JP2006111783A - New amino group-containing heterocyclic derivative and sensitizing dye for photoelectric conversion containing the heterocyclic derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new amino group-containing heterocyclic derivative having a wide absorption band in a visible region and suitable as a sensitizing dye for photoelectric conversion having high photoelectric conversion efficiency, and to provide a photoelectric converting material, a photoelectric converting electrode, and a photoelectric converting battery using the same. <P>SOLUTION: The terminal amino group containing heterocyclic derivative is represented by general formula (1) (wherein, R<SB>1</SB>, R<SB>2</SB>, R<SB>4</SB>and R<SB>5</SB>are each independently H or a monovalent organic residue which may be substituted; R<SB>3</SB>is an anchor group which can be connected to an inorganic porous substance showing semiconductor characteristics; X is a divalent aromatic heterocyclic group containing at least one selected from a sulfur atom, an oxygen atom and a selenium atom; Y is a divalent linking group which may be substituted, and m is an integer of 1-5). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel amino group-containing heterocyclic derivative, a sensitizing dye for photoelectric conversion using the same, a photoelectric conversion material using the same, a photoelectric conversion electrode, and a solar cell for photoelectric conversion using the same.

  At present, energy relies heavily on fossil fuels represented by oil, coal, and natural gas, and the depletion of fossil fuels has been greatly screamed in the future. In addition, carbon dioxide emissions inevitably remain a problem when obtaining energy from fossil fuels, and a large burden on the environment is regarded as a problem.

  Recently, solar power generation has attracted more attention due to these concerns. Currently, silicon solar cells using monocrystalline or polycrystalline crystalline silicon or amorphous silicon, or compound semiconductor solar cells using gallium or arsenic are actively used. Although development studies have been made, the current situation is that the versatility is poor because it is still necessary to overcome problems such as manufacturing costs. On the other hand, many solar cells using a photosensitizing dye have been proposed, but there is a problem in that conversion efficiency is low and durability is poor.

  Under such circumstances, there was a report by Gratzel et al. In 1991 (Non-patent Document 1), and photoelectric conversion electrodes and photoelectric conversion batteries using a porous inorganic semiconductor photosensitized with a dye attracted attention. became. The photoelectric conversion element in this report is manufactured using a relatively inexpensive inorganic oxide semiconductor such as titanium oxide, and it is possible to obtain a photoelectric conversion element at a lower cost than a silicon solar battery that is a general-purpose product. Have However, at present, a high photoelectric conversion efficiency cannot be obtained unless it is a ruthenium-based sensitizing dye. Therefore, there is a problem in the stable supply of the dye because of the high cost of the dye and the low number of Clarkes. On the other hand, although organic dyes are being actively studied, they have not been put into practical use because of their low conversion efficiency. Moreover, although the dye which has a specific acrylic acid site | part and the sensitizing dye which has an amide derivative are also disclosed (refer patent document 1 and patent document 2), it cannot be said that it has sufficient performance.

Brian O'Regan, Michael Gratzel, “A low-cost, high-efficiency solar cell based on dies 2” films, "Nature, UK, October 1991, Vol. 353, pp. 737-740. Japanese translation of PCT publication No. 2002-011213 JP 2004-143355 A

  The present invention provides a novel amino group-containing heterocyclic derivative useful as a sensitizing dye for photoelectric conversion used in a dye-sensitized photoelectric conversion battery having a wide absorption band in the visible region and high photoelectric conversion efficiency. Objective. Further, a photoelectric conversion material obtained by connecting an inorganic porous substance exhibiting semiconductor characteristics and the sensitizing dye for photoelectric conversion, a photoelectric conversion electrode formed by laminating the photoelectric conversion material on a transparent electrode, and the photoelectric conversion electrode and electrolyte An object of the present invention is to provide a photoelectric conversion battery comprising a layer and a conductive counter electrode.

上記一般式（１）において、Ｒ₁、Ｒ₂、Ｒ₄およびＲ₅は、それぞれ独立して、水素原子、または置換基を有していてもよい１価の有機残基である。ここで、Ｒ₁およびＲ₂は共同して環を形成してもよい。また、Ｒ₁またはＲ₂のいずれか一方は、Ｘと共同して環を形成してもよい。Ｒ₃は、半導体特性を示す無機多孔質物質と連結し得るアンカー基である。Ｘは、硫黄原子、酸素原子またはセレン原子を少なくとも１つ含有する２価の芳香族複素環基である。該２価の芳香族複素環基は、置換基を有していても良く、２個以上の環が縮合した構造を有するものであってもよい。Ｙは、置換基を有していてもよい２価の連結基であり、鎖状構造、環状構造またはこれらの組み合わせのいずれであってもよい。ただし、Ｙは、式（１）中のＸとπ電子が共役し、かつ式（１）中のＲ₃と結合する炭素原子およびＲ₅と結合する炭素原子間で形成される二重結合とπ電子が共役する構造である。ｍは、１〜５の整数である。式（１）中の二重結合は、シス−トランス異性体のいずれを生じさせるものであってもよい。 As a result of intensive efforts to solve the above problems, the present inventors have found that a compound having a specific partial structure is useful as a sensitizing dye for photoelectric conversion. That is, the present invention provides a terminal amino group-containing heterocyclic derivative represented by the following general formula (1).

In the above general formula (1), R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom or a monovalent organic residue which may have a substituent. Here, R ₁ and R ₂ may jointly form a ring. Further, either R ₁ or R ₂ may form a ring together with X. R ₃ is an anchor group that can be linked to an inorganic porous material exhibiting semiconductor properties. X is a divalent aromatic heterocyclic group containing at least one sulfur atom, oxygen atom or selenium atom. The divalent aromatic heterocyclic group may have a substituent or may have a structure in which two or more rings are condensed. Y is a divalent linking group that may have a substituent, and may be a chain structure, a cyclic structure, or a combination thereof. However, Y is a double bond formed between the carbon atom bonded to R ₃ and the carbon atom bonded to R _{5 in} which X in the formula (1) is conjugated with π electron and R ₃ in the formula (1). It is a structure in which π electrons are conjugated. m is an integer of 1-5. The double bond in formula (1) may give rise to any of the cis-trans isomers.

上記一般式（２）において、Ｘ₁は、硫黄原子、酸素原子またはセレン原子である。Ｘ₂はＣ−Ｒ₆またはＮであり、Ｘ₃はＣ−Ｒ₇またはＮである。ここで、Ｒ₆およびＲ₇は、それぞれ独立して、水素原子、または置換基を有していてもよい１価の有機残基である。Ｒ₆およびＲ₇は、共同して環を形成してもよい。ただし、Ｘ₂およびＸ₃は、少なくとも一方はＮ以外である。 X in the general formula (1) is a group having a ring structure represented by the following general formula (2) or a group having a structure in which ring structures represented by the following general formula (2) are condensed with each other. preferable.

In the general formula (2), X ₁ is a sulfur atom, an oxygen atom or a selenium atom. X ₂ is C—R ₆ or N, and X ₃ is C—R ₇ or N. Here, R ₆ and R ₇ are each independently a hydrogen atom or a monovalent organic residue which may have a substituent. R ₆ and R ₇ may jointly form a ring. However, at least one of X ₂ and X ₃ is other than N.

In the above formula (1), R ₃ is preferably a carboxyl group, a phosphoric acid group or a sulfonic acid group.

上記一般式（３）において、Ａ₁およびＡ₂は、それぞれ独立して、Ｏ、ＮＨまたはＳである。Ｂはカルボニル基、チオカルボニル基、スルフィニル基またはスルホニル基である。ｏおよびｐは、それぞれ独立して０または1である。Ｒ₈は、水素原子、置換基を有していてもよい１価の脂肪族炭化水素基、芳香族炭化水素基、もしくは芳香族複素環基、またはハロゲン原子、シアノ基、イソシアノ基、チオシアネート基、イソチオシアネート基、ニトロ基、ヒドロキシ基、メルカプト基、アミノ基もしくはアミド基である。 In the above formula (1), the monovalent organic residue of R ₁ , R ₂ , R ₄ , R ₅ and R ₆ is an aliphatic hydrocarbon group, aromatic carbonization which may have a substituent. A hydrogen group or an aromatic heterocyclic group, a halogen atom, a cyano group, an isocyano group, a thiocyanate group, an isothiocyanate group, a nitro group, a hydroxy group, a mercapto group, an amino group, an amide group, or the following general formula (3) It is preferable that it is group represented.

In the general formula (3), A ₁ and A ₂ are each independently O, NH, or S. B is a carbonyl group, a thiocarbonyl group, a sulfinyl group or a sulfonyl group. o and p are each independently 0 or 1. R ₈ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group or an aromatic heterocyclic group, or a halogen atom, cyano group, isocyano group or thiocyanate group. , Isothiocyanate group, nitro group, hydroxy group, mercapto group, amino group or amide group.

In the general formula (1), R ₄ is preferably an electron-withdrawing group, and particularly preferably a cyano group, an ester group, an amide group or a perfluoroalkyl group.

In the general formula (1), R ₃ is preferably a carboxyl group.

  In the general formula (1), Y preferably has a structure containing an aromatic heterocyclic group.

  In the general formula (1), X and Y preferably each have a structure having a 2,5-thienylene group or a 2,5-thienothienylene group.

Moreover, this invention provides the sensitizing dye for photoelectric conversion containing the terminal amino group containing heterocyclic derivative represented by the said General formula (1).
Furthermore, this invention provides the photoelectric conversion material containing this sensitizing dye for photoelectric conversion.
Furthermore, the present invention provides a photoelectric conversion electrode using the photoelectric conversion material.
Furthermore, this invention provides the photoelectric conversion battery using this photoelectric conversion electrode.

  Since the amino group-containing heterocyclic derivative of the present invention has a specific partial structure, it has a wide absorption band in the visible region, and can be used as an optical functional material, particularly as a sensitizing dye for photoelectric conversion. In particular, when used in a dye-sensitized photoelectric conversion battery, a photoelectric conversion battery having high conversion efficiency and high stability can be provided.

上記一般式（３）において、Ａ₁およびＡ₂は、それぞれ独立して、Ｏ、ＮＨまたはＳである。Ｂはカルボニル基、チオカルボニル基、スルフィニル基またはスルホニル基である。ｏおよびｐは、それぞれ独立して０または1である。Ｒ₈は、水素原子、置換基を有していてもよい１価の脂肪族炭化水素基、芳香族炭化水素基、もしくは芳香族複素環基、またはハロゲン原子、シアノ基、イソシアノ基、チオシアネート基、イソチオシアネート基、ニトロ基、ヒドロキシ基、メルカプト基、アミノ基もしくはアミド基である。 Hereinafter, the present invention will be described in detail.
In addition, in this specification, when it is described as “may have a substituent”, the substituent is specifically an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic heterocyclic group. Or a halogen atom, cyano group, isocyano group, thiocyanate group, isothiocyanate group, nitro group, hydroxy group, mercapto group, amino group, amide group, or a monovalent group represented by the following general formula (3) .

In the general formula (3), A ₁ and A ₂ are each independently O, NH, or S. B is a carbonyl group, a thiocarbonyl group, a sulfinyl group or a sulfonyl group. o and p are each independently 0 or 1. R ₈ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group or an aromatic heterocyclic group, or a halogen atom, cyano group, isocyano group or thiocyanate group. , Isothiocyanate group, nitro group, hydroxy group, mercapto group, amino group or amide group.

上記一般式（１）において、Ｒ₁、Ｒ₂、Ｒ₄およびＲ₅は、それぞれ独立して、水素原子、または置換基を有していてもよい１価の有機残基である。Ｒ₃は、半導体特性を示す無機多孔質物質と連結し得るアンカー基である。Ｘは、硫黄原子、酸素原子またはセレン原子を少なくとも１つ含有する２価の芳香族複素環基である。Ｙは、置換基を有していてもよい２価の連結基である。ｍは、１〜５の整数である。式（１）中の二重結合は、シス−トランス異性体のいずれを生じさせるものであってもよい。 The novel amino group-containing heterocyclic derivative of the present invention is an amino group-containing compound having a specific partial structure, specifically, a terminal amino group-containing compound represented by the following general formula (1).

In the above general formula (1), R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom or a monovalent organic residue which may have a substituent. R ₃ is an anchor group that can be linked to an inorganic porous material exhibiting semiconductor properties. X is a divalent aromatic heterocyclic group containing at least one sulfur atom, oxygen atom or selenium atom. Y is a divalent linking group which may have a substituent. m is an integer of 1-5. The double bond in formula (1) may give rise to any of the cis-trans isomers.

First, X in the general formula (1) will be described. X represents a divalent aromatic heterocyclic group containing at least one sulfur atom, oxygen atom or selenium atom. The divalent aromatic heterocyclic group may have a substituent, and two or more rings may be condensed. Moreover, when it has a substituent, two or more substituents may combine with each other to form a ring. Further, either R ₁ or R ₂ may form a ring together with X.

上記一般式（２）において、Ｘ₁は硫黄原子、酸素原子またはセレン原子である。Ｘ₂はＣ−Ｒ₆またはＮであり、Ｘ₃はＣ−Ｒ₇またはＮである。ここで、Ｒ₆およびＲ₇は、それぞれ独立して、水素原子、または置換基を有していてもよい１価の有機残基である。ここで、１価の有機残基としては、具体的には、置換基を有していてもよい１価の脂肪族炭化水素基、芳香族炭化水素基、もしくは芳香族複素環基、またはハロゲン原子、シアノ基、イソシアノ基、チオシアネート基、イソチオシアネート基、ニトロ基、ヒドロキシ基、メルカプト基、アミノ基、アミド基、あるいは下記一般式（３）で表される基を選択しうる。

上記一般式（３）において、Ａ₁およびＡ₂は、それぞれ独立して、Ｏ、ＮＨまたはＳである。Ｂはカルボニル基、チオカルボニル基、スルフィニル基またはスルホニル基である。ｏおよびｐは、それぞれ独立して０または1である。Ｒ₈は、水素原子、置換基を有していてもよい１価の脂肪族炭化水素基、芳香族炭化水素基、もしくは芳香族複素環基、またはハロゲン原子、シアノ基、イソシアノ基、チオシアネート基、イソチオシアネート基、ニトロ基、ヒドロキシ基、メルカプト基、アミノ基もしくはアミド基である。 The divalent aromatic heterocycle here is preferably represented by the following general formula (2).

In the general formula (2), X ₁ is a sulfur atom, an oxygen atom or a selenium atom. X ₂ is C—R ₆ or N, and X ₃ is C—R ₇ or N. Here, R ₆ and R ₇ are each independently a hydrogen atom or a monovalent organic residue which may have a substituent. Here, the monovalent organic residue specifically includes a monovalent aliphatic hydrocarbon group, aromatic hydrocarbon group, aromatic heterocyclic group, or halogen which may have a substituent. An atom, a cyano group, an isocyano group, a thiocyanate group, an isothiocyanate group, a nitro group, a hydroxy group, a mercapto group, an amino group, an amide group, or a group represented by the following general formula (3) may be selected.

In the general formula (3), A ₁ and A ₂ are each independently O, NH, or S. B is a carbonyl group, a thiocarbonyl group, a sulfinyl group or a sulfonyl group. o and p are each independently 0 or 1. R ₈ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group or an aromatic heterocyclic group, or a halogen atom, cyano group, isocyano group or thiocyanate group. , Isothiocyanate group, nitro group, hydroxy group, mercapto group, amino group or amide group.

In the general formula (2), X ₂ is preferably a structure represented by C—R ₆ or C—R ₇ , and among them, R ₆ or R ₇ may contain a hydrogen atom or a substituent. A structure which is an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferred. Particularly preferred is a structure wherein R ₆ or R ₇ is a hydrogen atom.

The divalent heterocyclic group represented by the general formula (2) is, for example, a simple group such as a 2,5-thienylene group, a 2,5-thiazoylene group, a 2,5-furylene group, or a 2,5-selenylene group. It may be a ring structure group, or may be a polycyclic aromatic heterocyclic group such as a condensed ring formed from these heterocyclic rings. Furthermore, R ₆ may jointly form a ring. Specific examples of the divalent heterocyclic group represented by the general formula (2) are shown below.

A specific example of a structure in which a ring is formed between R ₁ or R ₂ and X in the general formula (1) is shown below.

Next, Y in the general formula (1) will be described. Y is a divalent linking group that may have a substituent, and may be a chain structure, a cyclic structure, or a combination thereof. However, a structure in which π electrons are conjugated between the amino group of the general formula (1) and the anchor group represented by R ₃ is required. For this reason, Y is a double bond formed between carbon atoms in general formula (1) in which X in general formula (1) is conjugated with π electrons, and more specifically, R ₃ is bonded to R _3. It is necessary that the double bond formed between the carbon atom to be bonded and the carbon atom to be bonded to R ₅ be conjugated with the π electron. By having such a structure, when used as a sensitizing dye for photoelectric conversion, electrons can be efficiently injected from the dye into the inorganic porous material.

Y can be selected from a divalent unsaturated hydrocarbon group, an aromatic hydrocarbon group, an aromatic heterocyclic group, or a combination thereof. Here, the unsaturated hydrocarbon group may have a chain structure or a cyclic structure, and may have a structure in which two or more rings are condensed. In addition, the divalent unsaturated hydrocarbon group, aromatic hydrocarbon group or aromatic heterocyclic group may have a substituent.
The number of carbon atoms in Y is not particularly limited as long as a conjugated system can be maintained between the amino group of the general formula (1) and the anchor group represented by R ₃ , but it is easy to synthesize and economical. Therefore, the skeleton portion preferably has 2 to 60 carbon atoms. Therefore, when Y has a substituent, the carbon number of the skeleton part excluding the substituent may be in the above range, and the carbon number including the substituent may exceed the above range. The number of carbon atoms in the skeleton portion of Y is preferably 2-40.

  Examples of the divalent unsaturated hydrocarbon group include “—CH═CH—”, “—CH═CH—CH═CH—”, “—CH═CH—CH═CH—CH═CH—”, “—CH═ A conjugated chain linking group such as “CH—C≡C—” or a cyclic linking group having an unsaturated bond such as 1-cyclohexene-1,2-ylene, 1-cyclopentene-1,2-ylene, and the like. A structure in which the chain linking group and the cyclic linking group are combined may be used.

  The divalent aromatic hydrocarbon group may be a monocyclic structure, a condensed ring structure, or a ring-aggregated aromatic hydrocarbon group. For example, a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group , Triphenylene group, pyrylene group and the like.

  The divalent aromatic heterocyclic group may be a monocyclic structure, a condensed ring structure, or a ring assembly aromatic heterocyclic group. For example, 2,5-furylene group, 2,5 -Thiazoylene group, 2,5-pyrazolylene group, 2,5-pyrazolylene group, 2,5-pyrrolylene group, 2,5-pyrimidinylene group, 2,5-thienylene group, 2,5-selenylene group, 2,6- A quinolylene group, a 2,5-thienothienylene group, a 2,5-selenoselenylene group, and the like can be given.

上記式中、ｑ、ｒおよびｔは、それぞれ独立して１〜１０の整数である。Ｘ₂およびＸ₃は、一般式（２）について示したものと同じものを表す。 The combination of an unsaturated hydrocarbon group, an aromatic hydrocarbon group, and an aromatic heterocyclic group includes a structure in which two or more rings are directly connected, or a structure in which an unsaturated hydrocarbon group is connected. Can be mentioned. These combinations are not particularly limited as long as a π-conjugated system can be formed from X to the anchor group R ₃ in the general formula (1). Specific examples of such a combination structure include a biphenylene group, a bithienylene group, a bipyridylene group, or a group containing a repeating structure represented by the following general formula (4).

In the above formula, q, r and t are each independently an integer of 1 to 10. X ₂ and X ₃ represent the same as those shown for the general formula (2).

When Y is a group including two or more repeating structures represented by the general formula (4), all the repeating structures of the general formula (4) included in Y are not necessarily the same. That is, the repeating structure represented by the general formula (4) may include different structures.
In Y, the number of repeating structures represented by the general formula (4) is an integer of 1 to 10.

Specific examples of the repeating structure represented by the general formula (4) are shown below.

The terminal amino acid-containing heterocyclic derivative of the present invention represented by the general formula (1) is suitable as a sensitizing dye for photoelectric conversion used in a dye-sensitized photoelectric conversion battery.
The solar radiation spectrum reaching the ground is scattered or absorbed by the upper atmosphere surrounding the earth, and a distribution is seen at about 300 to 3000 nm. Here, in the dye-sensitized photoelectric conversion battery, it is considered that the absorption wavelength region in which sunlight can be converted into electric energy is effective in the range of 300 to 1200 nm due to the influence of the semiconductor electrode potential and the oxidation-reduction potential of the electrolyte. Furthermore, the irradiance of sunlight is large mainly in the visible region, and the energy in the visible region of 400 to 800 nm corresponds to 55% of the total solar energy.
Therefore, it is possible to efficiently use solar energy by using a dye having a wide absorption band in the visible region as a sensitizing dye for photoelectric conversion for a dye-sensitized photoelectric conversion battery.

In order for a dye used as a sensitizing dye for photoelectric conversion for a dye-sensitized photoelectric conversion battery to have a wider absorption band in the visible region, the absorption edge is preferably on the longer wavelength side. Furthermore, as a guideline, it is preferable that the absorption maximum wavelength specified by the UV-visible absorption spectrum measurement is on the longer wavelength side.
As one of methods for designing the structure of a dye satisfying these requirements, in the case of a long conjugated system and a skeleton represented by the general formula (1), an aromatic hydrocarbon group is introduced as X rather than an aromatic hydrocarbon group. It is preferable to introduce a group heterocyclic group. From this point, the terminal amino group-containing heterocyclic derivative of the present invention represented by the general formula (1) is suitable as a sensitizing dye for a dye-sensitized photoelectric conversion battery.

  For the same reason, both X and Y in the general formula (1) are preferably aromatic heterocyclic groups, and the aromatic heterocyclic group is preferably a 5-membered heterocyclic structure. Here, a structure formed by condensing a heterocyclic 5-membered ring structure is also preferable.

  In particular, X and Y in the general formula (1) have a structure having either a 2,5-thienylene group, a 2,5-furylene group, a 2,5-selenylene group, or a 2,5-thiazoylene group. Is preferred. Further, a structure having a 2,5-thienothienylene group or a 2,6-dithienothienylene group, which is a structure in which these groups are condensed, is preferable. Among these, a structure having a 2,5-thienylene group or a 2,5-thienothienylene group is preferable.

  In the skeleton represented by the general formula (1), X is preferably an aromatic heterocyclic group rather than an aromatic hydrocarbon group, and X and Y are more aromatic heterocycle than an aromatic hydrocarbon group. The reason why the aromatic heterocyclic group is preferably a hetero 5-membered ring structure is that the difference in HOMO-LUMO is reduced by the hetero atoms present in the ring, and as a result, an ultraviolet-visible absorption spectrum is obtained. The maximum absorption wavelength of the compound having an aromatic heterocyclic group introduced is shifted to a longer wavelength side than the compound having an aromatic hydrocarbon group introduced, and this tendency is observed in the case of a hetero 5-membered ring structure. Seems to be more prominent.

Next, R ₁ , R ₂ , R ₄ and R _{5 in the} general formula (1) will be described.
R ₁ , R ₂ , R ₄ and R ₅ are each independently a monovalent organic residue optionally having a hydrogen atom or a substituent. Here, R ₁ and R ₂ may jointly form a ring. Further, either R ₁ or R ₂ may form a ring together with X.

上記一般式（３）において、Ａ₁およびＡ₂は、それぞれ独立して、Ｏ、ＮＨまたはＳである。Ｂはカルボニル基、チオカルボニル基、スルフィニル基またはスルホニル基である。ｏおよびｐは、それぞれ独立して０または1である。Ｒ₈は、水素原子、置換基を有していてもよい１価の脂肪族炭化水素基、芳香族炭化水素基、もしくは芳香族複素環基、またはハロゲン原子、シアノ基、イソシアノ基、チオシアネート基、イソチオシアネート基、ニトロ基、ヒドロキシ基、メルカプト基、アミノ基もしくはアミド基である。 Specific examples of the monovalent organic residue represented by R ₁ , R ₂ , R ₄ and R ₅ include an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic group which may have a substituent. A heterocyclic group, or a halogen atom, a cyano group, an isocyano group, a thiocyanate group, an isothiocyanate group, a nitro group, a hydroxy group, a mercapto group, an amino group, an amide group, or a group represented by the following general formula (3) It is done.

In the general formula (3), A ₁ and A ₂ are each independently O, NH, or S. B is a carbonyl group, a thiocarbonyl group, a sulfinyl group or a sulfonyl group. o and p are each independently 0 or 1. R ₈ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group or an aromatic heterocyclic group, or a halogen atom, cyano group, isocyano group or thiocyanate group. , Isothiocyanate group, nitro group, hydroxy group, mercapto group, amino group or amide group.

  Here, the monovalent aliphatic hydrocarbon group means a monovalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, and may be any of a linear structure, a branched structure, or a cyclic structure, It may have an unsaturated bond. The monovalent aliphatic hydrocarbon group may have a substituent, and one or more carbon atoms may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. Specific examples of the monovalent aliphatic hydrocarbon group include an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkynyl group, a cycloalkyl group, and an alkoxy group.

  More specifically, as the monovalent aliphatic hydrocarbon group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, 1- An alkyl group having 1 to 8 carbon atoms such as a pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 2-ethyl-1-hexyl group; 1-propenyl group, isopropenyl group, allyl group, 1- C2-C4 alkenyl groups such as butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl; ethynyl, 1-propenyl, 2-propenyl Group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-3-propenyl group, alkynyl group having 2 to 4 carbon atoms; cyclopropyl group, cyclobutyl , A cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecanyl group, a saturated cycloalkyl group having 3 to 10 carbon atoms; a 2-cyclopenten-1-yl group, a 2-cyclohexen-1-yl group, etc. Examples thereof include unsaturated cycloalkyl groups having 3 to 7 carbon atoms.

  Examples of the monovalent aromatic hydrocarbon group include an aromatic hydrocarbon group having a monovalent monocyclic structure or a condensed ring structure, or a monovalent ring assembly aromatic hydrocarbon group. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a triphenyl group, and a pyrenyl group. In addition, the monovalent aromatic hydrocarbon may be bonded to the skeleton of the general formula (1) via an oxygen atom or a sulfur atom. A phenoxy group, a naphthyloxy group, etc. are mentioned.

  Preferred monovalent aromatic hydrocarbon groups are a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, an o-anisoyyl group, an m-anisoyyl group, a p-anisoyyl group, a 1-naphthyl group, 2 -Monovalent aromatic hydrocarbon groups having 6 to 14 carbon atoms such as naphthyl group and 9-phenanthryl group.

  Examples of the monovalent aromatic heterocyclic group include an aromatic heterocyclic group having a monovalent monocyclic structure or a condensed ring structure, and a monovalent ring assembly aromatic heterocyclic group. Specifically, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-selenyl group, 3-selenyl group, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 2-quinoxalyl group, 2-benzofuryl group, 2-benzothienyl group, 2-thienothienyl group, 3-thienothienyl group, 2-selenoselenyl group, 3-selenoselenyl group, 2-thiazoyl group, 2-thiazothiazoyl group Etc.

  Preferred monovalent aromatic heterocyclic groups include carbon numbers such as 2-thienyl group, 2-selenyl group, 2-benzothienyl group, 2-benzoselenyl group, 2-thienothienyl group, 2-selenoselenyl group, and 2-dithienyl group. Examples include 4 to 12 aromatic heterocyclic groups.

Examples of the aliphatic hydrocarbon group in which R ₁ and R ₂ jointly form a cyclic structure include a divalent linking group. Preferred examples of the divalent linking group include saturated alkylene groups having 4 to 6 carbon atoms such as a tetramethylene group, a pentamethylene group, and a hexamethylene group.
For example, in the case of a pentamethylene group, the ring formed by R ₁ and R ₂ and the nitrogen atom of the amine moiety of the general formula (1) forms a piperidine ring.

For example, when the aliphatic hydrocarbon group in which R ₁ and R ₂ jointly form a cyclic structure is a pentamethylene group and the carbon atom is substituted with an oxygen atom, R ₁ and R ₂ , The ring formed by the nitrogen atom of the amine moiety of (1) and the ring formed by the nitrogen atom of the amine moiety of general formula (1) form a morpholine ring or the like.

Examples of the aromatic hydrocarbon group in which R ₁ and R ₂ jointly form a cyclic structure include a divalent linking group consisting of an aromatic hydrocarbon group having a monocyclic structure or a condensed ring structure, or a ring assembly aromatic hydrocarbon group And a divalent linking group. Specific examples of such a divalent linking group include a 2,2′-biphenylene group, a —Ph—S—Ph— group, a 4,5-phenanthryl group, and the like, and preferably a 2,2′— Biphenylene group is mentioned.

Examples of the aromatic heterocyclic group in which R ₁ and R ₂ jointly form a cyclic structure include a divalent linking group composed of an aromatic heterocyclic group having a monocyclic structure or a condensed ring structure, or a ring assembly aromatic heterocyclic group And a divalent linking group. Specific examples of such a divalent linking group include a 3,3′-bithienylene group.

As R ₁ and R ₂ , an alkyl group having 1 to 4 carbon atoms is particularly preferable from the viewpoint of easy synthesis.

R ₄ and R ₅ are preferably a hydrogen atom, a halogen atom, or a monovalent organic residue having 1 to 20 carbon atoms. Here, the monovalent organic residue is preferably substituted. R ₄ and R ₅ are particularly preferably electron withdrawing groups.

The term “electron-withdrawing group” as used herein means a group having a Hammett's substituent constant σ greater than zero. Specific examples of the electron withdrawing group of R ₄ and R ₅ include cyano group, carboxyl group, acyl group, formyl group, aryloxycarbonyl group, alkyloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group. , Arylsulfinyl group, nitro group, perfluoroalkyl group and the like. However, the electron withdrawing group is not limited to these.

  Examples of the acyl group include an acetyl group, a propionyl group, a pivaloyl group, an acryloyl group, a methacryloyl group, a benzoyl group, a toluoyl group, and a cinnamoyl group.

  Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a naphthyloxycarbonyl group, and a 4-fluorophenyloxycarbonyl group.

  Examples of the alkylsulfonyl group include a mesyl group, an ethylsulfonyl group, a propylsulfonyl group, a trifluorosulfonyl group, and a nonafluoro-t-butylsulfonyl group.

  Examples of the arylsulfonyl group include a benzenesulfonyl group and a toluenesulfonyl group.

  Examples of the alkylsulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, and a propylsulfinyl group.

  Examples of the arylsulfinyl group include a phenylsulfinyl group and a toluylsulfinyl group.

  A perfluoroalkyl group is an all-fluorine-substituted group having 1 to 20 carbon atoms. The perfluoroalkyl group may contain oxygen or sulfur.

Among these, as R ₄ , a cyano group is preferable in view of ease of synthesis and electron withdrawing strength. R ₅ is preferably a hydrogen atom or a cyano group.

R ₃ is an anchor group that can be linked to an inorganic porous material exhibiting semiconductor properties. As the inorganic porous material exhibiting such semiconductor characteristics, specifically, particles in which inorganic oxides exhibiting semiconductor characteristics such as titanium oxide, tin oxide, and zinc oxide are made porous are used. Therefore, the anchor group widely includes groups that can be connected to the porous inorganic oxide particles. Such an anchor group is preferably a carboxyl group, a phosphoric acid group, a sulfonic acid group or the like. Among these, a carboxyl group is particularly preferable because it can be easily connected to porous inorganic oxide particles.
In addition, the said carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. may combine with a cation and form the salt for the purpose of improving solubility. Examples of the cation capable of forming a salt include quaternary ammonium ions, alkali metal ions, and alkaline earth metal ions. Examples of quaternary ammonium ions include tetraalkylammonium ions typified by tetramethylammonium ions. Examples of the alkali metal ion include sodium ion, potassium ion, lithium ion, and the like. Examples of alkaline earth metal ions include magnesium ions and calcium ions.

Specific examples of the terminal amino group-containing heterocyclic derivative of the present invention represented by the general formula (1) are shown below. However, these are for illustrative purposes, and the terminal amino group-containing heterocyclic derivative of the present invention is not limited thereto.
In the following examples, “Ph” represents a phenyl group. “Et”, “Pr”, and “Bu” represent an ethyl group, an n-propyl group, and an n-butyl group, respectively.

The sensitizing dye for photoelectric conversion of the present invention includes a terminal amino group-containing heterocyclic derivative represented by the above general formula (1).
The sensitizing dye for photoelectric conversion according to the present invention may further include other photosensitizing dyes in order to compensate for sunlight absorption in a region that cannot be covered by the terminal amino group-containing heterocyclic derivative represented by the general formula (1). May be included. As other sensitizing dyes used for such purposes, for example, sensitizing dyes described in JP-A No. 2004-143355 [0062] can be used.

  The photoelectric conversion material of the present invention is formed by connecting the above-described sensitizing dye for photoelectric conversion of the present invention and an inorganic porous material exhibiting semiconductor characteristics via an anchor group. As an inorganic porous substance used when forming a photoelectric conversion material, for example, a method for making an inorganic oxide and an inorganic oxide porous described in JP-A-2004-143355 [0064] and [0065] is used. What is obtained can be used.

  The photoelectric conversion electrode of the present invention is formed by laminating the photoelectric conversion material of the present invention obtained by the above procedure on a transparent electrode. Here, for the transparent electrode and the method for laminating the photoelectric conversion material on the transparent electrode, for example, the materials and laminating methods described in JP-A No. 2004-143355 [0066] to [0069] can be used. .

The photoelectric conversion battery of the present invention is formed by combining the above-described photoelectric conversion electrode with a conductive counter electrode via an electrolyte layer.
The electrolyte layer used for the photoelectric conversion battery is preferably composed of an electrolyte, a medium, and an additive. As these components, for example, those described in JP-A No. 2004-143355 [0070] to [0072] can be used. Moreover, the assembly of a photoelectric conversion battery can be implemented by the method described in Unexamined-Japanese-Patent No. 2004-143355 [0073], for example.

In order to efficiently inject electrons from the sensitizing dye for photoelectric conversion of the present invention into an inorganic porous material exhibiting semiconductor characteristics, a compound called “co-adsorbent” or the like can also be used. The co-adsorbent increases the photoelectric conversion efficiency by adsorbing to the inorganic porous material together with the sensitizing dye.
The sensitizing dye for photoelectric conversion of the present invention is connected to an inorganic porous material exhibiting semiconductor characteristics via an anchor group, and this “connection” is almost synonymous with the above “adsorption”.

  Examples of coadsorbents include steroid compounds having carboxyl groups or sulfonic acid groups, especially cholic acid derivatives (cholic acid, deoxycholic acid, chenodeoxycholic acid, taurochenodeoxycholic acid, lysocholic acid, ursodeoxycholic acid, dehydrocholic acid) And its sodium salts, amines (pyridine, 4-t-butylpyridine, polyvinylpyridine, etc.), quaternary ammonium salts (tetrabutylammonium iodide, tetrahexylammonium iodide, etc.), and the like.

  Examples of how to use the co-adsorbent include adding after adsorbing (linking) the dye to the inorganic porous material, adding to the electrolyte layer, and the like. It is not limited to this as long as it is adsorbed (connected) to the material.

¹Ｈ ＮＭＲ（ＣＤＣｌ₃；ＴＭＳ） δ０．９６（ｔ，J＝７．２Ｈｚ，−ＣＨ₃，６Ｈ），１．２５−１．４０（ｍ，−ＣＨ₂−，４Ｈ），１．５５−１．７０（ｍ，−ＣＨ₂−，４Ｈ），３．３３（ｍ，−Ｎ−ＣＨ₂−，４Ｈ），５．８９（ｄ，Ｊ＝４．５Ｈｚ，チオフェン環，１Ｈ），７．４４（ｄ，Ｊ＝４．５Ｈｚ，チオフェン，１Ｈ），９．４６（ｓ，−Ｃ（＝Ｏ）−Ｈ，１Ｈ） Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to these examples.
Synthesis of terminal amino group-containing heterocyclic derivative (1) of the present invention (1-1) Synthesis of 5- (di-n-butylamino) -thiophene-2-carboxaldehyde A condenser, thermometer, and magnetic rotor are attached. In a 500 mL four-necked flask, 50 g of 5-bromothiophene-2-carboxaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 42 g of di-n-butylamine (manufactured by Wako Pure Chemical Industries, Ltd.), triethylamine (Wako Pure Chemical Industries, Ltd.) 54 g and 200 mL of xylene were charged at room temperature, and the flask was purged with nitrogen, then heated to reflux and heated for 15 hours. After the completion of the reaction, the mixture was allowed to cool to room temperature, dried, evaporated under reduced pressure, concentrated, separated and purified by silica gel chromatography to obtain 42 g of product. The compound was subjected to ¹ H-NMR measurement with an FT-NMR apparatus (AL-300 (manufactured by JEOL Ltd.)), and 5- (di-n-butylamino) -thiophene-2-carboxaldehyde (the following formula). I confirmed that there was.

¹ H NMR (CDCl ₃ ; TMS) δ 0.96 (t, J = 7.2 Hz, —CH ₃ , 6H), 1.25 to 1.40 (m, —CH ₂ —, 4H), 1.55- 1.70 (m, —CH ₂ —, 4H), 3.33 (m, —N—CH ₂ —, 4H), 5.89 (d, J = 4.5 Hz, thiophene ring, 1H), 7. 44 (d, J = 4.5 Hz, thiophene, 1H), 9.46 (s, -C (= O) -H, 1H)

¹Ｈ ＮＭＲ（ＣＤＣｌ₃；ＴＭＳ） δ４．６３（ｓ，−ＣＨ₂−Ｂｒ，２Ｈ），δ６．８−７．０（ｍ，チオフェン，２Ｈ） (1-2) Synthesis of 5, α-dibromo-2-methylthiophene 56 g of dibromohydantoin and 200 mL of methylene chloride were added to a 500 mL four-necked flask equipped with a condenser, thermometer, magnetic rotor, and dropping funnel. . To the dropping funnel, 20 g of 2-methylthiophene (manufactured by Wako Pure Chemical Industries, Ltd.) and 20 mL of methylene chloride were slowly added. After the addition was completed, the mixture was further stirred for 1 hour, 1 g of azo polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated to reflux for 3 hours. After cooling, the white substance floating was filtered off, and the filtrate was washed with water. After drying, the solvent was distilled off to obtain 21 g of product. It was confirmed by ¹ H-NMR measurement that the product was 5, α-dibromo-2-methylthiophene (the following formula).

¹ H NMR (CDCl ₃ ; TMS) δ 4.63 (s, —CH ₂ —Br, 2H), δ 6.8-7.0 (m, thiophene, 2H)

¹Ｈ ＮＭＲ（ＣＤＣｌ₃；ＴＭＳ） δ１．３０（ｔ，Ｊ＝７．２Ｈｚ，−ＣＨ₃，３Ｈ），δ３．３１（ｄ，Ｊ＝１６．２Ｈｚ，Ａｒ−ＣＨ₂−Ｐ（＝Ｏ）＜，２Ｈ），δ４．０９（ｑｕｉｎｔｅｔ，−Ｏ−ＣＨ₂−Ｍｅ，２Ｈ），δ６．６５−６．８０（ｍ，チオフェン，１Ｈ），δ６．９０（ｄ，Ｊ＝３．９Ｈｚ，チオフェン，１Ｈ） (1-3) Synthesis of diethyl 5-bromo-2-thienylmethanephosphonate 5, α-Dibromo-2-methylthiophene 25 was added to a 500 mL four-necked flask equipped with a condenser, a thermometer and a magnetic rotor. 0.5 g, 16.5 g of triethyl phosphite (manufactured by Kanto Chemical Co., Inc.), and 200 mL of acetonitrile were charged and heated to reflux for 3 hours under a nitrogen stream. After cooling, the solvent and the like were distilled off to obtain 29 g of a product. It was confirmed by ¹ H-NMR measurement that the product was diethyl 5-bromo-2-thienylmethanephosphonate (the following formula).

¹ H NMR (CDCl ₃ ; TMS) δ 1.30 (t, J = 7.2 Hz, —CH ₃ , 3H), δ 3.31 (d, J = 16.2 Hz, Ar—CH ₂ —P (═O) <, 2H), δ 4.09 (quintet, —O—CH ₂ —Me, 2H), δ 6.65-6.80 (m, thiophene, 1H), δ 6.90 (d, J = 3.9 Hz, thiophene , 1H)

¹Ｈ ＮＭＲ（ＣＤＣｌ₃；ＴＭＳ） δ０．９５（ｔ，J＝７．２Ｈｚ，−ＣＨ₃，６Ｈ），１．３０−１．４５（ｍ，−ＣＨ₂−，４Ｈ），１．５５−１．７０（ｍ，−ＣＨ₂−，４Ｈ），３．２１（ｍ，−Ｎ−ＣＨ₂−，４Ｈ），５．６４（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），６．４６（ｄ，Ｊ＝１５．６Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），６．６０（ｄ，Ｊ＝３．９Ｈｚ，チオフェン環，１Ｈ），６．６９（ｄ，Ｊ＝３．９Ｈｚ，チオフェン環，１Ｈ），６．７８（ｄ，Ｊ＝１５．６Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），６．８６（ｄ，Ｊ＝３．９Ｈｚ，チオフェン，１Ｈ） (1-4) Synthesis of N, N-dibutyl-5- (2- (2-bromo-5-thienyl) -ethen-1-yl) -2-thienylamine Next obtained in (1-1) To 9.5 g of 5- (di-n-butylamino) -thiophene-2-carboxaldehyde and 15 g of diethyl 5-bromo-2-thienylmethanephosphonate obtained in (1-3) were added to 50 mL of dehydrated tetrahydrofuran. Next, lithium diisopropylamide-tetrahydrofuran solution (diisopropylamine (manufactured by Wako Pure Chemical Industries, Ltd.) 5.5 g containing tetrahydrofuran, 100 mL, n-butyllithium-hexane solution (manufactured by Kanto Chemical Co., Ltd.) (1.57 mol) / L) 32 mL was added under a stream of nitrogen, followed by N), N, N ′, N′-tetramethylethylenediamine. 6 g was added and allowed to stir at room temperature for 1 hour.
After completion of the reaction, 1N hydrochloric acid was added to stop the reaction, and the organic phase was washed with water. After separation and drying, the solvent was distilled off under reduced pressure and concentrated, followed by separation and purification by silica gel chromatography to obtain 12 g of a product. ^{According to 1} H-NMR measurement, the product is N, N-dibutyl-5- (2- (2-bromo-5-thienyl) -ethen-1-yl) -2-thienylamine (the following formula). It was confirmed.

¹ H NMR (CDCl ₃ ; TMS) δ 0.95 (t, J = 7.2 Hz, —CH ₃ , 6H), 1.30-1.45 (m, —CH ₂ —, 4H), 1.55- 1.70 (m, —CH ₂ —, 4H), 3.21 (m, —N—CH ₂ —, 4H), 5.64 (d, J = 4.2 Hz, thiophene ring, 1H), 6. 46 (d, J = 15.6 Hz, olefin, 1H), 6.60 (d, J = 3.9 Hz, thiophene ring, 1H), 6.69 (d, J = 3.9 Hz, thiophene ring, 1H) , 6.78 (d, J = 15.6 Hz, olefin, 1H), 6.86 (d, J = 3.9 Hz, thiophene, 1H)

¹Ｈ ＮＭＲ（ＣＤＣｌ₃；ＴＭＳ） δ０．９５（ｔ，J＝７．２Ｈｚ，−ＣＨ₃，６Ｈ），１．２５−１．４０（ｍ，−ＣＨ₂−，４Ｈ），１．５５−１．７０（ｍ，−ＣＨ₂−，４Ｈ），３．２６（ｍ，−Ｎ−ＣＨ₂−，４Ｈ），５．６９（ｄ，Ｊ＝３．９Ｈｚ，チオフェン環，１Ｈ），６．５１（ｄ，Ｊ＝１５．６Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），６．８３（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），６．９３（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），７．１３（ｄ，Ｊ＝１５．３Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），７．５７（ｄ，Ｊ＝３．９Ｈｚ，チオフェン，１Ｈ），９．７６（ｓ，−Ｃ（＝Ｏ）−Ｈ，１Ｈ） (1-5) Synthesis of 5- (2- (2- (2- (N, N-dibutylamino) -5-thienyl) -ethen-1-yl) -thiophene-2-carboxaldehyde (1- 4 g of N, N-dibutyl-5- (2- (2-bromo-5-thienyl) -ethen-1-yl) -2-thienylamine obtained in 4) and 80 mL of dehydrated tetrahydrofuran were added, and under a nitrogen stream. After cooling to −78 ° C., 14 mL of n-butyllithium-hexane solution (manufactured by Kanto Chemical Co., Inc.) (1.57 mol / L) was added. After stirring at −78 ° C. for 30 minutes, 2.5 g of 1-formylpiperidine was added. After stirring for 1 hour, the temperature was raised to room temperature, and 1N hydrochloric acid was added to stop the reaction. The organic phase was separated and washed with water. After drying, the solvent was distilled off under reduced pressure and concentrated, followed by separation and purification by silica gel chromatography to obtain 5.5 g of product. ^{By 1} H-NMR measurement, the product was found to be 5- (2- (2- (2- (N, N-dibutylamino) -5-thienyl) -ethen-1-yl) -thiophene-2-carboxaldehyde. confirmed.

¹ H NMR (CDCl ₃ ; TMS) δ 0.95 (t, J = 7.2 Hz, —CH ₃ , 6H), 1.25 to 1.40 (m, —CH ₂ —, 4H), 1.55- 1.70 (m, —CH ₂ —, 4H), 3.26 (m, —N—CH ₂ —, 4H), 5.69 (d, J = 3.9 Hz, thiophene ring, 1H), 6. 51 (d, J = 15.6 Hz, olefin, 1H), 6.83 (d, J = 4.2 Hz, thiophene ring, 1H), 6.93 (d, J = 4.2 Hz, thiophene ring, 1H) , 7.13 (d, J = 15.3 Hz, olefin, 1H), 7.57 (d, J = 3.9 Hz, thiophene, 1H), 9.76 (s, -C (= O) -H, 1H)

¹Ｈ ＮＭＲ（ＣＤＣｌ₃；ＴＭＳ） δ０．９７（ｔ，J＝７．２Ｈｚ，−ＣＨ₃，６Ｈ），１．３０−１．４５（ｍ，−ＣＨ₂−，４Ｈ），１．５０−１．７０（ｍ，−ＣＨ₂−，４Ｈ），１．５６（ｓ，−ＣＨ₃，９Ｈ），３．２７（ｍ，−Ｎ−ＣＨ₂−，４Ｈ），５．７２（ｄ，Ｊ＝３．９Ｈｚ，チオフェン環，１Ｈ），６．５２（ｄ，Ｊ＝１５．３Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），６．８７（ｄ，Ｊ＝３．９Ｈｚ，チオフェン環，１Ｈ），６．９０（ｄ，Ｊ＝３．９Ｈｚ，チオフェン環，１Ｈ），７．１９（ｄ，Ｊ＝１５．３Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），７．５１（ｄ，Ｊ＝４．２Ｈｚ，チオフェン，１Ｈ），８．１０（ｓ，Ａｒ−ＣＨ＝（ＣＮ）ＣＯＯ−，１Ｈ） (1-6) tert-Butyl 3- (5- (2- (2- (N, N-dibutylamino) -5-thienyl) -ethen-1-yl) -2-thienyl) -2-cyanoacrylate A 3-mL two-necked flask equipped with a Dean-Stark fractionator equipped with a condenser, a thermometer, and a magnetic rotor was attached to a 5- (2- (2- (N, N, N-dibutylamino) -5-thienyl) -ethen-1-yl) -thiophene-2-carboxaldehyde (3.5 g), tert-butyl cyanoacetate (3.5 g), and piperidine (4 g) are added to toluene (200 mL) to complete the reaction. Heated to reflux. After completion of the reaction, the reaction mixture was cooled to room temperature, and the solvent and the low boiling point reactant were distilled off and concentrated under reduced pressure, followed by separation and purification by silica gel chromatography to obtain 3.7 g of a product. ^{According to 1} H-NMR measurement, the product was found to be 3- (5- (2- (2- (N, N-dibutylamino) -5-thienyl) -ethen-1-yl) -2-thienyl) -2- It was confirmed that it was tert-butyl cyanoacrylate (the following formula).

¹ H NMR (CDCl ₃ ; TMS) δ 0.97 (t, J = 7.2 Hz, —CH ₃ , 6H), 1.30-1.45 (m, —CH ₂ —, 4H), 1.50— 1.70 (m, —CH ₂ —, 4H), 1.56 (s, —CH ₃ , 9H), 3.27 (m, —N—CH ₂ —, 4H), 5.72 (d, J = 3.9 Hz, thiophene ring, 1H), 6.52 (d, J = 15.3 Hz, olefin, 1H), 6.87 (d, J = 3.9 Hz, thiophene ring, 1H), 6.90 ( d, J = 3.9 Hz, thiophene ring, 1H), 7.19 (d, J = 15.3 Hz, olefin, 1H), 7.51 (d, J = 4.2 Hz, thiophene, 1H), 8. 10 (s, Ar-CH = (CN) COO-, 1H)

¹Ｈ ＮＭＲ（ＤＭＳＯ−ｄ₆；ＴＭＳ） δ０．９２（ｔ，J＝７．２Ｈｚ，−ＣＨ₃，６Ｈ），１．２５−１．４０（ｍ，−ＣＨ₂−，４Ｈ），１．５０−１．６５（ｍ，−ＣＨ₂−，４Ｈ），３．２９（ｍ，−Ｎ−ＣＨ₂−，４Ｈ），５．８６（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），６．６３（ｄ，Ｊ＝１５．３Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），７．０８（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），７．１９（ｄ，Ｊ＝３．９Ｈｚ，チオフェン環，１Ｈ），７．２９（ｄ，Ｊ＝１５．６Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），７．８３（ｄ，Ｊ＝３．９Ｈｚ，チオフェン，１Ｈ），８．３３（ｓ，Ａｒ−ＣＨ＝（ＣＮ）ＣＯＯＨ，１Ｈ） Synthesis of (1-7) 3- (5- (2- (2- (N, N-dibutylamino) -5-thienyl) -ethen-1-yl) -2-thienyl) -2-cyanoacrylic acid 100 mL 3- (5- (2- (2- (2- (N, N-dibutylamino) -5-thienyl) -ethen-1-yl) -2-thienyl) obtained in (1-6)) 1.9 g of tert-butyl-2-cyanoacrylate and 50 mL of acetic acid were added, 2 g of 48% hydrobromic acid was added, and the mixture was stirred at room temperature. After completion of the reaction, the reaction mixture was poured into 1 L of ion exchange water and extracted twice with 500 mL of methyl tert-butyl ether. The extract was washed once with aqueous ammonia and twice with water, and the solvent was distilled off under reduced pressure and concentrated to obtain 1.3 g of a product. ^{By 1} H-NMR measurement, the product was converted to a terminal amino group-containing heterocyclic derivative (1) 3- (5- (2- (2- (N, N-dibutylamino) -5-thienyl) -ethene of the present invention. -1-yl) -2-thienyl) -2-cyanoacrylic acid (the following formula)).

¹ H NMR (DMSO-d ₆ ; TMS) δ 0.92 (t, J = 7.2 Hz, —CH ₃ , 6H), 1.25 to 1.40 (m, —CH ₂ —, 4H), 1. 50-1.65 (m, —CH ₂ —, 4H), 3.29 (m, —N—CH ₂ —, 4H), 5.86 (d, J = 4.2 Hz, thiophene ring, 1H), 6.63 (d, J = 15.3 Hz, olefin, 1H), 7.08 (d, J = 4.2 Hz, thiophene ring, 1H), 7.19 (d, J = 3.9 Hz, thiophene ring, 1H), 7.29 (d, J = 15.6 Hz, olefin, 1H), 7.83 (d, J = 3.9 Hz, thiophene, 1H), 8.33 (s, Ar—CH = (CN) COOH, 1H)

^１Ｈ ＮＭＲ（ＣＤＣｌ₃；ＴＭＳ） δ１．５〜１．８（ｍ，−ＣＨ₂−，６Ｈ），δ３．２−３．５（ｍ，−ＣＨ₂−Ｎ，４Ｈ），δ６．０６（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），δ７．４７（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），δ９．５１（ｓ，−ＣＨＯ，１Ｈ） Synthesis of terminal amino group-containing heterocyclic derivative compound (2) of the present invention (2-1) Synthesis of 5-piperidinylthiophene-2-carboxaldehyde 500 mL of four tubes equipped with a condenser, thermometer and magnetic rotor Into the neck flask, 34 g of 5-bromothiophene-2-carboxaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 25 g of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 250 mL of ion-exchanged water were charged at room temperature, and the inside of the flask was streamed with nitrogen. Then, the temperature was raised until heating to reflux, and the mixture was heated to reflux for 15 hours. After completion of the reaction, the mixture was allowed to cool to room temperature and extracted with an organic solvent. The organic phase was washed with 1N hydrochloric acid followed by water. After washing with water, the organic phase was separated, dried, concentrated by evaporation of the solvent under reduced pressure, and then separated and purified by silica gel column chromatography to obtain 21 g of product. The compound was subjected to ¹ H-NMR measurement with an FT-NMR apparatus (AL-300 (manufactured by JEOL Ltd.)) and confirmed to be 5-piperidinylthiophene-2-carboxaldehyde (the following formula).

¹ H NMR (CDCl ₃ ; TMS) δ 1.5 to 1.8 (m, —CH ₂ —, 6H), δ 3.2-3.5 (m, —CH ₂ —N, 4H), δ 6.06 ( d, J = 4.2 Hz, thiophene ring, 1H), δ 7.47 (d, J = 4.2 Hz, thiophene ring, 1H), δ 9.51 (s, -CHO, 1H).

^１Ｈ ＮＭＲ（ＣＤＣｌ₃；ＴＭＳ） δ１．５−１．８（ｍ，−ＣＨ₂−，６Ｈ），δ３．０−３．３（ｍ，−ＣＨ₂−Ｎ，４Ｈ），５．８９（ｄ，Ｊ＝３．９Ｈｚ，チオフェン環，１Ｈ），δ６．５３（ｄ，Ｊ＝１５．６Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），δ６．６３（ｄ，Ｊ＝３．９Ｈｚ，チオフェン環，１Ｈ），δ６．７０（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），δ６．７８（ｄ，１５．９Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），６．８７（ｄ，Ｊ＝３．９Ｈｚ，チオフェン環，１Ｈ） (2-2) Synthesis of 1- (5- (2- (2-bromo-5-thienyl) -ethen-1-yl) -2-thienyl) piperidine Next, the 5- 4 g of piperidinylthiophene-2-carboxaldehyde and 7.7 g of diethyl 5-bromo-2-thienylmethanephosphonate obtained in (1-3) were put into 100 mL of dehydrated tetrahydrofuran, and then lithium diisopropylamide- Tetrahydrofuran solution (diisopropylamine (manufactured by Wako Pure Chemical Industries, Ltd.) (2.5 g) and tetrahydrofuran solution (20 mL) are mixed with n-butyllithium-hexane solution (manufactured by Kanto Chemical Co., Ltd.) (1.57 mol / L) (15.3 mL). Prepared under a stream of air) followed by 2.8 g of N, N, N ′, N′-tetramethylethylenediamine. In was allowed to stir for 1 hour.
After completion of the reaction, 1N hydrochloric acid was added to stop the reaction, and the organic phase was washed with water. After separation and drying, the solvent was distilled off under reduced pressure and concentrated, followed by separation and purification by silica gel column chromatography to obtain 6 g of a product. ¹ H-NMR measurement confirmed that the product was 1- (5- (2- (2-bromo-5-thienyl) -ethen-1-yl) -2-thienyl) piperidine (the following formula). did.

¹ H NMR (CDCl ₃ ; TMS) δ 1.5-1.8 (m, —CH ₂ —, 6H), δ 3.0-3.3 (m, —CH ₂ —N, 4H), 5.89 ( d, J = 3.9 Hz, thiophene ring, 1H), δ 6.53 (d, J = 15.6 Hz, olefin, 1H), δ 6.63 (d, J = 3.9 Hz, thiophene ring, 1H), δ6. .70 (d, J = 4.2 Hz, thiophene ring, 1H), δ 6.78 (d, 15.9 Hz, olefin, 1H), 6.87 (d, J = 3.9 Hz, thiophene ring, 1H)

^１Ｈ ＮＭＲ（ＣＤＣｌ₃；ＴＭＳ） δ１．５−１．８（ｍ，−ＣＨ₂−，６Ｈ），δ３．０−３．３（ｍ，−ＣＨ₂−Ｎ，４Ｈ），５．８９（ｄ，Ｊ＝３．９Ｈｚ，チオフェン環，１Ｈ），δ６．５３（ｄ，Ｊ＝１５．６Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），δ６．６３（ｄ，Ｊ＝３．９Ｈｚ，チオフェン環，１Ｈ），δ６．７０（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），δ６．７８（ｄ，１５．９Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），６．８７（ｄ，Ｊ＝３．９Ｈｚ，チオフェン環，１Ｈ） (2-3) Synthesis of 5- (2- (2-piperidinyl-5-thienyl) -ethen-1-yl) -thiophene-2-carboxaldehyde 1 obtained in (2-2) in a four-necked flask -(5- (2- (2-Bromo-5-thienyl) -ethen-1-yl) -2-thienyl) piperidine (5.8 g) and dehydrated tetrahydrofuran (80 mL) were added, and the mixture was cooled to -78 ° C under a nitrogen stream, 12.5 mL of n-butyllithium-hexane solution (manufactured by Kanto Chemical Co., Inc.) (1.57 mol / L) was added. After stirring at −78 ° C. for 30 minutes, 2.3 g of 1-formylpiperidine was added. After stirring for 1 hour, the temperature was raised to room temperature, and 1N hydrochloric acid was added to stop the reaction. The organic phase was washed with water and the organic phase was separated. After drying, the solvent was distilled off under reduced pressure and concentrated, followed by separation and purification by silica gel column chromatography to obtain 4 g of a product. ¹ H-NMR measurement confirmed that the product was 5- (2- (2-piperidinyl-5-thienyl) -ethen-1-yl) -thiophene-2-carboxaldehyde (the following formula).

¹ H NMR (CDCl ₃ ; TMS) δ 1.5-1.8 (m, —CH ₂ —, 6H), δ 3.0-3.3 (m, —CH ₂ —N, 4H), 5.89 ( d, J = 3.9 Hz, thiophene ring, 1H), δ 6.53 (d, J = 15.6 Hz, olefin, 1H), δ 6.63 (d, J = 3.9 Hz, thiophene ring, 1H), δ6. .70 (d, J = 4.2 Hz, thiophene ring, 1H), δ 6.78 (d, 15.9 Hz, olefin, 1H), 6.87 (d, J = 3.9 Hz, thiophene ring, 1H)

^１Ｈ ＮＭＲ（ＣＤＣｌ₃；ＴＭＳ） δ１．５５（ｓ，Ｃ−（Ｍｅ）₃，９Ｈ），δ１．５−１．８（ｍ，−ＣＨ₂−，６Ｈ），δ３．２０−３．２５（ｍ，−ＣＨ₂−Ｎ，４Ｈ），５．９２（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），δ６．５７（ｄ，Ｊ＝１５．６Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），δ６．８６（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），δ６．９２（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），δ７．１６（ｄ，１５．６Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），７．５１（ｓ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），８．１０（ｓ，３−Ｈ，１Ｈ） (2-4) Synthesis of 3- (5- (2- (2-piperidinyl-5-thienyl) -ethen-1-yl) -2-thienyl) -2-cyanoacrylic acid tert-butyl 5- (2- (2-piperidinyl-5-thienyl) -ethene-1 obtained in (2-3) in a 300 mL four-necked flask equipped with a Dean-Stark fractionator, thermometer, and magnetic rotor -Il) -thiophene-2-carboxaldehyde 3.6 g, 2.6 g of tert-butyl cyanoacetate and 1 g of piperidine were placed in 200 mL of toluene and heated to reflux until the reaction was completed. After completion of the reaction, the reaction mixture was cooled to room temperature, the solvent and the low boiling point reactant were distilled off under reduced pressure and concentrated, followed by separation and purification by silica gel column chromatography to obtain 4.8 g of a product. ^{According to 1} H-NMR measurement, the product was tert-butyl 3- (5- (2- (2-piperidinyl-5-thienyl) -ethen-1-yl) -2-thienyl) -2-cyanoacrylate ( The following formula was confirmed.

¹ H NMR (CDCl ₃ ; TMS) δ 1.55 (s, C— (Me) ₃ , 9H), δ 1.5-1.8 (m, —CH ₂ —, 6H), δ 3.20-3.25 (M, —CH ₂ —N, 4H), 5.92 (d, J = 4.2 Hz, thiophene ring, 1H), δ6.57 (d, J = 15.6 Hz, olefin, 1H), δ6.86. (D, J = 4.2 Hz, thiophene ring, 1H), δ 6.92 (d, J = 4.2 Hz, thiophene ring, 1H), δ 7.16 (d, 15.6 Hz, olefin, 1H), 7. 51 (s, J = 4.2 Hz, thiophene ring, 1H), 8.10 (s, 3-H, 1H)

^１Ｈ ＮＭＲ（ＤＭＳＯ−ｄ₆；ＴＭＳ） δ１．３−１．８（ｍ，−ＣＨ₂−，６Ｈ），δ２．８−４．０（ｍ，−ＣＨ₂−Ｎ，４Ｈ），６．０９（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），δ６．７０（ｄ，Ｊ＝１５．３Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），δ７．０８（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），δ７．２２（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），δ７．２９（ｄ，１５．６Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），７．８４（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），８．３４（ｓ，３−Ｈ，１Ｈ） (2-5) 3- (5- (2- (2-Piperidinyl-5-thienyl) -ethen-1-yl)
Synthesis of 2-thienyl) -2-cyanoacrylic acid 3- (5- (2- (2-piperidinyl-5-thienyl) -ethene-1-) obtained in (2-4) in a 100 mL eggplant-shaped flask Yl) -2-thienyl) -2-Cyanoic acid tert-butyl 3.6g and acetic acid 100mL were added, 48% hydrobromic acid 1g was added, and it was made to stir at room temperature. After completion of the reaction, the precipitated solid was recovered, washed with water, evaporated under reduced pressure and concentrated to obtain 2.7 g of product. ^{According to 1} H-NMR measurement, the product was converted to a terminal amino group-containing heterocyclic derivative (2) 3- (5- (2- (2-piperidinyl-5-thienyl) -ethen-1-yl) -2 of the present invention. -Thienyl) -2-cyanoacrylic acid (the following formula)).

¹ H NMR (DMSO-d ₆ ; TMS) δ 1.3-1.8 (m, —CH ₂ —, 6H), δ 2.8-4.0 (m, —CH ₂ —N, 4H), 6. 09 (d, J = 4.2 Hz, thiophene ring, 1H), δ 6.70 (d, J = 15.3 Hz, olefin, 1H), δ 7.08 (d, J = 4.2 Hz, thiophene ring, 1H) , Δ 7.22 (d, J = 4.2 Hz, thiophene ring, 1H), δ 7.29 (d, 15.6 Hz, olefin, 1H), 7.84 (d, J = 4.2 Hz, thiophene ring, 1H) ), 8.34 (s, 3-H, 1H)

¹Ｈ ＮＭＲ（ＤＭＳＯ−ｄ₆；ＴＭＳ） δ０．８−１．０（ｔ，−ＣＨ₃，６Ｈ），１．２５−１．４０（ｍ，−ＣＨ₂−，４Ｈ），１．４５−１．６０（ｍ，−ＣＨ₂−，４Ｈ），３．３１（ｔ，Ｊ＝９Ｈｚ，−Ｎ−ＣＨ₂−，４Ｈ），６．６４（ｄ，Ｊ＝９Ｈｚ，ベンゼン環，２Ｈ），７．１３（ｄ，Ｊ＝１６．２Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），７．２４（ｄ，Ｊ＝１５．９Ｈｚ，ｏｌｅｆｉｎ，１Ｈ），７．３０（ｄ，Ｊ＝３．９Ｈｚ，チオフェン環，１Ｈ），７．４６（ｄ，Ｊ＝８．７Ｈｚ，ベンゼン環，２Ｈ），７．８９（ｄ，Ｊ＝４．２Ｈｚ，チオフェン環，１Ｈ），８．４０（ｓ，−ＨＣ＝（ＣＮ）（ＣＯＯＨ），１Ｈ） Synthesis of Comparative Compound (A) In the above (1-4), instead of 5- (di-n-butylamino) -thiophene-2-carboxaldehyde, 4-di-n-butylaminobenzaldehyde (manufactured by Aldrich) A comparative compound in which the same procedure as in the above (1-4) to (1-7) is carried out except that 3.8 g is used, and in the above general formula (1), X is a 1,4-phenylene group (A) was synthesized.

¹ H NMR (DMSO-d ₆ ; TMS) δ 0.8-1.0 (t, —CH ₃ , 6H), 1.25-1.40 (m, —CH ₂ —, 4H), 1.45 1.60 (m, —CH ₂ —, 4H), 3.31 (t, J = 9 Hz, —N—CH ₂ —, 4H), 6.64 (d, J = 9 Hz, benzene ring, 2H), 7.13 (d, J = 16.2 Hz, olefin, 1H), 7.24 (d, J = 15.9 Hz, olefin, 1H), 7.30 (d, J = 3.9 Hz, thiophene ring, 1H ), 7.46 (d, J = 8.7 Hz, benzene ring, 2H), 7.89 (d, J = 4.2 Hz, thiophene ring, 1H), 8.40 (s, -HC = (CN) (COOH), 1H)

(UV-visible absorption spectrum)
A solution prepared by synthesizing the terminal amino group-containing heterocyclic derivative (1) of the present invention synthesized by the above procedure using dimethyl sulfoxide as a solvent was placed in a quartz cell (path length: 1 cm) and spectrophotometer (JASCO Corporation UV-mini 1240). ) To measure the UV-visible absorption spectrum. As a result, it was confirmed that the absorption maximum wavelength was at 580 nm and the absorption edge wavelength was at 765 nm.
In the same procedure, the ultraviolet-visible absorption spectrum was also measured for the comparative compound (A). From the measurement results, it was confirmed that the absorption maximum wavelength was at 523 nm and the absorption edge wavelength was at 700 nm.
From these results, it was confirmed that the terminal amino group-containing heterocyclic derivative (1) of the present invention has the absorption maximum wavelength and the absorption edge on the longer wavelength side as compared with the comparative compound (A).

  In addition, various terminal amino group-containing heterocyclic derivatives represented by the general formula (1) can be synthesized by the same procedure as described above. For example, as in the terminal amino group-containing heterocyclic derivatives represented by [0067] [Chemical Formula 18] and [0070] [Chemical Formula 21], X in the general formula (1) is 2,5-furylene group, 2,5-selenylene. Group or a 2,5-thiazoylene group, in the above procedure (1-4), instead of 5- (di-n-butylamino) -thiophene-2-carboxaldehyde, for example, 5-di- A corresponding aldehyde derivative such as n-butylaminofuran-2-carboxaldehyde may be used. In the general formula (1), the same procedure can be used when X is a condensed ring such as a 2,5-thienothienylene group. Similarly to the amino group-containing heterocyclic derivative (1), when Y in the general formula (1) is linked to X via a double bond, a known method for synthesizing an olefin represented by a Wittig reaction or the like. Can be used. On the other hand, when Y in the general formula (1) includes a cyclic group and the cyclic group is directly connected to X by a single bond, a known method such as a cross coupling method represented by Suzuki coupling is used. Can do.

  Since the terminal amino group-containing heterocyclic derivative of the present invention represented by the general formula (1) has a wide absorption band in the visible region, it is particularly a sensitizing dye for photoelectric conversion used in a dye-sensitized photoelectric conversion battery. It is suitable as. In addition to the applications listed here, the present invention can be applied to a wide range of applications such as non-linear optical materials within a range that does not impede its action.

Claims (15)

A terminal amino group-containing heterocyclic derivative represented by the following general formula (1).

(In the above general formula (1), R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom or a monovalent organic residue optionally having a substituent. R ₁ and R ₂ may form a ring together, and either R ₁ or R ₂ may form a ring together with X. R ₃ is a semiconductor. X is a divalent aromatic heterocyclic group containing at least one sulfur atom, oxygen atom or selenium atom. The heterocyclic group may have a substituent, or two or more rings may be condensed, Y is a divalent linking group which may have a substituent, and is a chain Any of a structure, a cyclic structure, or a combination thereof may be used, provided that Y is a conjugate of X in formula (1) and π electrons, and In (1), a double bond formed between a carbon atom bonded to R ₃ and a carbon atom bonded to R ₅ is conjugated with π electrons, where m is an integer of 1 to 5. (The double bond in (1) may give rise to any of the cis-trans isomers.) X in the general formula (1) is a group having a ring structure represented by the following general formula (2) or a group having a structure in which ring structures represented by the following general formula (2) are condensed with each other. The terminal amino group-containing heterocyclic derivative according to claim 1,

(In the general formula (2), X ₁ is a sulfur atom, an oxygen atom or a selenium atom. X ₂ is C—R ₆ or N, and X ₃ is C—R ₇ or N. R ₆ and R ₇ is independently a hydrogen atom or a monovalent organic residue optionally having substituent (s), and R ₆ and R ₇ may form a ring together. , X ₂ and X ₃ are not N at the same time.) The terminal amino group-containing heterocyclic derivative according to claim 1 or 2, wherein R ₃ in the general formula (1) is any one of a carboxyl group, a phosphoric acid group, and a sulfonic acid group. In the general formula (1), the monovalent organic residue of R ₁ , R ₂ , R ₄ , R ₅ or R ₆ may have an aliphatic hydrocarbon group or aromatic hydrocarbon which may have a substituent. Group or aromatic heterocyclic group, or a halogen atom, cyano group, isocyano group, thiocyanate group, isothiocyanate group, nitro group, hydroxy group, mercapto group, amino group, amide group, or the following general formula (3) The terminal amino group-containing heterocyclic derivative according to any one of claims 1 to 3, wherein the terminal amino group-containing heterocyclic derivative is a group.

(In the above general formula (3), A ₁ and A ₂ are each independently O, NH or S. B is a carbonyl group, a thiocarbonyl group, a sulfinyl group or a sulfonyl group. O and p Each independently represents 0 or 1. R ₈ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an aromatic heterocyclic group which may have a substituent, Or a halogen atom, cyano group, isocyano group, thiocyanate group, isothiocyanate group, nitro group, hydroxy group, mercapto group, amino group, or amide group.) The terminal amino group-containing heterocyclic derivative according to any one of claims 1 to 4, wherein R _{4 in the} general formula (1) is an electron-attracting group.   The terminal amino group-containing heterocyclic derivative according to claim 5, wherein the electron-withdrawing group is a cyano group, an ester group, an amide group or a perfluoroalkyl group. The terminal amino group-containing heterocyclic derivative according to any one of claims 1 to 6, wherein R ₃ in the general formula (1) is a carboxyl group.   The terminal amino group-containing heterocyclic derivative according to any one of claims 1 to 7, wherein Y in the general formula (1) has a structure containing an aromatic heterocyclic group.   The terminal amino group-containing heterocyclic ring according to claim 8, wherein X and Y in the general formula (1) each have a structure having a 2,5-thienylene group or a 2,5-thienothienylene group. Derivative.   A sensitizing dye for photoelectric conversion comprising the terminal amino group-containing heterocyclic derivative according to any one of claims 1 to 9.   Furthermore, the sensitizing dye for photoelectric conversion of Claim 10 containing photosensitizing dyes other than the terminal amino group containing heterocyclic derivative represented by General formula (1).   A photoelectric conversion material obtained by linking the sensitizing dye for photoelectric conversion according to claim 9 or 10 and an inorganic porous material exhibiting semiconductor characteristics.   The photoelectric conversion material according to claim 12, wherein the inorganic porous material exhibiting semiconductor characteristics is composed of an inorganic oxide.   A photoelectric conversion electrode obtained by laminating the photoelectric conversion material according to claim 12 or 13 on a transparent electrode.   A photoelectric conversion battery comprising the photoelectric conversion electrode according to claim 14, an electrolyte layer, and a conductive counter electrode.