JP2009184954A - Ruthenium complex and its production method, and dye-sensitized oxide semiconductor electrode - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ruthenium complex having a new structure that can efficiently take out an electric current. <P>SOLUTION: The ruthenium complex is represented by general formula (1) (wherein R<SP>1</SP>is a carboxy group or a chemically acceptable salt thereof; and R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>, X<SP>-</SP>and Y are each described in the specification). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a ruthenium complex having a high extinction coefficient and useful as a sensitizing dye, a production method thereof, and an oxide semiconductor electrode using the same.

As a new energy source that replaces fossil fuels, the use of solar light by solar cells has attracted attention. Currently, solar cells that are in practical use mainly use the photoelectric effect of inorganic materials (polycrystalline silicon or amorphous silicon), but there is a problem of high economic and energy costs for manufacturing. .
On the other hand, Patent Document 1 or 2 discloses a new solar cell using an organometallic complex as a photosensitizing dye. These dye-sensitized solar cells have a simple structure composed of an oxide electrode, a counter electrode, and an electrolyte layer, and have an advantage that they can be manufactured at low cost and have a large area.

  As a metal complex that can be used as the photosensitizing dye, for example, Patent Document 1 discloses a ruthenium complex containing bipyridine or terpyridine as a neutral ligand and thiocyanate ion as an anionic ligand. . Although it is desired that the photosensitizing dye used in the solar cell has a wide light absorption band extending over a long wavelength range, the ligand greatly affects the light absorption characteristics of the photosensitizing dye. Among the above ligands, those having high electron donating properties as anionic ligands are effective in increasing spectral sensitivity and range, and the thiocyanate ions and β-diketonates (Patent Document 3) are known. Yes.

On the other hand, 2-mercaptopyrimidines and 2-mercaptopyridines can be converted into good anionic ligands by reacting with a base, but the ruthenium complex of the present invention using these as anionic ligands is completely unknown. It is not done.
As a technique for introducing 2-mercaptopyrimidines or 2-mercaptopyridines into an anionic ligand as a metal complex, for example, it is disclosed in Non-Patent Document 1, etc., but in these examples, the ruthenium complex of the present invention is disclosed. There is no description about the case where such functional groups (carboxyl group or alkoxy group) exist in the reaction system.

  For the counter electrode of the dye-sensitized solar cell, a metal plate having high corrosion resistance, a metal substrate on which a corrosion-resistant film is formed, soda lime glass, borosilicate glass, or the like is used. Among these substrates, for example, when a non-conductive substrate glass or a metal plate with a high surface resistance film is used, indium tin oxide (ITO) or fluorine-added tin oxide (FTO) is formed on the substrate. A conductive oxide such as a conductive oxide, a noble metal element, carbon, or the like is formed by vapor deposition or sputtering, CVD, a metal salt thermal decomposition method, or the like. Further, a catalytic metal contributing to the redox reaction is supported on the counter electrode surface by vapor deposition or sputtering, metal salt pyrolysis, plating, or the like. For the electrolyte layer, an electrolytic solution made of a non-aqueous solution containing a redox pair such as iodine / iodine ions is used. The oxide electrode on the negative electrode side is provided with a transparent electrode layer made of indium-tin oxide (ITO) or fluorine-added tin oxide (FTO) on a transparent substrate made of glass or the like. An oxide semiconductor porous film is provided, and a photosensitizing dye is supported on the oxide semiconductor porous film.

The oxide semiconductor porous film is a porous film formed by bonding semiconducting metal oxide particles and having a number of fine pores therein. By impregnating innumerable pores of the porous oxide membrane with an aqueous solution or alcohol solution of the ruthenium complex of the present invention and drying, the ruthenium complex of the present invention can be supported in the fine pores.
Japanese Patent No. 2664194 International Publication No. 94/05025 Pamphlet Japanese Patent Laid-Open No. 2003-212851 Journal of Chemical Society, Dalton Transactions, 2851, 1996

  The present invention provides a ruthenium complex having a novel structure capable of improving the extinction coefficient of a ruthenium complex as a dye sensitizer used in a dye-sensitized solar cell and efficiently taking out an electric current, and further, a durability using the ruthenium complex. The present invention provides a dye-sensitized oxide semiconductor electrode and a dye-sensitized solar cell having high performance and high performance.

  As a result of investigations to solve the above-mentioned problems, the present inventors have expressed that the ruthenium complex represented by the general formula (1) is represented by the ruthenium complex represented by the general formula (2) and the general formula (3). It was found that the compound can be obtained by reacting with a ligand in the presence of a base, and furthermore, these ruthenium complexes were found to exhibit strong light absorption even in a long wavelength region, thereby completing the present invention. That is, the present invention relates to the general formula (1)

（式中、Ｒ^１はカルボキシル基又はその化学的に許容される塩を表す。Ｒ^２及びＲ^４は各々独立に水素原子、ハロゲン原子、置換されていてもよい炭素数１から８のアルキル基、置換されていてもよい炭素数１から８のアルコキシ基、置換されていてもよいアミノ基、水酸基、ニトロ基又はシアノ基を表す。Ｒ^３は水素原子又は置換されていてもよい炭素数１から８のアルキル基を表す。Ｙは置換されていてもよい炭素原子又は窒素原子を表す。Ｘ^-は対アニオンを表す。）で示されるルテニウム錯体、さらには、Ｒ^１で表されるカルボキシル基の許容される塩がアンモニウム塩、テトラブチルアンモニウム塩、ナトリウム塩又はカリウム塩であるルテニウム錯体、さらには、Ｒ^２及びＲ^４が水素原子、置換されていてもよい炭素数１から４のアルキル基、置換されていてもよい炭素数１から４のアルコキシ基又は置換されていてもよいアミノ基であり、Ｒ^３が水素原子であるルテニウム錯体、さらには、Ｘ^-で表される対アニオンがハロゲンイオン、パークロレートイオン（ＣｌＯ_４ ^-）、ニトレートイオン（ＮＯ_３ ^-）、ヘキサフルオロホスホネートイオン（ＰＦ_６ ^-）、テトラフルオロボレートイオン（ＢＦ_４ ^-）であるルテニウム錯体に関するものである。

(In the formula, R ¹ represents a carboxyl group or a chemically acceptable salt thereof. R ² and R ⁴ each independently represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 8 carbon atoms. Represents an optionally substituted alkoxy group having 1 to 8 carbon atoms, an optionally substituted amino group, a hydroxyl group, a nitro group, or a cyano group, and R ³ represents a hydrogen atom or an optionally substituted carbon number of 1. To Y. Y represents an optionally substituted carbon atom or nitrogen atom, X ⁻ represents a counter anion), and further a carboxyl group represented by R ^1. acceptable salts are ammonium salts, tetrabutylammonium salts, ruthenium complex is a sodium salt or potassium salt, more, R ² and R ⁴ are hydrogen atoms, optionally having 1 or carbon atoms which may be substituted 4 alkyl group, a substituted from good 1 carbon atoms which may have a 4 alkoxy group or an optionally substituted amino group, a ruthenium complex R ³ is a hydrogen atom, further, X ^- is represented by This relates to a ruthenium complex in which the counter anion is a halogen ion, perchlorate ion (ClO ₄ ⁻ ), nitrate ion (NO ₃ ⁻ ), hexafluorophosphonate ion (PF ₆ ⁻ ), or tetrafluoroborate ion (BF ₄ ⁻ ). is there.

  The present invention also provides a general formula (2)

（式中、Ｒ^１ａはカルボキシル基を表す。Ｘ^ａは塩素又は臭素原子を表す。）で表されるルテニウム錯体と一般式（３）

(Wherein R ^1a represents ^a carboxyl group, X ^a represents ^a chlorine or bromine atom) and a general formula (3)

（式中、Ｒ^２、Ｒ^３、Ｒ^４及びＹは前記と同じ意味を表す。）で表される複素環化合物を塩基存在下に反応させ、一般式（１ａ）

(Wherein R ² , R ³ , R ⁴ and Y represent the same meaning as described above) are reacted in the presence of a base to give a general formula (1a)

（式中、Ｒ^１ｂはカルボキシル基と用いた塩基との塩を表す。Ｒ^２、Ｒ^３、Ｒ^４及びＹは前記と同じ意味を表す。Ｘ^ａ-は塩素イオン又は臭素イオンを表す。）で表されるルテニウム錯体を得、次いで一般式（４）

(In the formula, R ^1b represents a salt of a carboxyl group and the used base. R ² , R ³ , R ⁴ and Y represent the same meaning as described above. X ^a− represents a chlorine ion or a bromine ion.) A ruthenium complex represented by the general formula (4)

（式中、Ｘ^ｂ-は対アニオンを表す。）で表される酸で処理することを特徴とする、一般式（１ｂ）

(In the formula, X ^b- represents a counter anion), and is treated with an acid represented by the general formula (1b)

（式中、Ｒ^１ａ、Ｒ^２、Ｒ^３、Ｒ^４、Ｙ及びＸ^ｂ-は前記と同じ意味を表す。）で表されるルテニウム錯体の製造法に関するものである。

(Wherein, R ^1a , R ² , R ³ , R ⁴ , Y and X ^b- represent the same meaning as described above).

  The present invention also provides a compound represented by the general formula (1b)

（式中、Ｒ^１ａ、Ｒ^２、Ｒ^３、Ｒ^４、Ｙ及びＸ^ｂ-は前記と同じ意味を表す。）で表されるルテニウム錯体と一般式（５）

(Wherein R ^1a , R ² , R ³ , R ⁴ , Y and X ^b- represent the same meaning as described above) and the general formula (5)

（式中、Ｍ^＋は対カチオンを表す。Ｘ^ｃ-は対アニオンを表す。）で表される塩を反応させることを特徴とする、一般式（１ｃ）

(Wherein M ⁺ represents a counter cation and X ^c- represents a counter anion). A salt represented by the general formula (1c) is reacted.

（式中、Ｒ^１ａ、Ｒ^２、Ｒ^３、Ｒ^４、Ｙ及びＸ^ｃ-は前記と同じ意味を表す。）で表されるルテニウム錯体の製造法に関するものである。
また本発明は、一般式（２）

(Wherein R ^1a , R ² , R ³ , R ⁴ , Y and X ^c- represent the same meaning as described above).
The present invention also provides a general formula (2)

（式中、Ｒ^１ａ、Ｘ^ａは前記と同じ意味を表す。）で表されるルテニウム錯体と一般式（３）

(Wherein R ^1a and X ^a represent the same meaning as described above) and the general formula (3)

（式中、Ｒ^２、Ｒ^３、Ｒ^４及びＹは前記と同じ意味を表す。）で表される複素環化合物を塩基存在下に反応させ、一般式（１ａ）

(Wherein R ² , R ³ , R ⁴ and Y represent the same meaning as described above) are reacted in the presence of a base to give a general formula (1a)

（式中、Ｒ^１ｂ、Ｒ^２、Ｒ^３、Ｒ^４、Ｙ及びＸ^ａ-は前記と同じ意味を表す。）で表されるルテニウム錯体を得、次いで一般式（４）

(Wherein R ^1b , R ² , R ³ , R ⁴ , Y and X ^a- represent the same meaning as described above), and then the ruthenium complex represented by the general formula (4) is obtained.

（式中、Ｘ^ｂ-は前記と同じ意味を表す。）で表される酸で処理することで一般式（１ｂ）

(In the formula, X ^b- represents the same meaning as described above.) By treating with an acid represented by the general formula (1b)

（式中、Ｒ^１ａ、Ｒ^２、Ｒ^３、Ｒ^４、Ｙ及びＸ^ｂ-は前記と同じ意味を表す。）で表されるルテニウム錯体を得、次いでこれを一般式（５）

(Wherein R ^1a , R ² , R ³ , R ⁴ , Y and X ^b- represent the same meaning as described above), a ruthenium complex represented by general formula (5) is obtained.

（式中、Ｍ^＋及びＸ^ｃ-は前記と同じ意味を表す。）で表される塩で処理することを特徴とする、一般式（１ｃ）

(Wherein M ⁺ and X ^c- represent the same meaning as described above), and the salt is treated with a salt represented by the general formula (1c)

（式中、Ｒ^１ａ、Ｒ^２、Ｒ^３、Ｒ^４、Ｙ及びＸ^ｃ-は前記と同じ意味を表す。）で表されるルテニウム錯体の製造法に関するものである。
また本発明は、一般式（１ｄ）

(Wherein R ^1a , R ² , R ³ , R ⁴ , Y and X ^c- represent the same meaning as described above).
Further, the present invention provides a compound represented by the general formula (1d)

（式中、Ｒ^１ａ、Ｒ^２、Ｒ^３、Ｒ^４及びＹは前記と同じ意味を表す。Ｘ^ｄ-は対アニオンを表す。）で示されるルテニウム錯体を０．１から１０当量の一般式（６ａ）

(Wherein R ^1a , R ² , R ³ , R ⁴ and Y represent the same meaning as described above. X ^d- represents a counter anion.) The ruthenium complex represented by the general formula of 0.1 to 10 equivalents (6a)

（式中、Ｒ^５ａ、Ｒ^５ｂ及びＲ^５ｃは各々独立に水素原子又は炭素数１から４のアルキル基を表す。）で表されるアミン類、又は一般式（６ｂ）

(Wherein R ^5a , R ^5b and R ^5c each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), or a general formula (6b)

（式中、Ｒ^５ａ、Ｒ^５ｂ、Ｒ^５ｃ及びＲ^５ｄは各々独立に水素原子又は炭素数１から４のアルキル基を表す。）で表される水酸化アンモニウムで処理することを特徴とする、一般式（１ｅ）

(Wherein R ^5a , R ^5b , R ^5c and R ^5d each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). General formula (1e)

（式中、Ｒ^１ｃはカルボキシル基又はそのアンモニウム塩を表す。Ｒ^２、Ｒ^３、Ｒ^４、Ｙ及びＸ^ｄ-は前記と同じ意味を表す。）で表されるルテニウム錯体の製造法に関するものである。

(Wherein R ^1c represents a carboxyl group or an ammonium salt thereof. R ² , R ³ , R ⁴ , Y and X ^d- represent the same meaning as described above). It is.

  Furthermore, the present invention relates to a general formula (1)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｘ^-及びＹは前記と同じ意味を表す。）で表されるルテニウム錯体が酸化物半導体に吸着されてなる色素増感酸化物半導体電極に関するものである。

(Wherein R ¹ , R ² , R ³ , R ⁴ , X ⁻ and Y are as defined above), a dye-sensitized oxide semiconductor in which a ruthenium complex represented by the above is adsorbed to an oxide semiconductor It relates to an electrode.

  Since the ruthenium complex of the present invention is a novel compound and has a high extinction coefficient and the ability to absorb light up to a long wavelength region, these are supported on an oxide semiconductor electrode as a sensitizing dye for a dye-sensitized solar cell. Available.

The present invention is described in further detail below. R ¹ , R ^1a , R ^1b , R ^1c , R ² , R ³ , R ⁴ , R ^5a , R ^5b , R ^5c , R ^5d , X ⁻ , X ^a− , X ^b− , X ^{c in this specification} The definitions of ⁻ , X ^d− , Y and M will be described.

Examples of the chemically acceptable salt of the carboxyl group represented by R ¹ include alkali metal salts or ammonium salts which may be substituted on nitrogen. Examples of the alkali metal salt include potassium salt, sodium salt, lithium salt and the like, and potassium salt and sodium salt are preferable in terms of yield and low cost. Examples of ammonium salts that may be substituted on the nitrogen include ammonium salts, primary ammonium salts, secondary ammonium salts, tertiary ammonium salts, and quaternary ammonium salts. Specifically, ammonium salts, Examples thereof include methylammonium salt, dimethylammonium salt, trimethylammonium salt, tetramethylammonium salt, triethylammonium salt, tetraethylammonium salt, and tetrabutylammonium salt. Ammonium salt, triethylammonium salt, and tetrabutylammonium salt are preferable in terms of yield and low cost. Further, in the general formula (1), all four R ¹ may be a carboxyl group or a chemically acceptable salt thereof at the same time, but when a carboxyl group and its acceptable salt are mixed (ruthenium Complexes) are also encompassed by the present invention.

R ^1a represents a carboxyl group.
^Examples of the salt of the carboxyl group represented by R ^1b and the base used include alkali metal carboxylate, alkaline earth metal carboxylate, ammonium carboxylate, pyridinium carboxylate, and the like. Specifically, lithium carboxylate, sodium carboxylate, potassium carboxylate, magnesium carboxylate, calcium carboxylate, barium carboxylate, cesium carboxylate, methylammonium carboxylate, dimethylammonium carboxylate, trimethylammonium carboxylate, carboxylic acid Ethylammonium, diethylammonium carboxylate, triethylammonium carboxylate, tributylammonium carboxylate, pyrrolidinium carboxylate, piperazinium carboxylate, morpholinium carboxylate, N-methylpyrrolidinium carboxylate, N-methylpiperazinium carboxylate, carboxylic acid Examples thereof include N-methylmorpholinium, pyridinium carboxylate, picolinium carboxylate and the like. Of these, sodium carboxylate and potassium carboxylate are preferred in that the yield of the target product is good and inexpensive.

^Examples of the ammonium salt of the carboxyl group represented by R ^1c include ammonium salt, primary ammonium salt, secondary ammonium salt, tertiary ammonium salt, and quaternary ammonium salt. Specifically, ammonium salt And methylammonium salt, dimethylammonium salt, trimethylammonium salt, tetramethylammonium salt, triethylammonium salt, tetraethylammonium salt, and tetrabutylammonium salt. Ammonium salt, triethylammonium salt, and tetrabutylammonium salt are preferable in terms of yield and low cost. In the general formula (1e), all four R ^1c may be a carboxyl group or an ammonium salt thereof at the same time, but the case where a carboxyl group and an ammonium salt are mixed (ruthenium complex) is also included in the present invention. Is.

Examples of the halogen atom represented by R ² and R ⁴ include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the optionally substituted alkyl group represented by R ² and R ⁴ include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert- Butyl group, pentyl group, tert-pentyl group, 2-pentyl group, 3-pentyl group, cyclopentyl group, 1-methylcyclopentyl group, hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, heptyl group, octyl Examples include groups. Further, one or more of these alkyl groups may be substituted with a halogen atom or the like, specifically, a trifluoromethyl group, a difluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 2,2,2-trimethyl group. A fluoroethyl group, a 2,2,2-trifluoroisopropyl group, a 3-chloropropyl group, a 2-chloroethyl group, a 3-chloropropyl group, and a 3-fluoropropyl group can be exemplified. In terms of yield, these alkyl groups are preferably optionally substituted alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec -Butyl group, tert-butyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trifluoroisopropyl group, and the like.

Examples of the optionally substituted alkoxy group represented by R ² and R ⁴ include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a tert-butyloxy group, and a pentyloxy group. Examples thereof include a 2-pentyloxy group, a cyclopentyloxy group, a hexyloxy group, a cyclohexyloxy group, a heptyloxy group, and an octyloxy group. Further, one or more of these alkoxy groups may be substituted with a halogen atom, an alkoxy group, etc., specifically, 2,2,2-trifluoroethoxy group, 2-hydroxyethoxy group, 2-methoxyethoxy group, etc. Can be mentioned. In view of the high solubility of the metal complex, these substituents are optionally substituted alkoxy groups having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a tertoxy group, -Butyloxy group, 2,2,2-trifluoroethoxy group, 2-hydroxyethoxy group, 2-methoxyethoxy group and the like are preferable.

Examples of the optionally substituted amino group represented by R ² and R ⁴ include amino group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, isopropylamino group, diisopropylamino group, butylamino group, dibutyl An amino group, a phenylamino group, a diphenylamino group, etc. can be mentioned. An amino group, a dimethylamino group, a diethylamino group, a butylamino group, and a dibutylamino group are preferable in terms of high light absorption capability.

In order to give the ruthenium complex of the present invention excellent performance in terms of light absorption ability, the substitution represented by R ² and R ⁴ is preferably a hydroxyl group, a nitro group, a cyano group or the like.
Examples of the optionally substituted alkyl group represented by R ³ having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, Pentyl group, tert-pentyl group, 2-pentyl group, 3-pentyl group, cyclopentyl group, 1-methylcyclopentyl group, hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, heptyl group, octyl group, etc. It can be illustrated. Further, one or more of these alkyl groups may be substituted with a halogen atom or the like, specifically, 2-chloroethyl group, 2-bromoethyl group, 2,2,2-trifluoroethyl group, 3-chloropropyl group. And so on. From the viewpoint of high yield, a methyl group, a butyl group, an isopropyl group, and a tert-butyl group are preferable.

^Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^5a , R ^5b , R ^5c , and R ^5d that are independent of each other include a methyl group, an ethyl group, a propyl group, and a butyl group.

  The carbon atom represented by Y may be substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a halogen atom, etc., specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group. Butyl group, isobutyl group, sec-butyl group, tert-butyl group, fluorine atom, chlorine atom, bromine atom and the like. From the viewpoint of high yield, Y is preferably a hydrogen atom or a methyl group.

In the ruthenium complex of the present invention, the ruthenium atom has an oxidation number of +2 and the heterocyclic compound (3) has a charge of −1. For this reason, the complex becomes cationic and has X ⁻ as a counter anion, and such X ⁻ includes chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), iodo ion (I ⁻ ), nitrate ion (NO). ₃ ⁻ ), perchlorate ion (ClO ₄ ⁻ ), hexafluorophosphonate ion (PF ₆ ⁻ ), tetrafluoroborate ion (BF ₄ ⁻ ), tetraphenylborate ion (B (C ₆ H ₅ ) ₄ ⁻ ), tetrakis (Pentafluorophenyl) borate ion (B (C ₆ F ₅ ) ₄ ⁻ ) and the like can be mentioned. In terms of good yield, chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), nitrate ion (NO ₃ ⁻ ), perchlorate ion (ClO ₄ ⁻ ), hexafluorophosphonate ion (PF ₆ ⁻ ), tetra Fluoroborate ion (BF ₄ ⁻ ) is preferred.

^Examples of the counter anion represented by X ^a− include chlorine ion (Cl ⁻ ) and bromine ion (Br ⁻ ).
The counter anion represented by X ^b− includes chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), iodo ion (I ⁻ ), nitrate ion (NO ₃ ⁻ ), perchlorate ion (ClO ₄ ⁻ ). Is mentioned. From the viewpoint of good yield, chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), nitrate ion (NO ₃ ⁻ ), and perchlorate ion (ClO ₄ ⁻ ) are preferable.
The counter anion represented by X ^c- includes perchlorate ion (ClO ₄ ⁻ ), hexafluorophosphonate ion (PF ₆ ⁻ ), tetrafluoroborate ion (BF ₄ ⁻ ), tetraphenylborate ion (B (C ₆ H ₅ ) ₄ ⁻ ), tetrakis (pentafluorophenyl) borate ion (B (C ₆ F ₅ ) ₄ ⁻ ). From the viewpoint of good yield, perchlorate ion (ClO ₄ ⁻ ), hexafluorophosphonate ion (PF ₆ ⁻ ), and tetrafluoroborate ion (BF ₄ ⁻ ) are preferable.
The counter anion represented by X ^d− includes chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), iodo ion (I ⁻ ), nitrate ion (NO ₃ ⁻ ), perchlorate ion (ClO ₄ ⁻ ). , Hexafluorophosphonate ion (PF ₆ ⁻ ), tetrafluoroborate ion (BF ₄ ⁻ ), tetraphenylborate ion (B (C ₆ H ₅ ) ₄ ⁻ ), tetrakis (pentafluorophenyl) borate ion (B (C ₆₎ F _{5) 4} ^-) and the like. In terms of good yield, chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), nitrate ion (NO ₃ ⁻ ), perchlorate ion (ClO ₄ ⁻ ), hexafluorophosphonate ion (PF ₆ ⁻ ), tetra Fluoroborate ion (BF ₄ ⁻ ) is preferred.

Examples of the counter cation represented by M ⁺ include lithium ion, potassium ion, sodium sodium, tetramethylammonium ion, and tetrabutylammonium ion.

  Since the heterocyclic compound represented by the general formula (3) can have a tautomeric structure, the ruthenium complex (1) of the present invention is represented by ruthenium when the σ bond is represented by a solid line and the coordination bond is represented by a broken line. A coordination structure represented by a complex (1-N) or a ruthenium complex (1-S) can be taken. Moreover, when taking a so-called π-allyl structure, the structure of the general formula (1-π) can be taken. The present invention includes all of these resonance structures, but for the sake of convenience, the structure of the general formula (1) will be described.

次に本発明の製造方法について説明する。本発明のルテニウム錯体（１）は下記反応式で示した方法により製造することができる。工程−１は、一般式（２）で示されるルテニウム錯体と一般式（３）で示される複素環化合物を塩基の存在下に反応させ、本発明に含まれるルテニルム錯体（１ａ）を得る工程である。

Next, the manufacturing method of this invention is demonstrated. The ruthenium complex (1) of the present invention can be produced by the method shown by the following reaction formula. Step-1 is a step in which the ruthenium complex represented by the general formula (2) and the heterocyclic compound represented by the general formula (3) are reacted in the presence of a base to obtain the ruthenium complex (1a) included in the present invention. is there.

（式中、Ｒ^１、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^１ｃ、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５ａ、Ｒ^５ｂ、Ｒ^５ｃ、Ｒ^５ｄ、Ｘ^-、Ｘ^ａ-、Ｘ^ｂ-、Ｘ^ｃ-、Ｘ^ｄ-、Ｙ及びＭは前記と同じ意味を表す。）
工程−１の反応は塩基の存在下に実施することが必須である。塩基としては、水酸化アルカリ金属、水酸化アルカリ土類金属、炭酸アルカリ金属、炭酸アルカリ土類金属、炭酸水素アルカリ金属、酢酸アルカリ金属、アンモニア、アミン類、ピリジン類を使用することができる。具体的には、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム、水酸化バリウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム、炭酸水素ナトリウム、炭酸水素カリウム、酢酸ナトリウム、酢酸カリウム、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、トリブチルアミン、ピロリジン、ピペラジン、モルホリン、Ｎ‐メチルピロリジン、Ｎ‐メチルピペラジン、Ｎ‐メチルモルホリン、ピリジン、ピコリン等を例示することができる。中でも目的物の収率がよく、安価である点で水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウムが好ましい。塩基の使用量や濃度に特に制限はないが、反応基質に対して４〜５０当量、好ましくは５〜１０当量用いることにより、収率よく目的物を得ることができる。
複素環化合物（３）の使用量に特に制限はないが、原料のルテニウム錯体（２）に対して１等量以上用いることにより、収率よく目的物を得ることができる。
反応は大気中で実施することもできるが、純度よく目的物を得ることができる点で窒素やアルゴン等の不活性ガス雰囲気下で実施することが好ましい。

(In the formula, R ¹ , R ^1a , R ^1b , R ^1c , R ² , R ³ , R ⁴ , R ^5a , R ^5b , R ^5c , R ^5d , X ⁻ , X ^a− , X ^b− , X ^{c -} , X ^d- , Y and M have the same meaning as described above.)
It is essential to carry out the reaction of step-1 in the presence of a base. As the base, alkali metal hydroxide, alkali earth metal hydroxide, alkali metal carbonate, alkaline earth metal carbonate, alkali metal hydrogen carbonate, alkali metal acetate, ammonia, amines, and pyridines can be used. Specifically, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, Sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, tributylamine, pyrrolidine, piperazine, morpholine, N-methylpyrrolidine, N-methylpiperazine, N-methyl Examples thereof include morpholine, pyridine, picoline and the like. Of these, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate are preferred because the yield of the target product is good and inexpensive. Although there is no restriction | limiting in particular in the usage-amount and density | concentration of a base, A target object can be obtained with a sufficient yield by using 4-50 equivalent with respect to a reaction substrate, Preferably 5-10 equivalent is used.
Although there is no restriction | limiting in particular in the usage-amount of a heterocyclic compound (3), A target object can be obtained with a sufficient yield by using 1 equivalent or more with respect to a raw material ruthenium complex (2).
Although the reaction can be carried out in the air, it is preferably carried out in an inert gas atmosphere such as nitrogen or argon because the desired product can be obtained with high purity.

  The reaction is preferably carried out in a solvent. As a solvent that can be used, any solvent that does not adversely affect the reaction can be used, and water, an organic solvent, or a mixture thereof can be used. The organic solvent is preferably a polar solvent such as alcohol, and examples thereof include methanol, ethanol, 2-propanol, butanol, cyclohexyl alcohol, N, N-dimethylformamide, dimethyl sulfoxide, and acetonitrile. Of these, water, ethanol, N, N-dimethylformamide, dimethyl sulfoxide, or a mixture thereof is preferable because the yield and selectivity of the target product are good and it is inexpensive. There is no restriction | limiting in particular in the usage-amount of a reaction solvent.

The reaction can be carried out at a reaction temperature appropriately selected from 0 to 200 ° C., preferably from 20 to 120 ° C., to obtain the target product with good yield. There is no particular limitation on the reaction time.
After completion of the reaction, the target ruthenium complex (1a) can be isolated by a general operation such as evaporation of the solvent, but it can also be used for the next step-2 without isolation.

In Step-2, the ruthenium complex represented by the general formula (1a) is treated with the acid represented by the general formula (4) to produce the ruthenium complex represented by the general formula (1b) included in the present invention. It is a process.
There is no restriction | limiting in particular in the usage-amount of the acid represented by General formula (4) used for this reaction, A target object can be obtained with a sufficient yield by using 5 equivalents or more with respect to a ruthenium complex (1a). .

Although the reaction can be carried out in the air, it is preferably carried out in an inert gas atmosphere such as nitrogen or argon because the desired product can be obtained with high purity.
The reaction is preferably carried out in a solvent. As a solvent that can be used, any solvent that does not adversely affect the reaction can be used, and water, an organic solvent, or a mixture thereof can be used. The organic solvent is preferably a polar solvent such as alcohol, and examples thereof include methanol, ethanol, 2-propanol, butanol, cyclohexyl alcohol, N, N-dimethylformamide, dimethyl sulfoxide, and acetonitrile. Of these, water, ethanol, N, N-dimethylformamide, dimethyl sulfoxide, or a mixture thereof is preferable because the yield and selectivity of the target product are good and it is inexpensive. There is no restriction | limiting in particular in the usage-amount of a reaction solvent.

The reaction can be carried out at a reaction temperature appropriately selected from 0 to 200 ° C., preferably from 20 to 120 ° C., to obtain the target product with good yield. There is no particular limitation on the reaction time.
After completion of the reaction, the target ruthenium complex (1b) can be isolated by ordinary operations such as filtration or evaporation of the solvent, but it can also be used for the next step-3 without isolation. it can.

  In Step-3, the ruthenium complex represented by the general formula (1b) is treated with the salt represented by the general formula (5) to produce the ruthenium complex represented by the general formula (1c) included in the present invention. It is a process.

There is no restriction | limiting in particular in the usage-amount of the salt represented by General formula (5) used for this reaction, A target object can be obtained with a sufficient yield by using 5 equivalent or more with respect to a ruthenium complex (1b). .
Although the reaction can be carried out in the air, it is preferably carried out in an inert gas atmosphere such as nitrogen or argon because the desired product can be obtained with high purity.
The reaction is preferably carried out in a solvent. As a solvent that can be used, any solvent that does not adversely affect the reaction can be used, and water, an organic solvent, or a mixture thereof can be used. The organic solvent is preferably a polar solvent such as alcohol, and examples thereof include methanol, ethanol, 2-propanol, butanol, cyclohexyl alcohol, N, N-dimethylformamide, dimethyl sulfoxide, and acetonitrile. Of these, water, ethanol, N, N-dimethylformamide, dimethyl sulfoxide, or a mixture thereof is preferable because the yield and selectivity of the target product are good and it is inexpensive. There is no restriction | limiting in particular in the usage-amount of a reaction solvent.

The reaction can be carried out at a reaction temperature appropriately selected from 0 to 200 ° C., preferably from 20 to 120 ° C., to obtain the target product with good yield. There is no particular limitation on the reaction time.
After completion of the reaction, the target ruthenium complex (1b) can be isolated by ordinary operations such as filtration or solvent distillation, but it can also be used for the next step-4 reaction without isolation. it can.
In Step-4, the ruthenium complex represented by the general formula (1d) is treated with an amine represented by the general formula (6a) or an ammonium hydroxide represented by the general formula (6b), and the general formula (1e) It is the process of manufacturing the ruthenium complex represented by these.
Examples of amines represented by the general formula (6a) include ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, tributylamine and the like. Triethylamine is preferred in terms of good yield.

Examples of ammonium hydroxide represented by the general formula (6b) include ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. Of these, tetrabutylammonium hydroxide is preferred because of its good yield and low cost.
Although there is no restriction | limiting in particular in the usage-amount and density | concentration of a base, The target object can be obtained with a sufficient yield by using 0.1-50 equivalent with respect to the reaction substrate, Preferably it uses 0.5-10 equivalent.

Although the reaction can be carried out in the air, it is preferably carried out in an inert gas atmosphere such as nitrogen or argon because the desired product can be obtained with high purity.
The reaction is preferably carried out in a solvent. As a solvent that can be used, any solvent that does not adversely affect the reaction can be used, and water, an organic solvent, or a mixture thereof can be used. The organic solvent is preferably a polar solvent such as alcohol, and examples thereof include methanol, ethanol, 2-propanol, butanol, cyclohexyl alcohol, N, N-dimethylformamide, dimethyl sulfoxide, and acetonitrile. Of these, water, ethanol, N, N-dimethylformamide, dimethyl sulfoxide, or a mixture thereof is preferable because the yield and selectivity of the target product are good and it is inexpensive. There is no restriction | limiting in particular in the usage-amount of a reaction solvent.

The reaction can be carried out at a reaction temperature appropriately selected from 0 to 200 ° C., preferably from 20 to 120 ° C., to obtain the target product with good yield. There is no particular limitation on the reaction time.
After completion of the reaction, the desired ruthenium complex (1e) can be isolated by a general operation such as evaporation of the solvent.
A part of the ruthenium complex represented by the general formula (2) used as a raw material for the production method of the present invention is commercially available, but can be easily prepared by a method described in the literature (see Non-Patent Document 2). . A part of the 2-mercaptopyridine derivative or 2-mercaptopyrimidine derivative represented by the general formula (3) is commercially available, but can be easily prepared by methods described in the literature (Patent Documents 4, 5 and 6). Further, the novel compound was synthesized by the method of the following reference example.
Journal of American Chemical Society, 115, 6382, 1993 US Patent No. 980628 U.S. Patent No. 67354 JP-A-6-411117

  EXAMPLES Hereinafter, although an Example and a reference example are given and this invention is demonstrated further in detail, this invention is not limited to these.

アルゴン雰囲気下、蒸留水（５０ｍＬ）に二塩化シス‐ビス（４，４’‐ジカルボキシ‐２，２’‐ビピリジン）ルテニウム（６６０ｍｇ，１．０３ｍｍｏｌ）、２‐メルカプトピリミジン（１３８ｍｍｇ，１．２３ｍｍｏｌ）及び１Ｎ‐水酸化カリウム水溶液（７．５ｍＬ）を加え６０℃で２時間、続いて室温で３０分間撹拌した。不溶物をろ別後、溶液から溶媒を減圧留去した。得られた粗生成物に１Ｎ‐塩酸（７．５ｍＬ）を加え、室温で１５分攪拌した。析出した固形物を遠心分離により分離し、濾過し、水で充分洗浄した後、乾燥させることにより、目的とするルテニウム錯体（錯体１−１）の暗赤色固体（７３６ｍｇ，収率７５％）を得た。
^１ＨＮＭＲ（Ｄ_２Ｏ）：δ６．７３（ｄｄ，Ｊ＝５．１，５．３Ｈｚ，１Ｈ），７．４０−７．４８（ｍ，２Ｈ），７．４９（ｄｄ，Ｊ＝２．２，５．３Ｈｚ，１Ｈ），７．７３（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．８４（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．９１（ｄ，Ｊ＝５．７Ｈｚ，１Ｈ），７．９２−７．９６（ｍ，１Ｈ），８．２１（ｄｄ，Ｊ＝２．２，５．１Ｈｚ，１Ｈ），８．３５（ｄ，Ｊ＝６．０Ｈｚ，１Ｈ），８．６７（ｓ，２Ｈ），８．７８（ｓ，１Ｈ），８．８３（ｓ，１Ｈ），９．６４（ｄ，Ｊ＝５．７５Ｈｚ，１Ｈ）．ＵＶ／ｖｉｓ（Ｈ_２Ｏ）：λ_ｍａｘ［ｎｍ］（ε×１０^-４［Ｌ／（ｍｏｌ×ｃｍ）］）２４６．０（４．１６），３０６．０（５．２７），３６６．０（１．５９），５０３．０（１．４２）．
実施例−２ Example-1

Distilled water (50 mL) in cis-bis (4,4′-dicarboxy-2,2′-bipyridine) ruthenium dichloride (660 mg, 1.03 mmol), 2-mercaptopyrimidine (138 mmg, 1.23 mmol) in an argon atmosphere And 1N aqueous potassium hydroxide solution (7.5 mL) were added, and the mixture was stirred at 60 ° C. for 2 hours and then at room temperature for 30 minutes. The insoluble material was filtered off, and the solvent was distilled off from the solution under reduced pressure. 1N-hydrochloric acid (7.5 mL) was added to the obtained crude product, and the mixture was stirred at room temperature for 15 minutes. The precipitated solid was separated by centrifugation, filtered, sufficiently washed with water, and dried to obtain a dark red solid (736 mg, yield 75%) of the target ruthenium complex (complex 1-1). Obtained.
¹ HNMR (D ₂ O): δ 6.73 (dd, J = 5.1, 5.3 Hz, 1H), 7.40-7.48 (m, 2H), 7.49 (dd, J = 2. 2, 5.3 Hz, 1H), 7.73 (d, J = 5.9 Hz, 1H), 7.84 (d, J = 5.9 Hz, 1H), 7.91 (d, J = 5.7 Hz) , 1H), 7.92-7.96 (m, 1H), 8.21 (dd, J = 2.2, 5.1 Hz, 1H), 8.35 (d, J = 6.0 Hz, 1H) , 8.67 (s, 2H), 8.78 (s, 1H), 8.83 (s, 1H), 9.64 (d, J = 5.75 Hz, 1H). UV / vis (H ₂ O): λ _max [nm] (ε × 10 ⁻⁴ [L / (mol × cm)]) 246.0 (4.16), 306.0 (5.27), 366. 0 (1.59), 503.0 (1.42).
Example-2

アルゴン雰囲気下、蒸留水（１００ｍＬ）に二塩化シス‐ビス（４，４’‐ジカルボキシ‐２，２’‐ビピリジン）ルテニウム（１．３４ｇ，２．０３ｍｍｏｌ）、４，６‐ジメチル‐２‐メルカプトピリミジン（３５５ｍｇ，２．５３ｍｍｏｌ）及び１Ｎ‐水酸化カリウム水溶液（１５ｍＬ）を加え６０℃で２時間、続いて室温で３０分間撹拌した。不溶物をろ別後、溶液から溶媒を減圧留去した。得られた粗生成物に１Ｎ‐塩酸（１５ｍＬ）を加え、室温で１５分攪拌した。析出した固形物を遠心分離により分離し、濾過し、水で充分洗浄した後、乾燥させることにより、目的とするルテニウム錯体（錯体１−２）の暗赤色固体（１．４９ｇ，収率８４％）を得た。
^１ＨＮＭＲ（Ｄ_２Ｏ−ＮａＯＤ）：δ１．３１（ｓ，３Ｈ），２．２７（ｓ，３Ｈ），６．５７（ｓ，１Ｈ），７．３９（ｄｄ，Ｊ＝５．９，１．６Ｈｚ，１Ｈ），７．４７（ｄｄ，Ｊ＝５．９，１．６Ｈｚ，１Ｈ），７．７５（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．８２（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．８５（ｄｄ，Ｊ＝５．８，１．６Ｈｚ，１Ｈ），７．９６（ｄｄ，Ｊ＝５．８，１．６Ｈｚ，１Ｈ），８．３７（ｄ，Ｊ＝５．８Ｈｚ，１Ｈ），８．６７（ｂｒｓ，１Ｈ），８．７３（ｂｒｓ，１Ｈ），８．８３（ｂｒｓ，２Ｈ），９．７５（ｄ，Ｊ＝５．８Ｈｚ，１Ｈ）．ＵＶ／ｖｉｓ（Ｈ_２Ｏ）：λ_ｍａｘ［ｎｍ］（ε×１０^-４［Ｌ／（ｍｏｌ×ｃｍ）］）２４６．０（４．１２），３０７．０（５．２９），３６８．０（１．６７），５１１（１．５０）．
実施例−３

Under an argon atmosphere, distilled water (100 mL) was mixed with cis-bis (4,4′-dicarboxy-2,2′-bipyridine) ruthenium dichloride (1.34 g, 2.03 mmol), 4,6-dimethyl-2-chloride. Mercaptopyrimidine (355 mg, 2.53 mmol) and 1N aqueous potassium hydroxide solution (15 mL) were added, and the mixture was stirred at 60 ° C. for 2 hours and then at room temperature for 30 minutes. The insoluble material was filtered off, and the solvent was distilled off from the solution under reduced pressure. 1N-hydrochloric acid (15 mL) was added to the obtained crude product, and the mixture was stirred at room temperature for 15 minutes. The precipitated solid was separated by centrifugation, filtered, thoroughly washed with water, and then dried to give a dark red solid (1.49 g, yield 84%) of the target ruthenium complex (complex 1-2). )
¹ HNMR (D ₂ O—NaOD): δ 1.31 (s, 3H), 2.27 (s, 3H), 6.57 (s, 1H), 7.39 (dd, J = 5.9, 1 .6 Hz, 1H), 7.47 (dd, J = 5.9, 1.6 Hz, 1H), 7.75 (d, J = 5.9 Hz, 1H), 7.82 (d, J = 5. 9 Hz, 1H), 7.85 (dd, J = 5.8, 1.6 Hz, 1H), 7.96 (dd, J = 5.8, 1.6 Hz, 1H), 8.37 (d, J = 5.8 Hz, 1 H), 8.67 (brs, 1 H), 8.73 (brs, 1 H), 8.83 (brs, 2 H), 9.75 (d, J = 5.8 Hz, 1 H). UV / vis (H ₂ O): λ _max [nm] (ε × 10 ⁻⁴ [L / (mol × cm)]) 246.0 (4.12), 307.0 (5.29), 368. 0 (1.67), 511 (1.50).
Example-3

アルゴン雰囲気下、蒸留水（２５ｍＬ）に二塩化シス‐ビス（４，４’‐ジカルボキシ‐２，２’‐ビピリジン）ルテニウム（３３４ｍｇ，０．５０５ｍｍｏｌ）、４，６‐ジアミノ‐２‐メルカプトピリミジン（８７ｍｇ，０．６０８ｍｍｏｌ）及び１Ｎ‐水酸化カリウム水溶液（３．５ｍＬ）を加え６０℃で２時間、続いて室温で３０分間撹拌した。不溶物をろ別後、溶液から溶媒を減圧留去した。得られた粗生成物に１Ｎ‐硝酸（３ｍＬ）を加え、室温で１５分攪拌した。析出した固形物を遠心分離により分離し、濾過し、水で充分洗浄した後、乾燥させることにより、目的とするルテニウム錯体（錯体１−３）の暗赤色固体（３３８ｍｇ，収率８７％）を得た。
^１ＨＮＭＲ（Ｄ_２Ｏ−ＮａＯＤ）：δ５．１２（ｓ，１Ｈ），７．３７ｄｄ，Ｊ＝５．９，１．７Ｈｚ，１Ｈ），７．４８（ｄｄ，Ｊ＝５．９，１．７Ｈｚ，１Ｈ），７．７４（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．８５（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．９４（ｄｄ，Ｊ＝５．８，１．５Ｈｚ，１Ｈ），８．０１（ｄｄ，Ｊ＝５．９，１．６Ｈｚ，１Ｈ），８．６４（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），８．６５（ｂｒｓ，１Ｈ），８．７４（ｂｒｓ，１Ｈ），８．８３（ｂｒｓ，２Ｈ），９．８２（ｄ，Ｊ＝５．８Ｈｚ，１Ｈ）．ＵＶ／ｖｉｓ（Ｈ_２Ｏ）：λ_ｍａｘ［ｎｍ］（ε×１０^-４［Ｌ／（ｍｏｌ×ｃｍ）］）２４８．０（３．１４０），３０９．０（３．７７５），３７８．０（１．０２０），５２３．０（１．０７０）．
実施例−４

Distilled water (25 mL) in cis-bis (4,4′-dicarboxy-2,2′-bipyridine) ruthenium (334 mg, 0.505 mmol), 4,6-diamino-2-mercaptopyrimidine in distilled water (25 mL) (87 mg, 0.608 mmol) and 1N aqueous potassium hydroxide solution (3.5 mL) were added, and the mixture was stirred at 60 ° C. for 2 hours and then at room temperature for 30 minutes. The insoluble material was filtered off, and the solvent was distilled off from the solution under reduced pressure. 1N-nitric acid (3 mL) was added to the obtained crude product, and the mixture was stirred at room temperature for 15 minutes. The precipitated solid was separated by centrifugation, filtered, sufficiently washed with water, and dried to obtain a dark red solid (338 mg, yield 87%) of the target ruthenium complex (complex 1-3). Obtained.
¹ HNMR (D ₂ O—NaOD): δ 5.12 (s, 1H), 7.37 dd, J = 5.9, 1.7 Hz, 1H), 7.48 (dd, J = 5.9, 1. 7 Hz, 1H), 7.74 (d, J = 5.9 Hz, 1H), 7.85 (d, J = 5.9 Hz, 1H), 7.94 (dd, J = 5.8, 1.5 Hz) , 1H), 8.01 (dd, J = 5.9, 1.6 Hz, 1H), 8.64 (d, J = 5.9 Hz, 1H), 8.65 (brs, 1H), 8.74. (Brs, 1H), 8.83 (brs, 2H), 9.82 (d, J = 5.8 Hz, 1H). UV / vis (H ₂ O): λ _max [nm] (ε × 10 ⁻⁴ [L / (mol × cm)]) 248.0 (3.140), 309.0 (3.775), 378. 0 (1.020), 523.0 (1.070).
Example-4

アルゴン雰囲気下、蒸留水（５０ｍＬ）に二塩化シス‐ビス（４，４’‐ジカルボキシ‐２，２’‐ビピリジン）ルテニウム（６８２ｍｇ，１．０３ｍｍｏｌ）、２‐メルカプトバルビツール酸（１７５ｍｇ，１．２１ｍｍｏｌ）及び１Ｎ‐水酸化カリウム水溶液（７．５ｍＬ）を加え８０℃で１８時間撹拌した。不溶物をろ別後、溶液から溶媒を減圧留去した。得られた粗生成物に１Ｎ‐塩酸（７．５ｍＬ）を加え、室温で１５分攪拌した。析出した固形物を遠心分離により分離し、濾過し、水で充分洗浄した後、乾燥させることにより、目的とするルテニウム錯体（錯体１−４）の暗赤色固体（７６８ｍｇ，収率８８％）を得た。
^１ＨＮＭＲ（Ｄ_２Ｏ−ＮａＯＤ）：δ６．６１（ｓ，１Ｈ），７．３２−７．３７（ｍ，２Ｈ），７．６９（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．８３（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．９２−７．９８（ｍ，２Ｈ），８．６０（ｄ，Ｊ＝１．４Ｈｚ，１Ｈ），８．６４（ｄ，Ｊ＝１．３Ｈｚ，１Ｈ），８．６９（ｄ，Ｊ＝５．８Ｈｚ，１Ｈ），８．７４（ｄ，Ｊ＝１．３Ｈｚ，１Ｈ），８．８０（ｄ，Ｊ＝１．２Ｈｚ，１Ｈ），９．８６（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ）．ＵＶ／ｖｉｓ（Ｈ_２Ｏ）：λ_ｍａｘ［ｎｍ］（ε×１０^-４［Ｌ／（ｍｏｌ×ｃｍ）］）３０９．０（４．６０５），３９１．０（１．２４５），５３６．０（１．２１０）．
実施例−５

Under argon atmosphere, distilled water (50 mL) in cis-bis (4,4′-dicarboxy-2,2′-bipyridine) ruthenium dichloride (682 mg, 1.03 mmol), 2-mercaptobarbituric acid (175 mg, 1 .21 mmol) and 1N aqueous potassium hydroxide solution (7.5 mL) were added, and the mixture was stirred at 80 ° C. for 18 hours. The insoluble material was filtered off, and the solvent was distilled off from the solution under reduced pressure. 1N-hydrochloric acid (7.5 mL) was added to the obtained crude product, and the mixture was stirred at room temperature for 15 minutes. The precipitated solid was separated by centrifugation, filtered, sufficiently washed with water, and dried to obtain a dark red solid (768 mg, yield 88%) of the target ruthenium complex (complex 1-4). Obtained.
¹ HNMR (D ₂ O—NaOD): δ 6.61 (s, 1H), 7.32-7.37 (m, 2H), 7.69 (d, J = 5.9 Hz, 1H), 7.83 (D, J = 5.9 Hz, 1H), 7.92-7.98 (m, 2H), 8.60 (d, J = 1.4 Hz, 1H), 8.64 (d, J = 1. 3 Hz, 1H), 8.69 (d, J = 5.8 Hz, 1H), 8.74 (d, J = 1.3 Hz, 1H), 8.80 (d, J = 1.2 Hz, 1H), 9.86 (d, J = 5.9 Hz, 1H). UV / vis (H ₂ O): λ _max [nm] (ε × 10 ⁻⁴ [L / (mol × cm)]) 309.0 (4.605), 391.0 (1.245), 536. 0 (1.210).
Example-5

アルゴン雰囲気下、蒸留水（５０ｍＬ）に二塩化シス‐ビス（４，４’‐ジカルボキシ‐２，２’‐ビピリジン）ルテニウム（６８５ｍｇ，１．０４ｍｍｏｌ）、４，６‐ジエトキシ‐２‐メルカプトピリミジン（２４６ｍｇ，１．２１ｍｍｏｌ）及び１Ｎ‐水酸化カリウム水溶液（７．５ｍＬ）を加え６０℃で１３時間、続いて１００℃で２時間撹拌した。不溶物をろ別後、溶液から溶媒を減圧留去した。得られた粗生成物に１Ｎ‐塩酸（７．５ｍＬ）を加え、室温で１５分攪拌した。析出した固形物を遠心分離により分離し、濾過し、エーテル及び水で充分洗浄した後、乾燥させることにより、目的とするルテニウム錯体（錯体１−５）の暗赤色固体（６３７ｍｇ，収率７４％）を得た。
^１ＨＮＭＲ（Ｄ_２Ｏ−ＮａＯＤ）：δ０．４８（ｔ，Ｊ＝７．０Ｈｚ，３Ｈ），１．２８（ｔ，Ｊ＝７．０Ｈｚ，３Ｈ），３．４５−３．５３（ｍ，１Ｈ），３．６１−３．７０（ｍ，１Ｈ），４．１９（ｑ，Ｊ＝７．０Ｈｚ，２Ｈ），５．５５（ｓ，１Ｈ），７．３９（ｄｄ，Ｊ＝５．９，１．５Ｈｚ，１Ｈ），７．４７（ｄｄ，Ｊ＝５．９，１．５Ｈｚ，１Ｈ），７．７６（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．８９（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．９０（ｂｒｄ，Ｊ＝５．８Ｈｚ，１Ｈ），７．９７（ｂｒｄ，Ｊ＝５．８Ｈｚ，１Ｈ），８．４７（ｄ，Ｊ＝５．８Ｈｚ，１Ｈ），８．６８（ｂｒｓ，１Ｈ），８．７１（ｂｒｓ，１Ｈ），８．７９（ｂｒｓ，１Ｈ），８．８３（ｂｒｓ，１Ｈ），９．７８（ｄ，Ｊ＝５．８Ｈｚ，１Ｈ）．ＵＶ／ｖｉｓ（Ｈ_２Ｏ）：λ_ｍａｘ［ｎｍ］（ε×１０^-４［Ｌ／（ｍｏｌ×ｃｍ）］）３０８．０（４．４１５），３７８．０（１．１７０），５１９．０（１．２４０）．
実施例−６

Distilled water (50 mL) in cis-bis (4,4'-dicarboxy-2,2'-bipyridine) ruthenium (685 mg, 1.04 mmol), 4,6-diethoxy-2-mercaptopyrimidine in distilled water (50 mL) (246 mg, 1.21 mmol) and 1N aqueous potassium hydroxide solution (7.5 mL) were added, and the mixture was stirred at 60 ° C. for 13 hours and then at 100 ° C. for 2 hours. The insoluble material was filtered off, and the solvent was distilled off from the solution under reduced pressure. 1N-hydrochloric acid (7.5 mL) was added to the obtained crude product, and the mixture was stirred at room temperature for 15 minutes. The precipitated solid was separated by centrifugation, filtered, thoroughly washed with ether and water, and then dried to give a dark red solid (637 mg, yield 74%) of the desired ruthenium complex (complex 1-5). )
¹ HNMR (D ₂ O—NaOD): δ 0.48 (t, J = 7.0 Hz, 3H), 1.28 (t, J = 7.0 Hz, 3H), 3.45-3.53 (m, 1H), 3.61-3.70 (m, 1H), 4.19 (q, J = 7.0 Hz, 2H), 5.55 (s, 1H), 7.39 (dd, J = 5. 9, 1.5 Hz, 1 H), 7.47 (dd, J = 5.9, 1.5 Hz, 1 H), 7.76 (d, J = 5.9 Hz, 1 H), 7.89 (d, J = 5.9 Hz, 1H), 7.90 (brd, J = 5.8 Hz, 1H), 7.97 (brd, J = 5.8 Hz, 1H), 8.47 (d, J = 5.8 Hz, 1H), 8.68 (brs, 1H), 8.71 (brs, 1H), 8.79 (brs, 1H), 8.83 (brs, 1H), 9.78 (d, J = 5.8 Hz) , 1 ). UV / vis (H ₂ O): λ _max [nm] (ε × 10 ⁻⁴ [L / (mol × cm)]) 308.0 (4.415), 378.0 (1.170), 519. 0 (1.240).
Example-6

アルゴン雰囲気下、蒸留水（２５ｍＬ）とエタノール（２５ｍ）の混合溶液に二塩化シス‐ビス（４，４’‐ジカルボキシ‐２，２’‐ビピリジン）ルテニウム（６６０ｍｇ，１．００ｍｍｏｌ）、４，６‐ジメトキシ‐２‐メルカプトピリミジン（２０７ｍｇ，１．２０ｍｍｏｌ）及び１Ｎ‐水酸化カリウム水溶液（７．５ｍＬ）を加え８０℃で３時間撹拌した。不溶物をろ別後、溶液から溶媒を減圧留去した。得られた粗生成物に１Ｎ‐塩酸（７．５ｍＬ）を加え、室温で１５分攪拌した。析出した固形物を遠心分離により分離し、濾過し、エーテル及び水で充分洗浄した後、乾燥させることにより、目的とするルテニウム錯体（錯体１−６）の暗赤色固体（７９６ｍｇ，収率８６％）を得た。
^１ＨＮＭＲ（Ｄ_２Ｏ−ＮａＯＤ）：δ．３．１８（ｓ，３Ｈ），３．８１（ｓ，３Ｈ），５．６６（ｓ，１Ｈ），７．４１（ｄｄ，Ｊ＝５．９，１．７Ｈｚ，１Ｈ），７．４５（ｄｄ，Ｊ＝５．９，１．７Ｈｚ，１Ｈ），７．７６（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．８８（ｄｄ，Ｊ＝５．８，１．７Ｈｚ，１Ｈ），７．９６（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．９７（ｄｄ，Ｊ＝５．８，１．７Ｈｚ，１Ｈ），８．４７（ｄ，Ｊ＝５．８Ｈｚ，１Ｈ），８．６７（ｂｒｓ，１Ｈ），８．６８（ｂｒｓ，１Ｈ），８．７７（ｂｒｓ，１Ｈ），８．８３（ｂｒｓ，１Ｈ），９．７６（ｄ，Ｊ＝５．８Ｈｚ，１Ｈ）．ＵＶ／ｖｉｓ（Ｈ_２Ｏ）：λ_ｍａｘ［ｎｍ］（ε×１０^-４［Ｌ／（ｍｏｌ×ｃｍ）］）２４７．０（３．９４５），３０７．０（５．１２５），３７５．０（１．３８０），５１７．０（１．４６５）．
実施例−７

Under an argon atmosphere, a mixed solution of distilled water (25 mL) and ethanol (25 m) was added to cis-bis (4,4′-dicarboxy-2,2′-bipyridine) ruthenium dichloride (660 mg, 1.00 mmol), 4, 6-Dimethoxy-2-mercaptopyrimidine (207 mg, 1.20 mmol) and 1N aqueous potassium hydroxide solution (7.5 mL) were added, and the mixture was stirred at 80 ° C. for 3 hr. The insoluble material was filtered off, and the solvent was distilled off from the solution under reduced pressure. 1N-hydrochloric acid (7.5 mL) was added to the obtained crude product, and the mixture was stirred at room temperature for 15 minutes. The precipitated solid was separated by centrifugation, filtered, thoroughly washed with ether and water, and then dried to give a dark red solid (796 mg, yield 86%) of the target ruthenium complex (complex 1-6). )
¹ HNMR (D ₂ O—NaOD): δ. 3.18 (s, 3H), 3.81 (s, 3H), 5.66 (s, 1H), 7.41 (dd, J = 5.9, 1.7 Hz, 1H), 7.45 ( dd, J = 5.9, 1.7 Hz, 1H), 7.76 (d, J = 5.9 Hz, 1H), 7.88 (dd, J = 5.8, 1.7 Hz, 1H), 7 .96 (d, J = 5.9 Hz, 1H), 7.97 (dd, J = 5.8, 1.7 Hz, 1H), 8.47 (d, J = 5.8 Hz, 1H), 8. 67 (brs, 1H), 8.68 (brs, 1H), 8.77 (brs, 1H), 8.83 (brs, 1H), 9.76 (d, J = 5.8 Hz, 1H). UV / vis (H ₂ O): λ _max [nm] (ε × 10 ⁻⁴ [L / (mol × cm)]) 247.0 (3.945), 307.0 (5.125), 375. 0 (1.380), 517.0 (1.465).
Example-7

アルゴン雰囲気下、蒸留水（２５ｍＬ）とエタノール（２５ｍ）の混合溶液に二塩化シス‐ビス（４，４’‐ジカルボキシ‐２，２’‐ビピリジン）ルテニウム（６６０ｍｇ，１．００ｍｍｏｌ）、４，６‐ジブトキシ‐２‐メルカプトピリミジン（３０８ｍｇ，１．２０ｍｍｏｌ）及び１Ｎ‐水酸化カリウム水溶液（７．５ｍＬ）を加え８０℃で３時間撹拌した。不溶物をろ別後、溶液から溶媒を減圧留去した。得られた粗生成物に１Ｎ‐塩酸（７．５ｍＬ）を加え、室温で１５分攪拌した。析出した固形物を遠心分離により分離し、濾過し、エーテル及び水で充分洗浄した後、乾燥させることにより、目的とするルテニウム錯体（錯体１−７）の暗赤色固体（８１６ｍｇ，収率９３％）を得た。
^１ＨＮＭＲ（Ｄ_２Ｏ-ＮａＯＤ）：δ０．５６（ｔ，Ｊ＝６．９Ｈｚ，３Ｈ），０．５８‐０．７１（ｍ，２Ｈ），０．７１‐０．８５（ｍ，２Ｈ），０．８５（ｔ，Ｊ＝７．４Ｈｚ，３Ｈ），１．２９‐１．３９（ｍ，２Ｈ），１．６０‐１．７０（ｍ，２Ｈ），３．３９（ｄｔ，Ｊ＝９．５，６．１Ｈｚ，１Ｈ），３．６０（ｄｔ，Ｊ＝９．５，６．４Ｈｚ，１Ｈ），４．０５‐４．２０（ｍ，２Ｈ），５．４９（ｓ，１Ｈ），７．３８（ｄｄ，Ｊ＝５．９，１．６Ｈｚ，１Ｈ），７．４８（ｄｄ，Ｊ＝５．９，１．６Ｈｚ，１Ｈ），７．７７（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．８６（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．８８（ｄｄ，Ｊ＝５．８，１．６Ｈｚ，１Ｈ），７．９７（ｄｄ，Ｊ＝５．８，１．６Ｈｚ，１Ｈ），８．４６（ｄ，Ｊ＝５．８Ｈｚ，１Ｈ），８．６６（ｂｒｓ，１Ｈ），８．７１（ｂｒｓ，１Ｈ），８．７８，（ｂｒｓ，１Ｈ），８．８２，（ｂｒｓ，１Ｈ），９．７７（ｄ，Ｊ＝５．８Ｈｚ，１Ｈ）．ＵＶ／ｖｉｓ（Ｈ_２Ｏ）：λ_ｍａｘ［ｎｍ］（ε×１０^-４［Ｌ／（ｍｏｌ×ｃｍ）］）２４８．０（３．６４５），３０８．０（４．６５０），３７４．０（１．２４５），５１７．０（１．３０５）．
実施例−８

Under an argon atmosphere, a mixed solution of distilled water (25 mL) and ethanol (25 m) was added to cis-bis (4,4′-dicarboxy-2,2′-bipyridine) ruthenium dichloride (660 mg, 1.00 mmol), 4, 6-Dibutoxy-2-mercaptopyrimidine (308 mg, 1.20 mmol) and 1N aqueous potassium hydroxide solution (7.5 mL) were added, and the mixture was stirred at 80 ° C. for 3 hr. The insoluble material was filtered off, and the solvent was distilled off from the solution under reduced pressure. 1N-hydrochloric acid (7.5 mL) was added to the obtained crude product, and the mixture was stirred at room temperature for 15 minutes. The precipitated solid was separated by centrifugation, filtered, thoroughly washed with ether and water, and then dried to give a dark red solid (816 mg, 93% yield) of the target ruthenium complex (complex 1-7). )
¹ HNMR (D ₂ O—NaOD): δ 0.56 (t, J = 6.9 Hz, 3H), 0.58-0.71 (m, 2H), 0.71-0.85 (m, 2H) , 0.85 (t, J = 7.4 Hz, 3H), 1.29-1.39 (m, 2H), 1.60-1.70 (m, 2H), 3.39 (dt, J = 9.5, 6.1 Hz, 1H), 3.60 (dt, J = 9.5, 6.4 Hz, 1H), 4.05-4.20 (m, 2H), 5.49 (s, 1H) ), 7.38 (dd, J = 5.9, 1.6 Hz, 1H), 7.48 (dd, J = 5.9, 1.6 Hz, 1H), 7.77 (d, J = 5. 9 Hz, 1H), 7.86 (d, J = 5.9 Hz, 1H), 7.88 (dd, J = 5.8, 1.6 Hz, 1H), 7.97 (dd, J = 5.8) , 1.6 Hz, 1 H), 8.46 ( , J = 5.8 Hz, 1H), 8.66 (brs, 1H), 8.71 (brs, 1H), 8.78, (brs, 1H), 8.82, (brs, 1H), 9. 77 (d, J = 5.8 Hz, 1H). UV / vis (H ₂ O): λ _max [nm] (ε × 10 ⁻⁴ [L / (mol × cm)]) 248.0 (3.645), 308.0 (4.650), 374. 0 (1.245), 517.0 (1.305).
Example-8

アルゴン雰囲気下、蒸留水（５０ｍＬ）に二塩化シス‐ビス（４，４’‐ジカルボキシ‐２，２’‐ビピリジン）ルテニウム（６６４ｍｇ，１．０１ｍｍｏｌ）と２‐メルカプトピリジン（１３５ｍｇ，１．２１ｍｍｏｌ）及び１Ｎ‐水酸化カリウム水溶液（７．５ｍＬ）を加え６０℃で１３時間撹拌した。不溶物をろ別後、溶液から溶媒を減圧留去した。得られた粗生成物に１Ｎ‐塩酸（７．５ｍＬ）を加え、室温で１５分攪拌した。析出した固形物を遠心分離により分離し、濾過し、水で充分洗浄した後、乾燥させることにより、目的とするルテニウム錯体（錯体１−８）の暗赤色固体（７３９ｍｇ，収率８１％）を得た。
^１ＨＮＭＲ（Ｄ_２Ｏ）：δ６．６２−６．６９（ｍ，１Ｈ），６．８０（ｄ，Ｊ＝８．３Ｈｚ，１Ｈ），７．０（ｄ，Ｊ＝６．０Ｈｚ，１Ｈ），７．３０−７．４３（ｍ，２Ｈ），７．４４（ｄ，Ｊ＝６．０Ｈｚ，１Ｈ），７．７４（ｄ，Ｊ＝６．０Ｈｚ，１Ｈ），７．８２（ｂｒｄ，Ｊ＝７．４Ｈｚ，１Ｈ），７．８９−７．９５（ｍ，２Ｈ），８．２８（ｄ，Ｊ＝５．８Ｈｚ，１Ｈ），８．６８（ｓ，１Ｈ），８．７０（ｓ，１Ｈ），８．７８（ｓ，１Ｈ），８．８２（ｓ，１Ｈ），９．９７（ｄ，Ｊ＝６．１Ｈｚ，１Ｈ）．ＵＶ／ｖｉｓ（Ｈ_２Ｏ）：λ_ｍａｘ［ｎｍ］（ε×１０^-４）３０８．０（５．１０），３６６．０（１．５０），５１８．０（１．４０）．
実施例−９

Under an argon atmosphere, distilled water (50 mL) was mixed with cis-bis (4,4′-dicarboxy-2,2′-bipyridine) ruthenium dichloride (664 mg, 1.01 mmol) and 2-mercaptopyridine (135 mg, 1.21 mmol). And 1N aqueous potassium hydroxide solution (7.5 mL) were added, and the mixture was stirred at 60 ° C. for 13 hours. The insoluble material was filtered off, and the solvent was distilled off from the solution under reduced pressure. 1N-hydrochloric acid (7.5 mL) was added to the obtained crude product, and the mixture was stirred at room temperature for 15 minutes. The precipitated solid was separated by centrifugation, filtered, sufficiently washed with water, and dried to obtain a dark red solid (739 mg, yield 81%) of the target ruthenium complex (complex 1-8). Obtained.
¹ HNMR (D ₂ O): δ 6.62-6.69 (m, 1H), 6.80 (d, J = 8.3 Hz, 1H), 7.0 (d, J = 6.0 Hz, 1H) 7.30-7.43 (m, 2H), 7.44 (d, J = 6.0 Hz, 1H), 7.74 (d, J = 6.0 Hz, 1H), 7.82 (brd, J = 7.4 Hz, 1H), 7.89-7.95 (m, 2H), 8.28 (d, J = 5.8 Hz, 1H), 8.68 (s, 1H), 8.70 ( s, 1H), 8.78 (s, 1H), 8.82 (s, 1H), 9.97 (d, J = 6.1 Hz, 1H). UV / vis (H ₂ O): λ _max [nm] (ε × 10 ⁻⁴ ) 308.0 (5.10), 366.0 (1.50), 518.0 (1.40).
Example-9

アルゴン雰囲気下、脱水エタノール（１００ｍＬ）に実施例−２で合成した錯体１−２（２００ｍｇ，０．２６ｍｍｏｌ）を懸濁し、２．０Ｍ‐アンモニア‐エタノール溶液（７．５ｍＬ）を、錯体が溶解するまで少量づつ加えた。反応溶液をグラスフィルターでろ過後、溶液から溶媒を減圧留去した。得られた粗生成物にエーテル（５０ｍＬ）を加え、濾過し、エーテルで充分洗浄した後、乾燥させることにより、目的とするルテニウム錯体（錯体１−９）の暗赤色固体（１８５ｍｇ，収率８５％）を得た。
^１ＨＮＭＲ（Ｄ_２Ｏ）：δ１．３５（ｓ，３Ｈ），２．３１（ｓ，３Ｈ），６．６１（ｓ，１Ｈ），７．４２（ｄｄ，Ｊ＝５．９，１．５Ｈｚ，１Ｈ），７．５１（ｄｄ，Ｊ＝５．９，１．５Ｈｚ，１Ｈ），７．７９（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．８６（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．８９（ｄｄ，Ｊ＝５．８，１．６Ｈｚ，１Ｈ），８．００（ｄｄ，Ｊ＝５．８，１．６Ｈｚ，１Ｈ），８．４０（ｄ，Ｊ＝５．８Ｈｚ，１Ｈ），８．７０（ｂｒｓ，１Ｈ），８．７７（ｂｒｓ，１Ｈ），８．８６（ｂｒｓ，２Ｈ），９．７９（ｄ，Ｊ＝５．８Ｈｚ，１Ｈ）．ＵＶ／ｖｉｓ（Ｈ_２Ｏ）：λ_ｍａｘ［ｎｍ］（ε×１０^-４）２４６．０（３．１７５），３０８．０（４．２０５），３５９．０（１．２６５），５１１．０（１．１１０）．
実施例−１０

In an argon atmosphere, the complex 1-2 (200 mg, 0.26 mmol) synthesized in Example-2 was suspended in dehydrated ethanol (100 mL), and the 2.0 M ammonia-ethanol solution (7.5 mL) was suspended. Added in small portions until The reaction solution was filtered through a glass filter, and the solvent was distilled off from the solution under reduced pressure. Ether (50 mL) was added to the obtained crude product, filtered, thoroughly washed with ether, and dried to give a dark red solid (185 mg, yield 85) of the desired ruthenium complex (complex 1-9). %).
¹ HNMR (D ₂ O): δ 1.35 (s, 3H), 2.31 (s, 3H), 6.61 (s, 1H), 7.42 (dd, J = 5.9, 1.5 Hz) , 1H), 7.51 (dd, J = 5.9, 1.5 Hz, 1H), 7.79 (d, J = 5.9 Hz, 1H), 7.86 (d, J = 5.9 Hz, 1H), 7.89 (dd, J = 5.8, 1.6 Hz, 1H), 8.00 (dd, J = 5.8, 1.6 Hz, 1H), 8.40 (d, J = 5 .8 Hz, 1H), 8.70 (brs, 1H), 8.77 (brs, 1H), 8.86 (brs, 2H), 9.79 (d, J = 5.8 Hz, 1H). UV / vis (H ₂ O): λ _max [nm] (ε × 10 ⁻⁴ ) 246.0 (3.175), 308.0 (4.205), 359.0 (1.265), 511. 0 (1.110).
Example-10

水（５０ｍＬ）に実施例−２で合成した錯体１−２（２００ｍｇ，０．２６ｍｍｏｌ）を懸濁し、１Ｎ‐水酸化カリウム水溶液を、錯体が溶解するまで少量づつ加えた。反応溶液をグラスフィルターでろ過後、６Ｎ‐過塩素酸水溶液を滴下し、ｐＨ＝２とした。生じた固体を遠心分離した後、ろ取し、水で充分洗浄した後、乾燥させることにより、目的とするルテニウム錯体（錯体１−１０）の暗赤色固体（１８２ｍｇ，収率９６％）を得た。
^１ＨＮＭＲ（Ｄ_２Ｏ）：δ１．３０（ｓ，３Ｈ），２．２７（ｓ，３Ｈ），６．５７（ｓ，１Ｈ），７．３８（ｄｄ，Ｊ＝５．９，１．６Ｈｚ，１Ｈ），７．４７（ｄｄ，Ｊ＝５．９，１．６Ｈｚ，１Ｈ），７．７５（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．８１（ｄ，Ｊ＝５．９Ｈｚ，１Ｈ），７．８４（ｄｄ，Ｊ＝５．８，１．６Ｈｚ，１Ｈ），７．９５（ｄｄ，Ｊ＝５．８，１．６Ｈｚ，１Ｈ），８．３６（ｄ，Ｊ＝５．８Ｈｚ，１Ｈ），８．６６（ｂｒｓ，１Ｈ），８．７２（ｂｒｓ，１Ｈ），８．８２（ｂｒｓ，２Ｈ），９．７５（ｄ，Ｊ＝５．８Ｈｚ，１Ｈ）．ＵＶ／ｖｉｓ（Ｈ_２Ｏ）：λ_ｍａｘ［ｎｍ］（ε×１０^-４）２４６．０（４．４０５），３０７．０（５．７４０），３６８．０（１．７２５），５１２．０（１．５６５）．

The complex 1-2 (200 mg, 0.26 mmol) synthesized in Example-2 was suspended in water (50 mL), and 1N aqueous potassium hydroxide solution was added in small portions until the complex was dissolved. The reaction solution was filtered through a glass filter, and 6N-perchloric acid aqueous solution was added dropwise to adjust to pH = 2. The resulting solid was centrifuged, filtered, washed thoroughly with water, and dried to obtain the dark red solid (182 mg, yield 96%) of the target ruthenium complex (complex 1-10). It was.
¹ HNMR (D ₂ O): δ 1.30 (s, 3H), 2.27 (s, 3H), 6.57 (s, 1H), 7.38 (dd, J = 5.9, 1.6 Hz) , 1H), 7.47 (dd, J = 5.9, 1.6 Hz, 1H), 7.75 (d, J = 5.9 Hz, 1H), 7.81 (d, J = 5.9 Hz, 1H), 7.84 (dd, J = 5.8, 1.6 Hz, 1H), 7.95 (dd, J = 5.8, 1.6 Hz, 1H), 8.36 (d, J = 5 .8 Hz, 1H), 8.66 (brs, 1H), 8.72 (brs, 1H), 8.82 (brs, 2H), 9.75 (d, J = 5.8 Hz, 1H). UV / vis (H ₂ O): λ _max [nm] (ε × 10 ⁻⁴ ) 246.0 (4.405), 307.0 (5.740), 368.0 (1.725), 512. 0 (1.565).

Example-11
In this example, the dye-sensitized solar cell was evaluated using the complex 1-2 synthesized in Example-2 as the dye. As the glass substrate for negative electrode used in the dye-sensitized solar cell, a glass plate having a thickness of 3 mm and a 2 × 3 cm square by cutting a glass plate (manufactured by Nippon Sheet Glass) on which a transparent conductive film was formed on a soda lime glass plate was used. A titanium oxide paste (SOLARONIX product name: Ti-Nanoxide D) was applied to the surface of the glass substrate on which the transparent conductive film was formed by screen printing at a thickness of 5 μm. The applied film was baked at 450 ° C. for 1 hour. Further, titanium oxide (product name: SSP manufactured by Sakai Chemical Co., Ltd.) was pasted thereon and applied with a thickness of 20 μm by a screen printing apparatus. The applied film was baked at 450 ° C. for 1 hour. Thereafter, the glass substrate on which the titanium oxide porous film was formed was immersed in an ethanol solution having a concentration of 3 × 10 ⁻⁴ mol / L of the complex 1-2 of the present invention and held for 16 hours. Then, it was immersed in absolute ethanol to remove excess dye and dried at 100 ° C. When the electrode film is formed, printing is performed so that the titanium oxide paste is not attached to a portion 3 mm from the peripheral edge of the glass plate. The peripheral edge of the glass plate has a thickness of 60 μm from the outside to the inside. An ionomer resin sheet (spacer manufactured by Mitsui DuPont Polychemical Co., Ltd. (trade name: “HIMILAN”)) was attached in a width of 3 mm. Similarly, the glass plate for positive electrodes used was a glass plate having a thickness of 3 mm and 2 × 3 cm by cutting a glass plate (manufactured by Nippon Sheet Glass) having a transparent conductive film formed on a soda lime glass plate. A Pt film with a thickness of 50 nm was formed on this substrate by sputtering, and two holes with a diameter of 1 mmΦ were formed at both ends in a diagonal direction by a drill. A load of 10 gf / cm ² was applied between the two substrates. In this state, it was heat-sealed with an ionomer resin sheet at 120 ° C. And acetonitrile electrolyte solution to produce the cells were dissolved LiI and I ₂ were placed from injection port formed in the metal supporting board was injected so as to be uniform throughout the cell.

The short-circuit current density (J _sc ), open-circuit voltage (V _oc ), fill factor (FF), and energy conversion efficiency (η (%)) of the dye-sensitized solar cell of the produced cell were measured. The energy conversion efficiency (η (%)) of the dye-sensitized solar cell is represented by the following formula. Here, in the following formula, P ₀ is the incident light intensity [mWcm ⁻² ], V _oc is the open circuit voltage [V], J _sc is the short-circuit current density [mA · cm ⁻² ], F.V. F. Indicates a fill factor.
η = 100 × (V _oc × J _sc × FF) / P ₀ (A)

The battery characteristic evaluation test uses a solar simulator (manufactured by Yamashita Denso, trade name: “YS-100H type”), and the irradiation condition of pseudo sunlight from a xenon lamp light source through an AM filter (AM1.5) is 100 mW. / Cm ² (so-called “1Sun” irradiation condition). Table 1 shows the results of photoelectric conversion efficiency. From this result, it was found that the photoelectric conversion efficiency of the dye-sensitized solar cell sufficiently shows the characteristics of the solar cell.

参考例−１

Reference Example-1

１，４‐ジオキサン（９０ｍＬ）にマロノニトリル（４．８ｍＬ，７５．６ｍｍｏｌ）とエタノール（８．８３ｍＬ，１５３ｍｍｏｌ）を加え、塩酸ガスを０℃で３時間通じた。溶媒を減圧濃縮し、析出した固体を濾過した後、エーテルで洗浄し、ジエトキシ‐１，３‐プロパンジイミデートの白色固体（１３．６ｇ，収率９３％）を得た。
水（２０ｍＬ）に炭酸水素ナトリウム（１．０９ｇ，１．３０ｍｍｏｌ）を加え、０℃に冷却した。ここにジエトキシ‐１，３‐プロパンジイミデート（３．０１ｇ，１３．０ｍｍｏｌ）を少量ずつ加え、完全に溶解させた。ここにシアナミド（０．６３０ｇ，１５．０ｍｍｏｌ）を加え、室温で２時間撹拌した。不溶物をろ別後、粗生成物を水で洗浄し、メタノールから再結晶することで、目的の３‐アミノ‐１，３‐ジエトキシ‐２‐プロペンイミデートの白色固体（１．７０ｇ，収率７１％）を得た。
続いてＴＨＦ（３０ｍＬ）に３‐アミノ‐１，３‐ジエトキシ‐２‐プロペンイミデート（１．１２ｇ，６．０９ｍｍｏｌ）を溶解し、−２０℃に冷却した。ここに塩酸ガス（４ｇ）を通じ５時間攪拌した。１０℃に昇温し、溶媒を減圧留去した。析出した固体を濾過した後、水で洗浄することにより、目的の２‐クロロ‐４，６‐ジエトキシピリミジンの白色固体（０．６４９ｇ，収率５３％）を得た。
^１Ｈ ＮＭＲ（ＣＤＣｌ_３）：δ１．３７（ｔ，Ｊ＝７．１Ｈｚ，６Ｈ），４．３８（ｑ，Ｊ＝７．１Ｈｚ，４Ｈ），５．９１（ｓ，１Ｈ）．
参考例−２

Malononitrile (4.8 mL, 75.6 mmol) and ethanol (8.83 mL, 153 mmol) were added to 1,4-dioxane (90 mL), and hydrochloric acid gas was passed at 0 ° C. for 3 hours. The solvent was concentrated under reduced pressure, and the precipitated solid was filtered and washed with ether to obtain diethoxy-1,3-propanediimidate as a white solid (13.6 g, yield 93%).
Sodium hydrogen carbonate (1.09 g, 1.30 mmol) was added to water (20 mL) and cooled to 0 ° C. Diethoxy-1,3-propanediimidate (3.01 g, 13.0 mmol) was added little by little to completely dissolve it. Cyanamide (0.630 g, 15.0 mmol) was added thereto and stirred at room temperature for 2 hours. The insoluble material was filtered off, and the crude product was washed with water and recrystallized from methanol to give the desired 3-amino-1,3-diethoxy-2-propenimidate as a white solid (1.70 g, yield). 71%) was obtained.
Subsequently, 3-amino-1,3-diethoxy-2-propenimidate (1.12 g, 6.09 mmol) was dissolved in THF (30 mL) and cooled to −20 ° C. The mixture was stirred for 5 hours through hydrochloric acid gas (4 g). The temperature was raised to 10 ° C., and the solvent was distilled off under reduced pressure. The precipitated solid was filtered and then washed with water to obtain the desired white solid (0.649 g, yield 53%) of 2-chloro-4,6-diethoxypyrimidine.
¹ H NMR (CDCl ₃ ): δ 1.37 (t, J = 7.1 Hz, 6H), 4.38 (q, J = 7.1 Hz, 4H), 5.91 (s, 1H).
Reference example-2

１，４‐ジオキサン（１８０ｍＬ）にマロノニトリル（９．５ｍＬ，１５１．４ｍｍｏｌ）とメタノール（１２．３ｍＬ，３０３ｍｍｏｌ）を加え、塩酸ガスを０℃で３時間通じた。溶媒を減圧濃縮し、析出した固体を濾過した後、エーテルで洗浄し、ジメトキシ‐１，３‐プロパンジイミデートの白色固体（３０．７ｇ，収率９６％）を得た。
水（２００ｍＬ）に炭酸水素ナトリウム（１０．６ｇ，１２６ｍｍｏｌ）を加え、０℃に冷却した。ここにジメトキシ‐１，３‐プロパンジイミデート（２５ｇ，１２３ｍｍｏｌ）を少量ずつ加え、完全に溶解させた。ここにシアナミド（５．９ｇ，１４０ｍｍｏｌ）を加え、室温で２時間撹拌した。不溶物をろ別後、粗生成物を水で洗浄し、減圧乾固することで、目的の３‐アミノ‐１，３‐ジメトキシ‐２‐プロペンイミデートの白色固体（１９．１ｇ，収率７７％）を得た。
続いてＴＨＦ（８０ｍＬ）に３‐アミノ‐１，３‐ジメトキシ‐２‐プロペンイミデート（７．０ｇ，４５ｍｍｏｌ）を溶解し、−２０℃に冷却した。ここに塩酸ガス（４５ｇ）を通じ５時間攪拌した。１０℃に昇温し、溶媒を減圧留去した。析出した固体を濾過した後、水で洗浄することにより、目的の２‐クロロ‐４，６‐ジメトキシピリミジンの白色固体（４．１ｇ，収率５２％）を得た。
^１Ｈ ＮＭＲ（ＣＤＣｌ_３）：δ３．９６（ｓ，６Ｈ），５．９６（ｓ，１Ｈ）．
参考例−３

To 1,4-dioxane (180 mL) were added malononitrile (9.5 mL, 151.4 mmol) and methanol (12.3 mL, 303 mmol), and hydrochloric acid gas was passed at 0 ° C. for 3 hours. The solvent was concentrated under reduced pressure, and the precipitated solid was filtered and washed with ether to obtain a white solid (30.7 g, yield 96%) of dimethoxy-1,3-propanediimidate.
Sodium hydrogen carbonate (10.6 g, 126 mmol) was added to water (200 mL) and cooled to 0 ° C. Dimethoxy-1,3-propanediimidate (25 g, 123 mmol) was added thereto in small portions and completely dissolved. Cyanamide (5.9 g, 140 mmol) was added thereto, and the mixture was stirred at room temperature for 2 hours. The insoluble material was filtered off, and the crude product was washed with water and dried under reduced pressure to give the desired 3-amino-1,3-dimethoxy-2-propenimidate as a white solid (19.1 g, yield). 77%).
Subsequently, 3-amino-1,3-dimethoxy-2-propenimidate (7.0 g, 45 mmol) was dissolved in THF (80 mL) and cooled to −20 ° C. The mixture was stirred for 5 hours with hydrochloric acid gas (45 g). The temperature was raised to 10 ° C., and the solvent was distilled off under reduced pressure. The precipitated solid was filtered and then washed with water to obtain the desired white solid (4.1 g, yield 52%) of 2-chloro-4,6-dimethoxypyrimidine.
¹ H NMR (CDCl ₃ ): δ 3.96 (s, 6H), 5.96 (s, 1H).
Reference example-3

１，４‐ジオキサン（１８０ｍＬ）にマロノニトリル（９．５ｍＬ，１５１ｍｍｏｌ）とブタノール（２７．７ｍＬ，３０３ｍｍｏｌ）を加え、塩酸ガスを０℃で３時間通じた。溶媒を減圧濃縮し、析出した固体を濾過した後、エーテルで洗浄し、ジブトキシ‐１，３‐プロパンジイミデートの白色固体（４３．５ｇ，収率９５％）を得た。
水（２００ｍＬ）に炭酸水素ナトリウム（１０．５ｇ，１２５ｍｍｏｌ）を加え、０℃に冷却した。ここにジブトキシ‐１，３‐プロパンジイミデート（３５ｇ，１２２ｍｍｏｌ）を少量ずつ加え、完全に溶解させた。ここにシアナミド（６．０ｇ，１４３ｍｍｏｌ）を加え、室温で２時間撹拌した。反応溶液ををエーテル（１００ｍＬ×３）で抽出し、得られた有機層を合わせ、硫酸ナトリウム（５０ｇ）を加えて乾燥させた。乾燥剤をろ別後、溶液を減圧乾固し、油状の３‐アミノ‐１，３‐ジブトキシ‐２‐プロペンイミデート（２６．２ｇ，収率９０％）を得た。
続いてＴＨＦ（９０ｍＬ）に３‐アミノ‐１，３‐ブエトキシ‐２‐プロペンイミデート（１２ｇ，５０ｍｍｏｌ）を溶解し、−２０℃に冷却した。ここに塩酸ガス（５０ｇ）を通じ５時間攪拌した。１０℃に昇温し、溶媒を減圧留去した。租生成物に水（１００ｍＬ）を加えた後、エーテル（１００ｍＬ×３）で抽出し、得られた有機層を合わせ、硫酸ナトリウム（５０ｇ）を加えて乾燥させた。乾燥剤をろ別後、溶液を減圧乾固し、油状の租生成物をカラムクロマトグラフィー（ＳｉＯ_２、溶離液：ヘキサン／クロロホルム＝５０／５０）により精製し、目的の２‐クロロ‐４，６‐ジブトキシピリミジン（６．６５ｇ，収率５１％）を得た。
^１Ｈ ＮＭＲ（ＣＤＣｌ_３）：δ０．９６（ｔ，Ｊ＝７．３Ｈｚ，６Ｈ），１．３６‐１．５１（ｍ，４Ｈ），１．６７‐１．８３（ｍ，４Ｈ），４．３０（ｔ，Ｊ＝６．６Ｈｚ，４Ｈ），５．９１（ｓ，１Ｈ）．
参考例−４

Malononitrile (9.5 mL, 151 mmol) and butanol (27.7 mL, 303 mmol) were added to 1,4-dioxane (180 mL), and hydrochloric acid gas was passed at 0 ° C. for 3 hours. The solvent was concentrated under reduced pressure, and the precipitated solid was filtered and washed with ether to obtain a white solid (43.5 g, yield 95%) of dibutoxy-1,3-propanediimidate.
Sodium hydrogen carbonate (10.5 g, 125 mmol) was added to water (200 mL) and cooled to 0 ° C. Dibutoxy-1,3-propanediimidate (35 g, 122 mmol) was added little by little to completely dissolve it. Cyanamide (6.0 g, 143 mmol) was added thereto and stirred at room temperature for 2 hours. The reaction solution was extracted with ether (100 mL × 3), and the obtained organic layers were combined and dried by adding sodium sulfate (50 g). After the desiccant was filtered off, the solution was evaporated to dryness to give oily 3-amino-1,3-dibutoxy-2-propenimidate (26.2 g, yield 90%).
Subsequently, 3-amino-1,3-butethoxy-2-propenimidate (12 g, 50 mmol) was dissolved in THF (90 mL) and cooled to −20 ° C. The mixture was stirred for 5 hours with hydrochloric acid gas (50 g). The temperature was raised to 10 ° C., and the solvent was distilled off under reduced pressure. Water (100 mL) was added to the crude product, followed by extraction with ether (100 mL × 3). The obtained organic layers were combined, and sodium sulfate (50 g) was added and dried. After filtering off the desiccant, the solution was dried under reduced pressure, and the oily product was purified by column chromatography (SiO ₂ , eluent: hexane / chloroform = 50/50) to obtain the desired 2-chloro-4 6-Dibutoxypyrimidine (6.65 g, 51% yield) was obtained.
¹ H NMR (CDCl ₃ ): δ 0.96 (t, J = 7.3 Hz, 6H), 1.36-1.51 (m, 4H), 1.67-1.83 (m, 4H), 4 .30 (t, J = 6.6 Hz, 4H), 5.91 (s, 1H).
Reference example-4

脱水エタノール（２１５ｍＬ）に２‐クロロ‐４，６‐ジエトキシピリミジン（４．０５ｇ，２０ｍｍｏｌ）を加え、５０℃で５分間撹拌した。ここにチオウレア（４．５７ｇ，６０ｍｍｏｌ）を加え、２４時間加熱還流した。放冷後、反応溶媒を留去し、５％‐水酸化ナトリウム水溶液（６５ｍＬ）を加えた。室温で３０分撹拌した後、不溶物をグラスフィルターでろ別し、ろ液に酢酸（６ｍＬ）を加えて中和した。これをクロロホルム（５０ｍＬ×３）で抽出し、得られた有機層を合わせ、硫酸ナトリウム（２０ｇ）を加えて乾燥させた。乾燥剤をろ別後、溶液を減圧乾固し、目的の４，６‐ジエトキシ‐２‐メルカプトピリミジンの白色固体（２．１２ｇ，収率５３％）を得た。
参考例−５

2-Chloro-4,6-diethoxypyrimidine (4.05 g, 20 mmol) was added to dehydrated ethanol (215 mL), and the mixture was stirred at 50 ° C. for 5 minutes. To this was added thiourea (4.57 g, 60 mmol), and the mixture was heated to reflux for 24 hours. After allowing to cool, the reaction solvent was distilled off, and 5% -aqueous sodium hydroxide solution (65 mL) was added. After stirring at room temperature for 30 minutes, insoluble matters were filtered off with a glass filter, and acetic acid (6 mL) was added to the filtrate for neutralization. This was extracted with chloroform (50 mL × 3), and the obtained organic layers were combined and dried by adding sodium sulfate (20 g). After the desiccant was filtered off, the solution was dried under reduced pressure to obtain the desired white solid (2.12 g, yield 53%) of 4,6-diethoxy-2-mercaptopyrimidine.
Reference Example-5

脱水エタノール（６５ｍＬ）に２‐クロロ‐４，６‐ジメトキシピリミジン（１．０５ｇ，６ｍｍｏｌ）を加え、５０℃で５分間撹拌した。ここにチオウレア（１．３７ｇ，１８ｍｍｏｌ）を加え、６５時間加熱還流した。放冷後、反応溶媒を留去し、５％‐水酸化ナトリウム水溶液（２０ｍＬ）を加えた。室温で３０分撹拌した後、ろ液に酢酸（６ｍＬ）を加えて中和した。ここをクロロホルム（２０ｍＬ×３）で抽出し、得られた有機層を合わせ、硫酸ナトリウム（２０ｇ）を加えて乾燥させた。乾燥剤をろ別後、溶液を減圧乾固し、カラムクロマトグラフィー（ＳｉＯ_２、溶離液：ヘキサン／クロロホルム＝５０／５０〜０／１００）により目的の４，６‐ジメトキシ‐２‐メルカプトピリミジンの白色固体（１８６ｍｇ，収率１８％）を得た。
^１ＨＮＭＲ（ＣＤＣｌ_３）：δ３．９１（ｓ，６Ｈ） ５．７１（ｓ，１Ｈ）．
参考例−６

2-Chloro-4,6-dimethoxypyrimidine (1.05 g, 6 mmol) was added to dehydrated ethanol (65 mL), and the mixture was stirred at 50 ° C. for 5 minutes. To this was added thiourea (1.37 g, 18 mmol), and the mixture was heated to reflux for 65 hours. After allowing to cool, the reaction solvent was distilled off, and 5% -aqueous sodium hydroxide solution (20 mL) was added. After stirring at room temperature for 30 minutes, the filtrate was neutralized by adding acetic acid (6 mL). This was extracted with chloroform (20 mL × 3), and the obtained organic layers were combined and dried by adding sodium sulfate (20 g). After filtering off the desiccant, the solution was evaporated to dryness under reduced pressure, and the desired 4,6-dimethoxy-2-mercaptopyrimidine was purified by column chromatography (SiO ₂ , eluent: hexane / chloroform = 50/50 to 0/100). A white solid (186 mg, 18% yield) was obtained.
¹ HNMR (CDCl ₃ ): δ 3.91 (s, 6H) 5.71 (s, 1H).
Reference Example-6

脱水エタノール（６０ｍＬ）に２‐クロロ‐４，６‐ジブトキシピリミジン（１．０４ｇ，４ｍｍｏｌ）を加え、５０℃で５分間撹拌した。ここにチオウレア（９１３ｍｇ，１２ｍｍｏｌ）を加え、４８時間加熱還流した。放冷後、反応溶媒を留去し、５％‐水酸化ナトリウム水溶液（２０ｍＬ）を加えた。室温で３０分撹拌した後、ろ液に酢酸（６ｍＬ）を加えて中和した。ここをクロロホルム（２０ｍＬ×３）で抽出し、得られた有機層を合わせ、硫酸ナトリウム（２０ｇ）を加えて乾燥させた。乾燥剤をろ別後、溶液を減圧乾固し、カラムクロマトグラフィー（ＳｉＯ_２、溶離液：ヘキサン／クロロホルム＝５０／５０〜０／１００）により目的の４，６‐ジブトキシ‐２‐メルカプトピリミジンの白色固体（４０６ｍｇ，収率４０％）を得た。
^１ＨＮＭＲ（ＣＤＣｌ_３）：δ０．９６（ｔ，Ｊ＝７．３Ｈｚ，６Ｈ），１．３５‐１．５２（ｍ，４Ｈ），１．６６‐１．８０（ｍ，４Ｈ），４．２５（ｔ，Ｊ＝６．６ Ｈｚ，４Ｈ），５．６２（ｓ，１Ｈ）．

2-Chloro-4,6-dibutoxypyrimidine (1.04 g, 4 mmol) was added to dehydrated ethanol (60 mL), and the mixture was stirred at 50 ° C. for 5 minutes. To this was added thiourea (913 mg, 12 mmol), and the mixture was heated to reflux for 48 hours. After allowing to cool, the reaction solvent was distilled off, and 5% -aqueous sodium hydroxide solution (20 mL) was added. After stirring at room temperature for 30 minutes, the filtrate was neutralized by adding acetic acid (6 mL). This was extracted with chloroform (20 mL × 3), and the obtained organic layers were combined and dried by adding sodium sulfate (20 g). After filtering off the desiccant, the solution was evaporated to dryness under reduced pressure, and the desired 4,6-dibutoxy-2-mercaptopyrimidine was purified by column chromatography (SiO ₂ , eluent: hexane / chloroform = 50/50 to 0/100). A white solid (406 mg, 40% yield) was obtained.
¹ HNMR (CDCl ₃ ): δ 0.96 (t, J = 7.3 Hz, 6H), 1.35-1.52 (m, 4H), 1.66-1.80 (m, 4H), 4. 25 (t, J = 6.6 Hz, 4H), 5.62 (s, 1H).

Claims (12)

General formula (1)

(In the formula, R ¹ represents a carboxyl group or a chemically acceptable salt thereof. R ² and R ⁴ each independently represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 8 carbon atoms. Represents an optionally substituted alkoxy group having 1 to 8 carbon atoms, an optionally substituted amino group, a hydroxyl group, a nitro group, or a cyano group, and R ³ represents a hydrogen atom or an optionally substituted carbon number of 1. To Y. Y represents an optionally substituted carbon atom or nitrogen atom, and X ⁻ represents a counter anion. The ruthenium complex according to claim 1, wherein an acceptable salt of the carboxyl group represented by R ¹ is an ammonium salt, a tetrabutylammonium salt, a sodium salt or a potassium salt. R ² and R ⁴ are a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted alkoxy group having 1 to 4 carbon atoms, or an optionally substituted amino group, The ruthenium complex according to claim 1 or 2, wherein R ³ is a hydrogen atom. Counter anions represented by X ⁻ are halogen ions, perchlorate ions (ClO ₄ ⁻ ), nitrate ions (NO ₃ ⁻ ), hexafluorophosphonate ions (PF ₆ ⁻ ), and tetrafluoroborate ions (BF ₄ ⁻ ). The ruthenium complex according to any one of claims 1 to 3. General formula (2)

(Wherein R ^1a represents ^a carboxyl group, X ^a represents ^a chlorine atom or a bromine atom) and a general formula (3)

(In the formula, R ² and R ⁴ each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkoxy group having 1 to 8 carbon atoms, or a substituted group. Represents an optionally substituted amino group, a hydroxyl group, a nitro group or a cyano group, R ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 8 carbon atoms, and Y represents an optionally substituted carbon. And a heterocyclic compound represented by the general formula (1a):

(In the formula, R ^1b represents a salt of a carboxyl group and the used base. R ² , R ³ , R ⁴ and Y represent the same meaning as described above. X ^a− represents a chlorine ion or a bromine ion.) A ruthenium complex represented by the general formula (4)

(In the formula, X ^b- represents a counter anion), and is treated with an acid represented by the general formula (1b)

(Wherein R ^1a , R ² , R ³ , R ⁴ , Y and X ^b- represent the same meaning as described above). The production method according to claim 5, wherein X ^b− is a halogen ion, a perchlorate ion (ClO ₄ ⁻ ), or a nitrate ion (NO ₃ ⁻ ). General formula (1b)

(In the formula, R ^1a represents a carboxyl group. R ² and R ⁴ each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted carbon number. R 1 represents an alkoxy group having 1 to 8 amino groups, an optionally substituted amino group, a hydroxyl group, a nitro group, or a cyano group, and R ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 8 carbon atoms. Represents a carbon atom or a nitrogen atom which may be substituted. X ^b- represents a counter anion) and a general formula (5)

( ^Wherein M ⁺ represents a counter cation and X ^c- represents a counter anion). A salt represented by the general formula (1c) is reacted.

(Wherein R ^1a , R ² , R ³ , R ⁴ , Y and X ^c- represent the same meaning as described above). X ^c- is perchlorate ion (ClO ₄ ^-), hexafluorophosphonate ion (PF ₆ ^-) or a tetrafluoroborate ion (BF ₄ ^-) is a process of claim 7. General formula (2)

(Wherein R ^1a represents ^a carboxyl group, X ^a represents ^a chlorine atom or a bromine atom) and a general formula (3)

(In the formula, R ² and R ⁴ each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkoxy group having 1 to 8 carbon atoms, or a substituted group. Represents an optionally substituted amino group, a hydroxyl group, a nitro group or a cyano group, R ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 8 carbon atoms, and Y represents an optionally substituted carbon. And a heterocyclic compound represented by the general formula (1a):

(Wherein R ^1b represents an acceptable salt of a carboxyl group. R ² , R ³ , R ⁴ and Y represent the same meaning as described above. X ^a− represents a chlorine ion or a bromine ion). Ruthenium complex is obtained, then general formula (4)

(In the formula, X ^b- represents a counter anion.) By reacting with an acid represented by the general formula (1b)

(Wherein R ^1a , R ² , R ³ , R ⁴ , Y and X ^b- represent the same meaning as described above), a ruthenium complex represented by general formula (5) is obtained.

( ^Wherein M ⁺ represents a counter cation and X ^c- represents a counter anion), and is reacted with a salt represented by the general formula (1c)

(Wherein R ^1a , R ² , R ³ , R ⁴ , Y and X ^c- represent the same meaning as described above). X ^b− is a halogen ion, perchlorate ion (ClO ₄ ⁻ ) or nitrate ion (NO ₃ ⁻ ), X ^c− is a perchlorate ion (ClO ₄ ⁻ ), hexafluorophosphonate ion (PF ₆ ⁻ ), tetrafluoroborate ion (BF 4 ^_-) is a process of claim 9. General formula (1d)

(In the formula, R ^1a represents a carboxyl group. R ² and R ⁴ each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted carbon number. R 1 represents an alkoxy group having 1 to 8 amino groups, an optionally substituted amino group, a hydroxyl group, a nitro group, or a cyano group, and R ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 8 carbon atoms. Represents an optionally substituted carbon atom or nitrogen atom. X ^d- represents a counter anion.) A ruthenium complex represented by 0.1 to 10 equivalents of the general formula (6a)

(Wherein R ^5a , R ^5b and R ^5c each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), or a general formula (6b)

(Wherein R ^5a , R ^5b , R ^5c and R ^5d each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). General formula (1e)

(Wherein R ^1c represents a carboxyl group or an ammonium salt thereof. R ² , R ³ , R ⁴ , Y and X ^d- represent the same meaning as described above). General formula (1)

(In the formula, R ¹ represents a carboxyl group or a chemically acceptable salt thereof. R ² and R ⁴ each independently represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 8 carbon atoms. Represents an optionally substituted alkoxy group having 1 to 8 carbon atoms, an optionally substituted amino group, a hydroxyl group, a nitro group, or a cyano group, and R ³ represents a hydrogen atom or an optionally substituted carbon number of 1. To Y. Y represents an optionally substituted carbon atom or nitrogen atom, X ⁻ represents a counter anion.) And dye-sensitized by adsorption of a ruthenium complex represented by an oxide semiconductor. Oxide semiconductor electrode.