JPWO2016108269A1 - Compound, support and photoelectric conversion element - Google Patents

Abstract

A compound represented by the following general formula (1). (In the formula, A1 is an optionally substituted aromatic hydrocarbon ring group or an optionally substituted aromatic heterocyclic group, and A2 is a direct bond or the following formulas (A2-1) to (A2-20) ) Is a group in which 1 to 9 groups selected from the groups represented by the above are linked, R1, R2 and R3 represent a hydrogen atom or an optionally substituted hydrocarbon group, and R1 and R2 are linked to each other. And R1 and R2 may be independently connected to A1 to form a ring, and R4 represents a hydrogen atom or a cyano group.)

Description

  The present invention relates to a novel compound, a support carrying the same, and further to a photoelectric conversion element provided with an electrode having the support.

  Conventionally, dyes are widely used in various technical fields. For example, in the field of photoelectric conversion elements such as solar cells, dyes having a photosensitizing action are used for dye-sensitized photoelectric conversion elements. This dye-sensitized photoelectric conversion element can be expected to have a theoretically high photoelectric conversion efficiency, and is considered to be manufactured at a lower cost than a conventional photoelectric conversion element using a silicon semiconductor. However, since the absorption wavelength of the sensitizing dye is limited as compared with silicon, there is a problem that the light use efficiency is low and the photoelectric conversion efficiency of the device is low. In addition, there is a problem that the dye supported on the metal oxide semiconductor is eluted into the electrolyte.

  As a technique for improving the conversion efficiency and durability of a dye-sensitized photoelectric conversion element, studies have been made on improving the supportability of a carrier and a dye. In other words, by improving physical and chemical adsorptivity, it becomes possible to transfer the excitation energy of the dye to the carrier with high efficiency, and the dye elutes into the element (specifically, electrolyte solution, etc. Elution). As a technique for improving the supportability, a dye molecule having a structure in which a carboxylic acid group is bonded with an amide bond (Patent Document 1), a dye molecule having two carboxyl groups (Patent Document 2), etc. It is disclosed. However, in a solar cell which is one of the main uses of a dye-sensitized photoelectric conversion element, high durability is required due to the characteristics of the use, and a known dye and a photoelectric conversion element using the dye are not yet used. Sufficient durability is not obtained.

JP 2011-122088 JP 2000-299139 A

  Accordingly, an object of the present invention is to provide a photoelectric conversion element having high light conversion efficiency and high durability.

  As a result of intensive studies, the present inventors have found that a novel compound having a specific structure is found, and that when the working electrode supporting the novel compound is used, the above problem is solved, and the present invention It has come.

That is, the present invention provides a compound represented by the following general formula (1).

（式中、Ａ^１は置換されていてもよい芳香族炭化水素環基又は置換されていてよい芳香族ヘテロ環基であり、Ａ^２は直接結合又は下記式（Ａ２−１）〜（Ａ２−２０）で表される基から選ばれる基を１〜９個連結した基であり、Ｒ^１、Ｒ^２及びＲ^３は、水素原子又は置換されていてもよい炭化水素基を表し、Ｒ^１及びＲ^２は、互いに連結して環を形成してもよく、Ｒ^１及びＲ^２は互いに独立してＡ^１と連結して環を形成してもよく、Ｒ^４は、水素原子又はシアノ基を表す。）

（式中、Ｘは、Ｓ、Ｏ、ＮＲを表し、Ｒは水素原子又は置換されていてもよい炭化水素基を表し、上記式（Ａ２−１）〜（Ａ２−２０）で表される基中の水素原子は、フッ素原子、塩素原子、臭素原子、ヨウ素原子、シアノ基、ニトロ基、−ＯＲ^５基、−ＳＲ^５基、−ＮＲ^５Ｒ^６基又は置換されていてもよい脂肪族炭化水素基で置換されていてもよく、Ｒ^５及びＲ^６は、水素原子又は置換されていてもよい炭化水素基を表す。）

(In the formula, A ¹ is an optionally substituted aromatic hydrocarbon ring group or an optionally substituted aromatic heterocyclic group, and A ² is a direct bond or the following formulas (A2-1) to (A2- 20) a group in which 1 to 9 groups selected from the groups represented by the formula (1) are linked, R ¹ , R ² and R ³ represent a hydrogen atom or an optionally substituted hydrocarbon group, and R ¹ and R ² may be linked to each other to form a ring, R ¹ and R ² may be independently linked to A ¹ to form a ring, and R ⁴ may be a hydrogen atom or a cyano group. Represents.)

Wherein X represents S, O, NR, R represents a hydrogen atom or an optionally substituted hydrocarbon group, and groups represented by the above formulas (A2-1) to (A2-20) hydrogen atoms in the fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, -OR ⁵ group, -SR ⁵ group, ^-NR 5 ^{R 6} group or optionally substituted aliphatic have carbonized (It may be substituted with a hydrogen group, and R ⁵ and R ⁶ represent a hydrogen atom or an optionally substituted hydrocarbon group.)

  Moreover, this invention provides the support body which carry | supports at least 1 sort (s) of the compound of the said General formula (1).

  Moreover, this invention provides the photoelectric conversion element provided with the electrode which has the said support body.

FIG. 1 is a schematic diagram showing a cross-sectional configuration of an example of the photoelectric conversion element of the present invention. FIG. 2 is an enlarged view of the main part of the photoelectric conversion element of the present invention shown in FIG.

  Hereinafter, the compound of the present invention, a support using the compound, and a photoelectric conversion element using the support will be described based on preferred embodiments.

First, the compound of the present invention will be described.
Examples of the optionally substituted hydrocarbon group represented by R ¹ , R ² and R ³ include an aromatic hydrocarbon group, an aromatic hydrocarbon group substituted with an aliphatic hydrocarbon, and an aliphatic hydrocarbon group. Can be mentioned.
Examples of the aromatic hydrocarbon group include phenyl, naphthyl, cyclohexylphenyl, biphenyl, terphenyl, fluoryl, thiophenylphenyl, furanylphenyl, 2′-phenyl-propylphenyl, benzyl, naphthylmethyl, and the like.
Examples of the aliphatic hydrocarbon group include aliphatic hydrocarbon groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t- Linear, branched and cyclic such as amyl, hexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, nonyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl Of the alkyl group. The aliphatic hydrocarbon group having 1 to 20 carbon atoms includes —O—, —COO—, —OCO—, —CO—, —S—, —SO—, —SO ₂ —, —NR ¹⁵ —, —C. = C-, -C≡C- may be interrupted. R ¹⁵ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include the above aliphatic hydrocarbon groups having 1 to 20 carbon atoms. When the group that interrupts an aliphatic hydrocarbon group having 1 to 20 carbon atoms contains a carbon atom, the number of carbon atoms including the interrupted group is 1 to 20.
Examples of the aromatic hydrocarbon group substituted with the aliphatic hydrocarbon group include phenyl, naphthyl, benzyl and the like substituted with the aliphatic hydrocarbon group.
Examples of the group that may substitute these hydrocarbon groups include a fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, thiol group, and —NR ¹⁰ R ²⁰ group. R ¹⁰ and R ²⁰ represent a hydrogen atom or an optionally substituted hydrocarbon group.

The group represented by A ¹ in the general formula (1) is a divalent group, and may be an optionally substituted aromatic hydrocarbon ring group or an optionally substituted aromatic heterocyclic group.
Examples of the aromatic hydrocarbon ring group include an unsubstituted aromatic hydrocarbon ring group and an aromatic hydrocarbon ring group substituted with an aliphatic hydrocarbon group. The aromatic heterocyclic group includes an unsubstituted group. An aromatic heterocyclic group, an aromatic heterocyclic group substituted with an aliphatic hydrocarbon group and the like can be mentioned.

  Examples of the divalent unsubstituted aromatic hydrocarbon ring group include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene- 1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2, 6-diyl, anthracene-1,4-diyl, anthracene-1,5-diyl, anthracene-1,10-diyl, anthracene-9,10-diyl, perylene-3,10-diyl, pyrene-1,6- Examples include diyl and pyrene-2,7-diyl.

Examples of the divalent aromatic hydrocarbon ring group substituted with an aliphatic hydrocarbon group include, for example, the above divalent unsubstituted aromatic hydrocarbon ring represented by 1 to 20 aliphatic hydrocarbon groups having 1 to 20 carbon atoms. The one substituted at three places is mentioned.
Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms are the same as those used in the description of R ^{1 to} R ³ .

  Examples of the divalent unsubstituted aromatic heterocyclic group include furan-2,5-diyl, furan-3,5-diyl, thiophene-2,5-diyl, thiophene-3,5-diyl, and 2H-chromene-3. , 7-diyl, benzothiophene-2,6-diyl, benzothiophene-2,5-diyl and the like.

  Examples of the divalent aromatic heterocyclic group substituted with an aliphatic hydrocarbon group include 1-alkyl-pyrrole-2,5-diyl, 1-alkyl-pyrrole-3,5-diyl, Examples thereof include those in which an unsubstituted aromatic heterocyclic group is substituted by 1 to 3 positions with an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Moreover, a C1-C20 aliphatic hydrocarbon group is a group similar to the above.

The aromatic hydrocarbon ring group and aromatic heterocyclic group listed above may be further substituted, and the group that may substitute the aromatic hydrocarbon ring group and aromatic heterocyclic group is a fluorine atom. Chlorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, thiol group, —NR ⁵⁰ R ⁶⁰ group and the like. R ⁵⁰ and R ⁶⁰ represent a hydrogen atom or an optionally substituted hydrocarbon group, and as the optionally substituted hydrocarbon group, the same groups as those described above for R ^{1 to} R ³ are used. be able to. Moreover, when it has a methylene in an aromatic hydrocarbon ring group or an aromatic heterocyclic group, two hydrogen atoms may be substituted by the same oxygen atom and may be carbonyl.

A ² in the partial structural formula (1) is a group in which 1 to 9 groups selected from direct bonds or groups represented by the formulas (A2-1) to (A2-20) are connected, preferably 1 to 7 linked groups, more preferably 2 to 4 linked groups. The groups represented by the above formulas (A2-1) to (A2-20) can be connected in any direction. Note that * in the above formulas (A2-1) to (A2-20) means that the groups represented by these formulas are bonded to adjacent groups at the * portion (the same applies hereinafter).

In the above formulas (A2-1) to (A2-19), X represents S, O, or NR, and R represents a hydrogen atom or an optionally substituted hydrocarbon group. The optionally substituted hydrocarbon group represented by R is the same as that described above as the optionally substituted hydrocarbon group represented by R ^{1 to} R ³ .

Hydrogen atoms contained in the group represented by the formula (A2-1) ~ (A2-19) is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, -OR ⁵ group, -SR ^It may be substituted with ⁵ groups, -NR ⁵ R ⁶ group or an optionally substituted aliphatic hydrocarbon group. R ⁵ and R ⁶ represent a hydrogen atom or an optionally substituted hydrocarbon group. These groups that substitute A ² may be linked to each other to form a ring.
Examples of the optionally substituted aliphatic hydrocarbon group represented by R ⁵ and R ⁶ include the aforementioned aliphatic hydrocarbon groups having 1 to 20 carbon atoms, which may be substituted. substituents are the same as those of the group which may be substituted with an aromatic hydrocarbon ring group and the aromatic heterocyclic group represented by a ^1.
In addition, examples of the optionally substituted hydrocarbon group represented by R ⁵ and R ⁶ include the same hydrocarbon groups as those described above as the optionally substituted hydrocarbon group represented by R ^{1 to} R ^3. . Examples of the group that may substitute the hydrocarbon group represented by R ⁵ and R ⁶ include those described above as the group that may substitute the hydrocarbon group represented by R ^{1 to} R ³ .

Specific examples of the structure of the A ¹ -A ² moiety in the general formula (1) include the following A (1) to (32). In A (1) ~ (32) shown below, the left end of the ring structure is ^{A 1,} the other portion corresponds to ^{A 2.}
Incidentally, in the following, shows what does not have a substituent, as described above, A ¹ may have a substituent, a hydrogen atom in A ² is substituted with a substituent May be. Further, in the following A (16) to (23), the bond described over a plurality of rings means that the bond is bonded to any of carbon atoms constituting those rings (the same applies hereinafter). .

R ¹ and R ² in the general formula (1) may be independently connected to a partial structure of A (1) to A (32) to form a ring.

Among the general formula (1), a compound in which the following partial structure (2) in the general formula (1) is any one of the following partial structures (2-1) to (2-14) is particularly used for photoelectric conversion. It is preferable because it shows good characteristics. In particular, those having the following partial structures (2-1), (2-2), (2-7) or (2-10) are preferable because they are easy to produce and have high photoelectric conversion efficiency.
In the following partial structures (2) and (2-1) to (2-14), the bond from A ¹ to A ² is omitted. In the following partial structures (2-1) to (2-14), the bond from A ¹ to A ² may be attached to any carbon atom constituting the aromatic hydrocarbon ring or aromatic heterocycle. Good.

（式中、Ａ¹、Ｒ¹及びＲ²は一般式（１）のＡ¹、Ｒ¹及びＲ²とそれぞれ同じである。）

(Wherein, A ^1, R ¹ and R ² is the general formula A ^1, R ¹ and R ² (1), respectively the same.)

（式中、Ｒ^１及びＲ^２は上記部分構造式（２）のＲ^１及びＲ^２を意味し、Ｒ^７、Ｒ^８及びＲ^９は、Ｍ^２に配位する公知の配位子を表し、Ｍ^１及びＭ^２は金属元素を表し、式中の水素原子は、フッ素原子、塩素原子、ヨウ素原子、シアノ基、ニトロ基、−ＯＲ^５基、−ＳＲ^５基又は置換されていてもよい脂肪族炭化水素基で置換されていてもよく、Ｒ^５は、水素原子又は置換されていてもよい炭化水素基を表す。）

(Wherein, ^{R 1} and ^{R 2} means ^{R 1} and ^{R 2} of the above partial structural formula ^{(2), R 7, R} 8 and ^{R 9} represents a known ligand coordinating to ^{M 2} , M ¹ and M ² represent a metal element, and a hydrogen atom in the formula may be a fluorine atom, a chlorine atom, an iodine atom, a cyano group, a nitro group, an —OR ⁵ group, an —SR ⁵ group or a substituted group. (It may be substituted with an aliphatic hydrocarbon group, and R ⁵ represents a hydrogen atom or an optionally substituted hydrocarbon group.)

In (2-6) representing the partial structure (2), as the metal element of M ¹ , specifically, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Sn, Yb, Ti, Zr, Hf, V, Nb, Ta, Th, U, Mn, Cu, Cr, Fe, Co, Zn, Mo, Ni, Rh, etc. Among these, Cu, Ti, Ni, Fe, and Zn are preferable, and Cu or Zn is more preferable.
In (2-11) and (2-12) representing the partial structure (2), examples of the metal element of M ² include metals capable of tetracoordination or hexacoordination, and more preferably Ru, Fe , Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn, Zn, more preferably Ru, Fe, Os, Cu, and particularly preferably Ru. .

In (2-11) and (2-12) representing the partial structure (2), examples of the known ligand coordinated to M ² represented by R ⁷ , R ⁸ and R ⁹ include monodentate, two It is a bidentate or tridentate ligand, and the ligand may be a neutral ligand or an anionic ligand. Although it does not specifically limit as a specific ligand, Preferably a halogen atom, -NCS, oxalic acid, PPh (OMe) _2, etc. are mentioned, More preferably, a halogen atom and -NCS are mentioned.

  Specific examples of the compound represented by the general formula (1) include the following compound Nos. 1-17 are mentioned, but it is not limited to these. In the structural formula, Bu represents an n-butyl group, Hex represents an n-hexyl group, Oct represents an n-octyl group, Non represents an n-nonyl group, and Un represents an n-undecyl group. Represent.

  The compound of the present invention can be obtained by a method using a known or well-known general reaction, and its synthesis method is not particularly limited. Examples of typical synthesis methods are given below.

  Carboxylic acid protected body (C) is synthesized by reacting carboxylic acid body (A) and aniline derivative (B) protected with carboxylic acid in 2-chloro-1-methylpyridinium iodide and a basic environment. Next, the target product (compound represented by the general formula (1)) is obtained by deprotection.

（式中、Ａ¹、Ａ²、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は上記一般式（１）のＡ¹、Ａ²、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴のそれぞれと同じである。）

^{(Wherein, A 1, A 2, R} 1, R 2, R 3 and R ⁴ are the same as each of ^{A 1, A 2, R 1} , R 2, R 3 and R ⁴ in the general formula (1) .)

  The compound of the present invention can be suitably used for applications such as photoelectric conversion elements in the form of a support by supporting it on a carrier described below, as well as synthesis of optical recording materials, pharmaceuticals, agricultural chemicals, fragrances, dyes, etc. Intermediates; various functional materials, various polymer raw materials; photoelectrochemical cells, nonlinear optical devices, electrochromic displays, holograms, organic semiconductors, organic ELs; silver halide photographic light-sensitive materials, photosensitizers; printing inks, inkjets, Colorants used in electrophotographic color toners, cosmetics, plastics, etc .; protein stains, luminescent dyes for substance detection; synthetic quartz raw materials, paints, synthetic catalysts, catalyst carriers, surface coat thin film materials, silicone rubber crosslinkers It can also be used for applications such as a binder.

Next, the carrier of the present invention will be described.
Examples of the material (carrier) used for the carrier of the present invention include organic resins such as acrylic resins and fluororesins, metal oxides such as titanium oxide, zinc oxide, and aluminum oxide, silicon oxide, zeolite, activated carbon, and the like. Those having a porous surface are preferred. The shape of the carrier is not particularly limited, and may be appropriately selected depending on the use of the carrier from, for example, a film shape, a powder shape, a granular shape and the like.

The carrier of the present invention is characterized in that the compound to be supported has at least one compound represented by the above general formula (1), but other compounds can also be used in combination. The amount of the compound represented by the general formula (1) is not particularly limited, and may be appropriately selected depending on the use of the support.
When the carrier of the present invention is used in the photoelectric conversion element described below, the amount of the compound represented by the general formula (1) is the compound represented by the general formula (1) in terms of excellent photoelectric conversion efficiency. And other compounds, 10% by mass or more, preferably 30% by mass or more, and more preferably 50% by mass or more.

  As a method for supporting the compound represented by the general formula (1) on the carrier, known methods such as gas phase adsorption and liquid phase adsorption can be used. For example, as an example of liquid phase adsorption, a compound represented by the general formula (1) is dissolved in a solvent, and the carrier represented by the general formula (1) is adsorbed on the carrier by immersing the carrier in the solution. The method of letting it be mentioned. When other compounds are used in combination, the compound represented by the general formula (1) and the other compounds are dissolved in different solvents, and the carrier is immersed in each solution to represent the general formula (1). The support of the present invention can be obtained by supporting a compound and other compounds on a carrier. In addition, the compound represented by the general formula (1) and other compounds may be dissolved in the same solvent, and the compound represented by the general formula (1) and other compounds may be simultaneously adsorbed on the carrier using this solution. it can.

  In a preferred production method of the carrier of the present invention, first, a metal oxide semiconductor layer 12 having a porous structure is formed on the surface of the conductive substrate 11 on which the conductive layer 11B is formed by electrolytic deposition or firing. Form. When the metal oxide semiconductor layer is formed by electrolytic deposition, for example, an electrolytic bath containing a metal salt that becomes a metal oxide semiconductor material is set to a predetermined temperature while bubbling with oxygen or air. The conductive substrate 11 is dipped in and a constant voltage is applied to the counter electrode. Thereby, a metal oxide semiconductor material is deposited on the conductive layer 11B so as to have a porous structure. At this time, the counter electrode may be appropriately moved in the electrolytic bath. When the metal oxide semiconductor layer is formed by a firing method, for example, a metal oxide slurry prepared by dispersing metal oxide semiconductor material powder in a dispersion medium is applied to the conductive substrate 11 and dried. Then, it is fired to have a porous structure. Subsequently, a dye solution in which the compound (dye 13) represented by the general formula (1) is dissolved in an organic solvent is prepared. By immersing the conductive substrate 11 on which the metal oxide semiconductor layer 12 is formed in this dye solution, the metal oxide semiconductor layer 12 carries the dye 13.

  The carrier of the present invention can be suitably used for a photoelectric conversion element described below, and can also be used for a catalyst, a toner, and the like.

Next, the photoelectric conversion element of the present invention will be described.
The photoelectric conversion element of the present invention is a dye-sensitized photoelectric conversion element, and is a conventional dye-sensitized photoelectric conversion element except that the compound represented by the general formula (1) (sensitizing dye) is used as the dye. And can be similar. Hereinafter, a typical configuration example of the photoelectric conversion element of the present invention will be described with reference to FIGS.

  FIG. 1 schematically shows a cross-sectional configuration of an example of the photoelectric conversion element of the present invention, and FIG. 2 shows an enlarged and extracted main part of the photoelectric conversion element shown in FIG. The photoelectric conversion element shown in FIGS. 1 and 2 is a main part of a so-called dye-sensitized solar cell. In this photoelectric conversion element, the working electrode 10 and the counter electrode 20 are arranged to face each other with the electrolyte-containing layer 30 interposed therebetween, and at least one of the working electrode 10 and the counter electrode 20 is an electrode having optical transparency. It is.

The working electrode 10 includes, for example, a conductive substrate 11, a metal oxide semiconductor layer 12 provided on one surface thereof (a surface on the counter electrode 20 side), and a dye 13 supported on the metal oxide semiconductor layer 12. And have. In the photoelectric conversion element of the present invention, the dye 13 contains at least one compound (sensitizing dye) represented by the general formula (1), and the dye 13 and a metal oxide supporting the dye 13 A composite with the semiconductor layer 12 is the carrier of the present invention.
The working electrode 10 functions as a negative electrode for the external circuit. For example, the conductive substrate 11 is obtained by providing a conductive layer 11B on the surface of an insulating substrate 11A.

  Examples of the material of the substrate 11A include insulating materials such as glass and plastic. The plastic is used, for example, in the form of a transparent polymer film. Examples of the plastic forming the transparent polymer film include tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and syndiotactic polystyrene ( Examples thereof include SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAR), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin, and brominated phenoxy.

As the conductive layer 11B, for example, a conductive metal oxide thin film containing indium oxide, tin oxide, indium-tin composite oxide (ITO), tin oxide doped with fluorine (FTO: F-SnO ₂ ), or the like , Gold (Au), silver (Ag), platinum (Pt) or the like, a metal thin film and metal mesh, those formed of a conductive polymer, and the like.

  In addition, the conductive substrate 11 may be configured to have a single-layer structure with, for example, a conductive material. In that case, examples of the material of the conductive substrate 11 include indium oxide, tin oxide, Examples thereof include conductive metal oxides such as indium-tin composite oxide or tin oxide doped with fluorine, metals such as gold, silver or platinum, and conductive polymers.

  The metal oxide semiconductor layer 12 is a carrier that supports the dye 13, and has, for example, a porous structure as shown in FIG. The metal oxide semiconductor layer 12 is formed of a dense layer 12A and a porous layer 12B. The dense layer 12A is formed at the interface with the conductive substrate 11, is preferably dense and has few voids, and more preferably is a film. The porous layer 12B is preferably formed on the surface in contact with the electrolyte-containing layer 30, has a large space and a large surface area, and more preferably has a structure in which porous fine particles are attached. Note that the metal oxide semiconductor layer 12 may be formed to have, for example, a film-like single layer structure. In the present invention, the term “support” refers to a state in which the dye 13 is chemically or physically or electrically bonded or adsorbed to the porous layer 12B.

  Examples of the material (metal oxide semiconductor material) included in the metal oxide semiconductor layer 12 include titanium oxide, zinc oxide, tin oxide, niobium oxide, indium oxide, zirconium oxide, tantalum oxide, vanadium oxide, yttrium oxide, and oxide. Aluminum, magnesium oxide, etc. are mentioned. Among these, titanium oxide and zinc oxide are preferable as the metal oxide semiconductor material because high conversion efficiency can be obtained. Further, any one of these metal oxide semiconductor materials may be used alone, or two or more of them may be used in combination (mixed, mixed crystal, solid solution, surface coating, etc.). A combination of titanium oxide and zinc oxide can also be used.

  Examples of a method for forming the metal oxide semiconductor layer 12 having a porous structure include an electrolytic deposition method, a coating method, and a firing method. In the case where the metal oxide semiconductor layer 12 is formed by electrolytic deposition, the fine particles are deposited on the conductive layer 11B of the conductive substrate 11 in the electrolytic bath liquid containing the fine particles of the metal oxide semiconductor material and the metal. An oxide semiconductor material is deposited. When the metal oxide semiconductor layer 12 is formed by a coating method, a dispersion liquid (metal oxide slurry) in which fine particles of a metal oxide semiconductor material are dispersed is applied on the conductive substrate 11, and then in the dispersion liquid. Dry to remove the dispersion medium. When the metal oxide semiconductor layer 12 is formed by the sintering method, the metal oxide slurry is applied onto the conductive substrate 11 and dried, as in the coating method, and then fired. In particular, if the metal oxide semiconductor layer 12 is formed by an electrolytic deposition method or a coating method, a plastic material or a polymer film material having low heat resistance can be used as the substrate 11A, and thus a highly flexible electrode is manufactured. Can do.

  Further, the metal oxide semiconductor layer 12 may be processed using an organic base, a urea derivative, or a cyclic sugar chain. Examples of the organic base include organic bases such as diarylamine, triarylamine, pyridine, 4-t-butylpyridine, polyvinylpyridine, quinoline, piperidine, and amidine. The treatment may be performed before or after adsorbing the dye 13 described below. The treatment method includes dipping treatment. When the treatment agent is solid, the dipping treatment may be performed after dissolving in an organic solvent.

  The dye 13 is, for example, adsorbed to the metal oxide semiconductor layer 12, and is capable of injecting electrons into the metal oxide semiconductor layer 12 by absorbing light and being excited. Contains more than one type of dye (sensitizing dye). In the photoelectric conversion element of the present invention, the one containing at least one compound represented by the general formula (1) corresponds to the dye 13. When at least one compound represented by the general formula (1) is used as the dye 13, the ratio of the amount of electrons injected into the metal oxide semiconductor layer 12 with respect to the amount of light irradiated as the entire dye 13 increases. Conversion efficiency is improved.

  The pigment | dye 13 should just contain at least 1 sort (s) of compounds represented by General formula (1), and may contain the other organic pigment | dye and organometallic complex compounds. Other organic dyes and metal complex compounds are preferably dyes having a group that can be adsorbed to the metal oxide semiconductor layer 12 (carrier). Examples of the group that can be adsorbed on the metal oxide semiconductor layer include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a silyl group.

Other organic dyes include eosin Y, dibromofluorescein, fluorescein, rhodamine B, pyrogallol, dichlorofluorescein, erythrosine B (erythrocin is a registered trademark), fluorescin, mercurochrome, merocyanine disazo dye, trisazo dye, anthraquinone dye, many Ring quinone dyes, indigo dyes, diphenylmethane dyes, trimethylmethane dyes, quinoline dyes, benzophenone dyes, naphthoquinone dyes, perylene dyes, fluorenone dyes, squarilium dyes, azurenium dyes, perinone dyes, Examples include quinacridone dyes, metal-free phthalocyanine dyes, metal-free porphyrin dyes, and metal-free azaporphyrin dyes.
As an organometallic complex compound, an ionic coordination bond formed between a nitrogen anion and a metal cation in an aromatic heterocyclic ring and a nonionic property formed between a nitrogen atom or a chalcogen atom and a metal cation Organometallic complex compounds having both coordination bonds, ionic coordination bonds formed by oxygen anions or sulfur anions and metal cations, and non-formations formed between nitrogen atoms or chalcogen atoms and metal cations And organometallic complex compounds having both ionic coordination bonds. Specifically, copper phthalocyanine, titanyl phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, iron phthalocyanine and other metal phthalocyanine dyes, metal naphthalocyanine dyes, metal porphyrin dyes, metal azaporphyrin dyes and ruthenium, iron, osmium are used. And ruthenium complexes such as bipyridyl metal complexes, terpyridyl metal complexes, phenanthroline metal complexes, bicinchoninic acid metal complexes, azo metal complexes, and quinolinol metal complexes.

  The ratio of the compound represented by the general formula (1) used in the photoelectric conversion element of the present invention is based on the total amount of the compound represented by the general formula (1) and other organic dyes and organometallic complex compounds. Usually, it is used at 10% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more.

  Moreover, the pigment | dye 13 may contain the 1 type (s) or 2 or more types of additive other than the above-mentioned compound of this invention and another pigment | dye. Examples of the additive include an association inhibitor that suppresses association of the compound in the dye, and specifically, a cholic acid compound represented by the chemical formula (14). These may be used alone or in combination of two or more.

（式中、Ｒ９１は酸性基又はアルコキシシリル基を有するアルキル基である。Ｒ９２は化学式中のステロイド骨格を構成する炭素原子の何れかに結合する基を表し、水酸基、ハロゲン基、アルキル基、アルコキシ基、アリール基、複素環基、アシル基、アシルオキシ基、オキシカルボニル基、オキソ基、酸性基あるいはアルコキシシリル基又はそれらの誘導体であり、それらは同一であってもよいし異なっていてもよい。ｔは１以上５以下の整数である。化学式中のステロイド骨格を構成する炭素原子と炭素原子との間の結合は、単結合であってもよいし、二重結合であってもよい。）

(In the formula, R91 is an alkyl group having an acidic group or an alkoxysilyl group. R92 represents a group bonded to any of the carbon atoms constituting the steroid skeleton in the chemical formula, and represents a hydroxyl group, a halogen group, an alkyl group, an alkoxy group. A group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an oxycarbonyl group, an oxo group, an acidic group, an alkoxysilyl group, or a derivative thereof, which may be the same or different. t is an integer of 1 to 5. The bond between the carbon atoms constituting the steroid skeleton in the chemical formula may be a single bond or a double bond.)

  The counter electrode 20 is, for example, a conductive substrate 21 provided with a conductive layer 22 and functions as a positive electrode for an external circuit. Examples of the material of the conductive substrate 21 include the same materials as those of the substrate 11 </ b> A of the conductive substrate 11 of the working electrode 10. The conductive layer 22 includes one type or two or more types of conductive material and a binder as necessary. Examples of the conductive material used for the conductive layer 22 include platinum, gold, silver, copper (Cu), rhodium (Rh), ruthenium (Ru), aluminum (Al), magnesium (Mg), and indium (In). Examples include metals, carbon (C), and conductive polymers. Examples of the binder used for the conductive layer 22 include acrylic resin, polyester resin, phenol resin, epoxy resin, cellulose, melamine resin, fluoroelastomer, and polyimide resin. The counter electrode 20 may have a single layer structure of the conductive layer 22, for example.

The electrolyte-containing layer 30 includes, for example, a redox electrolyte having a redox pair. Examples of the redox electrolyte include I ⁻ / I ₃ ⁻ system, Br ⁻ / Br ₃ ⁻ system, quinone / hydroquinone system, Co complex system, and nitroxy radical compound system. Specifically, a combination of an iodide salt and a simple substance of iodine, a combination of a halide salt and a simple substance of halogen, such as a combination of a bromide salt and simple substance of bromine, or the like. Examples of the halide salt include cesium halide, quaternary alkylammonium halides, imidazolium halides, thiazolium halides, oxazolium halides, quinolinium halides and pyridinium halides. Specifically, examples of the iodide salt include lithium iodide, sodium iodide, cesium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, tetrapentylammonium iodide, tetra Quaternary alkylammonium iodides such as hexylammonium iodide, tetraheptylammonium iodide or trimethylphenylammonium iodide, 3-methylimidazolium iodide or 1-propyl-2,3-dimethylimidazolium iodide, etc. Imidazolium iodides, 3-ethyl-2-methyl-2-thiazolium iodide, 3-ethyl-5- (2-hydroxyethyl) -4-methylthiazolium iodide or 3-ethyl- 2-methyl Thiazolium iodides such as nzothiazolium iodide, oxazolium iodides such as 3-ethyl-2-methyl-benzoxazolium iodide, and 1-ethyl-2-methylquinoli Examples thereof include quinolinium iodides such as nium iodide and pyridinium iodides. Examples of the bromide salt include quaternary alkyl ammonium bromide. Among the combinations of halide salts and simple halogens, combinations of at least one of the above-described iodide salts and simple iodine are preferable.

  The redox electrolyte may be, for example, a combination of an ionic liquid and a halogen simple substance. In this case, the above-described halide salt and the like may further be included. Examples of the ionic liquid include those that can be used in batteries, solar cells, and the like. For example, “Inorg. Chem” 1996, 35, p 1168 to 1178, “Electrochemistry” 2002, 2, p 130 to 136, and special table 9 And those disclosed in JP-A No. 507334 or JP-A-8-259543. Among them, as the ionic liquid, a salt having a melting point lower than room temperature (25 ° C.), or a salt that has a melting point higher than room temperature and is liquefied at room temperature by dissolving with another molten salt or the like is preferable. . Specific examples of the ionic liquid include the following anions and cations.

  Examples of the cation of the ionic liquid include ammonium, imidazolium, oxazolium, thiazolium, oxadiazolium, triazolium, pyrrolidinium, pyridinium, piperidinium, pyrazolium, pyrimidinium, pyrazinium, triazinium, phosphonium, sulfonium, carbazolium, indolium, or those And derivatives thereof. These may be used alone or as a mixture of plural kinds. Specific examples include 1-methyl-3-propylimidazolium, 1-butyl-3-methylimidazolium, 1,2-dimethyl-3-propylimidazolium, 1-ethyl-3-methylimidazolium, and the like. .

Examples of anions of the ionic liquid include metal chlorides such as AlCl ₄ ⁻ or Al ₂ Cl ₇ ^— , PF ₆ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , N (CF ₃ SO ₂ ) ₂ ⁻ , F ( _{HF) n} ^- or _CF 3 COO ^- or fluorine-containing substances such as ^{_{ions, NO 3 -, CH 3 COO}} -, C 6 H 11 COO -, CH 3 OSO 3 -, CH 3 OSO 2 -, CH 3 SO 3 - Non-fluorine compound ions such as CH ₃ SO ₂ ⁻ , (CH ₃ O) ₂ PO ₂ ⁻ , N (CN) ₂ ⁻ or SCN ⁻ , and halide ions such as iodide ions or bromide ions. These may be used alone or as a mixture of plural kinds. Among these, iodide ions are preferable as the anions of the ionic liquid.

  The electrolyte-containing layer 30 may be a liquid electrolyte (electrolytic solution) obtained by dissolving the above-described redox electrolyte in a solvent, or a solid polymer electrolyte in which the electrolytic solution is held in a polymer substance. May be. Alternatively, a quasi-solid (paste-like) electrolyte containing a mixture of an electrolytic solution and a particulate carbon material such as carbon black may be used. Note that in a quasi-solid electrolyte containing a carbon material, since the carbon material has a function of catalyzing a redox reaction, the electrolyte may not contain a single halogen. Such a redox electrolyte may contain any one kind or two or more kinds of organic solvents that dissolve the above-described halide salts, ionic liquids, and the like. Examples of the organic solvent include electrochemically inert ones such as acetonitrile, tetrahydrofuran, propionitrile, butyronitrile, methoxyacetonitrile, 3-methoxypropionitrile, valeronitrile, dimethyl carbonate, ethyl methyl carbonate, Examples include ethylene carbonate, propylene carbonate, N-methylpyrrolidone, pentanol, quinoline, N, N-dimethylformamide, γ-butyrolactone, dimethyl sulfoxide, or 1,4-dioxane.

  Further, the electrolyte-containing layer 30 is provided with a non-cyclic saccharide (Japanese Patent Laid-Open No. 2005-093313) and a pyridine-based compound (Japanese Patent Laid-Open No. 2003-331936) for the purpose of improving the power generation efficiency and durability of the photoelectric conversion element. ), Urea derivatives (Japanese Patent Laid-Open No. 2003-168493), layered clay minerals (Japanese Patent Publication No. 2007-531206), dibenzylidene-D-sorbitol, cholesterol derivatives, amino acid derivatives, trans- (1R, 2R) -1, An alkylamide derivative of 2-cyclohexanediamine, an alkylurea derivative, N-octyl-D-gluconamide benzoate, a double-headed amino acid derivative, a quaternary ammonium derivative, or the like may be added.

  In this photoelectric conversion element, when light (sunlight or ultraviolet light, visible light, or near infrared light equivalent to sunlight) is applied to the dye 13 carried on the working electrode 10, the light is absorbed. The excited dye 13 injects electrons into the metal oxide semiconductor layer 12. After the electrons move to the adjacent conductive layer 11B, they reach the counter electrode 20 via an external circuit. On the other hand, in the electrolyte-containing layer 30, the electrolyte is oxidized so that the oxidized dye 13 is returned (reduced) to the ground state as the electrons move. The oxidized electrolyte is reduced by receiving the electrons that have reached the counter electrode 20. In this way, the movement of electrons between the working electrode 10 and the counter electrode 20 and the accompanying oxidation-reduction reaction in the electrolyte-containing layer 30 are repeated. Thereby, continuous movement of electrons occurs, and photoelectric conversion is constantly performed.

  The photoelectric conversion element of this invention can be manufactured as follows, for example.

  First, the working electrode 10 is produced. First, the metal oxide semiconductor layer 12 having a porous structure is formed on the surface of the conductive substrate 11 on which the conductive layer 11B is formed by electrolytic deposition or firing. In the case of forming by electrolytic deposition, for example, an electrolytic bath containing a metal salt to be a metal oxide semiconductor material is set to a predetermined temperature while bubbling with oxygen or air, and the conductive substrate 11 is placed therein. Immerse and apply a constant voltage between the counter electrode. Thereby, a metal oxide semiconductor material is deposited on the conductive layer 11B so as to have a porous structure. At this time, the counter electrode may be appropriately moved in the electrolytic bath. In the case of forming by a firing method, for example, a metal oxide slurry prepared by dispersing a powder of a metal oxide semiconductor material in a dispersion medium is applied to the conductive substrate 11 and dried, followed by firing. Have a porous structure. Subsequently, a dye solution in which a dye 13 containing at least one compound represented by the general formula (1) is dissolved in an organic solvent is prepared. By immersing the conductive substrate 11 on which the metal oxide semiconductor layer 12 is formed in this dye solution, the metal oxide semiconductor layer 12 carries the dye 13.

The density | concentration of the pigment | dye (the compound represented by General formula (1), another organic pigment | dye, and a metal complex compound) in the said pigment | dye solution is 1.0 * 10 < ^-5 > -1.0 * 10 < ^-3 > mol / dm. ³ is preferable, and 5.0 × 10 ^{−5 to} 5.0 × 10 ⁻⁴ mol / dm ³ is more preferable. The organic solvent used in the dye solution is not particularly limited as long as it can dissolve the dye. Specific examples thereof include hydrocarbons such as toluene, benzene and xylene; alcohols such as methanol, ethanol and t-butanol; Ether alcohols such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, butyl diglycol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol; Esters such as ethyl acetate, butyl acetate, methoxyethyl acetate; Acrylic Acrylic acid esters such as ethyl acrylate and butyl acrylate; fluorinated alcohols such as 2,2,3,3-tetrafluoropropanol; chlorinated hydrocarbons such as methylene dichloride, dichloroethane and chloroform; acetonitrile Include tetrahydrofuran, it may be mixed with these organic solvents arbitrarily. Preferred are toluene, acetonitrile and alcohols, and more preferred are acetonitrile and alcohols.

  Next, the counter electrode 20 is produced by forming the conductive layer 22 on one surface of the conductive substrate 21. The conductive layer 22 is formed, for example, by sputtering a conductive material.

  Finally, a spacer (not shown) such as a sealant so that the surface of the working electrode 10 carrying the dye 13 and the surface of the counter electrode 20 on which the conductive layer 22 is formed face each other while maintaining a predetermined distance. For example, the whole is sealed except for the electrolyte inlet. Subsequently, the electrolyte containing layer 30 is formed by injecting an electrolyte between the working electrode 10 and the counter electrode 20 and then sealing the injection port. Thereby, the photoelectric conversion element shown in FIGS. 1 and 2 is completed.

  In the above-described photoelectric conversion element, the case where the electrolyte-containing layer 30 is provided between the working electrode 10 and the counter electrode 20 has been described, but a solid charge transfer layer may be provided instead of the electrolyte-containing layer 30. In this case, the solid charge transfer layer includes, for example, a material in which carrier movement in the solid is related to electric conduction. As this material, an electron transport material, a hole transport material, or the like is preferable.

  As the hole transport material, aromatic amines, triphenylene derivatives and the like are preferable. For example, oligothiophene compounds, polypyrrole, polyacetylene or derivatives thereof, poly (p-phenylene) or derivatives thereof, and poly (p-phenylene vinylene). Alternatively, organic conductive polymers such as derivatives thereof, polythienylene vinylene or derivatives thereof, polythiophene or derivatives thereof, polyaniline or derivatives thereof, polytoluidine or derivatives thereof, and the like can be given.

  Further, as the hole transport material, for example, a p-type inorganic compound semiconductor may be used. The p-type inorganic compound semiconductor preferably has a band gap of 2 eV or more, and more preferably 2.5 eV or more. Further, the ionization potential of the p-type inorganic compound semiconductor needs to be smaller than the ionization potential of the working electrode 10 from the condition that the holes of the dye can be reduced. The preferred range of the ionization potential of the p-type inorganic compound semiconductor varies depending on the dye used, but the ionization potential is preferably in the range of 4.5 eV to 5.5 eV, and more preferably 4.7 eV to 5. More preferably, it is within the range of 3 eV or less.

Examples of the p-type inorganic compound semiconductor include a compound semiconductor containing monovalent copper. Examples of the compound semiconductor containing monovalent _copper, there _{CuI, CuSCN, CuInSe 2, Cu} (In, Ga) Se 2, CuGaSe 2, Cu 2 O, CuS, CuGaS 2, CuInS 2, CuAlSe 2 and the like. Examples of other p-type inorganic compound semiconductors include GaP, NiO, CoO, FeO, Bi ₂ O ₃ , MoO _{2, and} Cr ₂ O ₃ .

  As a method of forming such a solid charge transfer layer, for example, there is a method of forming a solid charge transfer layer directly on the working electrode 10, and then the counter electrode 20 may be formed and applied.

  The hole transport material containing the organic conductive polymer is introduced into the electrode by a technique such as a vacuum deposition method, a casting method, a coating method, a spin coating method, a dipping method, an electrolytic polymerization method, or a photoelectrolytic polymerization method. Can do. Also in the case of an inorganic solid compound, it can be introduced into the electrode by a technique such as a casting method, a coating method, a spin coating method, a dipping method, or an electrolytic plating method. A part of the solid charge transfer layer (particularly, having a hole transport material) formed in this way partially penetrates into the gap of the porous structure of the metal oxide semiconductor layer 12 and is in direct contact with it. It is preferable to become.

  The usage application of the photoelectric conversion element of the present invention is not limited to the above-described application of the solar cell, but may be other usages. Examples of other applications include an optical sensor.

  Hereinafter, the present invention will be described in detail with reference to examples in which the compounds of the present invention were synthesized, examples of the support (working electrode) of the present invention using the compounds synthesized in the examples, and comparative examples. The invention is not limited by these.

  According to Example 1-1 below, the above compound No. 1 was synthesized.

Example 1-1 Compound No. 1 Synthesis of Compound 1 below A1 (0.72 mmol, 687 mg), the following compound No. While stirring B1 (1.08 mmol, 500 mg), 2-chloro-1-methylpyridinium iodide (1.44 mmol, 367 mg) and dimethylaminopyridine (0.72 mmol, 88 mg) as a base in chloroform (50 ml), 3 Heated to reflux for hours. Ethyl acetate and water were added to the reaction solution for oil / water separation, and the organic layer was purified by silica gel column chromatography (mobile phase; hexane: ethyl acetate = 85: 15) to obtain 910 mg of an intermediate. The resulting intermediate, trifluoroacetic acid (11.4 g) and dichloromethane (11.4 g) were stirred at room temperature for 15 hours. The reaction solution was added to ice water to precipitate a solid, and then the solid was filtered off (481 mg, yield 54%). The obtained solid was identified as Compound No. 1 above. 1 was confirmed using UV-VIS (λmax), ¹ H-NMR, and FT-IR. Data are shown in [Table 1] to [Table 3].

Examples 1-2 to 1-4 Compound No. 15 to Compound No. Synthesis of Compound 17 No. 17 was prepared in the same manner as in Example 1-1 except that a compound having a carboxylic acid corresponding to the target compound and an amine compound were used. 15-No. 17 was synthesized. It was confirmed using UV-VIS (λmax), ¹ H-NMR, and FT-IR that the obtained compound was the desired product. Data are shown in [Table 1] to [Table 3].

<Manufacture of titanium oxide carrier (conductive substrate 11)>
A conductive substrate 11 made of a conductive glass substrate (F-SnO ₂ ) having a length of 2.0 cm, a width of 1.5 cm, and a thickness of 1.1 mm was prepared. Subsequently, a masking tape having a thickness of 70 μm is attached to the conductive substrate 11 so as to enclose a square of 0.5 cm in length and 0.5 cm in width, and 3 cm ^{3 of} metal oxide slurry is uniformly thickened on the square portion. It was applied and dried. As the metal oxide slurry, a suspension of titanium oxide powder (TiO ₂ , Ti-Nanoxide D manufactured by Solaronix) in water so as to be 10% by weight was used. Subsequently, the masking tape on the conductive substrate 11 was peeled off, and this substrate was baked at 450 ° C. in an electric furnace to form a metal oxide semiconductor layer 12 having a thickness of about 5 μm.

(Example 2-1)
<Compound No. Of electrode (support) using 1 and durability evaluation>
Compound No. 1 obtained in Example 1-1. 1 was dissolved in toluene to a concentration of 3 × 10 ⁻⁴ mol / dm ³ to prepare a dye solution. Subsequently, the conductive substrate 11 using the titanium oxide produced above as a carrier was dipped in the dye solution to prepare a working electrode 10 carrying a compound. The obtained working electrode 10 was immersed in a solution of acetonitrile / water = 9: 1, and the solution after 246 hours was analyzed by UV spectrum. Compared with the UV spectrum before immersion, the residual ratio of the dye of the working electrode 10 was calculated. The higher the dye residual ratio, the stronger the supporting force and the better the durability. The results are shown in [Table 4].
<Manufacture of photoelectric conversion elements and evaluation of conversion efficiency>
As shown in FIG. 1, the produced working electrode 10 and the counter electrode 20 produced by coating graphite particles (conductive layer 22) on an ITO electrode (manufactured by Nishinoda Electric Co., Ltd.) as a conductive substrate 21. The electrolyte-containing layer 30 is placed between the spacers (63 μm), and the electrolyte-containing layer 30 is disposed between them. The clips are fixed with clips, and the electrolyte-containing layer 30 has an electrolyte solution [lithium iodide (0.5 mol with respect to acetonitrile). / Dm ³ ) and iodine (0.05 mol / dm ³ ) mixed so as to have a predetermined concentration] were infiltrated to produce a photoelectric conversion element. Covering the cell top with mask openings 1cm ^2, AM-1.5G, were measured conversion efficiency (%) in a solar simulator of 100 mW / cm ^2. The results are shown in [Table 4].

(Examples 2-2 to 2-4)
Compound No. 1 to compound No. 1 obtained in Examples 1-2 to 1-4. Except having changed into 15-17, manufacture of an electrode (supporting body) and durability evaluation were performed by the same method as Example 2-1. The results are shown in [Table 4].
Moreover, manufacture of a photoelectric conversion element and photoelectric conversion efficiency were evaluated by the same method as Example 2-1 using the obtained electrode. The results are shown in [Table 4].

(Comparative Example 1)
Compound No. A working electrode 10 and a photoelectric conversion element were produced in the same manner as in Example 2-1, except that 1 was replaced with the following comparative compound 1 or comparative compound 2. Durability and conversion efficiency were evaluated in the same manner as in Example 2-1. The results are shown in [Table 4].

  From the examples, it is clear that the carrier of the present invention is excellent in durability.

  From the above results, the carrier of the present invention is useful because it is clear that when used as an electrode for a photoelectric conversion element, high conversion efficiency can be maintained.

  The compound of the present invention and a support using the same are highly durable supports in which the detachment of the compound is unlikely to occur, and when used as a working electrode, it exhibits good photoelectric conversion efficiency. It is suitable for an element.

Claims (4)

A compound represented by the following general formula (1).

(In the formula, A ¹ is an optionally substituted aromatic hydrocarbon ring group or an optionally substituted aromatic heterocyclic group, and A ² is a direct bond or the following formulas (A2-1) to (A2 -20) is a group in which 1 to 9 groups selected from the groups represented by the above groups are linked, R ¹ , R ² and R ³ represent a hydrogen atom or an optionally substituted hydrocarbon group, and R ¹ And R ² may be connected to each other to form a ring, R ¹ and R ² may be independently connected to A ¹ to form a ring, and R ⁴ may be a hydrogen atom or a cyano group Represents.)

Wherein X represents S, O, NR, R represents a hydrogen atom or an optionally substituted hydrocarbon group, and groups represented by the above formulas (A2-1) to (A2-20) hydrogen atoms in the fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, -OR ⁵ group, -SR ⁵ group, ^-NR 5 ^{R 6} group or optionally substituted aliphatic have carbonized (It may be substituted with a hydrogen group, and R ⁵ and R ⁶ represent a hydrogen atom or an optionally substituted hydrocarbon group.) The compound according to claim 1, wherein the following partial structure (2) in the general formula (1) is any one of the following partial structures (2-1) to (2-14).

^(Wherein, A 1, ^{R 1} and ^{R 2} are respectively the same as ^A 1, ^{R 1} and ^{R 2} in the general formula (1).)

(Wherein, ^{R 1} and ^{R 2} means ^{R 1} and ^{R 2} of the above partial structural formula ^{(2), R 7, R} 8 and ^{R 9} represents a known ligand coordinating to ^{M 2} , M ¹ and M ² represent a metal element, and a hydrogen atom in the formula may be a fluorine atom, a chlorine atom, an iodine atom, a cyano group, a nitro group, an —OR ⁵ group, an —SR ⁵ group or a substituted group. (It may be substituted with an aliphatic hydrocarbon group, and R ⁵ represents a hydrogen atom or an optionally substituted hydrocarbon group.)   A support formed by supporting at least one compound according to claim 1.   A photoelectric conversion element comprising an electrode having the carrier according to claim 3.

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