TW201615653A - Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, and dye solution - Google Patents

Abstract

Provided are: a photoelectric conversion element provided with an electrically conductive support, an electrolyte-containing photosensitive layer, an electrolyte-containing charge-transfer layer, and a counter electrode, wherein said photosensitive layer is provided with semiconductor fine particles which support a metal complex dye represented by formula (I), namely M(LA)(LD)mD(LX)mX.(CI)mY; a dye-sensitized solar cell; the metal complex dye; and a dye solution. In formula (I): M represents a metal ion; LA represents a tridentate ligand represented by formula (AL-1); LD represents a bidentate ligand or a tridentate ligand different to LA; at least one of the ligand atoms of LD which are bonded to the metal ion (M) is nitrogen, and at least one of said ligand atoms is an anion; mD represents 0 or 1; LX represents a monodentate ligand; mX is 0, 1, or 3; CI represents a counter ion; and mY is an integer in the range of 0-3.

Description

Photoelectric conversion element, dye-sensitized solar cell, metal complex pigment, and pigment solution

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

The photoelectric conversion element is used in various photosensors such as photosensors, photocopiers, and solar cells. The photoelectric conversion element has been put into practical use in various forms such as a method using a metal, a method using a semiconductor, a method using an organic pigment or a coloring matter, or a combination of these methods. In particular, solar cells using non-exhaustive solar energy do not require fuel, and the use of endless clean energy is expected to be practical. Among them, the solar cells have been researched and developed since a long time ago, and countries have also made policy considerations to promote popularization. However, niobium is an inorganic material and naturally has limitations in terms of improvement in throughput and cost.

Therefore, research on a photoelectrochemical cell (also referred to as "dye-sensitized solar cell") using a metal complex dye is being carried out as much as possible. In particular, the research results of Graetzel and others at the University of Ecole Polytechnique Federale de Lausanne (EPFL) have become an opportunity. They use a structure in which a pigment containing a ruthenium complex is fixed on the surface of a porous titanium oxide film to achieve the same photoelectric conversion efficiency as that of amorphous ruthenium. Therefore, a dye-sensitized solar cell that can be manufactured without using an expensive vacuum device has attracted the attention of researchers all over the world.

After the report by Gretzer et al., the metal complex dye used in the dye-sensitized solar cell was developed as N3, N719, N749 (also known as "Black Dye"), Z907, J2 pigments, etc.

In addition to these pigments, development of a metal complex dye which can improve photoelectric conversion efficiency or durability of a photoelectric conversion element and a dye-sensitized solar cell is progressing. For example, Patent Document 1 describes a metal complex dye having a terpyridine ligand and three monodentate ligands, and the terpyridine ligand is composed of a ring on a metal ion with respect to a terminal pyridine ring. In the case of a nitrogen atom, a benzene ring group or a thiophene ring group is introduced at the 3-position. Further, it has been described that a photoelectrochemical cell using the metal complex dye achieves high photoelectric conversion efficiency and is excellent in durability. In Patent Document 2, a terpyridine ligand which can be used in a metal complex dye containing a donor ligand having a cyclic group substituted with a specific substituent is described as having a thiophene ring group bonded thereto. A terpyridine ligand having a substituent at the 3-position with respect to the ring on the metal ion of the terminal pyridine ring constituting the nitrogen atom. Further, it is also described that the photoelectrochemical cell using the metal complex dye described in Patent Document 2 can achieve both improvement in performance unevenness, improvement in photoelectric conversion efficiency, and durability. Patent Document 3 describes a metal complex dye having a terpyridine ligand and three monodentate ligands or a bipyridine ligand, and the terpyridine ligand is introduced into a terminal pyridine ring and At least one of the central pyridine rings is bonded to a plurality of thiophene ring groups. Further, it is also described that a photoelectrochemical cell using the metal complex dye has high photoelectric conversion efficiency and excellent durability. Patent Document 4 describes a tridentate ligand and a metal complex having the ligand and three isothiocyanate anions, and the coordination of the tridentate ligand with respect to the terminal pyridine ring In the case where the ring on the metal ion constitutes a nitrogen atom, a thiophene ring having a diarylaminophenyl group is bonded to the 3-position. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Publication No. 2012/0247561

[Problems to be solved by the invention]

However, in recent years, research and development of photoelectric conversion elements and dye-sensitized solar cells are prevailing, and performance is required to be further increased. Further improvement and improvement of photoelectric conversion efficiency and durability are particularly desired.

In the photoelectric conversion element and the dye-sensitized solar cell, a layer (also referred to as a "semiconductor layer") carrying a metal complex dye formed by semiconductor fine particles is usually formed into a layer having a thickness of from 10 μm to several hundreds μm. . In such a photoelectric conversion element and a dye-sensitized solar cell, thinning (small size) and weight reduction are also required. However, the photoelectric conversion efficiency fluctuates due to the film thickness of the semiconductor layer, and tends to decrease as the film thickness becomes thinner. Therefore, when the film thickness of the semiconductor layer is made thin, it is also desired to exhibit excellent photoelectric conversion efficiency.

An object of the present invention is to provide a photoelectric conversion element and a dye-sensitized solar cell which exhibit excellent photoelectric conversion efficiency and high durability even when the thickness of the semiconductor layer is small, and the film is thick. Metal complex dyes and pigment solutions used in these. [Means for solving the problem]

The present inventors have found that when the following ligands are used in combination as the metal complex dye used in the photoelectric conversion element and the dye-sensitized solar cell, the photoelectric conversion efficiency and durability can be further improved, and further, Even if the semiconductor layer is a thin film, high photoelectric conversion efficiency can be achieved: a 3-dentate ligand having a nitrogen-containing aromatic ring at the end, wherein a specific ring group substituted with an aromatic ring group is bonded to a coordinating atom The ring at the 4 position constitutes an atom; a 2 or 3 tooth ligand located on the metal ion by at least one nitrogen atom and an anion of at least one atom. Further, the inventors of the present invention have found that excellent photoelectric conversion efficiency and high durability can be achieved in the same manner even if a metal complex dye in which a single tooth ligand is coordinated in place of the two or three tooth ligands is obtained. Sex. The present invention has been completed based on these findings.

That is, the problem of the present invention can be achieved by the following means. <1> A photoelectric conversion element comprising a conductive support, a photoreceptor layer containing an electrolyte, a charge transfer body layer containing an electrolyte, and a counter electrode, wherein the photoreceptor layer is supported by the following formula (I) Semiconductor microparticles of metal complex pigment:

Formula (I) M(LA)(LD) _mD (LX) _mX ·(CI) _mY

Wherein M represents a metal ion; LA represents a tridentate ligand represented by the following formula (AL-1); LD represents a bidentate ligand or a tridentate ligand different from LA; LD and metal ion At least one of the M-bonded coordinating atoms is a nitrogen atom, at least one is an anion; mD represents 0 or 1; LX represents a monodentate ligand; mX represents 1 when mD is 1 and LD is a 2-dental ligand When mD is 1 and LD is a 3-dental ligand, it represents 0, and when mD is 0, it represents 3; CI represents a counter ion required to neutralize the charge of the metal complex dye; mY represents an integer of 0-3. ;

[Chemical 1]

Wherein Za and Zb each independently represent a group of non-metal atoms required to form a ring of 5 or 6 members; wherein at least one of the rings formed by Za and Zb respectively has an acidic group; L ^{W is} independently represented a nitrogen atom or CR ^W , R ^W represents a hydrogen atom or a substituent; L ¹ represents a cyclic group represented by the following formula (X-1) or formula (X-2); and L ² represents a vinyl group, an ethynyl group or An aromatic ring group; n represents an integer of 1 to 4; Z represents a hydrogen atom or a substituent; -L ¹ -[L ² ]nZ group does not have an acidic group and an amine group;

[Chemical 2]

In the formula (X-1), E ¹ represents -O-, ^-Se- , -NR ^X2c -, -C(R ^X2c ) ₂ -, -(R ^X2c )C=C(R ^X2c )- or -Si( R ^X2c ) ₂ -; R ^X2c represents a hydrogen atom or a substituent; R ^T1 represents a substituent; PT1 represents an integer of 0 to 2; and in the formula (X-2), E ² represents -O-, -S- or -NR ^X2c -; E ³ and E ⁴ each independently represent -N= or -C(R ^X2c )=, at least one of E ³ and E ⁴ is -N=; R ^X2c represents a hydrogen atom or a substituent; 1) In the formula (X-2), * represents a bonding position with a ring having L ^W or L ² .

<2> The photoelectric conversion element according to <1>, wherein L ¹ is a ring group represented by the formula (X-1). (3) The photoelectric conversion element according to the above formula (X-1), wherein the ring group represented by the formula (X-1) is an arbitrary formula of the following formula (X-1a) to formula (X-1c) The ring base represented:

[Chemical 3]

Wherein, E E ¹ of the formula (X-1) ¹ synonymous; R ^T1a ~ R ^T1c each independently represent a hydrogen atom or a substituent; ** represents the bonding position of the ring having L or ^{W is} L ^2.

<4><1> to <3> The photoelectric conversion element according to any preceding claim, wherein, L ² is an aromatic ring group. The photoelectric conversion element according to any one of <1> to <4> wherein n is 1 or 2.

The photoelectric conversion element according to any one of <1>, wherein the ring formed by Za is selected from the group consisting of a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, and a triazine ring. Teazine ring, quinoline ring, isoquinoline ring, imidazole ring, pyrazole ring, triazole ring, thiazole ring, oxazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring and benzo At least one of the group consisting of thiazole rings, the ring formed by Zb is selected from the group consisting of a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, a tetrazine ring, a quinoline ring, and an isoquinoline ring. At least one of the group consisting of an imidazole ring, a triazole ring, a thiazole ring, an oxazole ring, a benzimidazole ring, a benzotriazole ring, a benzoxazole ring, and a benzothiazole ring, including L ^W The ring is at least one selected from the group consisting of a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a tetrazine ring, a quinoline ring, and an isoquinoline ring. <7> The <1> to <6> The photoelectric conversion element according to any preceding claim, wherein, M is Ru ^{2 +} or Os ^{2 +.} The photoelectric conversion element according to any one of the aspects of the present invention, wherein LA is a 3-dental ligand represented by the following formula (AL-2):

[Chemical 4]

In the formula, Anc represents an acidic group; L ¹ , L ² , Z and n are synonymous with L ¹ , L ² , Z and n of the formula (AL-1).

The photoelectric conversion element according to any one of <1>, wherein the acidic group is a carboxyl group or a salt thereof. The photoelectric conversion element according to any one of the following formulas (2L-1) to (2L-4), wherein the LD is a two-dimensional formula represented by any one of the following formulas (2L-1) to (2L-4). Bit body:

[Chemical 5]

In the formula, ring D ^2L represents an aromatic ring; A ¹¹¹ to A ¹⁴¹ each independently represent an anion of a nitrogen atom or an anion of a carbon atom; and R ¹¹¹ to R ¹⁴³ each independently represent a hydrogen atom or a substituent having no acidic group; Base; * indicates the coordination position on the metal ion M.

The photoelectric conversion element according to any one of the above formulas (3L-1) to (3L-4), wherein the LD is a three-dimensional configuration represented by any one of the following formulas (3L-1) to (3L-4). Bit body:

[Chemical 6]

Wherein ring D ^2L represents an aromatic ring; A ²¹¹ to A ²⁴² each independently represent a nitrogen atom or a carbon atom; wherein, A ²¹¹ and A ²¹² , A ²²¹ and A ²²² , A ²³¹ and A ²³² , A ²⁴¹ At least one of each of A ²⁴² is an anion; R ²¹¹ to R ²⁴¹ each independently represent a hydrogen atom or a substituent having no acidic group; * represents a coordination position on the metal ion M.

The photoelectric conversion element according to any one of the above aspects, wherein the metal complex dye represented by the formula (I) is represented by the following formula (I-1) or (I- 2) indicates:

[Chemistry 7]

Wherein M and LX are synonymous with M and LX of formula (I); Anc, L ¹ , L ² , Z and n are synonymous with the acidic group of formula (AL-1), L ¹ , L ² , Z and n; Ring D and Ring E each independently represent an aromatic ring of 5 or 6 members; D ¹ and D ² each independently represent an anion of a carbon atom or an anion of a nitrogen atom; here, D ¹ in Ring D and Ring E And a bond between D ² and a carbon atom bonded to the pyridine ring is a single bond or a double bond; R ^a1 to R ^a4 each independently represent a substituent; and ma1, ma2 and ma4 each independently represent 0 to 3; An integer; ma3 represents an integer from 0 to 4.

<13> The photoelectric conversion element according to <12>, wherein each of the ring D and the ring E is independently a pyrazole ring, a triazole ring or a benzene ring. <14> A dye-sensitized solar cell, comprising the photoelectric conversion element according to any one of <1> to <13> above. <15> A metal complex dye which is represented by the following formula (I):

Formula (I) M(LA)(LD) _mD (LX) _mX ·(CI) _mY

In the formula, M represents a metal ion; LA represents a 3-dentate ligand represented by the following formula (AL-1); LD represents a 2-dentate ligand or a 3-dental ligand different from the LA; At least one of the coordination atoms of the metal ion M bond is a nitrogen atom, at least one is an anion; mD represents 0 or 1; LX represents a monodentate ligand; mX is when mD is 1 and LD is a 2 tooth ligand Indicates that 1 represents 0 when mD is 1 and LD is a 3-dental ligand, and 3 when mD is 0; CI represents a counter ion required to neutralize the charge of the metal complex dye; mY represents 0 to 3 Integer

[化8]

Wherein Za and Zb each independently represent a group of non-metal atoms required to form a ring of 5 or 6 members; wherein at least one of the rings formed by Za and Zb respectively has an acidic group; L ^{W is} independently represented a nitrogen atom or CR ^W , R ^W represents a hydrogen atom or a substituent; L ¹ represents a cyclic group represented by the following formula (X-1) or formula (X-2); and L ² represents a vinyl group, an ethynyl group or An aromatic ring group; n represents an integer of 1 to 4; Z represents a hydrogen atom or a substituent; -L ¹ -[L ² ]nZ group does not have the acidic group and the amine group;

[Chemistry 9]

In the formula (X-1), E ¹ represents -O-, ^-Se- , -NR ^X2c -, -C(R ^X2c ) ₂ -, -(R ^X2c )C=C(R ^X2c )- or -Si( R ^X2c ) ₂ -; R ^X2c represents a hydrogen atom or a substituent; R ^T1 represents a substituent; PT1 represents an integer of 0 to 2; and in the formula (X-2), E ² represents -O-, -S- or -NR ^X2c -; E ³ and E ⁴ each independently represent -N= or -C(R ^X2c )=, at least one of E ³ and E ⁴ is -N=; R ^X2c represents a hydrogen atom or a substituent; 1) In the formula (X-2), * represents a bonding position with a ring having L ^W or L ² .

<16> A dye solution containing the metal complex dye according to <15> above and a solvent.

In the present specification, unless otherwise specified, the double bond may be any of the E-type and the Z-type in the molecule, and may be a mixture of these. When a plurality of substituents, a linking group, a ligand, and the like (hereinafter referred to as "substituent or the like") represented by a specific symbol are present, or when a plurality of substituents are specified at the same time, unless otherwise specified, each The substituents and the like may be the same or different from each other. The same applies to the regulation of the number of substituents and the like. Further, when a plurality of substituents or the like are brought close to each other (particularly in the case of adjacent), the substituents may be bonded to each other to form a ring unless otherwise specified.

In the present invention, the ring represents the following ring unless otherwise specified. The same applies to the ring group. In the present invention, the ring is not particularly limited, and a 4-membered ring to an 8-membered ring is preferable, and a 5-membered ring or a 6-membered ring is more preferable. Moreover, the ring may also be a condensed ring. That is, the ring contains a single ring and a plurality of ring-condensed rings (condensed rings). The number of rings forming the polycyclic ring (the number of condensed rings) is not particularly limited, and for example, it is preferably a total of 2 rings to 5 rings.

Further, in the present invention, the ring contains an aromatic ring and an aliphatic ring. The aromatic ring contains an aromatic hydrocarbon ring and an aromatic hetero ring. The aromatic hydrocarbon ring means a hydrocarbon ring which exhibits aromaticity. The monocyclic aromatic hydrocarbon ring is exemplified by a benzene ring, and the polycyclic aromatic hydrocarbon ring (also referred to as a "condensed polycyclic aromatic hydrocarbon ring") may, for example, be a naphthalene ring or an anthracene ring. The aromatic heterocyclic ring refers to a heterocyclic ring which exhibits aromaticity, and includes a monocyclic aromatic hetero ring and a polycyclic aromatic hetero ring (also referred to as "condensed polycyclic aromatic hetero ring"). The aromatic hydrocarbon ring group also means an aryl group or an aryl group according to the valence number, and the aromatic heterocyclic group means a heteroaryl group or a heteroaryl group. The aliphatic ring means a ring other than the aromatic ring, and includes an aliphatic hydrocarbon ring and an aliphatic heterocyclic ring. Examples of the aliphatic hydrocarbon ring include a saturated hydrocarbon ring and an unsaturated hydrocarbon ring which does not exhibit aromaticity. For example, a monocyclic saturated hydrocarbon ring (cycloalkane), a polycyclic saturated hydrocarbon ring, a monocyclic unsaturated hydrocarbon ring (cycloalkene, cycloalkyne), and a polycyclic unsaturated hydrocarbon ring may, for example, be mentioned. Further, the aromatic heterocyclic ring and the aliphatic heterocyclic ring may be collectively referred to as a "heterocyclic ring". The heterocyclic ring refers to a ring in which a carbon atom and a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, a ruthenium atom, a selenium atom or a phosphorus atom) form a ring.

In the present specification, the expression of the compound (including the complex compound and the coloring matter) is used for the meaning of the salt and the ion thereof in addition to the compound itself. Further, it is indicated that a part of the structure is changed within a range that does not impair the target effect. Further, the compound which is not substituted or unsubstituted is not specifically described, and includes a compound having an arbitrary substituent within a range not detracting from the intended effect. Such a substituent is preferably a substituent which is appropriately selected from the group of substituents described later. The same applies to the substituent, the linking group and the ligand.

In addition, in this specification, the numerical range shown using "-" shows the range which contains the numerical value of the [---- [Effects of the Invention]

The photoelectric conversion element and the dye-sensitized solar cell of the present invention comprise a metal complex dye in which a ligand having a nitrogen-containing aromatic ring at the end, wherein an aromatic ring group is used, in combination An aromatic heterocyclic group or an aromatic hydrocarbon ring group represented by the above formula (X-1) or (X-2), which is substituted with a coordinating atom of a central metal, is bonded to a ring at the 4-position. And a 2- or 3-dentate ligand or three monodentate ligands on the metal ion by at least one nitrogen atom and an anion of at least one atom. Thereby, even if the film thickness of the semiconductor layer is made thin, excellent photoelectric conversion efficiency and high durability can be exhibited. Therefore, according to the present invention, it is possible to provide a photoelectric conversion element and a dye-sensitized solar cell which exhibit excellent photoelectric conversion efficiency and high durability even when the film thickness is reduced, and the film thickness of the semiconductor layer is small. Metal complex dyes and pigment solutions used in these. The above and other features and advantages of the present invention will become more apparent from the appended claims appended claims.

[Photoelectric Conversion Element and Pigment Sensitized Solar Cell] The photoelectric conversion element of the present invention has a conductive support, a photoreceptor layer containing an electrolyte, a charge transport layer containing an electrolyte, and a counter electrode (counter electrode). A photoreceptor layer, a charge transport layer, and a counter electrode are sequentially provided on the conductive support.

In the photoelectric conversion element of the present invention, at least one portion of the semiconductor fine particles forming the photoreceptor layer carries a metal complex dye represented by the formula (I) to be described later as a sensitizing dye. Here, the embodiment in which the metal complex dye is carried on the surface of the semiconductor fine particles includes an embodiment adsorbed on the surface of the semiconductor fine particles, an embodiment deposited on the surface of the semiconductor fine particles, and an embodiment in which the embodiments are mixed. Adsorption includes chemisorption and physical adsorption, preferably chemisorption. The semiconductor fine particles may also carry other metal complex dyes together with the metal complex dye of the formula (I) to be described later. It is preferable that the semiconductor fine particles carry the metal complex dye and a co-adsorbent described later.

Moreover, the photoreceptor layer contains an electrolyte. The electrolyte contained in the photoreceptor layer may be of the same kind as the electrolyte contained in the charge transport layer, or may be of a different species, preferably the same species. Here, the term "electrolyte is the same species" means an embodiment in which the components contained in the electrolyte of the photoreceptor layer are the same as those contained in the electrolyte of the charge transport layer, and the content of each component is also the same. And an embodiment in which the components contained in the electrolyte of the photoreceptor layer are the same as those contained in the electrolyte of the charge transport layer, but the content of each component is different.

The photoelectric conversion element of the present invention is not particularly limited to a configuration other than the configuration defined in the present invention, and a known configuration related to the photoelectric conversion element can be employed. The respective layers constituting the photoelectric conversion element of the present invention may be designed according to the purpose, and may be formed, for example, as a single layer or as a plurality of layers. Further, layers other than the respective layers may be included as needed.

The dye-sensitized solar cell of the present invention is obtained by using the photoelectric conversion element of the present invention. Hereinafter, preferred embodiments of the photoelectric conversion element and the dye-sensitized solar cell of the present invention will be described.

The system 100 shown in FIG. 1 is a system in which the photoelectric conversion element 10 according to the first embodiment of the present invention is applied to a battery application in which an operation unit M (for example, an electric motor) is operated by an external circuit 6. The photoelectric conversion element 10 includes a conductive support 1 including a photoreceptor layer 2 of a semiconductor fine particle 22 sensitized by a dye (metal complex dye) 21 and an electrolyte between the semiconductor fine particles 22 as a hole The charge transfer body layer 3 of the transport layer is opposite to the electrode 4. In the photoelectric conversion element 10, the light-receiving electrode 5 includes the conductive support 1 and the photoreceptor layer 2, and functions as a working electrode.

In the system 100 to which the photoelectric conversion element 10 is applied, the light incident on the photoreceptor layer 2 excites the metal complex dye 21. The excited metal complex dye 21 has electrons having high energy, and the electrons are transferred from the metal complex dye 21 to the conduction band of the semiconductor fine particles 22, and further diffused to reach the conductive support 1. At this time, the metal complex dye 21 becomes an oxidant (cation). The electrons reaching the conductive support 1 are operated by the external circuit 6, and reach the oxidized body of the metal complex dye 21 via the counter electrode 4 and the charge transfer body layer 3, thereby reducing the oxidized body, thereby causing the system 100 to be cooled. It functions as a solar battery.

The dye-sensitized solar cell 20 shown in Fig. 2 includes the photoelectric conversion element according to the second embodiment of the present invention. The photoelectric conversion element to be the dye-sensitized solar cell 20 differs from the photoelectric conversion element shown in FIG. 1 in the configuration of the conductive support 41 and the photoreceptor layer 42 and the spacer S, except for the above. Other than this, it is configured similarly to the photoelectric conversion element 10 shown in FIG. That is, the conductive support 41 has a two-layer structure including the substrate 44 and the transparent conductive film 43 formed on the surface of the substrate 44. Further, the photoreceptor layer 42 has a two-layer structure including a semiconductor layer 45 and a light scattering layer 46 formed adjacent to the semiconductor layer 45. A spacer S is provided between the conductive support 41 and the opposite electrode 48. In the dye-sensitized solar cell 20, 40 is a light receiving electrode, and 47 is a charge transporting body layer.

In the same manner as the system 100 to which the photoelectric conversion element 10 is applied, the dye-sensitized solar cell 20 functions as a solar cell by causing light to enter the photoreceptor layer 42.

The photoelectric conversion element and the dye-sensitized solar cell of the present invention are not limited to the above-described preferred embodiments, and the configuration and the like of the respective embodiments may be appropriately combined between the embodiments without departing from the scope of the invention. .

In the present invention, materials and members used in the photoelectric conversion element or the dye-sensitized solar cell can be produced by a usual method. For example, U.S. Patent No. 4,927,721, U.S. Patent No. 4,684,537, U.S. Patent No. 5,084,365, U.S. Patent No. 5,084,365, U.S. Patent No. 5,350,644, U.S. Patent No. 5,463,057, U.S. Patent No. 5,525,440, Japanese Patent Laid-Open No. -249790, Japanese Patent Laid-Open No. 2001-185244, Japanese Patent Laid-Open No. 2001-210390, Japanese Patent Laid-Open No. 2003-217688, Japanese Patent Laid-Open No. 2004-220974, and Japanese Patent Publication No. 2008 -135197.

<Metal complex dye represented by the formula (I)> The metal complex dye of the present invention is represented by the following formula (I). The metal complex dye of the present invention has the ligand LA represented by the following formula (AL-1), whereby the photoelectric conversion element and the dye-sensitized solar cell can be imparted with a small influence on the change in the thickness of the semiconductor layer. Photoelectric conversion efficiency, excellent thermal stability. Therefore, the metal complex dye of the present invention can be preferably used as a sensitizing dye in a dye-sensitized solar cell.

Formula (I) M(LA)(LD) _mD (LX) _mX ·(CI) _mY

In the formula (I), M represents a metal ion. LA represents a 3-dentate ligand represented by the following formula (AL-1).

[化10]

Wherein Za and Zb each independently represent a group of non-metal atoms required to form a ring of 5 or 6 members. Among them, at least one of the rings formed by Za and Zb respectively has an acidic group. L ^W each independently represents a nitrogen atom or CR ^W , and R ^W represents a hydrogen atom or a substituent. L ¹ represents a cyclic group represented by the following formula (X-1) or formula (X-2). L ² represents a vinyl group, an ethynyl group or an aromatic ring group. n represents an integer of 1 to 4. Z represents a hydrogen atom or a substituent. Among them, the -L ¹ -(L ² )nZ group does not have an acidic group and an amine group.

[11]

In the formula (X-1), E ¹ represents -O-, ^-Se- , -NR ^X2c -, -C(R ^X2c ) ₂ -, -(R ^X2c )C=C(R ^X2c )- or -Si( R ^X2c ) ₂ -. R ^X2c each independently represents a hydrogen atom or a substituent. R ^T1 represents a substituent. PT1 represents an integer of 0 to 2. In the formula (X-2), E ² represents -O-, -S- or -NR ^X2c -. E ³ and E ⁴ each independently represent -N= or -C(R ^X2c )=, and at least one of E ³ and E ⁴ is -N=. R ^X2c represents a hydrogen atom or a substituent. In the formula (X-1) and the formula (X-2), * represents a bonding position with a ring having L ^W or L ² .

LD represents a 2-dental ligand or a 3-dental ligand different from LA. At least one of the coordinating atoms of the LD bonded to the metal ion M is a nitrogen atom, and at least one is an anion. mD represents 0 or 1, preferably 1. LX represents a single tooth ligand. mX represents 1 when mD is 1 and LD is a 2-dental ligand, 0 when mD is 1 and LD is a 3-dental ligand, and 3 when mD is 0.

CI represents the counter ion required to neutralize the charge of the metal complex pigment. mY represents an integer of 0 to 3, preferably 0 or 1, more preferably 0.

- The metal ion M - M is a central metal of the metal complex dye, and examples include ions of each of the elements of Groups 6 to 12 of the long period table. Examples of such a metal ion include ions of Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn, and Zn. The metal ion M may be one type of ion or two or more types of ions. In the present invention, the metal ion M is preferably Os ^{2 +} , Ru ^{2 +} or Fe ^{2 +} , more preferably Os ^{2 +} or Ru ^{2 +} , and particularly preferably Ru ^{2 +} . In the state of being incorporated into the photoelectric conversion element, there is a phenomenon in which the valence of M changes due to the redox reaction with the surrounding material.

- Ligand LA - Ligand LA is a 3-dentate ligand or compound represented by formula (AL-1) and coordinated to metal ion M by three nitrogen atoms in formula (AL-1) . The ligand LA has an acidic group (also referred to as an "adsorption group") on at least one of the ring formed by Za and the ring formed by Zb. The ligand LA has a function of supporting the metal complex dye of the present invention on the semiconductor fine particles due to the acidic group.

The ligand LA is 4-position in terms of a nitrogen atom constituting a ring on the metal ion M with respect to a ring formed of a nitrogen atom, a carbon atom, and L ^W (also referred to as a "ring containing L ^W "). The ring constitutes a "-L ¹ -[L ² ]nZ" group on a carbon atom. In the ligand LA, if a "-L ¹ -[L ² ]nZ" group is bonded to a carbon atom at the 4-position ring of the ring containing L ^W , the metal having the ligand LA is misaligned. The absorbance of the pigmentation becomes large. As a result, the photoelectric conversion efficiency of the photoelectric conversion element and the dye-sensitized solar cell including the metal complex dye having an increased absorbance in the photoreceptor layer is improved. Further, even if the thickness of the semiconductor layer on which the photoreceptor layer is provided is reduced, excellent photoelectric conversion efficiency can be exhibited. In addition, the durability of the photoelectric conversion element and the dye-sensitized solar cell is also improved. Therefore, the ligand LA can be preferably used as a ligand of the metal complex dye used in the dye-sensitized solar cell.

In the formula (AL-1), Za and Zb each independently represent a group of non-metal atoms required to form a 5-membered ring or a 6-membered ring. Za and Zb are preferably a group of non-metal atoms selected from a carbon atom and the hetero atom, more preferably a group of non-metal atoms selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. The ring formed by Za and Zb is preferably a 5-membered aromatic heterocyclic ring and a 6-membered aromatic heterocyclic ring. The rings include, in addition to the single ring, a condensed ring having at least one of an aromatic ring and an aliphatic ring condensed on the single ring.

The aromatic heterocyclic ring of the 5-membered ring may be a 5-membered ring containing the hetero atom as a ring-constituting atom. For example, at least one of a pyrazole ring, an imidazole ring, a triazole ring, a thiazole ring, an oxazole ring, a benzimidazole ring, a benzotriazole ring, a benzoxazole ring, and a benzothiazole ring is preferred. The aromatic heterocyclic ring of the 6-membered ring may be a 6-membered ring containing the hetero atom as a ring-constituting atom. For example, at least one of a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, a tetrazine ring, a quinoline ring, and an isoquinoline ring is preferred.

The ring formed by Za and Zb is at least one selected from the group consisting of a group of the aromatic heterocyclic ring of the 5-membered ring and a group of the aromatic heterocyclic ring of the 6-membered ring, respectively. An aromatic heterocyclic ring suitable for the structure of each ring shown in the formula (AL-1) is selected. The ring formed by Za is preferably selected from the group consisting of a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, a tetrazine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, a pyrazole ring, and three. At least one of the group consisting of an azole ring, a thiazole ring, an oxazole ring, a benzimidazole ring, a benzotriazole ring, a benzoxazole ring, and a benzothiazole ring. The ring formed by Zb is preferably selected from the group consisting of a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, a tetrazine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, a triazole ring, and a thiazole. At least one of the group consisting of a ring, an oxazole ring, a benzimidazole ring, a benzotriazole ring, a benzoxazole ring, and a benzothiazole ring. Among them, the ring formed by Za and Zb is more preferably an imidazole ring, a pyridine ring or a pyrimidine ring, and particularly preferably a pyridine ring.

At least one of the rings formed by Za and Zb has an acidic group. Preferably, the rings each have at least one acidic group. The heterocyclic ring formed by Za and Zb each preferably has 1 to 3 acid groups, more preferably 1 or 2, and still more preferably one. More preferably, the rings each have an acidic group. The substitution position of the acidic group is not particularly limited. In each ring, it is preferred that the ring which is the farthest from the nitrogen atom coordinated to the metal ion M constitutes an atom, and in the case where the ring is a 6-membered ring, it is preferably 4 positions with respect to the nitrogen atom. .

In the present invention, the "acid group" is a substituent having a dissociative proton and is a substituent having a pKa of 11 or less. The pKa of the acidic group can be determined by the method of "SMD/M05-2X/6-31G ^* " described in J. Phys. Chem. A 2011, 115, pages 6641 to 6645. Examples of the acidic group include an acid group which exhibits acidity such as a carboxyl group, a phosphonium group, a phosphoric acid group, a sulfo group or a boronic acid group, or a group having such an acid group. The group having an acid group may be a group having an acid group and a linking group. The linking group is not particularly limited, and examples thereof include a divalent group, and preferred examples thereof include an alkyl group, an alkenyl group, an alkynylene group, an extended aryl group, and a heteroaryl group. The linking group may have a substituent selected from the group of substituents Z ^R described later as a substituent. The acidic group having an acid group and a linking group is preferably, for example, a carboxymethyl group, a carboxyl group-extended vinyl group, a dicarboxy-vinyl group, a cyanocarboxy group-extended vinyl group, a 2-carboxy-1-propenyl group, or a 2-carboxy group. 1-butenyl group, carboxyphenyl group, and the like. The acidic group is preferably a carboxyl group, a phosphonium group, a sulfo group or a group having a carboxyl group, more preferably a carboxyl group.

When the acidic group is incorporated into the metal complex dye represented by the formula (I), protons may be released to form dissociated anions, or may be salts. The counter ion in the case where the acidic group is a salt is not particularly limited, and examples thereof include examples of positive ions in the counter ion CI described below. Further, the acidic group may be esterified as described later.

The ring formed by Za and the ring formed by Zb may each have a substituent other than an acidic group. The substituent which the ring may have may be a substituent selected from the substituent group Z ^R described later. Further, a ring formed of Za and Zb may form a condensed ring bonded to each other via the substituent. Examples of such a condensed ring include a 1,10-phenanthroline ring.

Ring in the formula (AL-1), the comprising L ^W include monocyclic and condensed ring, the condensed ring in the case, also including the condensed ring formed by Zb.

L ^W represents a nitrogen atom or CR ^W . R ^W represents a hydrogen atom or a substituent, preferably a hydrogen atom. The substituent which can be used as R ^W is not particularly limited, and examples thereof include a group selected from the substituent group Z ^R described later (preferably, -L ¹ -[L ² ]nZ). In the case where the ring containing L ^W has a plurality of R ^W , R ^W may also be bonded to each other to form a ring. The ring containing L ^W may be preferably selected from the group of aromatic rings of a 6-membered ring described as a ring formed of Za and Zb, which is suitable for the ring structure in the formula (AL-1). Heterocyclic. More preferably, it is at least one of a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a tetrazine ring, a quinoline ring, and an isoquinoline ring, and more preferably a pyridine ring or a pyrimidine ring, and particularly preferably a pyridine. ring.

In the ligand LA, L ¹ is a cyclic group represented by the following formula (X-1) or formula (X-2). The ring groups are preferably aromatic ring groups. In the formula (X-1) and the formula (X-2), a single ring is shown for convenience. Here, as described above, the ring groups represented by the respective formulas each include a polycyclic ring having a single ring as a condensed ring. The respective ring groups represented by the formulae (X-1a) to (X-1c) which will be described later are also the same.

The ring group (monocyclic ring) represented by the following formula (X-1) and formula (X-2) will be described.

[化12]

In the formula (X-1), E ¹ represents -O-, ^-Se- , -NR ^X2c -, -C(R ^X2c ) ₂ -, -(R ^X2c )C=C(R ^X2c )- or -Si (R ^X2c ) ₂ -. In terms of photoelectric conversion efficiency and durability, E ^{1 is} preferably -O-, -NR ^X2c -, -C(R ^X2c ) ₂ - or -Si(R ^X2c ) ₂ -, more preferably - O- or -NR ^X2c -, especially -O-. In terms of cost and productivity, -(R ^X2c )C=C(R ^X2c )- is also preferred.

Here, R ^X2c represents a hydrogen atom or a substituent. In the case where E ¹ has a plurality of R ^X2c , the plurality of R ^X2c may be the same or different. The substituent which can be used for R ^X2c is not particularly limited, and examples thereof include a group selected from the substituent group Z ^S described later. Preferred are alkyl, alkenyl, alkynyl, alkoxy, alkylthio, arylthio, cycloalkyl, aryl, alkenyloxy, alkynyloxy, aryloxy, cyano or halogen atoms.

R ^T1 represents a substituent. The substituent is not particularly limited, and examples thereof include a group selected from the substituent group Z ^S described later. Preferred substituents are the same as R ^X2c . More preferred is an alkyl group, an alkoxy group, an alkylthio group, an arylthio group or an aryloxy group, and still more preferably an alkyl group, an alkoxy group or an alkylthio group. In the case of having a plurality of R ^T1 , the adjacent R ^T1 may be bonded to each other to form an aliphatic ring together with the ring constituting atom of L ¹ . The group which can form such an aliphatic ring is preferably an alkylenedioxy group (-OR ^ve -O- group) to which two alkoxy groups are bonded. Here, R ^ve represents an alkylene group, and examples thereof include an ethyl group and a propyl group.

The substituent of L ¹ may be a substituent corresponding to -[L ² ]nZ described below as described above.

When the ring group represented by the formula (X-1) has R ^T1 , the substitution position is not particularly limited. The R ^T1 number PT1 is an integer of 0 to 2, preferably 0 or 1.

The bonding position of the ring group represented by the formula (X-1) is not particularly limited, and any ring may constitute a carbon atom. Preferably, the at least one bonding position is 2 bits with respect to E ¹ .

The ring group represented by the formula (X-1) is preferably a ring group represented by any one of the following formulae (X-1a) to (X-1c).

[Chemistry 13]

In each formula, E ^{1 is} synonymous with E ¹ of the above formula (X-1), and preferably the same. R ^T1a to R ^T1c each represent a hydrogen atom or a substituent. R ^T1a to R ^T1c are all synonymous with R ^{T1 of the} formula (X-1), and preferably the same. R ^T1a and R ^T1b , and R ^T1b and R ^T1c may be bonded to each other to form an aliphatic ring. In the ring group represented by the formula (X-1a) to the formula (X-1c), ** represents a bonding position with a ring having L ^W or L ² . Any of the two bonding positions can be bonded to the ring containing L ^W . The bonding position of 2 bits with respect to E ¹ is preferably bonded to the ring containing L ^W .

In the formula (X-2), E ² represents -O-, -S- or -NR ^X2c -. Preferred is -S- or -O-, more preferably -S-. E ³ and E ⁴ represent -N= or -C(R ^X2c )=, respectively, and at least one of E ³ and E ⁴ is -N=. The ring group represented by the formula (X-2) is not particularly limited as long as it is a ring group in which the above E ² , E ³ and E ^{4 are} appropriately combined. For example, an oxazole ring, an oxadiazole ring, a thiazole ring, a thiadiazole ring, an imidazole ring or a triazole ring can be mentioned. Among them, preferred are an oxazole ring, a thiazole ring, and an imidazole ring.

R ^X2c represents a hydrogen atom or a substituent. The R ^X2c is synonymous with R ^X2c formula (X-1), desirable Zheyi same.

The bonding position of the ring group represented by the formula (X-2) is not particularly limited, and any ring may constitute a carbon atom. Preferably, at least one of the bonding positions is 2 bits with respect to E ² . More preferably, the ring in which E ² and E ^{3 are} bonded constitutes a carbon atom bonded to a ring containing L ^W .

In the ring group represented by the above formula, the ring group represented by the formula (X-1) is more preferable in terms of photoelectric conversion efficiency, and more preferably, it is represented by the formula (X-1a). Ring base.

Next, the ring group including the ring group represented by the above formula as a polycyclic ring of a condensed ring will be described. Examples of the polycyclic ring group include a ring group in which a ring group (monocyclic ring) represented by each formula is condensed, and a ring group in which the single ring is condensed with another different ring. The other different ring is not particularly limited as long as it is a ring different from the single ring, and examples thereof include a thiophene ring and a phospholene ring. Among them, preferred is a polycyclic ring group containing a preferred ring group represented by the formula (X-1) or the formula (X-1a) as a condensed ring.

The polycyclic ring group is preferably an aromatic ring group. For example, a cyclic group containing a cyclic group represented by the above formula as a condensed ring in a condensed polycyclic aromatic hydrocarbon ring or a condensed polycyclic aromatic hetero ring may be mentioned. The total number of rings forming the polycyclic ring group is not particularly limited, and for example, it is preferably 2 to 5 rings.

Examples of the condensed polycyclic aromatic hydrocarbon ring group include a naphthalene ring, an anthracene ring, a phenanthrene ring, and a linked triphenyl ring. Rings, anthracene rings, anthracene rings, anthracene rings, and anthracene rings. Among them, preferred are a naphthalene ring, an anthracene ring, a phenanthrene ring, a linked triphenyl ring, and an anthracene ring.

Examples of the condensed polycyclic aromatic heterocyclic group include a benzofuran ring, an isobenzofuran ring, a benzothiophene ring, a benzisothiophene ring, an indazole ring, an anthracene ring, an isoindole ring, and a pyridazine ring. , oxazole ring, quinoline ring, isoquinoline ring, benzoxazole ring, benzoisoxazole ring, benzothiazole ring, benzisothiazole ring, benzimidazole ring, dibenzofuran ring, two a benzothiophene ring, a thienopyridine ring, an anthracene ring (dibenzofluorenyl ring), a thieno[3,2-b]thiophene ring, a thieno[3,4-b]thiophene ring, Trithiophene ring, cyclopentadithiophene ring, benzodithiophene ring, dithienopyrrole ring, dithienofuran ring, dithienofluorene heterocycle ring, thiophene ring-fluorene heterocycle ring - each group of the 3-ring condensed ring of the thiophene ring. Among them, preferred are a benzofuran ring, a benzothiophene ring, an anthracene ring, a carbazole ring, a quinoline ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, a dibenzothiophene ring, Thienopyridine ring, thieno[3,2-b]thiophene ring, thieno[3,4-b]thiophene ring, trithiophene ring, cyclopentadithiophene ring, benzodithiophene ring, dithienopyrrole Each group of a ring, a dithienofuran ring.

The condensed ring may also have a substituent. The substituent is synonymous with the R ^T1 , preferably the same. The number of substitution groups is an integer of 0 or more. The upper limit is that when the polycyclic ring is unsubstituted, the polycyclic ring group has a hydrogen atom number or less. The range is not particularly limited as long as it is in the above range, and is preferably 0 to 2, more preferably 0 or 1.

In the case where the ring group represented by each formula is a polycyclic ring, the atom bonded to the ring containing L ^W preferably has a ring of a ring group (monocyclic ring) represented by each formula to constitute a carbon atom. Therefore, L ¹ does not include an aromatic ring group bonded to the ring containing L ^W by a thiophene ring. The aromatic ring group not contained in L ¹ may, for example, be a cyclopentadithiophene ring, a thieno[3,2-b]thiophene ring or a thieno[3,4] in the condensed polycyclic aromatic heterocyclic group. -b] each ring group such as a thiophene ring, a trithiophene ring, a benzodithiophene ring, or a dithienopyrrole ring.

In the ligand LA, L ² is a vinyl group, an ethynyl group or an aromatic ring group (aromatic hydrocarbon ring group and aromatic heterocyclic group). Among them, preferred are aromatic ring groups.

The aromatic hydrocarbon ring group is not particularly limited, and may be a monocyclic ring or a condensed polycyclic aromatic hydrocarbon ring group. The condensed polycyclic aromatic hydrocarbon ring group is synonymous with the condensed polycyclic aromatic hydrocarbon ring group described in L ¹ . The aromatic hydrocarbon ring group is preferably a group of a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring or an anthracene ring.

The aromatic heterocyclic group is not particularly limited, and may be a monocyclic aromatic heterocyclic ring or a polycyclic aromatic heterocyclic ring. Preferred are monocyclic aromatic heterocycles. The monocyclic heterocyclic group is preferably a 5-membered or 6-membered ring. The group of the 5-membered ring may be a thiophene ring, a ring group represented by the above formula (X-1) or the formula (X-2), preferably a thiophene ring or represented by the formula (X-1) Ring base. Examples thereof include a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring, a thiazole ring, an oxazole ring, an isothiazole ring, an isoxazole ring, an imidazole ring, a pyrazole ring, a thiadiazole ring, an oxadiazole ring, and a hydrazine ring. Each group such as a heterocyclopentadiene ring or a triazole ring. Examples of the group of the 6-membered ring include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring or a tetrazine ring. The polycyclic heterocyclic group is synonymous with the condensed polycyclic aromatic heterocyclic group described in L ¹ (including an aromatic ring group bonded to another ring by a thiophene ring), and is preferably the same.

L ² may also have a substituent. The substituent is synonymous with the R ^T1 , preferably the same. The number of substitution bases is an integer of 0 or more. The upper limit is that when the monocyclic or polycyclic ring is unsubstituted, the monocyclic or polycyclic ring group has a hydrogen atom number or less. The range is not particularly limited, and is preferably 0 to 4, more preferably 0 to 2, still more preferably 0 or 1. When L ² is an alkenyl group or an aromatic ring group, the substituent of L ² and the substituent of L ¹ may be bonded to each other to form a ring.

In the ligand LA, n represents an integer of 1 to 4. It is preferably an integer of 1 to 3, more preferably 1 or 2. When n is an integer of 2 or more, two or more L ^{2 's} may be the same or different.

The LA bound ligand, L ¹ and [L ^2] n a combination of -L ¹ - [L ^2] n- is not particularly limited. For example, specific examples of the ligand LA described later and each -L ¹ -[L ² ]n- shown in the specific example of the metal complex dye can be mentioned. Among them, -L ¹ -[L ² ]n- which is possessed by the ligand LA in the metal complex dye D-1 to the metal complex dye D-19 to be described later is preferable.

Z represents a hydrogen atom or a substituent. The substituent which can be used as Z is not particularly limited, and examples thereof include a group selected from the substituent group Z ^S described later. Among them, preferred are an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkenyl group, a decyl group or the like.

The group represented by "-L ¹ -[L ² ]nZ" does not have the acidic group. Moreover, it does not have an amine group. In the present invention, the amine group includes an alkylamino group, an arylamino group, and a heteroarylamino group in addition to the unsubstituted amino group (-NH ₂ ).

The ligand LA is preferably a tridentate ligand (tripyridine compound) represented by the following formula (AL-2).

[Chemistry 14]

In the formula, two Anc each independently represent an acidic group. The acidic group is synonymous with the acidic group of the formula (AL-1), and preferably the same. L ^1, L ^2, Z and n are L ^1, L ^2, Z and n have the same meaning as formula (AL-1), preferably Zheyi same.

The terpyridine compound is the ligand LA itself. However, in the present invention, the ligand LA may be used as a precursor compound of the ligand LA as described later. Therefore, in the present invention, when the ligand LA is mentioned, in addition to the ligand LA itself (the terpyridine compound), the precursor compound of the ligand LA is also contained. A preferred precursor compound is exemplified by at least one esterified ester body of an acidic group Anc of the terpyridine compound (also referred to as "esterified compound of a terpyridine compound"). The esterified product is a compound which is protected by the acidic group, and is an ester which can be regenerated into an acidic group by hydrolysis or the like, and is not particularly limited. For example, an alkyl ester compound, an aryl ester compound, a heteroaryl ester compound or the like of the acidic group may be mentioned. Preferred among these are alkyl esterified compounds. The alkyl group forming the alkyl ester compound is not particularly limited, and is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a carbon number of 1 to 4 carbon atoms. alkyl. The aryl group forming the aryl ester compound and the heteroaryl group forming the heteroaryl ester compound are not particularly limited, and those exemplified in the substituent group Z ^R described later are exemplified. These groups may have one or more substituents selected from the group of substituents Z ^R described later. The esterified acidic groups are preferably two. In this case, the two esters may be the same or different.

The ligand LA can be synthesized by a usual method. For example, the ligand LA represented by the formula (L1-4) can be synthesized by expressing the compound represented by the formula (L1-1) and the compound represented by the formula (L1-2) as shown in the following scheme. The coupling reaction is carried out to hydrolyze the ester group of the precursor compound represented by the formula (L1-3). In the synthesis method, an ester compound of a carboxyl group is exemplified as the precursor compound. However, the present invention is not limited thereto, and may be a precursor compound obtained by esterifying any of the acidic groups. The coupling reaction at this time can be, for example, "Suzuki Coupling Reaction" or "Application" as described in the Chemical Society of Japan, "Experimental Chemistry Lecture 5th Edition", Maruzen Co., Ltd., Vol. 13, pp. 92-117. The Stille coupling reaction or the like or a combination of these is carried out. Further, the hydrolysis can be carried out, for example, according to the method described in the Japanese Chemical Society, "Experimental Chemistry Lecture 5th Edition", Maruzen Co., Ltd., Vol. 16, pp. 10 to 15. For example, a method of performing synthesis in the examples described later can be mentioned. In the present invention, the metal complex dye of the present invention can be synthesized by using the ligand LA synthesized by hydrolysis of the precursor compound. Further, the metal complex can be dyed by using a precursor compound as in the first embodiment to be described later, and then the ester group can be hydrolyzed according to the method to synthesize the metal complex dye of the present invention.

[化15]

In the formula, L ^{V is} synonymous with the group represented by the -L ¹ -[L ² ]nZ. Y ¹ represents a trialkyltinyl group, a boronic acid group, a boronic acid ester group, a halogen atom or a perfluoroalkylsulfonyloxy group. In the formula (L1-2), in the case where Y ¹ of the formula (L1-1) is a trialkyltinyl group, a boronic acid group or a boronic acid ester group, Y ² represents a halogen atom or a perfluoroalkylsulfonyloxy group. In the case where Y ¹ of the formula (L1-1) is a halogen atom or a perfluoroalkylsulfonyloxy group, Y ² represents a trialkyltinyl group, a boronic acid group or a boronic acid ester group. In the formula (L1-2) and the formula (L1-3), R represents an alkyl group, an aryl group or a heteroaryl group.

Specific examples of the ligand LA are shown below. Further, the ligand LA may also be a ligand LA in the metal complex dye described later. The ligand LA which is a specific example of the following specific examples and the metal complex dye, and a compound in which at least one of -COOH is a salt of a carboxyl group is also mentioned. In the compound, the counter cation of the salt forming a carboxyl group is exemplified by the positive ion described in the following CI. In addition, examples of the esterified compound of the terpyridine compound include a compound obtained by esterifying at least one of the acidic groups with respect to the ligand LA in the specific examples of the following specific examples. The present invention is not limited to the ligands LA, salts or esterified products thereof.

[Chemistry 16]

[化17]

[化18]

[Chemistry 19]

- The ligand LD - LD is a bidentate ligand or a tridentate ligand different from the ligand LA. The ligand LD is preferably an acidic group which does not have a surface adsorbed on the semiconductor fine particles. Even if the ligand LD contains a group corresponding to an acidic group, it is preferably a group which is not adsorbed on the surface of the semiconductor fine particles.

At least one of the coordinating atoms of the ligand LD bonded to the metal ion M is a nitrogen atom. Preferably, the nitrogen atom is coordinated to the metal ion M by a lone pair of electrons. Such a nitrogen atom is exemplified by a nitrogen atom in which a ring constitutes an atom and does not have a hydrogen atom. For example, a nitrogen atom of a pyridine ring can be mentioned. In the ligand LD, at least one of the coordinating atoms is an anion. The term "is an anion" means that any hydrogen atom in the molecule or a hydrogen atom bonded to the coordination atom can be dissociated and bonded to the metal ion M. Here, the coordinating atom to be an anion may be a nitrogen atom coordinated to the metal ion M, or may be another atom such as a carbon atom. In the present invention, the ring constituting the metal ion M may be the same as or different from the coordinating atom which becomes an anion. When the metal complex dye has a ligand LD disposed on the metal ion M by the anion of a nitrogen atom and a coordinating atom, and the ligand LA, the photoelectric conversion element or the dye-sensitized solar cell is thermally stable. Improvement in performance, in addition to high photoelectric conversion efficiency, in particular, high durability.

The ligand LD is preferably a ligand represented by the following formula (DL).

[Chemistry 20]

Wherein the ring D ^DL, E ^DL rings and ring F each independently represents a 5-membered ring or 6-membered ring aromatic rings. R ^a , R ^a1 and R ^a4 each independently represent a substituent which does not have an acidic group. Mb stands for 0 or 1. Each of ma1 and ma4 independently represents an integer of 0 to 3. Ma represents an integer of 0 to 4 when mb is 0, and represents an integer of 0 to 3 when mb is 1. Here, when each of ma, ma1, and ma4 is an integer of 2 or more, a plurality of R ^a , a plurality of R ^{a1 ,} and a plurality of R ^a4 may be the same or different, and may be bonded to each other to form a ring. Further, R ^a and R ^a1 , R ^a and R ^a4 may be bonded to each other to form a ring.

Examples of the aromatic ring of the 5-membered ring or the 6-membered ring in the ring D ^DL , the ring E ^DL and the ring F include an aromatic hydrocarbon ring and an aromatic hetero ring, and an aromatic hetero ring is preferred. Each ring of the ring D ^DL , the ring E ^DL and the ring F may also condense at least one of an aromatic ring and an aliphatic hydrocarbon ring. In the case where the ring D ^DL , the ring E ^DL and the ring F are aromatic hydrocarbon rings, a benzene ring is preferred. The aromatic heterocyclic ring may be an aromatic ring containing the hetero atom as a ring-constituting atom. For example, a 6-membered ring having a non-condensed ring, a 6-membered ring having a 5-membered ring in a condensed ring, and a benzene ring having a condensed ring are preferable. The 5-member ring or the 6-membered ring with a benzene ring, more preferably a non-retracted 6-member ring, a 5-member ring with a 5-member ring, and even more preferably a non-retracted 6-member ring.

Examples of the aromatic heterocyclic ring include a 6-membered ring of a pyridine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a quinoline ring or a quinazoline ring. Further, examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, an anthracene ring, an indazole ring, a triazole ring, and a thiophene ring. Rings, furan rings and other 5 member rings. The ring D ^DL and the ring E ^{DL are} preferably a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring or a benzene ring, more preferably a pyrazole ring, a triazole ring or a benzene ring. The ring F is preferably an aromatic hetero ring containing a nitrogen atom, more preferably a pyridine ring, a pyrimidine ring, a pyrazine ring or a triazine ring, still more preferably a pyridine ring or a pyrimidine ring, and particularly preferably a pyridine ring. .

Here, the ring D ^DL , the ring E ^{DL ,} and the ring F contain a coordinating atom bonded to the metal ion M. The coordinating atom is not particularly limited, and is preferably a carbon atom, a nitrogen atom, a sulfur atom, an oxygen atom or an anion of the atoms. The anion bonded to the metal ion M is not particularly limited, and preferably a carbon anion such as a =C ^- - ion, or a nitrogen anion such as an N ^- ion.

In the case of the ring having R ^a is F, F in the ring, R ^a are bonded position (position of substitution) is not particularly limited. In the case where the ring F is a 5-membered ring, it is preferably a 3-position with respect to the ring which is bonded to the metal atom M to constitute a nitrogen atom. In the case where the ring F is a 6-membered ring, it is preferably 3 or 4, more preferably 4, with respect to the ring which is bonded to the metal atom M. Further, when the ring D ^DL and the ring E ^DL have R ^a1 or R ^a4 , respectively, the position where R ^a1 or R ^a4 is bonded to each of the ring D ^DL and the ring E ^DL is not particularly limited.

The substituent of R ^a , R ^a1 and R ^a4 may be a group selected from the substituent group Z ^R described later. Wherein R ^{a is} preferably an aromatic heterocyclic group, an aromatic hydrocarbon ring group, a vinyl group, an ethynyl group, a halogen atom, an alkyl group or an amine group (including an alkylamino group, a dialkylamino group, an arylamine) Alkyl, diarylamino, N-alkyl-N-arylamino, etc.), alkoxy, aryloxy, alkylthio, arylthio, decyl, more preferably aromatic heterocyclic An aromatic hydrocarbon ring group, a vinyl group, an ethynyl group, an alkyl group, an alkoxy group or an amine group (including an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, etc.). Further, a group in which the respective groups are combined is also preferable. As R ^a employed carbon atoms of each substituent group is not particularly limited, on the same type of substituents as R ^AA employed various substituents as R ^a and used in the later-described substituent group, more It is preferred that the carbon number is the same as the substituent which can be used as R ^AA . Further preferably, the preferred range of carbon numbers is also the same. Among the substituents which can be used as R ^a , the substituent which is not a substituent which can be used as R ^AA to be described later is preferably the same as the carbon number of each substituent of the substituent group Z ^R described later. The scope is also the same. In this regard, the respective substituents which can be used as R ^a1 or R ^a4 are also the same.

R ^a1 and R ^a4 are each preferably an alkyl group, a cycloalkyl group, an alkenyl group (preferably a vinyl group), an alkynyl group (preferably an ethynyl group), an aryl group or a heterocyclic group (preferably Aromatic heterocyclic group), halogen atom, alkoxy group, alkoxycarbonyl group, cycloalkoxycarbonyl group, aryloxy group, alkylthio group, arylthio group, amine group, cyano group, alkylsulfonyl group, aromatic a sulfonyl group, a halogenated alkyl group (e.g., a fluoroalkyl group), a halogenated aryl group, more preferably a halogenated alkyl group, a halogenated aryl group, a halogen atom, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, further More preferred are halogenated alkyl groups, halogenated aryl groups, halogen atoms, and cyano groups. Further, a group in which the respective groups are combined is also preferable. The halogenated alkyl group and the halogenated aryl group are as described later.

R ^a , R ^a1 and R ^a4 are each preferably a group R ^VU represented by the following formula (V ^U -1) or (V ^U -2) as a substituent, and particularly preferably ^Ra has the following Base R ^VU .

[Chem. 21]

In the formula (V ^U -1), T represents an oxygen atom, a sulfur atom, -NR ^CA -, -C(R ^CA ) ₂ - or -Si(R ^CA ) ₂ -, and R ^CA represents a hydrogen atom or a substituent, respectively. R ^AA , R ^AB and R ^AC each independently represent a hydrogen atom or a substituent, and at least one of R ^AA to R ^AC represents a substituent. It is preferred that at least one of R ^AA and R ^AC is a substituent, and more preferably R ^AA is a substituent. In the formula (V ^U -2), R ^BA to R ^BE each independently represent a hydrogen atom or a substituent, and at least one of R ^BA , R ^BB , R ^BD and R ^BE represents a substituent.

The number of bases R ^VU of the ligand LD may be one or more, preferably one to three, and more preferably one or two.

In the formula (V ^U -1), T is preferably a sulfur atom. Here, R ^{CA is} preferably a hydrogen atom. The substituent which can be used as R ^CA may, for example, be a group selected from the substituent group Z ^R described later.

The substituent which can be used as the R ^AA is not particularly limited, and examples thereof include a group selected from the substituent group Z ^R described later. Preferred are alkyl, alkenyl (preferably vinyl), alkynyl (preferably ethynyl), cycloalkyl, alkoxy, cycloalkoxy, aryloxy, alkylthio, Cycloalkylthio, arylthio, amine, alkylamino, cycloalkylamino, arylamino, heterocyclic amine, decyl or decyloxy. The substituent which may be employed as R ^AA , more preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an amine group or an alkyl group in the respective groups. Further, an amino group, a cycloalkylamino group or an arylamine group, still more preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylamino group, a cycloalkylamino group or an arylamino group. More preferably, it is an alkyl group, an alkoxy group or an alkylamino group, and most preferably an alkyl group or an alkoxy group. In terms of photoelectric conversion efficiency, preferred substituents of the R ^AA are preferably bonded to a thiophene ring (where T is a sulfur atom). The substituent which can be used as R ^AA may be further substituted with a group selected from the substituent group Z ^R described later.

Alkyl groups include straight chain alkyl groups and branched alkyl groups. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 4 to 30 carbon atoms, still more preferably 5 to 26 carbon atoms, and particularly preferably 6 to 20 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, and 3,7-dimethyloctyl group. , isodecyl, second fluorenyl, n-dodecyl, 2-butyloctyl, n-hexadecyl, isohexadecyl, n-icosyl, n-hexadecyl, heterodi Octadecyl, trifluoromethyl or pentafluoroethyl.

The carbon number of the cycloalkyl group is preferably from 3 to 30, more preferably from 5 to 30, still more preferably from 6 to 26, and particularly preferably from 6 to 20. Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group. The cycloalkyl group can also be condensed by a heterocyclic ring.

Alkoxy groups include straight chain alkoxy groups and branched alkoxy groups. The alkyl portion of the alkoxy group is synonymous with the alkyl group, preferably the same. Examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a third butoxy group, a n-pentyloxy group, a n-hexyloxy group, a n-octyloxy group, and 2 -ethylhexyloxy, 3,7-dimethyloctyloxy, n-decyloxy, isodecyloxy, second nonyloxy, 2-butyloctyloxy, n-dodecyloxy, positive Hexadecenyloxy, isohexadecanyloxy, n-eicosyloxy, n-hexadecanyloxy or isooctadecyloxy.

The cycloalkyl moiety of the cycloalkoxy group is synonymous with the cycloalkyl group, preferably the same. Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group or a cyclooctyloxy group.

The aryloxy group includes a hydrocarbon ring-based aryloxy group whose aryl group is an aromatic hydrocarbon ring group, and a heteroaryloxy group whose aryl group is an aromatic heterocyclic group. The carbon number of the aryloxy group is preferably from 3 to 30, more preferably from 3 to 25, still more preferably from 3 to 20, particularly preferably from 3 to 16. Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, an imidazolyloxy group, a benzimidazolyloxy group, a pyridin-4-yloxy group, a pyrimidinyloxy group, a quinazolinyloxy group, and a decyloxy group. Or thiophen-3-yloxy and the like. The heterocyclic heteroaryloxy group is preferably a thiophene ring.

The alkylthio group includes a linear alkylthio group and a branched alkylthio group. The alkyl moiety of the alkylthio group is synonymous with the alkyl group, preferably the same. Examples of the alkylthio group include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, tert-butylthio group, n-pentylthio group, n-hexylthio group, n-octylthio group, and 2 -ethylhexylthio, 3,7-dimethyloctylthio, n-decylthio, isodecylthio, second indenylthio, n-dodecylthio, 2-butyloctylthio, positive Hexadecanethio, isohexadecylthio, n-eicosylthio, n-hexadecanethio or isooctadecylthio.

The cycloalkyl moiety of the cycloalkylthio group is synonymous with the cycloalkyl group, preferably the same. Examples of the cycloalkylthio group include a cyclopropylthio group, a cyclopentylthio group, a cyclohexylthio group, a cycloheptylthio group or a cyclooctylthio group.

The arylthio group includes a hydrocarbon ring-based arylthio group whose aryl group is an aromatic hydrocarbon ring group, and a heteroarylthio group whose aryl group is an aromatic heterocyclic group. The carbon number of the arylthio group is preferably from 3 to 30, more preferably from 3 to 25, still more preferably from 3 to 20, particularly preferably from 3 to 16. Examples of the arylthio group include a phenylthio group, a naphthylthio group, an imidazolylthio group, a benzimidazolylthio group, a pyridin-4-ylthio group, a pyrimidinylthio group, a quinazolinylthio group, a mercaptothio group. Or thiophen-3-ylthio and the like. The heteroarylthio group heterocyclic ring is preferably a thiophene ring.

The alkylamino group includes an N-alkylamino group and an N,N-dialkylamino group, and the alkyl group preferably has 1 to 30 carbon atoms, more preferably 2 to 30 carbon atoms. The alkylamino group may, for example, be an ethylamino group, a diethylamino group, a 2-ethylhexylamino group, a bis(2-ethylhexyl)amino group or an n-octadecylamino group.

The cycloalkylamino group includes an N-cycloalkylamino group and an N,N-dicycloalkylamino group. The cycloalkyl moiety of the cycloalkylamino group is synonymous with the cycloalkyl group, preferably the same. Examples of the cycloalkylamino group include a cyclopropylamino group, a dicyclopropylamino group, an N-cyclopropyl-N-ethylamino group, a cyclopentylamino group, a dicyclopentylamino group, and an N-ring. A pentyl-N-methylamino group, a cyclohexylamino group, a dicyclohexylamino group, a cycloheptylamino group or a cyclooctylamino group.

The arylamine group includes a hydrocarbon ring-based arylamine group whose aryl group is an aromatic hydrocarbon ring group, and a heteroarylamine group whose aryl group is an aromatic heterocyclic group. Further, the hydrocarbon ring arylamine group includes an N-arylamino group, an N-alkyl-N-arylamino group, and an N,N-diarylamino group. Heteroarylamino groups include N-heteroarylamine, N-alkyl-N-heteroarylamine, N-aryl-N-heteroarylamine and N,N-diheteroarylamine . The carbon number of the arylamine group is preferably from 3 to 30, more preferably from 3 to 25, still more preferably from 3 to 20, particularly preferably from 3 to 16. Examples of the arylamine group include a phenylamino group, an N-phenyl-N-ethylamino group, a naphthylamino group, an imidazolylamino group, a benzimidazolylamino group, a pyridin-4-ylamino group, and a pyrimidine. Amino group, quinazolinylamino group, mercaptoamino group or thiophen-3-ylamino group, and the like.

The heterocyclic amino group is a heterocyclic amino group other than a heteroarylamino group (aliphatic heterocyclic amine group). The carbon number is preferably from 0 to 30, more preferably from 1 to 25, still more preferably from 2 to 20, and particularly preferably from 2 to 16. Further, the heterocyclic ring is preferably a hetero ring in which a hetero atom is selected from an oxygen atom, a sulfur atom or a nitrogen atom, and a ring member is preferably a 5-membered ring to a 7-membered ring, more preferably a 5-membered ring or 6 Member ring. Examples of the heterocyclic amino group include a pyrrolidin-3-ylamino group, an imidazolidinylamino group, a benzimidazolylamino group, a piperidin-4-ylamino group or a tetrahydrothiophen-3-ylamino group.

The decyl group includes an alkyl fluorenyl group, a cycloalkyl fluorenyl group, an aryl decyl group, an alkoxy decyl group, a cycloalkoxy fluorenyl group, and an aryloxy fluorenyl group. Preferred decylalkyl groups are alkylalkylalkyl, cycloalkylalkyl or arylalkyl. The carbon number of the alkyl group is preferably from 3 to 30, more preferably from 3 to 24, still more preferably from 3 to 20, and particularly preferably from 3 to 18. Examples of the decyl group include a trimethyl decyl group, a triethyl decyl group, a tert-butyl dimethyl decyl group, a cyclohexyl dimethyl decyl group, a triisopropyl decyl group, and a tert-butyl diphenyl decane. Alkyl, methyldimethoxydecyl, phenyldimethoxydecyl or phenoxydimethylalkyl.

The decyloxy group includes an alkyl decyloxy group, a cycloalkyl decyloxy group, and an aryl decyloxy group. The carbon number of the decyloxy group is preferably from 3 to 30, more preferably from 3 to 24, still more preferably from 3 to 20, particularly preferably from 3 to 18. Examples of the decyloxy group include a trimethyldecyloxy group, a triethyldecyloxy group, a tert-butyldimethylstanoxy group, a triisopropyldecyloxy group, a cyclohexyldimethylstannyloxy group or a third group. Butyl diphenyl decyloxy.

R ^AB represents a hydrogen atom or a substituent, preferably a hydrogen atom. R ^AC represents a hydrogen atom or a substituent. Substituents which can be employed as R ^AB and R ^AC are synonymous with the R ^AA , preferably the same. When R ^AB or R ^AC is a substituent, the substituents of R ^AA to R ^AC may be the same or different from each other.

In the group R ^VU represented by the formula (V ^U -2), R ^BA to R ^BE each independently represent a hydrogen atom or a substituent. Substituents which may be employed in R ^BA to R ^BE , respectively, are synonymous with the R ^AA , preferably the same. Wherein at least one of R ^BA , R ^BB , R ^BD and R ^BE is a substituent. At least one or both of R ^BA and R ^BE are a substituent, and R ^BB , R ^BC and R ^BD are each a hydrogen atom, or at least one or both of R ^BB and R ^BD are a substituent, particularly preferably R ^BA , R ^BC and R ^BE are all hydrogen atoms. In the case where two or more of R ^BA to R ^BE are a substituent, two or more substituents may be the same or different from each other.

In the formula (DL), ma, ma1 and ma4 are preferably an integer of 0 to 2, more preferably 1 or 2.

The ligand represented by the formula (DL) is preferably represented by the following formula (DL-1) or formula (DL-2).

[化22]

R ^a2 and R ^a3 each independently represent a substituent which does not have an acidic group. Ma2 represents 0 or 1, preferably 1. Ma3 represents an integer of 0 to 2, more preferably 1 or 2. X1 and X2 each independently represent CR ^a5 or a nitrogen atom. R ^a5 represents a hydrogen atom or a substituent. This substituent is synonymous with R ^a in the formula (DL), and the preferred range is also the same. The ring containing X1 and X2 (also referred to as "ring F") is synonymous with ring F in the formula (DL), and the preferred range is also the same. R ^a1, R ^a4, ma1 and ma4 the formula (DL) of R ^a1, R ^a4, ma1 and ma4 synonymous, preferred ranges are also the same. The substituent represented by R ^a2 and R ^a3 has the same meaning as R ^a in the formula (DL), and the preferred range is also the same. When each of ma1, ma3, and ma4 is an integer of 2 or more, a plurality of R ^a1 , R ^{a3 ,} and R ^a4 may be the same or different, and may be bonded to each other to form a ring.

Ring D and ring E each independently represent an aromatic ring of a 5-membered ring or a 6-membered ring. Examples of such an aromatic ring include the ring exemplified in the ring D ^DL and the ring E ^DL in the formula (DL), and the preferred aromatic ring is also the same as those exemplified in the ring D ^DL and the ring E ^DL . The bond between D ¹ and D ² in ring D and ring E and the carbon atom bonded to ring F may be a single bond or a double bond. D ¹ and D ² each independently represent an anion of a carbon atom or an anion of a nitrogen atom.

Ring D and ring E are preferably a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring or a benzene ring, more preferably a pyrazole ring, a triazole ring or a benzene ring.

When the ligand LD is a bidentate ligand, a bidentate ligand represented by any of the following formulas (2L-1) to (2L-4) is preferred.

[化23]

In the formula, * represents a coordination position (bonding position) with the metal ion M. Ring D ^2L represents an aromatic ring. A ¹¹¹ to A ¹⁴¹ each independently represent an anion of a nitrogen atom or an anion of a carbon atom. R ¹¹¹ to R ¹⁴³ each independently represent a hydrogen atom or a substituent having no acidic group.

Here, A ¹¹¹ to A ¹⁴¹ are anions of a carbon atom or a nitrogen atom which constitutes a nitrogen atom or a hydrogen atom bonded to a carbon atom of the ring D ^2L . In the formula (2L-1) to the formula (2L-4), examples of the ring D ^2L include an aromatic hydrocarbon ring, an oxygen-containing aromatic hetero ring, a sulfur-containing aromatic hetero ring, and a nitrogen-containing aromatic hetero ring. The aromatic hydrocarbon ring may, for example, be a benzene ring or a naphthalene ring, and is preferably a benzene ring, more preferably a benzene ring substituted with a halogen atom, a halogenated alkyl group or a halogenated aryl group. The halogenated alkyl group is an alkyl group substituted with a halogen atom, preferably a fluorinated alkyl group (e.g., trifluoromethyl group). The halogenated aryl group is preferably a phenyl group substituted with 1 to 5 halogen atoms. The oxygen-containing aromatic heterocyclic ring is preferably a furan ring, and the sulfur-containing aromatic heterocyclic ring is preferably a thiophene ring. The nitrogen-containing aromatic heterocyclic ring is preferably a pyrrole ring, a pyrazole ring, an imidazole ring or a triazole ring. The ring D ^2L is preferably, for example, a ring which is an anion of a ring of a benzene ring, a thiophene ring or a furan ring, or a formula (a-1) to a formula (a-5) or a formula (a-). 1a), each ring represented by formula (a-2a), formula (a-1b), and formula (a-4a).

[Chem. 24]

In the formula, Rd represents a substituent which does not have an acidic group. B1 represents an integer of 0 to 2, b2 represents an integer of 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 the same or different. Further, a plurality of Rds may be bonded to each other to form a ring. For example, Rd may be a group selected from the group of substituents Z ^R described later.

[化25]

In the formula, Rd and b1 to b3 have the same meanings as Rd and b1 to b3 in the above formulas (a-1) to (a-5), and the preferred ranges are also the same. B4 represents an integer of 0 to 4, and b5 represents an integer of 0 to 5. In the formula (a-1a) and the formula (a-1b), it is indicated that R is not contained only on the benzene ring but also on the pyrrole ring.

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, a cyano group, an alkylsulfonyl group, Further, the arylsulfonyl group and the group in which these are combined are more preferably a linear or branched alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and a combination thereof, and more preferably It is a linear or branched halogenated alkyl group or a halogenated aryl group.

The substituent represented by R ¹¹¹ to R ¹⁴³ has the same meaning as R ^a in the above formula (DL), and the preferred range is also the same. Preferably, at least one of R ¹¹¹ to R ¹¹⁴ , at least one of R ¹²¹ to R ¹²³ , at least one of R ¹³¹ to R ¹³³ , and at least one of R ¹⁴¹ to R ¹⁴³ are substituted, more preferably one or two. As a substituent.

When the ligand LD is a 3-dental ligand, a 3-dentate ligand represented by any of the following formulas (3L-1) to (3L-4) is preferred.

[Chem. 26]

In the formula, * represents a coordination position (bonding position) with the metal ion M. Ring D ^2L represents an aromatic ring. A ²¹¹ to A ²⁴² each independently represent a nitrogen atom or a carbon atom. Wherein at least one of A ²¹¹ and A ²¹² , A ²²¹ and A ²²² , A ²³¹ and A ²³² , A ²⁴¹ and A ²⁴² are anions, respectively. R ²¹¹ to R ²⁴¹ each independently represent a hydrogen atom or a substituent having no acidic group.

A ²¹¹ ~ A ²⁴² as A ¹¹¹ ~ A ¹⁴¹ are synonymous with the anion of formula (2L-1) ~ formula (2L-4) a. ^Any one of A ²¹¹ to A ²⁴² which does not have an anion is a nitrogen atom which does not have a hydrogen atom. ^2L of the formula (2L-1) ~ formula (2L-4) D ^2L synonymous ring, the same preferable scope of formula (3L-1) ~ ring of formula D (3L-4) in. More preferably, the ring D ^2L is an aromatic ring containing any one of A ²¹¹ to A ²⁴² and a carbon atom or two carbon atoms. At this time, in each formula, the two rings D ^2L may be the same or different. The substituent represented by R ²¹¹ to R ²⁴¹ is the same as R ^a in the above formula (DL), and the preferred range is also the same. Preferably, at least one of R ²¹¹ to R ²¹³ , at least one of R ²²¹ and R ²²² , at least one of R ²³¹ and R ²³² , and R ²⁴¹ are a substituent.

In the present invention, the atom coordinated to the metal ion M in the 2- or 3-dentate ligand in the ligand LD is a nitrogen anion or a carbon anion having a (hetero)arylamino group or a substituent in the substituent. The (hetero)arylamine group is particularly preferred because it absorbs long wavelengths. Specifically, the preferred ligand is a ligand in which at least one of the atoms bonded to the metal ion M is a nitrogen anion or a carbon anion and has a formula (SA) in a partial structure.

[化27]

In the formula, R ^DA1 represents an aryl group or a heteroaryl group, and R ^DA2 represents an alkyl group, an aryl group or a heteroaryl group. R ^DA1 and R ^DA2 may also be bonded to each other to form a ring. LL represents a vinyl group, an ethynyl group, an extended aryl group or a heteroaryl group. a represents an integer of 0 to 5, and when a is 2 or more, a plurality of existing LLs may be the same or different.

The group represented by the formula (SA) is preferably substituted with an aromatic hydrocarbon ring or a nitrogen-containing aromatic heterocyclic ring disposed on the metal ion M, more preferably an aromatic heterocyclic ring containing a nitrogen atom. Replace it. It is preferred that at least one of R ^DA1 and R ^DA2 in the group represented by the formula (SA) is an aryl group or a heteroaryl group, and more preferably, it is an aryl group. The alkyl group, the aryl group, and the heteroaryl group may have a substituent, and examples of such a substituent include a group selected from the substituent group Z ^R described later. The aryl group is not particularly limited, and examples thereof include a phenyl group and a naphthyl group, and a phenyl group is preferred. The heteroaryl group is not particularly limited, and a furyl group or a thienyl group is preferred.

LL may also form a condensed ring structure together with an aromatic hydrocarbon ring or a nitrogen-containing aromatic heterocyclic ring containing a coordinating atom of a ligand. For example, LL is a vinyl group which may also be bonded to a nitrogen-containing aromatic heterocyclic ring containing a coordinating atom of a ligand to form a quinoline ring. The aryl group in LL may be a phenyl group or a naphthyl group. The heteroaryl group is preferably a divalent 5-membered ring or a 6-membered ring, and contains an oxygen atom, a sulfur atom, and a nitrogen atom as a ring-constituting atom. Alternatively, the ring may be condensed by a benzene ring or a heterocyclic ring. Examples of the heterocyclic heterocyclic ring include a furan ring, a thiophene ring, a pyrrole ring, and a pyridine ring, and a furan ring or a thiophene ring is preferred.

The vinyl group, the aryl group, and the heteroaryl group in LL may have a substituent, and the substituent may be a group selected from the group of substituents Z ^R described later.

In the formula (SA), it is preferred that a is 0, or a is 1 and LL is a vinyl group, an ethynyl group, a phenyl group or a heteroaryl group; more preferably, a is 0, or a is 1 and LL is a phenyl or heteroaryl group; further preferably a is 0, or a is 1 and LL is a phenyl group, a divalent furan ring group, a divalent thiophene ring group, The good one is that a is 0.

In the present invention, it is also preferred that R ^DA1 and R ^DA2 are bonded to each other to form a ring. The ring formed is preferably a 5-membered ring or a 6-membered ring, and more preferably bonded in the case where both R ^DA1 and R ^DA2 are aryl groups. The ring formed by bonding R ^DA1 and R ^{DA2 to} each other is preferably the following ring.

[化28]

Here, R ^DA3 and R ^DA4 each independently represent an alkyl group. The ring may have a substituent, and examples of such a substituent include a group selected from the substituent group Z ^R described later.

The ligand represented by the formula (DL) can be obtained from the specification of US Patent Application Publication No. 2010/0258175A1, Japanese Patent No. 4298799, and International Edition of Applied Chemistry (Angew. Chem. Int. Ed.), 2011, 50. The methods described in pages 2054 to 2058, the methods described in the references cited in the literature, or the methods according to the methods are synthesized.

Specific examples of the ligand represented by the formula (DL) are shown below. Further, the ligand LD may be a ligand LD in the metal complex dye described later. The present invention is not limited to the ligands LD. In the following specific examples, Me represents a methyl group, and * represents a bonding position at which the rings are bonded to each other or the pyridine ring and the substituent R ²⁰¹ are bonded to each other.

[化29]

[化30]

[化31]

[化32]

[化33]

[化34]

[化35]

[化36]

[化37]

[化38]

[39]

[化40]

[化41]

[化42]

[化43]

[化44]

[化45]

[Chem. 46]

- Ligand LX - Ligand LX may be a monodentate ligand, preferably selected from the group consisting of a decyloxy group, a thiol group, a thiomethoxy group, a thiosulfanyl group, a mercaptoamine group. Oxyl, thiocarbamate, ethyl dithiocarbamate, thiocarbonate, dithiocarbonate, trithiocarbonate, sulfhydryl, thiocyanate, iso a group or atom in the group consisting of a thiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, and a halogen atom or an anion thereof . In the case where the ligand LX contains an alkyl group, an alkenyl group, an alkynyl group, an alkylene group or the like, these may or may not have a substituent. Further, in the case of containing an aryl group, a heterocyclic group, a cycloalkyl group or the like, these may or may not have a substituent, and may be a monocyclic ring or a condensed ring.

Among them, the ligand LX is preferably a cyanate group, an isocyanate group, a thiocyanate group, and an isothiocyanate group or an anion thereof, more preferably an isocyanate group (isocyanate anion) or An isothiocyanate group (isothiocyanate anion), particularly preferably an isothiocyanate group (isothiocyanate anion).

- Charge Neutralization Counterion CI-CI represents the counterion required to neutralize the charge of the metal complex pigment. In general, the metal complex dye is a cation or an anion, or a metal having a substantial ionic charge depending on the metal complex dye, a ligand, and a substituent. Since the substituent has a dissociable group or the like, the metal complex dye can also be dissociated to have a negative charge. In this case, all of the charge of the metal complex dye becomes electrically neutral by CI.

In the case where the counter ion CI is a positive counter ion, for example, the counter ion CI is an inorganic or organic ammonium ion (for example, a tetraalkylammonium ion, a pyridinium ion, etc.), a phosphonium ion (for example, a tetraalkylphosphonium ion, an alkyl group). Triphenylphosphonium ions, etc., alkali metal ions (Li ions, Na ions, K ions, etc.), alkaline earth metal ions, metal complex ions or protons. The positive counter ion is preferably an inorganic or organic ammonium ion (tetraethylammonium ion, tetrabutylammonium ion, tetrahexylammonium ion, tetraoctylammonium ion, tetradecylammonium ion, etc.), an alkali metal ion, Proton.

In the case where the counter ion CI is a negative counter ion, for example, the counter ion CI may be an inorganic anion or an organic anion. For example, hydroxide ions, halogen anions (for example, fluoride ions, chloride ions, bromide ions, iodide ions, etc.), substituted or unsubstituted alkyl carboxylate ions (acetate ion, trifluoroacetic acid) may be mentioned. Root ion, etc.), substituted or unsubstituted aryl carboxylate ion (benzoate ion, etc.), substituted or unsubstituted alkylsulfonate ion (methanesulfonate ion, triflate ion, etc.) ), substituted or unsubstituted aryl sulfonate ion (eg p-toluenesulfonate ion, p-chlorobenzenesulfonate ion, etc.), aryl disulfonate ion (eg 1,3-benzenedisulfonate 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 ion, picric acid ion. In addition, the charge-balancing counter ion may also use an ionic polymer or other pigment having a charge opposite to that of the dye, or a metal counter ion (for example, Bisbenzene-bis-2,2-dithiol). 1,2-dithiolato nickel (III)), etc.). The negative counter ion is preferably a halogen anion, a substituted or unsubstituted alkyl carboxylate ion, a substituted or unsubstituted alkyl sulfonate ion, a substituted or unsubstituted aryl sulfonate ion, An aryl disulfonate ion, a perchlorate ion, a hexafluorophosphate ion, more preferably a halogen anion or a hexafluorophosphate ion.

- Metal complex dye - The metal complex dye of the present invention is represented by the following formula (I). In the metal complex dye represented by the formula (1), the ligand LA, the ligand LD, and the ligand LX are as described above, and the combination of the ligands is not particularly limited. A preferred combination of ligands is a combination of a preferred ligand LA, a preferred ligand LD, and a preferred combination with the ligand LX.

M (LA) (LD) _mD (LX) _mX · (CI) In the formula _mY , M, LA, LD, mD, LX, mX, CI and mY are as described above, and preferably the same.

The metal complex dye represented by the formula (I) is preferably a metal complex dye represented by the following formula (I-1) or (I-2).

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In the formula, M and LX are synonymous with M and LX of the formula (I), and preferably the same. Anc, L ¹ , L ² , Z and n are synonymous with the acidic group of the formula (AL-1), L ¹ , L ² , Z and n, and preferably the same. Ring D and Ring E each independently represent an aromatic ring of 5 or 6 members. D ¹ and D ² each independently represent an anion of a carbon atom or an anion of a nitrogen atom. Here, the bond between D ¹ and D ² in the ring D and the ring E and the carbon atom bonded to the pyridine ring is a single bond or a double bond. Ring D and ring E are synonymous with ring D and ring E of the formula (DL-1) and formula (DL-2), and preferably the same. R ^a1 to R ^a4 each independently represent a substituent. R ^a1 ~ R ^a4 are the same meaning as R ^a1 ~ R ^a4 of the formula (DL-1) and the formula (DL-2), preferably Zheyi same. Each of ma1, ma2, and ma4 independently represents an integer of 0 to 3. Ma3 represents an integer of 0-4. Ma1 and ma4 are synonymous with ma1 and ma4 of the above formula (DL-1) and formula (DL-2), respectively, and preferably the same. The preferred range of ma2 and ma3 is the same as the preferred range of ma of the formula (DL). When each of ma1 to ma4 represents an integer of 2 or more, a plurality of R ^a1 to R ^a4 may be bonded to each other to form a ring.

The metal complex dye represented by the formula (I-1) has the ligand LA and the ligand LD represented by the formula (2L-1). Further, the metal complex dye represented by the formula (I-2) has the ligand LA and the ligand LD represented by the formula (3L-1).

The metal complex dye represented by the formula (I) can be, for example, the method described in JP-A-2013-084594, the method described in Japanese Patent No. 4298799, and the US Patent Application Publication No. 2013/ International Application (Angew.Chem.Int.Ed.), the method described in the specification of U.S. Patent Application Publication No. 2012/0073660 A1, U.S. Patent Application Publication No. 2012/0111410 A1, and U.S. Patent Application Publication No. 2010/0258175 A1. ), 2011, 50, the methods described in pages 2054 to 2058, the methods described in the references cited in the literature, the patent documents related to solar cells, known methods, or Synthesize by some methods.

The metal complex dye represented by the formula (I) has the ligand LA and is excellent in absorption characteristics in a long wavelength region. The maximum absorption wavelength of the metal complex pigment 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 particularly preferably in the range of 370 nm to 900 nm.

Specific examples of the metal complex dye represented by the formula (I) are shown in the following description (including the examples). Moreover, as a specific example of the following specific examples and examples, a metal complex dye in which at least one of -COOH is a salt of a carboxyl group is also mentioned. In the metal complex dye, the counter cation of the salt forming a carboxyl group is exemplified by the positive ion described in the CI. The present invention is not limited to these metal complex dyes. In the case where the metal complex dye has an optical isomer or a geometric isomer, it may be any of the isomers, or may be a mixture of the isomers. In the following specific examples, regardless of the specific combination of the ligand LA, the ligand LD, and the ligand LX in each specific example, the ligand LA, the ligand LD, and the ligand LX are each independently represented. Specific examples of each. Further, in the specific example, Me represents a methyl group, and TBA represents tetrabutylammonium.

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<Substituent Group> In the present invention, preferred substituents include a substituent selected from the group of substituents described below. In the present specification, when an alkyl group is described differently from a cycloalkyl group (for example, a description of a substituent which can be used as R ^AA ), and an alkyl group is used in the meaning of a linear alkyl group and a branched alkyl group. On the other hand, when an alkyl group is not described in a difference from a cycloalkyl group (only when it is described as an alkyl group), and unless otherwise specified, an alkyl group contains a linear alkyl group and a branched alkyl group. It is used in the meaning of a group and a cycloalkyl group. a compound (alkoxy group, alkylthio group, alkenyloxy group, or the like) containing a group having a cyclic structure (alkyl group, alkenyl group, alkynyl group, etc.), and a compound containing a group having a cyclic structure (described above) Alkyl esters, etc.) are also the same. In the description of the group of substituents described below, for example, in order to clarify the group of the linear or branched structure and the group of the cyclic structure as in the case of an alkyl group and a cycloalkyl group, the above may be separately described.

(Substituent Group Z ^R) Z ^R substituent group is a substituent group having no acidic group. In the present specification, when only a substituent is described, the substituent group Z ^{R is} referred to. Further, in the case where each group, for example, only an alkyl group is described, a preferred range and a specific example of the corresponding group of the substituent group Z ^R are applied.

The group contained in the substituent group Z ^R includes the following group or a group in which a plurality of the following groups are combined. An alkyl group (preferably having a carbon number of 1 to 20, such as methyl, ethyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 1-B) A pentyl group, a benzyl group, a 2-ethoxyethyl group, a 1-carboxymethyl group or a trifluoromethyl group, an alkenyl group (preferably having a carbon number of 2 to 20, such as a vinyl group, an allyl group, or a butyl group) Alkenyl or oleyl), alkynyl (preferably having a carbon number of 2 to 20, such as ethynyl, butynyl or phenylethynyl), cycloalkyl (preferably having a carbon number of 3 to 20) , for example, cyclopropyl, cyclopentyl, cyclohexyl or 4-methylcyclohexyl), cycloalkenyl (preferably having a carbon number of 5 to 20, such as cyclopentenyl or cyclohexenyl), aryl (Aromatic hydrocarbon ring group, preferably having a carbon number of 6 to 26, such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, difluoro Phenyl or tetrafluorophenyl), heterocyclic group (preferably having a carbon number of 2 to 20, more preferably a 5-membered ring or a 6-membered ring having at least one oxygen atom, sulfur atom or nitrogen atom) a heterocyclic ring including an aromatic ring and an aliphatic ring; an aromatic heterocyclic group (for example, a heteroaryl group) may be listed. a group such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl or 2-oxazolyl), alkoxy (preferably having a carbon number of 1 to 20, such as methoxy, ethoxy, isopropoxy or benzyloxy), alkenyloxy (preferably having a carbon number of 2 to 20, such as a vinyloxy or allyloxy group), an alkyne An oxy group (preferably having a carbon number of 2 to 20, such as 2-propynyloxy or 4-butynyloxy) or a cycloalkoxy group (preferably having a carbon number of 3 to 20, such as cyclopropoxyl) a group, a cyclopentyloxy group, a cyclohexyloxy group or a 4-methylcyclohexyloxy group, an aryloxy group (preferably having a carbon number of 6 to 26, such as a phenoxy group, a 1-naphthyloxy group, or a 3- Methylphenoxy or 4-methoxyphenoxy), heterocyclic oxy (eg imidazolyloxy, benzimidazolyloxy, thiazolyloxy, benzothiazolyloxy, triazinyloxy) Base or thioloxy),

An alkoxycarbonyl group (preferably having a carbon number of 2 to 20, such as an ethoxycarbonyl group or a 2-ethylhexyloxycarbonyl group) or a cycloalkoxycarbonyl group (preferably having a carbon number of 4 to 20, for example Cyclopropoxycarbonyl, cyclopentyloxycarbonyl or cyclohexyloxycarbonyl), aryloxycarbonyl (preferably having a carbon number of 6 to 20, such as phenoxycarbonyl or naphthyloxycarbonyl), an amine group ( 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, Amine, N,N-dimethylamino, N,N-diethylamino, N-ethylamino, N-allylamino, N-(2-propynyl)amine, N-cyclohexylamino, N-cyclohexenylamino, anilino, pyridylamino, imidazolylamino, benzimidazolylamino, thiazolylamine, benzothiazolylamine or triazine Alkyl sulfhydryl 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 sulfonate Anthracenyl, N-cyclohexylamine sulfonyl or N-phenylamine sulfonyl), fluorenyl (preferably having a carbon number of 1 to 20, Such as ethenyl, cyclohexylcarbonyl or benzhydryl), anthracenyloxy (preferably having a carbon number of 1 to 20, such as ethoxylated, cyclohexylcarbonyloxy or benzylideneoxy), amine Mercapto (preferably a carbomethyl group having a carbon number of 1 to 20, preferably an alkyl group, a cycloalkyl group or an aryl group, such as N,N-dimethylaminecarbamyl, N-ring Hexylamine methyl sulfhydryl or N-phenylamine methyl sulfhydryl),

a mercaptoamine group (preferably a mercaptoamine group having a carbon number of 1 to 20, such as an ethyl decylamino group, a cyclohexylcarbonylamino group or a benzhydrylamino group) or a sulfonylamino group (preferably Is a sulfonium amino group having a carbon number of 0 to 20, preferably an alkyl group, a cycloalkyl group or an aryl group, such as metosulfamide, benzenesulfonamide, N-methylformamide, N-ring Hexylsulfonamide or N-ethylbenzenesulfonamide), alkylthio (preferably having a carbon number of 1 to 20, such as methylthio, ethylthio, isopropylthio, pentylthio or benzylsulfide) a cycloalkylthio group (preferably having a carbon number of 3 to 20, such as a cyclopropylthio group, a cyclopentylthio group, a cyclohexylthio group or a 4-methylcyclohexylthio group) or an arylthio group (more) Preferred is a carbon number of 6 to 26, such as phenylthio, 1-naphthylthio, 3-methylphenylthio or 4-methoxyphenylthio), alkylsulfonyl, cycloalkylsulfonate Or an arylsulfonyl group (preferably having a carbon number of 1 to 20, such as methylsulfonyl, ethylsulfonyl, cyclohexylsulfonyl or phenylsulfonyl),

a decyl group (preferably having 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 trimethyldecyl group, a triethyl decyl group, Triisopropyldecyl, triphenylsulfonyl, diethylbenzylnonyl or dimethylphenylsulfanyl, decyloxy (preferably having a carbon number of from 1 to 20, preferably by weight) Alkyl, aryl, alkoxy and aryloxy substituted decyloxy, such as triethyl decyloxy, triphenyl decyloxy, diethylbenzyl decyloxy or dimethylphenyl decyloxy A hydroxy group, a cyano group, a nitro group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom).

More preferably, the group selected from the substituent group Z ^R may be an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group or an alkylthio group. a cycloalkylthio group, an arylthio group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an amine group, a mercaptoamine group, a cyano group or a halogen atom, and particularly preferably an alkyl group, an alkenyl group or a heterocyclic group. Alkoxy, alkylthio, alkoxycarbonyl, amine, decylamino or cyano.

(Substituent Group Z ^S) substituent group Z ^S is a substituent group having no acidic group and an amine group. Examples of the substituent group included in the group Z ^S, the substituents include a substituent in the group Z ^R substituents exemplified in the group other than the amine, and a combination of a plurality of the plurality of groups The basis of the formation.

(Substituent Group Z ^T ) The substituent group Z ^T is a group of substituents further containing no aryl group, aromatic heterocyclic group, vinyl group and ethynyl group in addition to an acidic group or an amine group. The group contained in the substituent group Z ^T may be an amine group, an aryl group, an aromatic heterocyclic group, an alkenyl group and an alkynyl group in the group of substituents exemplified in the substituent group Z ^R . A substituent other than the substituent and a group obtained by combining a plurality of these groups.

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

Next, a preferred embodiment of the main components of the photoelectric conversion element and the dye-sensitized solar cell will be described with reference to FIGS. 1 and 2 .

<Electrically Conductive Support> The conductive support is not particularly limited as long as it has conductivity and can support the photoreceptor layer 2 and the like. The conductive support is preferably an electrically conductive support 1 formed of a conductive material such as a metal, or a conductive film 43 comprising a glass or plastic and a transparent conductive film 43 formed on the surface of the substrate 44. Sex support 41.

Further, more preferably, the conductive support 41 is formed by coating a surface of the substrate 44 with a conductive metal oxide to form the transparent conductive film 43. The substrate 44 formed of plastic is, for example, a transparent polymer film described in Paragraph No. 0153 of JP-A-2001-291534. 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 metal oxide is preferably tin oxide (TO), and particularly preferably indium oxide-tin (tin-doped indium oxide; ITO) or fluorine-doped tin oxide (FTO). The coating amount of the metal oxide at this time is preferably from 0.1 g to 100 g per 1 m ^{2 of the} substrate 44. In the case where the conductive support 41 is used, it is preferable that light is incident from the substrate 44 side.

The conductive support 1 and the conductive support 41 are preferably substantially transparent. The term "substantially transparent" means that the transmittance of light (wavelength: 300 nm to 1200 nm) is 10% or more, preferably 50% or more, and particularly preferably 80% or more. The thickness of the conductive support 1 and the conductive support 41 is not particularly limited, but is preferably 0.05 μm to 10 mm, more preferably 0.1 μm to 5 mm, and particularly preferably 0.3 μm to 4 mm. In the case where the transparent conductive film 43 is provided, the thickness of the transparent conductive film 43 is preferably 0.01 μm to 30 μm, more preferably 0.03 μm to 25 μm, and particularly preferably 0.05 μm to 20 μm.

The conductive support 1 and the conductive support 41 may have a light management function on the surface. For example, an antireflection film in which an oxide film having a high refractive index and a low refractive index is laminated and laminated as described in Japanese Laid-Open Patent Publication No. 2003-123859, and the like, may be provided in Japanese Patent Laid-Open Publication No. 2002-260746. The light guide function described.

<Photosensitive Layer> The photoreceptor layer is not particularly limited as long as it includes the semiconductor fine particles 22 and the electrolyte carrying the dye 21 . Preferably, the photoreceptor layer 2 and the photoconductor layer 42 are exemplified.

- Semiconductor microparticles (layer formed by conductor microparticles) - The semiconductor microparticles 22 are preferably chalcogenides of a metal (e.g., oxides, sulfides, selenides, etc.) or have a perovskite type crystal structure. Microparticles of the compound. The chalcogenide of the metal is preferably an oxide of titanium, tin, zinc, tungsten, zirconium, hafnium, yttrium, indium, lanthanum, cerium, lanthanum, vanadium, niobium or tantalum, cadmium sulfide, cadmium selenide, etc. . The compound having a perovskite crystal structure is preferably barium titanate or calcium titanate. Particularly preferred among these are titanium oxide (titanium dioxide), zinc oxide, tin oxide, and tungsten oxide.

The crystal structure of titanium dioxide may be an anatase type, a brookite type, or a rutile type, and an anatase type or a brookite type is preferable. The titanium dioxide nanotube/nanowire/nano rod can be used alone or in combination with titanium dioxide microparticles.

The particle diameter of the semiconductor fine particles 22 is preferably 0.001 μm to 1 μm in primary particles and 0.01 μm in average particle diameter in terms of average particle diameter (the diameter when the projected area is converted into a circle). 100 μm. Examples of the method of coating the semiconductor fine particles 22 on the conductive support 1 or the conductive support 41 include a wet method, a dry method, and other methods.

The semiconductor fine particles 22 preferably have a large surface area to facilitate adsorption of the pigment 21 . For example, in a state where the semiconductor fine particles 22 are coated on the conductive support 1 or the conductive support 41, the surface area thereof is preferably 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. In general, the larger the thickness of the semiconductor layer 45 (synonymous with the photoconductor layer 2 in the photoelectric conversion element 10) formed by the semiconductor fine particles 22, the more the amount of the dye 21 that can be carried per unit area is increased, and thus the light absorption is performed. The efficiency becomes high, but since the diffusion distance of the generated electrons increases, the loss due to charge recombination also becomes large.

As described above, in the photoelectric conversion element and the dye-sensitized solar cell, the shorter the diffusion distance of the excitation electrons, the higher the electron transport efficiency can be expected. However, when the thickness of the semiconductor layer is made thin, the photoelectric conversion efficiency is lowered. The photoelectric conversion element and the dye-sensitized solar cell of the present invention comprise the metal complex dye of the present invention in which the ligand LA and the ligand LD or the ligand LX are used in combination. Thereby, even when the semiconductor layer has the above-described conventional thickness, and even if it is thinner than the conventional thickness, excellent photoelectric conversion efficiency can be exhibited. As described above, according to the present invention, the influence of the film thickness of the semiconductor layer can be reduced, and excellent photoelectric conversion efficiency can be exhibited.

The preferred thickness of the semiconductor layer 45 (the photoreceptor layer 2 in the photoelectric conversion element 10) varies depending on the use of the photoelectric conversion element, and is typically 0.1 μm to 100 μm. In the case of being used as a dye-sensitized solar cell, it is more preferably 1 μm to 50 μm, still more preferably 3 μm to 30 μm. In the present invention, since the metal complex dye represented by the above formula (I) is used, the thickness of the semiconductor layer 45 can be made thin. For example, in the above preferred range, it may be 8 μm or less and further set to 6 μm or less.

The semiconductor fine particles 22 are preferably applied to the conductive support 1 or the conductive support 41, and then calcined at a temperature of 100 to 800 ° C for 10 minutes to 10 hours to adhere the particles to each other. In the case where glass is used as the material of the conductive support 1 or the substrate 44, the film formation temperature is preferably 60 to 600 °C.

The coating amount of the semiconductor fine particles 22 on the surface area per 1 m ^{2 of the} conductive support 1 or the conductive support 41 is preferably 0.5 g to 500 g, and more preferably 5 g to 100 g.

Between the conductive support 1 or the conductive support 41 and the photoreceptor layer 2 or the photoreceptor layer 42 , in order to prevent the electrolyte contained in the photoreceptor layer 2 or the photoreceptor layer 42 from being directly connected to the conductive support 1 or the conductive support 41 The reverse current generated by the contact is preferably formed as a short circuit preventing layer. Further, in order to prevent contact between the light receiving electrode 5 or the light receiving electrode 40 and the opposite electrode 4 or the opposite electrode 48, it is preferable to use a spacer S (refer to FIG. 2) or a spacer.

- Pigment - In the photoelectric conversion element 10 and the dye-sensitized solar cell 20, at least one metal complex dye represented by the above formula (I) is used as a sensitizing dye. The metal complex dye represented by the formula (I) is as described above.

In the present invention, a pigment which can be used in combination with the metal complex dye of the formula (I) includes a Ru complex dye, a squarylium cyanine dye, an organic dye, a porphyrin dye, a phthalocyanine dye, or the like. .

The Ru complex dye is exemplified by the Ru complex dye described in Japanese Patent Laid-Open Publication No. Hei 7-500630 (especially in the fifth row from the lower left column on page 5 to the seventh row on the seventh upper right column). The pigments synthesized in Examples 1 to 19) and the Ru complex dyes described in JP-A-2002-512729 (particularly, the third row to the twenty-thirdth page on page 20, by the example of In the case of the pigment of the composition of the first embodiment, the pigment of the composition of the invention is disclosed in JP-A-2001-59062 (in particular, the pigment described in paragraph No. 0087 to paragraph 0104), and Japanese Patent Laid-Open No. 2001 The Ru complex dye (hereinafter, the pigment described in Paragraph No. 0093 to Paragraph No. 0102) and the Ru complex dye described in JP-A-2001-253894 (Special) The pigment of the Ru complex described in JP-A-2003-212851 (especially the pigment described in Paragraph No. 0005), International Publication No. 2007 Ru complex pigments as described in /91525 (special The pigment of the present invention, which is described in JP-A-2001-291534 (especially the pigment described in paragraph No. 0120 to paragraph No. 0144), Japanese Patent Laid-Open No. 2012 The Ru complex dye (hereinafter, the pigment described in Paragraph No. 0095 to Paragraph No. 0103) and the Ru metal complex dye described in JP-A-2013-084594 (Japanese Laid-Open Patent Publication No. 2013-084594) In particular, the pigments described in Paragraph No. 0072 to Paragraph No. 0081, and the Ru complex dyes (especially those described in [0286] to [0293]) described in International Publication No. 2013/088898, The Ru complex dye (especially the pigment described in [0078] to [0082]) described in International Publication No. 2013/47615.

The squarylium dyes described in Japanese Laid-Open Patent Publication No. Hei 11-214730 (especially the pigments described in paragraph No. 0036 to paragraph No. 0047), and JP-A-2012-144688 The squarylium pigment described in the above (in particular, the pigments described in Paragraph No. 0039 to Paragraph No. 0046 and Paragraph No. 0054 to Paragraph No. 0060), or the squaraine crystals described in JP-A-2012-84503 Pigment (especially the pigment described in paragraph number 0066 to paragraph number 0076, etc.).

For example, the organic dyes described in JP-A-2004-063274 (especially the pigments described in paragraph No. 0017-paragraph No. 0021), and those described in JP-A-2005-123033 The organic coloring matter (especially the coloring matter described in Paragraph No. 0021 to Paragraph No. 0028) and the organic coloring matter described in JP-A-2007-287694 (especially the coloring matter described in Paragraph No. 0091 to Paragraph No. 0096) An organic dye (especially a pigment described in Paragraph No. 0030 to Paragraph No. 0034) or an organic dye described in International Publication No. 2007/119525 (especially [0024] The pigment described).

Examples of the porphyrin dye include a porphyrin dye described in Angew. Chem. Int. Ed., 49, pages 1 to 5 (2010), and examples of the phthalocyanine dye include application chemistry. The phthalocyanine dye described in International Edition (Angew. Chem. Int. Ed.), 46, p. 8358 (2007).

The pigment which can be used in combination is preferably a Ru complex dye, a squarylium dye or an organic dye.

The amount of the pigment to be used is preferably from 0.01 millimolar to 100 millimolar per 1 m ^{2 of the} conductive support 1 or the conductive support 41 in the total surface, more preferably from 0.1 millimolar to 50. Millions of ears, especially good is 0.1 millimoles to 10 millimoles. Further, the amount of adsorption of the pigment 21 to the semiconductor fine particles 22 is preferably 0.001 millimoles to 1 millimole, more preferably 0.1 millimoles to 0.5 millimoles, per 1 g of the semiconductor fine particles 22. By setting the amount of the pigment, the sensitizing effect in the semiconductor fine particles 22 can be sufficiently obtained.

When the metal complex dye represented by the formula (I) is used in combination with other dyes, the mass of the metal complex dye represented by the formula (I)/the mass of the other dye is preferably 95/5 to 10 /90, more preferably 95/5~50/50, further better is 95/5~60/40, especially good is 95/5~65/35, the best is 95/5~70/ 30.

After the dye is carried on the semiconductor fine particles 22, the surface of the semiconductor fine particles 22 may be treated with an amine compound. Preferred examples of the amine compound include a pyridine compound (for example, 4-tert-butylpyridine or polyvinylpyridine). When these amine compounds are liquid, they can be used as they are, or can be used by being dissolved in an organic solvent.

- Co-adsorbent - In the present invention, it is preferred to use a co-adsorbent together with the metal complex dye represented by the formula (I) 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, linoleic acid, and sub-Asian. Sesame oil and so on. Examples of the compound having a steroid skeleton include cholic acid, glycocholic acid, chenodeoxycholic acid, hyocholic acid, deoxycholic acid, and lithocholic. Acid), ursodeoxycholic acid, etc. Preferred are cholic acid, deoxycholic acid, chenodeoxycholic acid, and even more preferred is deoxycholic acid.

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

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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 is synonymous with the acidic group in the formula (AL-1), and the preferred range is also the same. Among these, R ^{A1 is} preferably an alkyl group substituted with a carboxyl group or a sulfonic acid group or a salt thereof, more preferably -CH(CH ₃ )CH ₂ CH ₂ CO ₂ H, -CH(CH ₃ ) CH ₂ CH ₂ CONHCH ₂ CH ₂ SO ₃ H.

R ^A2 may be a group selected from the group of substituents Z ^R . Of these, an alkyl group, a hydroxyl group, a decyloxy group, an alkylaminocarbonyloxy group or an arylaminocarbonyloxy group is preferred, and an alkyl group, a hydroxyl group or a decyloxy group is more preferred. nA is preferably 2 to 4.

The co-adsorbent is adsorbed on the semiconductor fine particles 22 to have an effect of suppressing an inefficient association of the metal complex pigment and preventing a redox system from the surface of the semiconductor fine particles to the electrolyte. The effect of reverse electron transfer. The amount of the co-adsorbent used is not particularly limited, and from the viewpoint of effectively exhibiting the effect, it is preferably from 1 mol to 200 mol with respect to 1 mol of the metal complex dye. Further preferably, it is 10 moles to 150 moles, and particularly preferably 20 moles to 50 moles.

- Light Scattering Layer - In the present invention, the light scattering layer is different from the semiconductor layer in that it has a function of scattering incident light. In the dye-sensitized solar cell 20, the light-scattering layer 46 preferably contains rod-shaped or plate-shaped metal oxide particles. Examples of the metal oxide particles used in the light-scattering layer 46 include particles of a chalcogenide (oxide) of the metal. In the case where the light scattering layer 46 is provided, it is preferable that the thickness of the light scattering layer is set to 10% to 50% of the thickness of the photoreceptor layer 42. The light-scattering layer 46 is preferably a light-scattering layer described in Japanese Laid-Open Patent Publication No. 2002-289274, and the disclosure of the Japanese Patent Publication No. 2002-289274 can be directly incorporated into the present specification.

<Charge Transfer Body Layer> The charge transport layer 3 and the charge transport layer 47 used in the photoelectric conversion device of the present invention are layers having a function of supplementing electrons to the oxidant of the dye 21, and are provided on the light receiving electrode 5 or the light receiving electrode 40 and are opposite to each other. Between the electrode 4 or the opposite electrode 48. The charge transporting body layer 3 and the charge transporting body layer 47 contain an electrolyte. Here, the "charge-transporting body layer-containing electrolyte" means an embodiment including the following two embodiments: an embodiment in which the charge-transporting body layer contains only an electrolyte, and an embodiment in which a substance other than the electrolyte and the electrolyte is contained. The charge transporting body layer 3 and the charge transporting body layer 47 may be in the form of a solid, a liquid, a gel, or any of these mixed states.

- Electrolyte - Examples of the electrolyte include a liquid electrolyte obtained by dissolving a redox pair in an organic solvent, a molten salt containing a redox pair, and a liquid obtained by dissolving a redox pair in an organic solvent. A so-called gel electrolyte or the like which is impregnated in a polymer matrix. Among them, a liquid electrolyte is preferred in terms of photoelectric conversion efficiency.

Examples of the redox pair include iodine and iodide (preferably an iodide salt, an iodinated ionic liquid, preferably lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, iodide Combination of propylidene oxime), alkyl viologen (eg, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate) in combination with its reducing body, polyhydroxybenzene (eg, para-benzene) Combination of diphenol, naphthalenediol, etc.) with its oxidant, combination of divalent iron complex and trivalent iron complex (for example, a combination of red blood salt and yellow blood salt), bivalent cobalt a combination of a substance and a trivalent cobalt complex, and the like. Among these, a combination of iodine and iodide or a combination of a divalent cobalt complex and a trivalent cobalt complex is preferred, and a combination of iodine and iodide is particularly preferred.

The cobalt complex is preferably a complex represented by the formula (CC) described in Paragraph No. 0144 to Paragraph No. 0156 of JP-A-2014-82189, Japanese Patent Laid-Open No. 2014-82189 The description of paragraph number 0144 to paragraph number 0156 of the publication can be directly and preferably incorporated into the present specification.

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 of a 5-membered ring or a 6-membered ring.

The organic solvent used in the liquid electrolyte and the gel electrolyte is not particularly limited, and is preferably an aprotic polar solvent (for example, acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl group). Aaquinone, cyclobutyl hydrazine, 1,3-dimethylimidazolinone, 3-methyloxazolidinone, etc.). In particular, the organic solvent used in the liquid electrolyte is preferably a nitrile compound, an ether compound, an ester compound or the like, more preferably a nitrile compound, particularly preferably acetonitrile or methoxypropionitrile.

The molten salt is preferably an ionic liquid containing an imidazolium or triazolium type cation, an ionic liquid containing an oxazole cation, an ionic liquid containing a pyridinium type cation, or an ionic liquid containing a sulfonium salt type cation. And combinations of these. Moreover, specific anions may also be combined with respect to the cations. Additives may also be added to the molten salts. The molten salt may also have a liquid crystalline substituent. Further, a molten salt of a quaternary ammonium salt can also be used as the molten salt.

Examples of the molten salt other than the above may be a melt which imparts fluidity at room temperature by mixing polyethylene oxide with lithium at least one lithium salt (for example, lithium acetate or lithium perchlorate). Salt and so on. The amount of the polymer added in this case is from 1% by mass to 50% by mass. Further, γ-butyrolactone can be contained in the electrolytic solution, whereby the diffusion efficiency of the iodide ions can be increased, and the photoelectric conversion efficiency can be improved.

The polymer (polymer matrix) used in the matrix of the gel electrolyte may, for example, be polyacrylonitrile, polyvinylidene fluoride or the like.

The gelling agent may be added to the electrolytic solution containing the electrolyte and the solvent to gelatinize the electrolyte, whereby the electrolyte is pseudo-solidified (hereinafter, the pseudo-solidified electrolyte is also referred to as "quasi-solid electrolyte"). Examples of the gelling agent 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 obtained from a specific acidic compound and a basic compound, a sorbitol derivative, and polyvinylpyridine.

Further, a method of blocking a polymer matrix, a crosslinked polymer compound or a monomer, a crosslinking agent, an electrolyte, and a solvent in a polymer may be used. The polymer matrix is preferably a polymer having a nitrogen-containing hetero ring in a repeating unit of a main chain or a side chain, and a crosslinked body obtained by reacting the nitrogen-containing hetero ring with an electrophilic compound. A polymer having a triazine structure, a polymer having a urea structure, a polymer containing a liquid crystal compound, a polymer having an ether bond, a polyvinylidene fluoride, a methacrylate, an acrylate, a thermosetting resin, or a crosslinked polyoxyalkylene oxide. Polyvinyl alcohol (Poly Vinyl Alcoho, PVA), clathrates such as polyalkylene glycol and dextrin, systems containing oxygen-containing or sulfur-containing polymers, natural polymers, and the like. 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 polymer matrix, a system containing a crosslinked polymer obtained by reacting a bifunctional or higher isocyanate with a functional group such as a hydroxyl group, an amine group or a carboxyl group can also be used. Further, a crosslinking method of reacting a hydroquinone alkyl group with a double bond compound, a polysulfonic acid or a polycarboxylic acid, or the like, and a bivalent or higher metal ion compound may be used.

The solvent which can be preferably used in combination with the pseudosolid electrolyte may, for example, be a mixed solvent containing a specific phosphate ester or ethylene carbonate, a solvent having a specific relative dielectric constant, or the like. The liquid electrolyte solution can also be held in the solid electrolyte membrane or pores. The method of holding the liquid electrolyte solution is preferably a method of using a cloth-like solid such as a conductive polymer film, a fibrous solid, or a filter.

The electrolyte may contain, in addition to the pyridine compound such as 4-tert-butylpyridine, an aminopyridine compound, a benzimidazole compound, an aminotriazole compound, an aminothiazole compound, an imidazole compound, an aminotriazine compound, a urea compound, A guanamine compound, a pyrimidine compound or a nitrogen-free heterocycle is used as an additive.

Further, in order to improve the photoelectric conversion efficiency, a method of controlling the moisture of the electrolytic solution may be employed. A preferred method of controlling the moisture may be a method of controlling the concentration or a method of coexisting the dehydrating agent. It is preferred to adjust the moisture content (content ratio) of the electrolytic solution to 0% by mass to 0.1% by mass. Iodine can also be used as a cage compound for iodine and cyclodextrin. Further, a cyclic ruthenium may be used, and an antioxidant, a hydrolysis inhibitor, a decomposition inhibitor, and zinc iodide may also be added.

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

The redox pair acts as a carrier for electrons, so it is preferred that a certain concentration is required. The preferred concentration is 0.01 mol/L or more in total, more preferably 0.1 mol/L or more, and particularly preferably 0.3 mol/L or more. The upper limit in this case is not particularly limited and is usually about 5 mol/L.

<Counter Electrode> The counter electrode 4 and the counter electrode 48 preferably function as a positive electrode of the dye-sensitized solar cell. The counter electrode 4 and the counter electrode 48 can be generally configured to have the same configuration as the conductive support 1 or the conductive support 41, and the substrate 44 is not necessarily required to sufficiently maintain the strength. The structure of the counter electrode 4 and the counter electrode 48 is preferably a structure having a high current collecting effect. In order to allow light to reach the photoreceptor layer 2 and the photoreceptor layer 42, at least one of the conductive support 1 or the conductive support 41 and the counter electrode 4 or the counter electrode 48 must be substantially transparent. In the dye-sensitized solar cell of the present invention, it is preferable that the conductive support 1 or the conductive support 41 is transparent and the sunlight is incident from the conductive support 1 or the conductive support 41 side. In this case, it is further preferable that the opposite electrode 4 and the opposite electrode 48 have a property of reflecting light. The counter electrode 4 and the counter electrode 48 of the dye-sensitized solar cell are preferably glass or plastic in which a metal or a conductive oxide is vapor-deposited, and particularly 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 by a polymer or an adhesive.

The present invention is applicable to, for example, Japanese Patent No. 4260494, Japanese Patent Laid-Open No. 2004-146425, Japanese Patent Laid-Open No. 2000-340269, Japanese Patent Laid-Open Publication No. 2002-289274, and Japanese Patent Laid-Open No. 2004-152613 A photoelectric conversion element and a dye-sensitized solar cell described in Japanese Laid-Open Patent Publication No. Hei 9-27352. Further, it is applicable to Japanese Patent Laid-Open Publication No. 2004-152613, Japanese Patent Laid-Open No. 2000-90989, Japanese Patent Laid-Open Publication 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.

[Photoelectric conversion element and method for producing a dye-sensitized solar cell] The photoelectric conversion element and the dye-sensitized solar cell of the present invention preferably use a dye solution (the pigment of the present invention) containing the metal complex dye of the present invention and a solvent. Manufactured from solution).

In such a dye solution, the metal complex dye of the present invention is dissolved in a solvent, and a co-adsorbent or other component may be contained as needed.

The solvent to be used in JP-A-2001-291534 is exemplified, but is not particularly limited thereto. In the present invention, an organic solvent is preferred, and an alcohol solvent, a guanamine solvent, a nitrile solvent, a hydrocarbon solvent, and a mixed solvent of two or more of these are more preferred. The mixed solvent is preferably a mixed solvent of an alcohol solvent and a solvent selected from the group consisting of a guanamine solvent, a nitrile solvent, and a hydrocarbon solvent. Further more preferably, it is a mixed solvent of an alcohol solvent and a guanamine solvent, a mixed solvent of an alcohol solvent and a hydrocarbon solvent, a mixed solvent of an alcohol solvent and a nitrile solvent, and particularly preferably a mixed solvent of an alcohol solvent and a guanamine solvent, and an alcohol solvent and A mixed solvent of a nitrile solvent. Specifically, preferred is a mixed solvent of at least one of methanol, ethanol, propanol and tert-butanol with at least one of dimethylformamide and dimethylacetamide, methanol, ethanol, propanol and A mixed solvent of at least one of tributanol and acetonitrile.

The dye solution preferably contains a co-adsorbent, and the co-adsorbent is preferably the co-adsorbent, of which the compound represented by the formula (CA) is preferred. Here, in the case of producing the photoelectric conversion element or the dye-sensitized solar cell of the dye solution of the present invention, in order to directly use the solution, a dye solution in which the concentration of the metal complex dye or the co-adsorbent is adjusted is preferable. In the present invention, the dye solution of the present invention preferably contains 0.001% by mass to 0.1% by mass of the metal complex dye of the present invention. The amount of the co-sorbent used is as described above.

The pigment solution preferably has a moisture content adjusted. In the present invention, it is preferred to adjust the moisture content to 0% by mass to 0.1% by mass.

In the present invention, it is preferred to use the dye solution to carry a metal complex dye represented by the formula (I) or a dye containing the same on the surface of the semiconductor fine particles, thereby producing a photoreceptor layer. That is, it is preferred to apply (including a dipping method) the dye solution on the semiconductor fine particles provided on the conductive support to dry or harden it to form a photoreceptor layer. Further, a charge transfer layer or a counter electrode or the like is further provided on the light-receiving electrode including the photoreceptor layer produced as described above, whereby the photoelectric conversion element or the dye-sensitized solar cell of the present invention can be obtained.

A dye-sensitized solar cell was produced by connecting the external circuit 6 to the conductive support 1 and the counter electrode 4 of the photoelectric conversion element produced as described above. [Examples]

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

Hereinafter, a method of synthesizing the metal complex dye of the present invention will be described in detail. In the present specification, "room temperature" means 25 ° C. Moreover, Et represents an ethyl group and TBA represents tetrabutylammonium. The metal complex dye and the synthesis intermediate synthesized in Example 1 were identified by mass spectrum (MS) measurement. The TBA salt of the synthesized metal complex dye is protonated in the MS measurement to have the same mass as the electrically neutral metal complex dye. Therefore, the results of the MS measurement are omitted for the TBA salt.

Example 1 (Synthesis of Metal Complex Pigment) The metal complex dye D-1 to the metal complex dye D-19 synthesized in the present Example are as follows.

[化56]

(Synthesis of metal complex dye (D-1) and metal complex dye (D-1TBA)) The metal complex dye (D-1) and the metal complex dye (D-1TBA) were synthesized according to the following scheme. ).

[化57]

(i) Synthesis of Compound (1-3) In a three-necked flask, THF (100 mL), Compound (1-1) (10 g), Compound (1-2) (7.1 g), and XPhosPdG3 (2-2) were placed. cyclohexyl phosphino-2 ', 4', 6'-triisopropylbiphenyl, 1.22 g) and _{K 3 PO 4 (13.3 g)} , the mixture was heated to reflux under a nitrogen atmosphere. The resulting solution was returned to room temperature, and 20 mL of H ₂ O was added and filtered over Celite, and the reaction product was extracted with ethyl acetate. The organic phase was concentrated, and the concentrated residue was purified by silica gel column chromatography to give compound (1-3).

(ii) Synthesis of Compound (1-6) Compound (1-3) (5 g) and THF (80 mL) were placed in a three-neck flask, and the mixture was cooled to -78 ° C under a nitrogen atmosphere. n-BuLi (1.6 M hexane solution, 23 mL) was added thereto, and the mixture was stirred at -78 ° C for 30 minutes. Thereafter, Bu ₃ SnCl (10 mL) was added to the mixture, and the mixture was stirred at room temperature. The resulting solution was neutralized by ammonium chloride, and the reaction product was extracted with ethyl acetate. The organic phase is concentrated to obtain a compound (1-4). The obtained compound (1-4), the compound (1-5) (9.58 g), Pd(PPh ₃ ) ₄ (1.17 g), and toluene (40 mL) were placed in an eggplant-shaped flask under a nitrogen atmosphere. The mixture was stirred at 90 °C. The obtained solution was concentrated to room temperature and concentrated, and the concentrated residue was purified by a silica gel column chromatography to obtain a compound (1-6).

(iii) Synthesis of Compound (1-8) In a three-necked flask, Compound (1-6) (2 g), toluene (60 mL), Pd(PPh ₃ ) ₄ (1 g), and Me ₃ SnSnMe ₃ ( 2.6 g), the mixture was heated under reflux for 3 hours under a nitrogen atmosphere. The resulting solution was returned to room temperature, was added 60 mL of H ₂ O for diatomaceous earth and filtered. The reaction product was extracted by toluene. The organic phase was concentrated and the concentrated residue was dried at 50 °C. The Sn body of the compound (1-6) is obtained as described above. The resulting Sn was placed in a three-necked flask, and further taken up in toluene (60 mL), Pd (PPh 3) 4 (1 g) and the compound (1-7) (2.5 g), the mixture was under a nitrogen atmosphere 4 hours of heating and reflux. The resulting solution was returned to room temperature and concentrated to give a crude material. This crude product was recrystallized from dichloromethane and isopropyl alcohol to obtain a compound (1-8) as a diethyl ester of a terpyridine compound. The compound (1-8) can be confirmed based on the following information. MS (ESI ⁺ ) m/z: 524.7 ([M+H] ⁺ )

(iv) Synthesis of Compound (1-9) The compound (1-8) (0.5 g), cerium chloride (0.25 g) and ethanol (10 mL) were placed in an eggplant-shaped flask, and the mixture was subjected to a nitrogen atmosphere. Heated back for 3 hours. The resulting precipitate was collected by filtration, and washed with ethanol to give Compound (1-9).

(v) Synthesis of Compound (1-11) In an eggplant-shaped flask, a compound (1-9) (0.6 g), a compound (1-10) (0.32 g), and DMF (N, N-dimethyl group) were placed. The guanamine, 10 mL), and tributylamine (1 mL) were heated under a nitrogen atmosphere at 140 ° C for 3 hours. After the reaction mixture was returned to room temperature, it was concentrated, and the concentrated residue was purified by silica gel column chromatography to give compound (1-11).

(vi) Synthesis of Compound (1-12) In an eggplant-shaped flask, Compound (1-11) (0.6 g), ammonium thiocyanate (0.42 g), DMF (40 mL), and H ₂ O (4 mL) were placed. The mixture was heated at 100 ° C for 3 hours. After the reaction mixture was returned to room temperature, it was concentrated, and the residue was purified by silica gel column chromatography to give compound (1-12).

(vii) Synthesis of metal complex dye (D-1) In the eggplant-shaped flask, compound compound (1-12) (200 mg), DMF (50 mL) and 1 N aqueous NaOH solution (1.7 mL) were placed. The mixture was allowed to react at room temperature. To the obtained solution, TfOH (trifluoromethanesulfonic acid) was added to adjust the pH to 2.9. The precipitate was collected by filtration, and washed with ultrapure water to obtain a metal complex dye (D-1). The metal complex dye (D-1) can be confirmed based on the following information. MS (ESI+) m/z: 1006.4 ([M+H] ⁺ )

(viii) Synthesis of metal complex dye (D-1TBA) Into an eggplant-shaped flask, a metal complex dye (D-1) (100 mg), 10% TBAOH (tetrabutylammonium hydroxide, methanol solution) was charged. 0.26 g), allowed to react at room temperature. The resulting solution was concentrated to obtain a metal complex dye (D-1 TBA).

(Synthesis of metal complex dye (D-2) to metal complex dye (D-19) and metal complex dye (D-2TBA) to metal complex dye (D-17TBA)) Metal mismatch The dye (D-2) to the metal complex dye (D-17) were synthesized in the same manner as the metal complex dye (D-1) except that the compound used was changed. That is, in the above-described synthesis method (the above-described scheme) of the metal complex dye, the compound (1-1), the compound (1-2), and the compound (1-10) are respectively changed to the metal of the synthesis target. A compound of a complex compound (D-2) to a metal complex dye is synthesized by a method similar to the synthesis of the metal complex dye (D-1). D-17). The metal complex dye (D-2TBA) to the metal complex dye (D-17TBA) were also synthesized in the same manner. Further, the metal complex dye (D-18) and the metal complex dye (D-19) are respectively used as a compound (1-9) which is an intermediate of the metal complex dye (D-1), or relative to The intermediate of the metal complex dye (D-3) of the compound (1-9) is synthesized by the same method as the method of synthesizing the dye-104 described in Patent Document 1. The synthesized metal complex dye (D-2) to metal complex dye (D-19) can be confirmed based on the data in Table 1 below.

[Table 1]

Example 2 (Production of dye-sensitized solar cell) The metal complex dye (D-1) to the metal complex dye (D-19) and the metal complex dye (D) synthesized in Example 1 were used, respectively. -1TBA) - metal complex dye (D-17TBA) or the following comparative compound (C-1) to comparative compound (C-5), the dye-sensitized solar cell 20 shown in Fig. 2 was produced (5 mm × 5) Mm scale). Manufacturing is performed by the order shown below. The following properties of each of the produced dye-sensitized solar cells 20 were evaluated. The results are shown in Table 2.

SnO ₂ conductive film (transparent conductive film 43, film thickness: 500 nm) doped with fluorine is formed on the (Preparation receiving electrode precursor [A]) of a glass substrate (substrate 44, a thickness of 4 mm), making conductive support 41. Then, (DyeSol Manufacturing Company) to the SnO ₂ film conductive paste is screen printed titania "18NR-T", dried at 120 ℃. Next, the titanium oxide paste "18NR-T" was screen-printed again and dried at 120 ° C for 1 hour. Thereafter, the dried titanium oxide paste was fired in air at 500 ° C to form a semiconductor layer 45 (layer thickness: 10 μm). Further, a titanium oxide paste "18NR-AO" (manufactured by DyeSol Co., Ltd.) was screen-printed on the semiconductor layer 45, and dried at 120 ° C for 1 hour. Thereafter, the dried titanium oxide paste was calcined at 500 ° C to form a light-scattering layer 46 (layer thickness: 5 μm) on the semiconductor layer 45. The photoreceptor layer 42 was formed on the SnO ₂ conductive film as described above (area of the light-receiving surface: 5 mm × 5 mm, layer thickness: 15 μm, and no metal complex dye was carried), and an unsupported metal complex was prepared. The light-receiving electrode precursor of the pigment [A].

SnO ₂ conductive film (transparent conductive film 43, film thickness: 500 nm) doped with fluorine is formed on the (Preparation receiving electrode precursor [B]) of a glass substrate (substrate 44, a thickness of 4 mm), making conductive support 41. Then, a titanium oxide paste "18NR-T" (manufactured by DyeSol Co., Ltd.) was screen-printed on the SnO ₂ conductive film, and dried at 120 °C. Thereafter, the dried titanium oxide paste was fired in an open atmosphere at 500 ° C to form a semiconductor layer 45 (area of the light-receiving surface: 5 mm × 5 mm, layer thickness: 6 μm). The photoreceptor layer 42 was formed on the SnO ₂ conductive film as described above (area of the light-receiving surface: 5 mm × 5 mm, layer thickness: 6 μm, unsupported metal complex pigment), and an unsupported metal complex was prepared. The light-receiving electrode precursor of the pigment [B].

(Pigment adsorption) Next, each of the metal complex dyes ((D-1) to (D-19) and (D-1TBA) to (D-17TBA))) synthesized in Example 1 was carried out as follows. It is carried on the photoreceptor layer 42 which does not carry the metal complex pigment. First, in a third butanol and acetonitrile 1: dissolving the metal complex dye 1 (volume ratio) mixed solvent so that the concentration of, respectively, 2 × 10 ^-4 mol / L, which is further added with respect to Each of the pigment solutions was prepared by using 30 moles of deoxycholic acid as a co-adsorbent for the metal complex dye of 1 mol. Next, the light-receiving electrode precursor [A] was immersed in each dye solution at 25 ° C for 20 hours, and was dried from the dye solution. The light-receiving electrode 40 on which the respective metal complex dyes are carried on the light-receiving electrode precursor [A] is produced as described above.

The light-receiving electrode precursor [B] is also carried in the same manner to carry the respective metal complex dyes, and the light-receiving electrodes 40 on which the respective metal complex dyes are carried on the light-receiving electrode precursor [B] are produced.

(Assembling of Pigment Sensitized Solar Cell) A platinum electrode (thickness of Pt film: 100 nm) having the same shape and size as that of the conductive support 41 was produced as the counter electrode 48. Further, as the electrolytic solution, 0.1 M (mol/L) of iodine, 0.1 M of lithium iodide, 0.5 M of 4-tert-butylpyridine, and 0.6 M of 1,2-dimethyl-3-propylimidazolium iodide Dissolved in acetonitrile to prepare a liquid electrolyte. Further, a spacer S "Surlyn" (trade name, manufactured by DuPont) having a shape matching the size of the photoreceptor layer 42 is prepared. Each of the light-receiving electrodes 40 produced as described above and the counter electrode 48 are thermally pressed against each other via the spacer S, and then the liquid is filled between the photoconductor layer 42 and the counter electrode 48 from the electrolyte injection port. The electrolyte forms a charge transporting body layer 47. The outer periphery of the battery prepared as described above and the electrolyte injection port were sealed and cured by using resin XNR-5516 (manufactured by Nagase Chemical Co., Ltd.) to produce each dye-sensitized solar cell (sample No. 1 to sample No. 19). .

The dye-sensitized solar cell of each sample No. 1 to sample No. 17 contains a dye-sensitized solar cell using an electrically neutral metal complex dye (D-1 to D-17) and a carboxyl group. The TBA salt metal complex pigment (D-1TBA to D-17TBA) is a dye-sensitized solar cell of the two types. The dye-sensitized solar cell of sample No. 18 and sample No. 19 used the metal complex dye (D-18 or D-19) as described above. Further, in the dye-sensitized solar cell of each sample No., a dye-sensitized solar cell using an electrically neutral metal complex dye (D-1 to D-19) as described above includes a precursor using a light-receiving electrode. A dye-sensitized solar cell manufactured by the object [A] (with "A" attached to the sample number) and a dye-sensitized solar cell manufactured using the light-receiving electrode precursor [B] (attached to the sample number) "B") These two. Similarly, a dye-sensitized solar cell using a metal complex dye (D-1TBA to D-17TBA) of a TBA salt includes a dye-sensitized solar cell manufactured using a photodetector precursor [A], and a precursor using a light-receiving electrode The dye-sensitized solar cell manufactured by the object [B] is either of two types.

For comparison, in the production of the dye-sensitized solar cell, the following metal complex dye (C-1) to metal complex dye (C-5) were used instead of the metal synthesized in Example 1. In the same manner as in the production of the dye-sensitized solar cell, a dye-sensitized solar cell (sample No. c1 to sample number c5) was produced. The metal complex dye (C-1) is a compound "pigment-607" described in Patent Document 1. The metal complex dye (C-2) is an electrically neutral metal complex dye in which the carboxyl group described in [0042] of Patent Document 3 is not salted. The metal complex dye (C-3) is the compound "D-9" described in Patent Document 2. The metal complex dye (C-4) is a compound of Example 4 (Example 2 (A-2)". The metal complex dye (C-5) is a compound "pigment-401" of Patent Document 1.

[化58]

<Test of Photoelectric Conversion Efficiency> A battery characteristic test was carried out using the produced dye-sensitized solar cells. Battery characteristic test can be by using a solar simulator (solar simulator) (WXS-85H , and the crown (the WACOM) Co., Ltd.), since the simulated AM1.5 sunlight filter xenon lamp 1000 W / m ² of And proceed. The photoelectric conversion efficiency was determined by measuring the current-voltage characteristics using an IV tester.

(Conversion efficiency (A)) A dye-sensitized solar cell (sample No. 1A to sample No. 19A and sample number) produced by using the photoelectrode precursor [A] in the dye-sensitized solar cell of each sample number From c1A to sample number c5A), the photoelectric conversion efficiency (referred to as "conversion efficiency (A)") was measured as described above. The conversion efficiency (A) measured was evaluated. The evaluation was based on the conversion efficiency (S _A ) of the dye-sensitized solar cell (sample No. c1A) produced using the light-receiving electrode precursor (A). In the evaluation criteria of conversion efficiency (A), "A" and "B" are the acceptable levels of this test, and preferably "A". On the other hand, the conversion efficiency of "C" and "D" is insufficient, and the level of acceptance (required level) of the present invention is not achieved. (Conversion efficiency (A) of the evaluation criteria) with respect to the conversion efficiency (S _A), the conversion efficiency (A) A: more than 1.2 times the case where B: greater than 1.1 times, 1.2 times or less in the case of C: greater than 1.0 times, Case of 1.1 times or less D: 1.0 times or less

(Conversion efficiency (B)) A dye-sensitized solar cell (sample No. 1B to sample No. 19B and sample number) produced by using the light-receiving electrode precursor [B] in the dye-sensitized solar cell of each sample number From c1B to sample number c5B), the photoelectric conversion efficiency (referred to as "conversion efficiency (B)") was measured as described above. The measured conversion efficiency (B) was evaluated. The conversion efficiency (S _A ) of the dye-sensitized solar cell (sample No. c1A) produced using the light-receiving electrode precursor [A] was evaluated. In the evaluation criteria of conversion efficiency (B), "A" and "B" are the acceptable levels of this test, and preferably "A". On the other hand, the conversion efficiency of "C" and "D" is insufficient, and the level of acceptance (required level) of the present invention is not achieved. (Evaluation Criteria for Conversion Efficiency (B)) Conversion efficiency (B) A: greater than 1.1 times with respect to conversion efficiency (S _A ) B: Case of more than 1.0 times and 1.1 times or less C: more than 0.9 times Case of 1.0 times or less D: 0.9 times or less

<Evaluation of Durability> A dye-sensitized solar cell (sample No. 1A to sample No. 19A and sample number) produced by using the photoreceptor precursor [A] in the dye-sensitized solar cell of each sample number was used. From c1A to sample number c5A), a heat cycle test was performed as durability (heat deterioration) evaluation. Each of the dye-sensitized solar cells was alternately placed in a freezer at -10 ° C and a thermostat at 50 ° C every 12 hours, and was repeatedly cooled and heated (thermal cycle test). Regarding the dye-sensitized solar cell before the heat cycle test and the dye-sensitized solar cell after 72 hours of the heat cycle test, the current was measured. The current value (short-circuit current density) obtained by measuring the current-voltage characteristics in the dye-sensitized solar cell after 72 hours of the heat cycle test was divided by the current value measured in the dye-sensitized solar cell before the heat cycle test. (short circuit current density). This value is taken as the current holding ratio. The durability was evaluated on the basis of the current holding ratio obtained as described above. In the evaluation criteria of durability, "A" and "B" are the acceptable levels of this test, and preferably "A". On the other hand, the current holding ratios of "C" and "D" are insufficient, and the level of acceptance (required level) of the present invention is not achieved. (Evaluation criteria for durability) A: 0.9 times or more B: Less than 0.9 times and 0.8 times or more C: Less than 0.8 times and 0.7 times or more D: Less than 0.7 times

[Table 2] Table 2

The following results are known from the results shown in Table 2. In sample No. 1 to sample No. 19 (present invention), all of the ligands LA represented by the above formula (AL-1) are used, and an anion of one nitrogen atom and at least one atom is used. A metal complex dye (D-1 to D-19) having a 2- or 3-dental ligand LD on the metal ion M or a single-dental ligand LX as a ligand. The photoelectric conversion element of the present invention and the dye-sensitized solar cell (sample No. 1 to sample No. 19) which are supported on the semiconductor fine particles by the metal complex dyes (D-1 to D-19) are conversion efficiency ( A) and conversion efficiency (B) are both high and the current retention rate is also high. The metal complex dye of the present invention imparts the above-described characteristics excellent in the photoelectric conversion element and the dye-sensitized solar cell, as shown in Table 2, whether it is an electrically neutral or a TBA salt.

Further, it is understood that when L ¹ is a ring group represented by formula (X-1), particularly a furan ring group, in the -L ¹ -[L ² ]nZ group, the conversion efficiency (B) becomes high. Further, it is understood that when L ² is an aromatic ring group, the conversion efficiency (B) becomes high. Further, it is understood that when n is 1 or 2, the conversion efficiency (B) becomes high. It is understood that when the two- or three-dental ligand is used as the ligand LD, the conversion efficiency (A), the conversion efficiency (B), and the current retention ratio are both high.

Further, the metal complex dye of the present invention can be suitably used as the sensitizing dye of the photoelectric conversion element and the dye-sensitized solar cell of the present invention. The dye solution of the present invention containing the metal complex dye of the present invention and a solvent can be suitably used in the preparation of semiconductor fine particles carrying the metal complex dye of the present invention.

On the other hand, when a metal complex dye which does not have the ligand LA represented by the above formula (AL-1) is used, it is not sufficient in terms of conversion efficiency and durability. In other words, in the sample No. c1, the sample No. c2, the sample No. c4, and the sample No. c5, the ligand LA not represented by the formula (AL-1) and the ligand are used. A metal complex dye of a 2- or 3-tooth ligand of LD. However, both conversion efficiency and durability have not reached the level of qualification. In the sample No. c3, a metal complex dye which does not have the ligand LA represented by the above formula (AL-1) is used. However, the conversion efficiency has not reached the level of qualification.

The invention will be described based on this embodiment, but we do not limit our invention in any detail of the description unless otherwise specified, and should not violate the spirit of the invention as shown in the attached patent application. Explain widely with scope.

The present application claims priority to Japanese Patent Application No. 2014-199252, filed on Sep. 29,,,,,,,,,,,,,,, In this manual.

1, 41‧‧‧ Conductive support
2, 42‧‧‧ photoreceptor layer
3, 47‧‧‧ charge transfer body layer
4, 48‧‧‧ relative electrode
5, 40‧‧‧Acceptance electrode
6‧‧‧External circuit
10‧‧‧ photoelectric conversion components
20‧‧‧Pigment sensitized solar cells
21‧‧‧ pigment
22‧‧‧Semiconductor particles
43‧‧‧Transparent conductive film
44‧‧‧Substrate
45‧‧‧Semiconductor layer
46‧‧‧Light scattering layer
100‧‧‧Systems for applying photoelectric conversion elements to battery applications
M‧‧‧ action unit (eg electric motor)
S‧‧‧ spacers

1 is a cross-sectional view schematically showing a photoelectric conversion element according to a first embodiment of the present invention, including an enlarged view of a circular portion in a layer, in a system to which the battery is applied. FIG. 2 is a cross-sectional view schematically showing a dye-sensitized solar cell including the photoelectric conversion element according to the second embodiment of the present invention.

1‧‧‧Electrical support

2‧‧‧Photoreceptor layer

3‧‧‧ Charge Transfer Body Layer

4‧‧‧relative electrode

5‧‧‧Photoelectrode

6‧‧‧External circuit

10‧‧‧ photoelectric conversion components

21‧‧‧ pigment

22‧‧‧Semiconductor particles

100‧‧‧Systems for applying photoelectric conversion elements to battery applications

M‧‧‧ action unit (eg electric motor)

Claims (17)

A photoelectric conversion element comprising a conductive support, a photoreceptor layer containing an electrolyte, a charge transfer body layer containing an electrolyte, and a photoelectric conversion element of an opposite electrode, the photoreceptor layer comprising a metal represented by the following formula (I) the semiconductor fine particle complexes dye: formula (I) M (LA) ( LD) mD (LX) mX · (CI) mY formula, M represents a metal ion; LA represented by the following formula (AL-1) represented by a dental ligand; LD represents a 2-dental ligand or a 3-dental ligand different from the LA; at least one of the coordination atoms of the LD bonded to the metal ion M is a nitrogen atom, at least one Is an anion; mD represents 0 or 1; LX represents a monodentate ligand; mX represents 1 when mD is 1 and LD is a 2 tooth ligand, and 0 when mD is 1 and LD is a 3 tooth ligand. When mD is 0, it represents 3; CI represents a counter ion required for neutralizing the charge of the metal complex dye; mY represents an integer of 0 to 3; Wherein Za and Zb each independently represent a group of non-metal atoms required to form a ring of 5 or 6 members; wherein at least one of the rings formed by Za and Zb respectively has an acidic group; L ^{W is} independently represented a nitrogen atom or CR ^W , R ^W represents a hydrogen atom or a substituent; L ¹ represents a cyclic group represented by the following formula (X-1) or formula (X-2); and L ² represents a vinyl group, an ethynyl group or An aromatic ring group; n represents an integer of 1 to 4; Z represents a hydrogen atom or a substituent; -L ¹ -[L ² ]nZ group does not have the acidic group and the amine group; Of formula (X-1) in, E ¹ represents -O -, - Se -, - NR X2c -, - C (R X2c) 2 -, - (R X2c) C = C (R X2c) - or -Si ( R ^X2c ) ₂ -; R ^X2c represents a hydrogen atom or a substituent; R ^T1 represents a substituent; PT1 represents an integer of 0 to 2; and in the formula (X-2), E ² represents -O-, -S- or -NR ^X2c -; E ³ and E ⁴ each independently represent -N= or -C(R ^X2c )=, at least one of E ³ and E ⁴ is -N=; R ^X2c represents a hydrogen atom or a substituent; 1) and in the formula (X-2), * represents a bonding position with the ring having L ^W or L ² . The photoelectric conversion element according to claim ¹ , wherein the L ¹ is a ring group represented by the formula (X-1). The photoelectric conversion element according to the first aspect of the invention, wherein the ring group represented by the formula (X-1) is represented by any formula of the following formula (X-1a) to formula (X-1c). Ring base: ^Wherein E ^{1 has the} same meaning as E ¹ of the formula (X-1); R ^T1a to R ^T1c each independently represent a hydrogen atom or a substituent; ** represents a bond with the ring having L ^W or L ² Knot position. The photoelectric conversion element according to claim 1, wherein the L ² is an aromatic ring group. The scope of the patent application, paragraph 2 of the photoelectric conversion element, wherein the L ² is an aromatic ring group. The photoelectric conversion element according to claim 1, wherein the n is 1 or 2. The photoelectric conversion element according to claim 1, wherein the ring formed by the Za is selected from the group consisting of a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, a tetrazine ring, and a quinoline. a group consisting of a ring, an isoquinoline ring, an imidazole ring, a pyrazole ring, a triazole ring, a thiazole ring, an oxazole ring, a benzimidazole ring, a benzotriazole ring, a benzoxazole ring, and a benzothiazole ring At least one of the group, the ring formed by the Zb is selected from the group consisting of a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, a tetrazine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, At least one of the group consisting of a triazole ring, a thiazole ring, an oxazole ring, a benzimidazole ring, a benzotriazole ring, a benzoxazole ring, and a benzothiazole ring, the ring comprising the L ^W is At least one selected from the group consisting of a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a tetrazine ring, a quinoline ring, and an isoquinoline ring is selected. The photoelectric conversion element as defined in claim 1 in the range of item, wherein said M is Ru ^{2 +} or Os ^{2 +.} The photoelectric conversion element according to claim 1, wherein the LA is a 3-dental ligand represented by the following formula (AL-2): In the formula, Anc represents an acidic group; L ¹ , L ² , Z and n are synonymous with L ¹ , L ² , Z and n of the formula (AL-1). The photoelectric conversion element according to claim 1, wherein the acidic group is a carboxyl group or a salt thereof. The photoelectric conversion element according to any one of the following formulas (2L-1) to (2L-4), wherein the LD is represented by any one of the following formulas (2L-1) to (2L-4) Dental ligand: In the formula, ring D ^2L represents an aromatic ring; A ¹¹¹ to A ¹⁴¹ each independently represent an anion of a nitrogen atom or an anion of a carbon atom; and R ¹¹¹ to R ¹⁴³ each independently represent a hydrogen atom or do not have the acidic group; Substituent; * indicates the coordination position on the metal ion M. The photoelectric conversion element according to any one of the above formulas (3L-1) to (3L-4), wherein the LD is 3, which is represented by any one of the following formulas (3L-1) to (3L-4) Dental ligand: Wherein ring D ^2L represents an aromatic ring; A ²¹¹ to A ²⁴² each independently represent a nitrogen atom or a carbon atom; wherein, A ²¹¹ and A ²¹² , A ²²¹ and A ²²² , A ²³¹ and A ²³² , A ²⁴¹ At least one of each of A ²⁴² is an anion; R ²¹¹ to R ²⁴¹ each independently represent a hydrogen atom or a substituent having no such acidic group; * represents a coordination position on the metal ion M. The photoelectric conversion element according to the above aspect of the invention, wherein the metal complex dye represented by the formula (I) is represented by the following formula (I-1) or (I-2): Wherein M and LX are synonymous with M and LX of the formula (I); Anc, L ¹ , L ² , Z and n and the acidic group of the formula (AL-1), L ¹ , L ² , Z And n are synonymous; Ring D and Ring E each independently represent an aromatic ring of 5 or 6 members; D ¹ and D ² each independently represent an anion of a carbon atom or an anion of a nitrogen atom; here, Ring D and Ring E The bond between D ¹ and D ² and the carbon atom bonded to the pyridine ring is a single bond or a double bond; R ^a1 to R ^a4 each independently represent a substituent; and ma1, ma2 and ma4 each independently represent An integer of 0 to 3; ma3 represents an integer of 0 to 4. The photoelectric conversion element according to claim 13, wherein the ring D and the ring E are each independently a pyrazole ring, a triazole ring or a benzene ring. A dye-sensitized solar cell comprising the photoelectric conversion element according to any one of claims 1 to 14. A metal complex dye represented by the following formula (I): Formula (I) M (LA) (LD) _mD (LX) _mX · (CI) _mY wherein M represents a metal ion; LA represents the following a 3-dental ligand represented by the formula (AL-1); LD represents a 2-dental ligand or a 3-dental ligand different from the LA; and a coordinating atom of the LD bonded to the metal ion M At least one is a nitrogen atom, at least one is an anion; mD represents 0 or 1; LX represents a monodentate ligand; mX represents 1 when mD is 1 and LD is a 2 tooth ligand, and 1 is at mD and LD is 3 teeth ligand represents 0, when mD is 0, represents 3; CI represents the counter ion required to neutralize the charge of the metal complex pigment; mY represents an integer of 0 to 3; Wherein Za and Zb each independently represent a group of non-metal atoms required to form a ring of 5 or 6 members; wherein at least one of the rings formed by Za and Zb respectively has an acidic group; L ^{W is} independently represented a nitrogen atom or CR ^W , R ^W represents a hydrogen atom or a substituent; L ¹ represents a cyclic group represented by the following formula (X-1) or formula (X-2); and L ² represents a vinyl group, an ethynyl group or An aromatic ring group; n represents an integer of 1 to 4; Z represents a hydrogen atom or a substituent; -L ¹ -[L ² ]nZ group does not have the acidic group and the amine group; In the formula (X-1), E ¹ represents -O-, ^-Se- , -NR ^X2c -, -C(R ^X2c ) ₂ -, -(R ^X2c )C=C(R ^X2c )- or -Si( R ^X2c ) ₂ -; R ^X2c represents a hydrogen atom or a substituent; R ^T1 represents a substituent; PT1 represents an integer of 0 to 2; and in the formula (X-2), E ² represents -O-, -S- or -NR ^X2c -; E ³ and E ⁴ each independently represent -N= or -C(R ^X2c )=, at least one of E ³ and E ⁴ is -N=; R ^X2c represents a hydrogen atom or a substituent; 1) and in the formula (X-2), * represents a bonding position with the ring having L ^W or L ² . A pigment solution containing the metal complex dye and a solvent as described in claim 16 of the patent application.