No. 201 to sample No. 205 and sample No. 219 to sample No. 238 (except sample No. 236), the use is relative to the use. Each of the dye-sensitized solar cells of the comparative compound has a large improvement in photoelectric conversion efficiency and durability at a wavelength of 900 nm, and is excellent in an absorption coefficient ε at 750 nm. It is known that the above ligand LX having a sulfur atom as a coordinating atom can The high level achieves both improved sensitivity characteristics and improved durability in the long wavelength range.

Further, as shown in FIG. 5 and FIG. 6, the yaw of the absorption peak of each of the dye-sensitized solar cells of sample No. 201 (Dye-201) and sample No. 202 (Dye-202) was not broadened to the wavelength. It is near 350nm~500nm, and especially broadens to a long wavelength range with wavelengths over 700nm.

1‧‧‧Electrical support

2‧‧‧Photoreceptor layer

3‧‧‧Charge mobile body layer

4‧‧‧relative electrode (opposite electrode)

5‧‧‧Photoelectrode

6‧‧‧ Circuitry

10‧‧‧ photoelectric conversion components

21‧‧‧ pigment

22‧‧‧Semiconductor particles

100‧‧‧Systems using photoelectrochemical cells (systems using dye-sensitized solar cells)

M‧‧‧Electric motor (fan)

Claims (22)

A photoelectric conversion element comprising a conductive support, a photoreceptor layer containing an electrolyte, a charge transporting body layer containing an electrolyte, and a counter electrode, and the photoreceptor layer has a semiconductor carrying a metal complex dye represented by the following formula (I) Microparticles, M(LD)(LA)(LX). (Y)n In the formula (I), M represents a metal ion; LD represents a bidentate ligand represented by the following formula (2L-1) or (2L-2); LA represents the following formula (LA) a tridentate ligand represented by the formula; LX represents a chlorine atom, a bromine atom, an iodine atom, or -S(Rz1), -O(Rz1), -N(Rz1) ₂ or the following formula (Z1-1)~ a monodentate ligand represented by any one of (Z1-3), Rz1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a decyl group, an alkyl sulfonyl group or an aromatic group. a sulfonyl group; Y represents a counter ion necessary for neutralizing the charge; n represents an integer of 0 to 4; Wherein ring A, ring B and ring C each independently represent a nitrogen-containing aromatic heterocyclic ring; here, the bond between Z ¹ and the N atom, and the bond between Z ² and the N atom may be a single bond. Is a double bond; Z ¹ and Z ² each independently represent a carbon atom or a nitrogen atom; Anc1 to Anc3 each independently represent an acidic group; and X ¹ , X ² and X ³ each independently represent a single bond or a linking group; l1 to l3 Each of the integers 1 to 5 is independently represented; m1 and m3 independently represent integers of 0 to 4, and m2 represents an integer of 0 to 3; wherein, the sum of m1 to m3 is 1 or more; and R ¹ to R ³ are independently Representing a substituent other than Anc1~Anc3; n1 and n3 each independently represent an integer of 0-4, and n2 represents an integer of 0~3; Wherein Xz1 represents -ORz1, -SRz1, -N(Rz1) ₂ or -Rz1, and Zz1 and Zz2 each independently represent a non-metal atomic group necessary for forming a 5-membered ring to a 7-membered ring; Wherein * represents a bonding position with the above metal ion M; ring D represents an aromatic ring; A ¹¹¹ represents a nitrogen anion or a carbon anion, A ¹²¹ represents a nitrogen anion, an oxyanion or a sulfur anion; and R ¹¹¹ - R ¹²⁴ represents a hydrogen; Atom or a substituent having no Anc1, Anc2, and Anc3. The photoelectric conversion element according to claim 1, wherein the semiconductor fine particles are adsorbed by the metal complex dye represented by the above formula (I). The photoelectric conversion element as defined in claim 1 item range, wherein said M is Fe ^2+, Ru ²⁺ or Os ^2+. The photoelectric conversion element according to any one of claims 1 to 3, wherein the LX is an iodine atom. The photoelectric conversion element according to any one of claims 1 to 3, wherein the LX is -S(Rz1), -O(Rz1) or -N(Rz1) ₂ or the above formula (Z1- 1) a monodentate ligand represented by any one of formula (Z1-3), wherein Rz1 is an aryl group, a heterocyclic group or a decyl group, and Xz1 is an aryl group, and Zz1 and Zz2 are independently It is a nitrogen-containing heterocyclic group. The photoelectric conversion element according to any one of the items 1 to 3, wherein the LX is represented by any one of the following formulas (Z1-4) to (Z1-18). Wherein Xz2 represents O, S, N or NRz1, Xz3 represents N or CRz1, and Xz4~Xz7 independently represents O, S, NRz1 or C(Rz1) ₂ ; when Xz2 is N, nz1 represents 2, and in Xz2 O1 represents 1 in O, S and NRz1; Rz1 has the same meaning as Rz1 in the first item of the patent application, and Rz2 to Rz12 and Rz16 to Rz45 independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, An alkenyl group, an alkynyl group, a halogen atom, an aryl group, a heterocyclic group, an amine group, a cyano group or a nitro group, and Rz13 to Rz15 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. . The photoelectric conversion element according to any one of claims 1 to 3, wherein in the above formula (LA), Anc1 to Anc3 represent -CO ₂ H, -SO ₃ H, -PO ₃ H ₂ , -OH, -SH or such salts. The photoelectric conversion element according to any one of claims 1 to 3, wherein the ring A, the ring B and the ring C of the above formula (LA) are both pyridine rings. The photoelectric conversion element according to any one of the first aspect, wherein the formula (LA) is any one of the following formulas (AL-1) to (AL-4), In the formula, Anc1 to Anc3 each independently represent -CO ₂ H, -SO ₃ H, -PO ₃ H ₂ , -SH or the like; R ^AL represents a substituent other than Anc1 to Anc3, and b1 represents 0 to 4; An integer of X ^2a represents -O-, -S-, -NR'-, a saturated aliphatic group, an aromatic hydrocarbon ring group, a non-aromatic hydrocarbon ring group, an aromatic heterocyclic group, a non-aromatic heterocyclic group or linking group of a combination of those being formed; here, R 'represents a hydrogen atom or a substituent group; X ^1a represents a linking group, X ³ represents a single bond or a linking group; M4 represents 0 or 1. The photoelectric conversion element according to any one of claims 1 to 3, wherein the semiconductor fine particles further carry a co-adsorbent having one or more acidic groups. The photoelectric conversion element according to claim 10, wherein the co-adsorbent is represented by the following formula (CA), In the formula, R ^A1 represents a substituent having an acidic group; R ^A2 represents a substituent; and nA represents an integer of 0 or more. A dye-sensitized solar cell, comprising the photoelectric conversion element according to any one of claims 1 to 3. A metal complex pigment represented by the following formula (I), M(LD)(LA)(LX). (Y)n In the formula (I), M represents a metal ion; LD represents a bidentate ligand represented by the following formula (2L-1) or (2L-2); LA represents the following formula (LA) a tridentate ligand represented by the formula; LX represents a chlorine atom, a bromine atom, an iodine atom, or -S(Rz1), -O(Rz1), -N(Rz1) ₂ or the following formula (Z1-1)~ a monodentate ligand represented by any one of (Z1-3), Rz1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a decyl group, an alkyl sulfonyl group or an aromatic group. a sulfonyl group; Y represents a counter ion necessary for neutralizing the charge; n represents an integer of 0 to 4; Wherein ring A, ring B and ring C each independently represent a nitrogen-containing aromatic heterocyclic ring; here, the bond between Z ¹ and the N atom, and the bond between Z ² and the N atom may be a single bond. Is a double bond; Z ¹ and Z ² each independently represent a carbon atom or a nitrogen atom; Anc1 to Anc3 each independently represent an acidic group; and X ¹ , X ² and X ³ each independently represent a single bond or a linking group; l1 to l3 each independently represents an integer of 1 to 5; M1 and m3 each independently represents an integer of 0 to 4, m2 represents an integer of 0 to 3; wherein the sum of M1 ~ m3 is at least ^1; R 1 ~ R ³ are each independently Representing a substituent other than Anc1~Anc3; n1 and n3 each independently represent an integer of 0-4, and n2 represents an integer of 0~3; Wherein Xz1 represents -ORz1, -SRz1, -N(Rz1) ₂ or -Rz1, and Zz1 and Zz2 each independently represent a non-metal atomic group necessary for forming a 5-membered ring to a 7-membered ring; Wherein * represents a bonding position with the above metal ion M; ring D represents an aromatic ring; A ¹¹¹ represents a nitrogen anion or a carbon anion, A ¹²¹ represents a nitrogen anion, an oxyanion or a sulfur anion; and R ¹¹¹ - R ¹²⁴ represents a hydrogen; Atom or a substituent having no Anc1, Anc2, and Anc3. The metal complex dye according to claim 13, wherein the LX is an iodine atom. The metal complex dye according to claim 13, wherein the LX is represented by any one of the following formulas (Z1-4) to (Z1-18). Wherein Xz2 represents O, S, N or NRz1, Xz3 represents N or CRz1, Xz4~Xz7 represents O, S, NRz1 or C(Rz1) ₂ ; when Xz2 is N, nz1 represents 2, and Xz2 is O, S. And NRz1, nz1 represents 1; Rz1 has the same meaning as Rz1 as in the first item of the patent application, and Rz2 to Rz12 and Rz16 to Rz45 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkenyl group, An alkynyl group, a halogen atom, an aryl group, a heterocyclic group, an amine group, a cyano group or a nitro group, and Rz13 to Rz15 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. a pigment solution dissolved as in the 13th to 15th of the patent application scope The metal complex dye according to any one of the preceding claims. The dye solution according to Item 16 of the invention, which contains 0.001% by mass to 0.1% by mass of the metal complex dye in an organic solvent, and contains 0.1% by mass or less of water. The dye solution according to claim 16, wherein the dye solution further contains a co-adsorbent. The dye solution according to claim 18, wherein the co-adsorbent is represented by the following formula (CA), In the formula, R ^A1 represents a substituent having an acidic group; R ^A2 represents a substituent; and nA represents an integer of 0 or more. A dye-adsorbing electrode for a dye-sensitized solar cell, which is obtained by coating a composition obtained by the dye solution according to claim 16 on a conductive support, and curing the composition after coating A photoreceptor layer is formed. A method for producing a dye-sensitized solar cell, comprising the dye-adsorbing electrode, the electrolyte, and the counter electrode according to claim 20, and assembling the member using the above member. A metal complex represented by the following formula (III), M(LD)(LA')(LX). (Y)n In the formula (III), M represents a metal ion; LD represents a bidentate ligand coordinated to M with an anion and an isolated electron pair; LA' represents a formula represented by the following formula (LA') a tridentate ligand; LX represents a chlorine atom, a bromine atom, an iodine atom, or -S(Rz1), -O(Rz1), -N(Rz1) ₂ or the following formula (Z1-1)~(Z1- a monodentate ligand represented by any one of 3), Rz1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a decyl group, an alkylsulfonyl group or an arylsulfonyl group. Base; Y represents the counter ion necessary to neutralize the charge; n represents an integer from 0 to 4; Wherein ring A, ring B and ring C each independently represent a nitrogen-containing aromatic heterocyclic ring; here, the bond between Z ¹ and the N atom, and the bond between Z ² and the N atom may be a single bond. Is a double bond; Z ¹ and Z ² each independently represent a carbon atom or a nitrogen atom; and G represents an alkoxycarbonyl group, an aryloxycarbonyl group, a decyl group or a group which may have a substituent represented by any of the following structures X ¹⁰ , X ²⁰ and X ³⁰ each independently represent a single bond or a linking group; p1 and p3 each independently represent an integer of 0 to 4, and p2 represents an integer of 0 to 3; wherein the sum of p1 to p3 is 1 or more ; R ¹ to R ³ each independently represent a substituent; n1 and n3 each independently represent an integer of 0 to 4, and n2 represents an integer of 0 to 3; Wherein, R ^G each independently represent an alkyl group; and * denotes X ^10, X ²⁰ and X ³⁰ or the ring A, ring B or the bonding position of ring C; In the formula, Xz1 represents -ORz1, -SRz1, -N(Rz1) ₂ or -Rz1, and Zz1 and Zz2 each independently represent a group of non-metal atoms necessary for forming a 5-membered ring to a 7-membered ring.