JP2012188401A - Method of manufacturing metallic complex, and metallic complex composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a metallic complex having a target pyridine ligand in a high yield and in a high purity, wherein the metallic complex is produced as a suitable product utilization even if a by-product is generated.SOLUTION: In this method of manufacturing metallic complex represented by general formula (1), a base where pKa of conjugate acid is three or larger is added in the step or after the step introducing a ligand containing an acidic group out of LLand LL. Formula (1) is M(LL)(LL)(X)-CI. M shows a metal atom, LLis a specific bidentate ligand, LLis a specific bidentate ligand, X shows a specific ligand, m1, m2 and m3 show a specific integer, and CI shows a counter ion when a counter ion is required for neutralizing charge.

Description

  The present invention relates to a method for producing a metal complex and a metal complex composition.

  Metal complexes having a pyridine ligand are used in various fields as useful materials. A typical example is use as a coloring material for photoelectric conversion elements such as dye-sensitized solar cells (see Patent Documents 1 and 2).

On the other hand, when the production method of a ruthenium metal complex is seen, it is not the situation where research is fully progressing, The following nonpatent literatures 1 and 2 are mentioned as what disclosed the synthesis example.
In Non-Patent Document 1, 0.1M NaOHaq is added to a ruthenium dichloro complex (Ru (mcphen) ₂ Cl ₂ ) solution to dissociate the carboxyl group of the complex, and then NH ₄ NCSaq is added to add an NCS complex (Ru (mcphen). ) ₂ NCS ₂ ). Here, mcphen means 4-carboxy-1,10-phenanthroline. As a result, the target product is obtained in a corresponding yield. However, it is unclear whether it is effective for introducing a ligand other than phenanthroline, and it is unclear whether it is effective for a compound having a highly hydrophobic ligand in particular. In addition, when water derived from an aqueous sodium hydroxide solution enters the reaction system, there is a concern that decomposition of the target complex proceeds and by-products are generated.
In Non-Patent Document 2, dcbpy (4,4′-dicboxy-2) to Ru (bmipy) Cl ₃ (where bmipy represents 2,6-bis (1-methylbenzimidazol-2-yl) pyridine)). , 2'-bipyridine) is added to the DMF system. However, this synthesis example in which a bidentate ligand (bmipy) has already been introduced and a bidentate ligand is introduced where the remaining three coordinations are possible is different from this synthesis example (for example, a bidentate ligand is introduced). After that, it is not known whether the remaining four coordinations are useful suggestions for the synthesis of introducing bidentate ligands where possible. In the subsequent NCS group introduction step, no base is added, and the effect is not fully utilized. The same applies to Patent Document 3 (terpyridine ligand) and Patent Document 4 (quarterpyridine ligand) to which tetrabutylammonium hydroxide (TBAOH) is added because the valence of the ligand to be introduced is different. It is.

US Pat. No. 5,463,057 JP 2007-73289 A JP 2002-512729 A JP-A-2005-190875

Journal of Photochemistry and Photobiology A: Chemistry, 145 (2001) 117 Inorganic Chemistry, 35 (1996) 4779

  By applying a method as described in the above non-patent document, it is generally possible to synthesize a complex of a metal such as ruthenium having a specific pyridine ligand. However, considering the use as a coloring material of a photoelectric conversion element that requires a high-purity material, it is desirable to further increase the yield. In particular, the metal complex is not easily purified, and if there are by-products, a very complicated operation such as separation by HPLC is required. Even if a small amount can be dealt with, considering production on an industrial scale, it is desirable to prepare a product suitable for the desired product quality without using such an operation.

  Therefore, the present invention provides a production method for synthesizing a metal complex having a target pyridine ligand with high yield and high purity, and producing it as a product suitable for product use even when a by-product is produced. Objective. Another object of the present invention is to provide a metal complex composition containing a main component and subcomponents that can be obtained by the above production method and that is particularly suitable for use in products.

（Ｒ^１０１およびＲ^１０２はそれぞれ独立にカルボキシル基、スルホン酸基、ヒドロキシル基、ヒドロキサム酸基、ホスホリル基またはホスホニル基を表し、Ｒ^１０３およびＲ^１０４はそれぞれ独立に置換基を表し、Ｒ^１０５およびＲ^１０６はそれぞれ独立にアルキル基、アリール基および／またはヘテロ環基を表し、Ｌ^１およびＬ^２はそれぞれ独立にエテニレン基および／またはエチニレン基からなる共役鎖を表し、ａ１およびａ２はそれぞれ独立に０又は１の整数を表し、ｂ１およびｂ２はそれぞれ独立に０〜３の整数を表し、ｂ１が２以上のときＲ^１０３は同じでも異なっていてもよく互いに連結して環を形成してもよく、ｂ２が２以上のときＲ^１０４は同じでも異なっていてもよく互いに連結して環を形成してもよく、ｂ１およびｂ２が共に１以上のときＲ^１０３とＲ^１０４が連結して環を形成してもよく、ｄ１およびｄ２はそれぞれ独立に０〜５の整数を表し、ｄ３は０または１を表す。）

（Ｚａ、Ｚｂはそれぞれ独立に５または６員環を形成しうる非金属原子群を表す。）
（２）前記ＬＬ^１及びＬＬ^２の一方を導入する第１工程、ＬＬ^１及びＬＬ^２のうち他方の酸性基を含む配位子を導入する第２工程を含み、該第２工程で前記塩基を添加することを特徴とする（１）に記載の金属錯体の製造方法。
（３）前記塩基は水を実質的に含有しないかもしくは水を系内で生成しないものであることを特徴とする（１）又は（２）記載の金属錯体の製造方法。
（４）前記塩基がη_CH3Iにおいて６．７以下のものであることを特徴とする（１）〜（３）のいずれか１項に記載の金属錯体の製造方法。
（５）前記一般式（３）で表わされる配位子が酸性基を有することを特徴とする（１）〜（４）のいずれか１項に記載の金属錯体の製造方法。
（６）前記ＬＬ^１を第１工程で導入し、前記ＬＬ^２を第２工程で導入することを特徴とする（２）〜（５）のいずれか１項に記載の金属錯体の製造方法。
（７）（１）〜（６）のいずれか１項に記載の工程を経て金属錯体を含有する組成物を調製し、この成分を精製せずに適用することを特徴とする光電変換素子の製造方法。
（８）下記一般式（１）で表される化合物と下記一般式（４）で表わされる化合物とを含有する金属錯体組成物。

Ｍ（ＬＬ^１）_ｍ１（ＬＬ^２）_ｍ２（Ｘ）_ｍ３・ＣＩ ・・・（１）
Ｍ（ＬＬ^１）_ｍ１（ＬＬ^２）_ｍ２（Ｙ^１）（Ｙ^２）・ＣＩ ・・・（４）

・Ｍは金属原子を表し、
・ＬＬ^１は下記一般式（２）により表される２座の配位子であり、ＬＬ^２は下記一般式（３）により表される２座の配位子であり、ＬＬ^１とＬＬ^２は異なる構造を表し、ＬＬ^１及びＬＬ^２の少なくとも一方は酸性基を有し、
・Ｘはアシルオキシ基、アシルチオ基、チオアシルオキシ基、チオアシルチオ基、アシルアミノオキシ基、チオカルバメート基、ジチオカルバメート基、チオカルボネート基、ジチオカルボネート基、トリチオカルボネート基、アシル基、チオシアネート基、イソチオシアネート基、シアネート基、イソシアネート基、シアノ基、アルキルチオ基、アリールチオ基、アルコキシ基およびアリールオキシ基からなる群から選ばれた基で配位する１座または２座の配位子、あるいはハロゲン原子、カルボニル、ジアルキルケトン、１，３−ジケトン、カルボンアミド、チオカルボンアミド、またはチオ尿素からなる１座または２座の配位子を表し、
・ｍ１は１〜３の整数を表し、ｍ１が２以上のときＬＬ^１は同じでも異なっていてもよく、
・ｍ２は１又は２の整数を表し、ｍ２が２のときＬＬ^２は同じでも異なっていてもよく、
・ｍ３は０〜３の整数を表し、ｍ３が２のときＸは同じでも異なっていてもよく、またＸ同士が連結していてもよく、
・ＣＩは電荷を中和させるのに対イオンが必要な場合の対イオンを表す。

（Ｒ^１０１およびＲ^１０２はそれぞれ独立にカルボキシル基、スルホン酸基、ヒドロキシル基、ヒドロキサム酸基、ホスホリル基またはホスホニル基を表し、Ｒ^１０３およびＲ^１０４はそれぞれ独立に置換基を表し、Ｒ^１０５およびＲ^１０６はそれぞれ独立にアルキル基、アリール基および／またはヘテロ環基を表し、Ｌ^１およびＬ^２はそれぞれ独立にエテニレン基および／またはエチニレン基からなる共役鎖を表し、ａ１およびａ２はそれぞれ独立に０又は１の整数を表し、ｂ１およびｂ２はそれぞれ独立に０〜３の整数を表し、ｂ１が２以上のときＲ^１０３は同じでも異なっていてもよく互いに連結して環を形成してもよく、ｂ２が２以上のときＲ^１０４は同じでも異なっていてもよく互いに連結して環を形成してもよく、ｂ１およびｂ２が共に１以上のときＲ^１０３とＲ^１０４が連結して環を形成してもよく、ｄ１およびｄ２はそれぞれ独立に０〜５の整数を表し、ｄ３は０または１を表す。）

（Ｚａ、Ｚｂはそれぞれ独立に５または６員環を形成しうる非金属原子群を表す。）
（Ｙ^１は塩基の共役酸をＨ−ＡとするときのＡを表す。Ｙ^２はＹ^１と同一もしくは、Ｘと同一である。）
（９）（８）に記載の前記金属錯体組成物に含まれる前記一般式（１）で表わされる化合物及び前記一般式（４）で表わされる化合物を増感色素として適用した光電変換素子。 The above problems have been solved by the following means.
(1) In the production of the metal complex represented by the following general formula (1), a base having a pKa of a conjugate acid of 3 or more is introduced after the step of introducing a ligand containing an acidic group among LL ¹ and LL ^2. A method for producing a metal complex, comprising adding the metal complex.

M (LL ¹ ) _m1 (LL ² ) _m2 (X) _m3 · CI (1)

M represents a metal atom,
LL ¹ is a bidentate ligand represented by the following general formula (2), LL ² is a bidentate ligand represented by the following general formula (3), and LL ¹ and LL ² Represents different structures, at least one of LL ¹ and LL ² has an acidic group,
X is acyloxy group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, dithiocarbonate group, trithiocarbonate group, acyl group, thiocyanate group A monodentate or bidentate ligand coordinated by a group selected from the group consisting of an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a halogen atom Represents a monodentate or bidentate ligand consisting of an atom, carbonyl, dialkyl ketone, 1,3-diketone, carbonamide, thiocarbonamide, or thiourea;
· M1 represents an integer of 1 to 3, LL ¹ when m1 is 2 or more may be the same or different,
· M2 represents an integer of 0 to 2, LL ² when m2 is 2 may be the same or different,
M3 represents an integer of 0 to 3, and when m3 is 2, Xs may be the same or different, and Xs may be linked together,
CI represents a counter ion when a counter ion is required to neutralize the charge.

^{(R 101} and ^{R 102} are each independently a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, represents a phosphoryl group or a phosphonyl ^{group, R 103} and ^{R 104} each independently represents a ^{substituent, R 105} and R ¹⁰⁶ independently represents an alkyl group, an aryl group and / or a heterocyclic group, L ¹ and L ² each independently represent a conjugated chain composed of an ethenylene group and / or an ethynylene group, and a 1 and a 2 each independently represents 0 Or an integer of 1, b1 and b2 each independently represents an integer of 0 to 3, and when b1 is 2 or more, R ¹⁰³ may be the same or different and may be linked together to form a ring; When b2 is 2 or more, R ¹⁰⁴ may be the same or different and may be connected to each other to form a ring. Preliminary b2 are both 1 or more when linked is ^{R 103} and ^{R 104} may form a ring, d1 and d2 each independently represents an integer of 0 to 5, d3 represents 0 or 1.)

(Za and Zb each independently represents a nonmetallic atom group capable of forming a 5- or 6-membered ring.)
(2) a first step of introducing one of said LL ¹ and LL ^2, comprising a second step of introducing a ligand containing the other acid groups of LL ¹ and LL ^2, wherein the base in the second step The method for producing a metal complex according to (1), wherein
(3) The method for producing a metal complex according to (1) or (2), wherein the base does not substantially contain water or does not produce water in the system.
(4) The method for producing a metal complex according to any one of (1) to (3), wherein the base is 6.7 or less in η _CH3I .
(5) The method for producing a metal complex according to any one of (1) to (4), wherein the ligand represented by the general formula (3) has an acidic group.
(6) wherein the LL ¹ is introduced in the first step, the method of producing the metal complex according to any one of the and introducing the LL ² in the second step (2) to (5).
(7) A composition containing a metal complex is prepared through the process described in any one of (1) to (6), and the component is applied without purification. Production method.
(8) A metal complex composition comprising a compound represented by the following general formula (1) and a compound represented by the following general formula (4).

M (LL ¹ ) _m1 (LL ² ) _m2 (X) _m3 · CI (1)
M (LL ¹ ) _m1 (LL ² ) _m2 (Y ¹ ) (Y ² ) · CI (4)

M represents a metal atom,
LL ¹ is a bidentate ligand represented by the following general formula (2), LL ² is a bidentate ligand represented by the following general formula (3), and LL ¹ and LL ² Represents different structures, at least one of LL ¹ and LL ² has an acidic group,
X is acyloxy group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, dithiocarbonate group, trithiocarbonate group, acyl group, thiocyanate group A monodentate or bidentate ligand coordinated by a group selected from the group consisting of an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a halogen atom Represents a monodentate or bidentate ligand consisting of an atom, carbonyl, dialkyl ketone, 1,3-diketone, carbonamide, thiocarbonamide, or thiourea;
· M1 represents an integer of 1 to 3, LL ¹ when m1 is 2 or more may be the same or different,
· M2 represents an integer of 1 or 2, LL ² when m2 is 2 may be the same or different,
M3 represents an integer of 0 to 3, and when m3 is 2, Xs may be the same or different, and Xs may be linked together,
CI represents a counter ion when a counter ion is required to neutralize the charge.

^{(R 101} and ^{R 102} are each independently a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, represents a phosphoryl group or a phosphonyl ^{group, R 103} and ^{R 104} each independently represents a ^{substituent, R 105} and R ¹⁰⁶ independently represents an alkyl group, an aryl group and / or a heterocyclic group, L ¹ and L ² each independently represent a conjugated chain composed of an ethenylene group and / or an ethynylene group, and a 1 and a 2 each independently represents 0 Or an integer of 1, b1 and b2 each independently represents an integer of 0 to 3, and when b1 is 2 or more, R ¹⁰³ may be the same or different and may be linked together to form a ring; When b2 is 2 or more, R ¹⁰⁴ may be the same or different and may be connected to each other to form a ring. Preliminary b2 are both 1 or more when linked is ^{R 103} and ^{R 104} may form a ring, d1 and d2 each independently represents an integer of 0 to 5, d3 represents 0 or 1.)

(Za and Zb each independently represents a nonmetallic atom group capable of forming a 5- or 6-membered ring.)
(Y ¹ represents A when the conjugate acid of the base is H-A. Y ² is the same as Y ¹ or the same as X.)
(9) A photoelectric conversion element in which the compound represented by the general formula (1) and the compound represented by the general formula (4) contained in the metal complex composition according to (8) are applied as a sensitizing dye.

  According to the production method of the present invention, a metal complex having a target pyridine ligand is synthesized with high yield and high purity, and even if a by-product is produced, it can be produced as a product suitable for product use. it can. Moreover, the metal complex composition of this invention contains the main component and subcomponent which are especially suitable for product utilization which can be obtained with the said manufacturing method.

It is sectional drawing shown typically about one embodiment of the photoelectric conversion element manufactured by this invention.

In the present invention, in the production of a metal complex having a specific pyridine ligand, a specific base is added after the step of introducing a ligand containing an acidic group among LL ¹ and LL ² of the general formula (1). To do. Here, the pyridine ligand is meant to include a ligand (ligand) having a structure having a substituent in the residue of pyridine. The metal complex represented by the general formula (1) will be described in detail later. First, preferred embodiments of process conditions for introducing each ligand will be described. At this time, it is assumed that the ligand LL ¹ does not have an acidic group and the ligand LL ² has an acidic group. In addition, LL ¹ is introduced in the first step, and LL ² is introduced in the second step. The central metal is ruthenium. The reaction scheme of this embodiment is shown in Scheme A below. However, the present invention is not construed as being limited to this embodiment.

上記スキーム中、Ｘは塩素（原子数は１〜３）及び／又は任意の配位子を表わす。原子数を示していないが、任意の個数であってよい。ＬＬ^１’及びＬＬ^２’は、それぞれ、ＬＬ^１及びＬＬ^２をなす化合物を表わす。

In the above scheme, X represents chlorine (having 1 to 3 atoms) and / or any ligand. Although the number of atoms is not shown, it may be any number. LL ¹ ′ and LL ² ′ represent compounds forming LL ¹ and LL ² , respectively.

[First step]
The ruthenium raw material charged for the reaction is not particularly limited, and RuCl ₃ may be used as shown in Scheme A above. Examples of other ones accessible, and the like _{[Ru (p-cymene) cl} 2] 2. In the first step, this ruthenium raw material is mixed in a solvent together with the ligand compound LL ¹ ′. The mixing method is not particularly limited. Although the amount to be mixed is not particularly limited, it is preferable to add 0.5 to 2 mol of the ligand compound LL ¹ ′ with respect to 1 mol of ruthenium atom in the ruthenium raw material, and to add 0.8 to 1.5 mol. Is more preferable. When this amount is not less than the lower limit, a decrease in yield and an increase in impurities are effectively suppressed, and even when the amount is not more than the upper limit, a decrease in yield and an increase in impurities are effectively suppressed.

  The mixed solution is heated to allow the ligand introduction reaction to proceed, but the temperature at this time is not particularly limited, and is preferably 0 to 200 ° C, more preferably 30 to 180 ° C. In the present embodiment, this heating is also preferably performed using microwave irradiation, and for example, the technique disclosed in the pamphlet of WO 2004/099128 A1 can be applied. This reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. By doing in this way, mixing of the water etc. which cause the by-product mentioned later can be suppressed and prevented. In addition, the reaction is preferably performed in the dark. In particular, it is preferable to block the short wavelength side, and it is more preferable to block a wavelength of 500 nm or less.

Ligand compounds LL 1 to be applied as reaction substrate ^'may be appropriately selected depending on the structure of the ligand to be introduced. The ligand LL ¹ will be described in detail later in the description relating to the general formula (1). The synthesis of such a pyridine ligand compound may be performed by a conventional method, and for example, the information described in Non-Patent Documents 1 and 2 can be referred to.

  The reaction solvent applied to the first step is not particularly limited, and those generally applied to this type of reaction can be used. Preferably, aprotic polar solvents (amide solvents such as DMF, DMAc, NMP, DMEU, nitrile solvents such as acetonitrile, propionitrile, etc.), alcohol solvents, ketone solvents and combinations thereof are mentioned. be able to.

[Second step]
In the second step of this embodiment, the ligand compound LL ² ′ is added to the reaction solution containing the first intermediate a generated in the first step. In the present embodiment, LL ² ′ is a compound having an acidic group, and typically has a structure in which a carboxylic acid group is introduced into a pyridine ring. This ligand compound LL ² ′ may also be appropriately selected depending on the structure of the ligand to be introduced, and the ligand will be described later. The synthesis of such a pyridine ligand compound may be performed by a conventional method, and for example, the information described in Non-Patent Documents 1 and 2 can be referred to. At this time, it is preferable to heat the system in order to advance the introduction reaction of the ligand LL ² ′, and a preferred embodiment relating to this heating is the same as that described in the first step. The addition amount of the ligand compound LL ² ′ is not particularly limited. However, in terms of the relationship with 1 mol of ruthenium atoms in the ruthenium raw material, it is preferable to add 0.5 to 2 mol relative to this, 0.8 to 1 More preferably, 5 mol is added. When this amount is not less than the lower limit, a decrease in yield and an increase in impurities can be effectively suppressed, and even when the amount is not more than the upper limit, a decrease in yield and an increase in impurities can be effectively suppressed.

In the present embodiment, it is preferable to introduce a base simultaneously with the addition of the ligand compound LL ² ′. Here, “simultaneously” is not limited to being completely the same period, and may be within a range that does not impair the effects of the present invention. Preferably, a base coexists when the introduction reaction of LL ² ′ proceeds, and it is preferable that the addition of the base is completed by the time of the heating.

[base]
Here, the base (sometimes referred to as a base species) will be described. The base used in the present invention is preferably non-aqueous. Non-aqueous means that water is not introduced or generated in the reaction system. The thing which suppressed content of water as what does not introduce | transduce water is preferable, It is preferable that the presence rate of the water in a base is 20 mass% or less, and it is more preferable that it is 10 mass% or less. In addition, in this specification, a base (seed) is used with the meaning which shows the compound itself which makes a base, or the meaning of the composition containing this. The case where the water is contained includes a case where it is an aqueous solution or a case where it is a hydrate. On the other hand, when water is not generated, it is preferable that the base does not have a hydroxyl group. This is preferably avoided because it reacts with the hydrogen of the acidic group of the ligand compound to produce water.

  The addition amount of the base (seed) is not particularly limited, but is adjusted according to the number of acidic groups, and for example, 1 to 10 mol is preferably added to 1 mol of a ligand compound having two acidic groups. It is more preferable to add 5 to 5 mol. When this amount is not less than the lower limit, the effect of the present invention is sufficiently exerted, and when it is not more than the upper limit, a decrease in yield due to an increase in impurities is effectively suppressed.

  The base used in the present embodiment has a pKa of 3 or more, preferably 4 or more, and more preferably 5 or more. If this value is equal to or higher than the lower limit, the acidic group can be sufficiently dissociated, which is preferable in terms of improving the solubility of the target product. Although there is no particular upper limit, it is preferably 16 or less, and more preferably 12 or less. In this specification, unless otherwise specified, pKa refers to a value measured at 25 ° C., and a value published in “Chemical Handbook” (5th revised edition) edited by the Chemical Society of Japan can be referred to.

In this embodiment, n _CH3I that is an index of nucleophilicity of the base is preferably 6.7 or less, and more preferably 6.5 or less. Although there is no particular lower limit, it is practical that it is 2 or more. If the nucleophilicity is too high, the base itself coordinates instead of the target ligand, and the by-product represented by the general formula (4) tends to increase. It is preferable to do.

The above n _CH3I (nucleophilic parameter) is obtained from the rate constant of the reaction between methyl iodide and the nucleophile in methanol, and its definition and concept is “Graduate Lecture Organic Chemistry I. Molecular Structure and Reactions. Organometallic Chemistry "(edited by Ryoji Noyori, Masakatsu Shibasaki, Keisuke Suzuki, Junpei Tamao, Kazuhiro Nakasuji, Junichi Narazaka, Tokyo Chemical Doujin) p203," J. Am. Chem. Soc., 89, 1827 (1967) "( RGPearson, J.Songstad) can be found in detail. Below, examples of each base and their pKa and _nCH3I values are shown.

In the present embodiment, the base is introduced after the step of introducing the ligand having an acidic group, whereby a metal complex having the target pyridine ligand can be obtained with good yield. The reason for this can be explained as follows, although there are some unclear parts. A pyridine derivative having an acidic group has low solubility in a solvent. Therefore, the reaction speed of the ligand introduction process and the processes after the introduction is slow. Generally, after the same ligand introduction step, it is often carried out at a high temperature, and when the target reaction is slow, the intermediate is exposed for a long time at a high temperature, so that a side reaction such as decomposition proceeds, The purity decreases and the yield decreases accordingly. On the other hand, by applying the production method of the present invention, the solubility of the pyridine derivative having an acidic group and its introduced product is increased, so that the reaction rate is improved and a good yield is achieved by suppressing side reactions. It is assumed.
Unlike addition of a basic compound for the purpose of salt formation of a carboxyl group or hydrolysis of a carboxyl group introduced into a complex as an ester, in the present invention, the addition of a base dissolves intermediates and the like. It is understood that the improvement in the properties led to the above-mentioned specific effects.
In particular, when the ligand represented by the general formula (2) having a fat-soluble substituent is introduced, if the solubility of the intermediate after introduction of the substituent having a carboxyl group is in a low state, the dissolved concentration is It becomes unbalanced and it becomes difficult to control the number of ligands represented by the general formula (2). Therefore, when producing a metal complex having a specific structure of the present application, it is assumed that the great effect is achieved.

Furthermore, to give an important advantage in the present embodiment, since a specific base is selected and mixing of water is suppressed / prevented, even if a by-product in which the base is coordinated as described above is generated, it is used. It can be obtained as a metal complex composition having a favorable action in the application. Specifically, it is assumed that it is used as a dye of a photoelectric conversion element. For example, when a metal complex represented by the following general formula (4) is formed, it is represented by the general formula (1) which is the main component. Acts as a co-adsorbent for metal complexes.


M (LL ¹ ) _m1 (LL ² ) _m2 (Y ¹ ) (Y ² ) · CI (4)

Here, M, LL ¹ , _{m 1} , LL ² , _m ² , _and CI are synonymous with general formula (1) described later. However, it may coexist as a different compound from the compound represented by the general formula (1). Y ¹ represents an A at the time of the conjugate acid of the base with H-A. Y ² is the same as Y ¹ or the same as X. Y ¹ is preferably the same as the base added in the reaction. That is, it is preferable that pKa is 3 or more, pKa is 4 or more and n _CH3I is 6.7 or less, and pKa is 5 or more and n _CH3I is 6.5 or less. preferable.
From the viewpoint of the co-adsorption action as described above, the content of the metal complex represented by the general formula (4) is 0.05 to 0.05 in terms of HPLC area ratio with respect to the total amount with the metal complex represented by the general formula (1). It is preferably 20%, more preferably 0.1 to 10%. If this amount is not less than the lower limit, the effect of coexistence becomes prominent, and if it is not more than the upper limit, performance degradation due to a decrease in the amount of dye adsorbed can be effectively suppressed.

[Third step]
In this embodiment, in the subsequent third step, an NCS ligand is introduced (see reaction scheme A above). The substrate used at this time is not particularly limited, and examples thereof include ammonium thiocyanate, lithium thiocyanate, sodium thiocyanate, potassium thiocyanate, and tetrabutylammonium thiocyanate. At this time, it is preferable to heat the inside of the system in order to advance the introduction reaction of the ligand, and a preferred embodiment relating to this heating is the same as that described in the first step. The addition amount of the compound forming the NCS ligand is not particularly limited, but it is preferably 2 to 100 mol, more preferably 5 to 50 mol, per 1 mol of ruthenium atom in the ruthenium raw material. If this amount is not less than the lower limit, an increase in the amount of impurities and a decrease in yield are effectively suppressed, and if it is not more than the upper limit, an increase in the amount of impurities generated can be suppressed and it is difficult to remove the excess. It is preferable.

  In the production method of this embodiment, the yield of the target product (specifically, the metal complex represented by the general formula (1)) is preferably 40% or more, and preferably 50% or more. More preferred. Such a high yield not only provides good production efficiency, but also provides the product as a high-quality product without complicated purification operations when applied as a raw material for product production. It has great industrial advantages.

  For the method for synthesizing the metal complex dye, known production methods can be referred to, for example, Journal of Photochemistry and Photobiology A: Chemistry, 145 (2001) 117, Inorganic Chemistry, 35 (1996) 4779, WO2004 / 099128A1, JPA2001-139587, JPA2001-302558, JPA2007-302642, JPA2007-332098, JPB4377148, etc. can be referred to.

[Dye]
The metal complex represented by the general formula (1) prepared in the present embodiment can be used as a useful dye in a photoelectric conversion element. Hereinafter, preferred embodiments of the metal complex will be further described.

M (LL ¹ ) _m1 (LL ² ) _m2 (X) _m3 · CI (1)

(Metal atom M)
M represents a metal atom. M is preferably a metal capable of tetracoordinate or hexacoordinate, and more preferably Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn Or it is Zn. Particularly preferred is Ru, Os, Zn or Cu, and most preferred is Ru.

(Ligand LL ¹ )
The ligand LL ¹ is a bidentate ligand represented by the general formula (2). M1 representing the number of the ligand LL ¹ is an integer of 1 to 3, and is more preferably 1. When m1 is 2 or more, ligands LL ¹ may be the same or different. Note that the ligand LL ¹ does not have a phenanthroline structure. Moreover, when it is referred to as xxx group regarding a substituent, the xxx group may have an arbitrary substituent. Examples of optional substituents include preferred substituents of ^{R 103, R 104} to be described later.

R ¹⁰¹ and R ¹⁰² in the general formula (2) are each independently a carboxyl group, a sulfonic acid group, a hydroxyl group, or a hydroxamic acid group (preferably a hydroxamic acid group having 1 to 20 carbon atoms, such as —CONOHH, — CONCH ₃ OH etc.), phosphoryl groups (eg —OP (O) (OH) ₂ etc.) and phosphonyl groups (eg —P (O) (OH) ₂ etc.), preferably carboxyl groups and phosphonyl groups. More preferably, a carboxyl group is used. R ¹⁰¹ and R ¹⁰² may be substituted on any carbon atom on the pyridine ring.

In the general formula (2), R ¹⁰³ and R ¹⁰⁴ each independently represent a substituent, preferably an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl. , Heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), an alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), an alkynyl group ( Preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like, a cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, 4 -Methylcyclohexyl, etc.), aryl groups (preferably the number of carbon atoms To 26 aryl groups such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc., heterocyclic groups (preferably having 2 to 20 carbon atoms, such as 2 -Pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropyloxy, benzyl Oxy, etc.), aryloxy groups (preferably aryloxy groups having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), alkoxycarbonyl groups (preferably carbon atoms) A number 2 to 20 alkoxycarbonyl group such as ethoxy Rubonyl, 2-ethylhexyloxycarbonyl, etc.), amino group (preferably an amino group having 0-20 carbon atoms, such as amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.) A sulfonamide group (preferably a sulfonamide group having 0 to 20 carbon atoms, such as N, N-dimethylsulfonamide, N-phenylsulfonamide, etc.), an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms) For example, acetyloxy, benzoyloxy, etc.), carbamoyl groups (preferably carbamoyl groups having 1 to 20 carbon atoms, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl etc.), acylamino groups (preferably carbon atoms) 1-20 acylamino groups such as acetylamino, benzoy A cyano group, a cyano group, or a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), more preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group. , Alkoxycarbonyl group, amino group, acylamino group, cyano group or halogen atom, particularly preferably alkyl group, alkenyl group, heterocyclic group, alkoxy group, alkoxycarbonyl group, amino group, acylamino group or cyano group.

When the ligand LL ¹ contains an alkyl group, an alkenyl group or the like, these may be linear or branched, and may be substituted or unsubstituted. Further, when the ligand LL ¹ contains an aryl group, a heterocyclic group or the like, they may be monocyclic or condensed and may be substituted or unsubstituted.

In the general formula (2), R ¹⁰⁵ and R ¹⁰⁶ are each independently an alkyl group, an aryl group (preferably an aromatic group having 6 to 30 carbon atoms, such as phenyl, substituted phenyl, naphthyl, substituted naphthyl, etc.), Or a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms such as 2-thienyl, 5-2, 2′-bithienyl, 2-pyrrolyl, 2-imidazolyl, 1-imidazolyl, 4-pyridyl, 3 -Indolyl) and may further have a substituent. . ^Examples of the substituent that R ¹⁰⁵ and R ¹⁰⁶ may have include those listed as the substituents represented by R ¹⁰³ and R ¹⁰⁶ . R ¹⁰⁵ and R ¹⁰⁶ are preferably heterocyclic groups having 1 to 3 electron donating groups, more preferably thienyl having 1 to 3 electron donating groups. The electron donating group is an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an amino group, an acylamino group (preferred examples are the same as those for R ¹⁰³ and R ¹⁰⁴ ) or a hydroxyl group. Are more preferable, and an alkyl group, an alkynyl group, an alkoxy group, an amino group or a hydroxyl group is more preferable, and an alkyl group is particularly preferable. R ¹⁰⁵ and R ¹⁰⁶ may be the same or different, but are preferably the same.

R ¹⁰⁵ and R ¹⁰⁶ may be directly bonded to the pyridine ring. R ¹⁰⁵ and R ¹⁰⁶ may be bonded to the pyridine ring via one or both of L ¹ and L ² .

Here, L ¹ and L ² each independently represent a conjugated chain composed of an ethenylene group and / or an ethynylene group. When the ethenylene group has a substituent, the substituent is preferably an alkyl group, and more preferably methyl. L ¹ and L ² are each independently preferably a conjugated chain having 2 to 6 carbon atoms, more preferably ethenylene, butadienylene, ethynylene, butadienylene, methylethenylene or dimethylethenylene, particularly ethenylene or butadienylene. Preferably, ethenylene is most preferred. L ¹ and L ² may be the same or different, but are preferably the same. When the conjugated chain includes a carbon-carbon double bond, each double bond may be a trans isomer, a cis isomer, or a mixture thereof.
d1 and d2 each independently represent an integer of 0 to 5, preferably 0 to 3, more preferably 0 to 1. When there are a plurality of the above linking groups whose number is defined by d1 and d2, they may be different or the same.

d3 is 0 or 1.
a1 and a2 each independently represent an integer of 0 or 1.

b1 and b2 each independently represent an integer of 0 to 3, preferably an integer of 0 to 2. When b1 is 2 or more, R ¹⁰³ may be the same or different and may be connected to each other to form a ring. When b2 is 2 or more, R ¹⁰⁴ may be the same or different, and may be connected to each other to form a ring. When b1 and b2 are both 1 or more, R ¹⁰³ and R ¹⁰⁴ may be linked to form a ring. Preferable examples of the ring to be formed include a benzene ring, a pyridine ring, a thiophene ring, a pyrrole ring, a cyclohexane ring, a cyclopentane ring and the like.

When the sum of a1 and a2 is 1 or more and the ligand LL ¹ has at least one acidic group, m1 in the general formula (1) is preferably 2 or 3, and preferably 2. Is more preferable.

The ligand LL ¹ in the general formula (1) is preferably represented by the following general formula (4-1), (4-2) or (4-3).

In the general formulas (4-1) to (4-3), R ^{101 to} R ¹⁰⁴ , a1, a2, b1, b2, and d3 have the same meanings as those in the general formula (2).

In General Formula (4-2), R ¹⁰⁷ represents an acidic group, preferably a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group, or a phosphonyl group, more preferably a carboxyl group or a phosphoryl group. Yes, particularly preferably a carboxyl group.

In the general formula (4-2), R ¹⁰⁸ represents a substituent, preferably an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an amino group or an acylamino group (above preferred examples are R ¹⁰³ and R ¹⁰⁴ in the general formula (2)), and more preferably an alkyl group, an alkoxy group, an amino group, or an acylamino group.

In general formulas (4-1) and (4-2), R ^{121 to} R ¹²⁴ each independently represents hydrogen, an alkyl group, an alkenyl group, or an aryl group. Preferred examples of R ^{121 to} R ¹²⁴ are the same as the preferred examples of R ¹⁰³ and R ¹⁰⁴ in formula (2). R ^{121 to} R ¹²⁴ are more preferably an alkyl group or an aryl group, and more preferably an alkyl group. When R ^{121 to} R ¹²⁴ are alkyl groups, they may further have a substituent, and the substituent is preferably an alkoxy group, a cyano group, an alkoxycarbonyl group or a carbonamido group, particularly preferably an alkoxy group. R ¹²¹ and R ¹²² and R ¹²³ and R ¹²⁴ may be connected to each other to form a ring. As the ring to be formed, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring or the like is preferable.

In General Formulas (4-1) to (4-3), R ¹²⁵ , R ¹²⁶ , R ¹²⁷ and R ¹²⁸ each independently represent a substituent, preferably an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, An alkoxy group, an aryloxy group, an amino group, an acylamino group (preferred examples are the same as those in the case of R ¹⁰³ in the general formula (2)) or a hydroxyl group, and more preferably an alkyl group, an alkenyl group, and an alkynyl group. Group, an alkoxy group, an amino group or an acylamino group, particularly preferably an alkyl group or an alkynyl group.

In general formula (4-2), a3 represents the integer of 0-3, Preferably the integer of 0-2 is represented. When d3 is 0, a3 is preferably 1 or 2, and when d3 is 1, a3 is preferably 0 or 1. a3 is the ^{R 107} when two or more may be the same or different.

In general formulas (4-1) and (4-2), d1 and d2 each independently represent an integer of 0 to 4. When d1 is 1 or more, R ¹²⁵ may be linked to one or both of R ¹²¹ and R ¹²² to form a ring. The ring formed is preferably a piperidine ring or a pyrrolidine ring. When d1 is 2 or more, R ¹²⁵ may be the same or different, and may be linked to each other to form a ring. When d2 is 1 or more, R ¹²⁶ may be linked to one or both of R ¹²³ and R ¹²⁴ to form a ring. The ring formed is preferably a piperidine ring or a pyrrolidine ring. When d2 is 2 or more, R ¹²⁶ may be the same or different, and may be linked to each other to form a ring.

(Ligand LL ² )
In the general formula (1), the ligand LL ² represents a bidentate ligand. M2 representing the number of ligands LL ² is an integer of 0 to 2, and is preferably 0 or 1. m2 is the ligand LL ² when the two may be the same or different.

Ligand LL ² is a bidentate ligand represented by the following general formula (3).

一般式（３）中、Ｚａ、Ｚｂはそれぞれ独立に、５員環又は６員環を形成しうる非金属原子群を表す。形成される５員環又は６員環は置換されていても無置換でもよく、単環でも縮環していてもよい。ただし、一般式（３）で表される配位子がフェナントロリン構造を有するものであることはない。

In general formula (3), Za and Zb each independently represent a nonmetallic atom group capable of forming a 5-membered ring or a 6-membered ring. The formed 5-membered or 6-membered ring may be substituted or unsubstituted, and may be monocyclic or condensed. However, the ligand represented by the general formula (3) does not have a phenanthroline structure.

  Za and Zb are preferably a 5-membered or 6-membered ring having a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, and the 5-membered or 6-membered ring includes a hydrogen atom or a halogen atom. You may have. Za, Zb or Zc is preferably an aromatic ring. In the case of a 5-membered ring, an imidazole ring, an oxazole ring, a thiazole ring or a triazole ring is preferably formed. In the case of a 6-membered ring, a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferably formed. Of these, an imidazole ring or a pyridine ring is more preferable.

The ligand LL ² is preferably represented by any one of the following general formulas (3-1) to (3-5), and is represented by the general formulas 3-1, 3-2, and 3-4. Are more preferable, represented by general formulas 3-1 and 3-2, and more preferably represented by general formula 3-1.

なお、一般式（３−１）〜（３−５）中の置換基Ｒ^ＸＸＸは図示の都合上１つの環上に置換したように描写しているが、その環上にあっても、または図示されたものとは異なる環状に置換していてもよい。

Although the general formula (3-1) to (3-5) substituents R ^XXX in depicts as substituted on convenience one illustrated ring, even on the ring, or You may substitute in the cyclic | annular form different from what was shown in figure.

In general formulas (3-1) to (3-5), R ^{151 to} R ¹⁵⁵ each independently represent an acidic group. R ^{151 to} R ¹⁵⁵ are, for example, a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group (preferably a hydroxamic acid group having 1 to 20 carbon atoms, such as —CONHOH, —CONCH ₃ OH, etc.), a phosphoryl group ( For example, -OP (O) (OH) ₂ etc.) or a phosphonyl group (for example, -P (O) (OH) ₂ etc.) is represented. R ^{151 to} R ¹⁵⁸ are preferably a carboxyl group, a phosphoryl group, or a phosphonyl group, more preferably a carboxyl group or a phosphonyl group, and more preferably a carboxyl group.

In formulas (3-1) to (3-5), R ^{161 to} R ¹⁶⁵ each independently represent a substituent, preferably an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or an alkoxy group. , Aryloxy group, alkoxycarbonyl group, amino group, acyl group, sulfonamido group, acyloxy group, carbamoyl group, acylamino group, cyano group or halogen atom (above preferred examples are R ¹⁰³ and R ¹⁰⁴ in formula (2)) More preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group or a halogen atom, particularly preferably an alkyl group or an alkenyl group. An alkoxy group, an alkoxycarbonyl group, an amino group or an acylamino group That.

In General Formulas (3-1) to (3-5), R ¹⁷¹ and R ¹⁷² each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom. An aliphatic group and an aromatic group are preferable, and an aliphatic group having a carboxyl group is more preferable. When the ligand LL ² contains an alkyl group, an alkenyl group or the like, they may be linear or branched and may be unsubstituted substituted. Also, when the ligand LL ² contains an aryl group, a heterocyclic group, they may be a condensed ring may be monocyclic or be unsubstituted substituted.

In the general formulas (3-1) to (3-5), R ^{15X to} R ^16X may be bonded to any position on the ring. E1 to e5 each independently represents an integer of 0 to 4, preferably an integer of 1 to 2. e9 to e11 each independently represents an integer of 0 to 6, and e13 and e14 each independently represents an integer of 0 to 4. It is preferable that e9-e11, e13, e14 are each independently an integer of 0-3.

When e1 to e5 is 2 or more, R ^15X may be the same or different, and when e9 to e11, e13, e14 is 2 or more, R ^15X and R ^16X may be the same or different, and They may be linked to form a ring.

(Ligand X)
In the general formula (1), the ligand X represents a monodentate or bidentate ligand. M3 representing the number of ligands X represents an integer of 0 to 3, and m3 is preferably 1 or 2. When the ligand X is a monodentate ligand, m3 is preferably 2. When the ligand X is a bidentate ligand, m3 is preferably 1. When m3 is 2, the ligands X may be the same or different, and the ligands X may be linked to each other.

The ligand X is an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy, benzoyloxy, salicylic acid, glycyloxy, N, N-dimethylglycyloxy, oxalylene (—OC (O) C (O) O-) etc.), an acylthio group (preferably an acylthio group having 1 to 20 carbon atoms, such as acetylthio, benzoylthio, etc.), a thioacyloxy group (preferably a thioacyloxy group having 1 to 20 carbon atoms, For example, a thioacetyloxy group (CH ₃ C (S) O—) and the like)), a thioacylthio group (preferably a thioacylthio group having 1 to 20 carbon atoms, such as thioacetylthio (CH ₃ C (S) S—) , Thiobenzoylthio (PhC (S) S-) and the like)), acylaminooxy group (preferably an acetylene having 1 to 20 carbon atoms) Silaminooxy groups such as N-methylbenzoylaminooxy (PhC (O) N (CH ₃ ) O—), acetylaminooxy (CH ₃ C (O) NHO—) etc.)), thiocarbamate groups (preferably A thiocarbamate group having 1 to 20 carbon atoms such as N, N-diethylthiocarbamate), a dithiocarbamate group (preferably a dithiocarbamate group having 1 to 20 carbon atoms such as N-phenyldithiocarbamate, N, N-dimethyldithiocarbamate, N, N-diethyldithiocarbamate, N, N-dibenzyldithiocarbamate, etc.), a thiocarbonate group (preferably a thiocarbonate group having 1 to 20 carbon atoms, such as ethylthiocarbonate) Etc.), dithiocarbonate (preferably dithiocarbonate having 1 to 20 carbon atoms) Such as ethyl dithiocarbonate (C ₂ H ₅ OC (S) S—) and the like, trithiocarbonate group (preferably a trithiocarbonate group having 1 to 20 carbon atoms, such as ethyl trithiocarbonate) sulphonate _{(C 2 H 5 SC (S} ) S-) and the like), an acyl group (preferably an acyl group having 1 to 20 carbon atoms, e.g., acetyl, benzoyl, etc.), a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate Group, cyano group, alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms such as methanethio, ethylenedithio, etc.), arylthio group (preferably an arylthio group having 6 to 20 carbon atoms such as benzenethio, 1, 2 -Phenylenedithio etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as metho A monodentate or bidentate coordinated with a group selected from the group consisting of an aryloxy group (preferably an aryloxy group having 6 to 20 carbon atoms, such as phenoxy, quinoline-8-hydroxyl, etc.) A ligand, or a halogen atom (preferably a chlorine atom, a bromine atom, an iodine atom, etc.), a carbonyl (... CO), a dialkyl ketone (preferably a dialkyl ketone having 3 to 20 carbon atoms, such as acetone ((CH ₃ ) ₂ ). CO ...), etc.), 1,3-diketone (preferably having 3 to 20 carbon atoms 1,3-diketones, for example, acetylacetone _{(CH 3 C (O ...)} CH = C (O-) CH 3), tri fluoro acetylacetone _{(CF 3 C (O ...)} CH = C (O-) CH 3), dipivaloylmethane _{(tC 4 H 9 C (O} ...) CH = C (O-) tC 4 H ), Dibenzoylmethane (PhC (O ...) CH = C (O-) Ph), 3- chloro-acetylacetone _{(CH 3 C (O ...)} CCl = C (O-) CH 3) , etc.), carbonamido (preferably Is a carbonamide having 1 to 20 carbon atoms, such as CH ₃ N═C (CH ₃ ) O—, —OC (═NH) —C (═NH) O—, etc.), thiocarbonamide (preferably having carbon atoms) 1 to 20 thiocarbonamides, such as CH ₃ N═C (CH ₃ ) S—, or thiourea (preferably thioureas having 1 to 20 carbon atoms, such as NH (...) = C (S— ) NH ₂ , CH ₃ N (...) = C (S—) NHCH ₃ , (CH ₃ ) ₂ N—C (S...) N (CH ₃ ) _2, etc.). "..." indicates a coordination bond.

  The ligand X is preferably an acyloxy group, a thioacylthio group, an acylaminooxy group, a dithiocarbamate group, a dithiocarbonate group, a trithiocarbonate group, a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, A ligand coordinated by a group selected from the group consisting of an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a ligand consisting of a halogen atom, carbonyl, 1,3-diketone or thiourea, More preferably, a ligand coordinated with a group selected from the group consisting of acyloxy group, acylaminooxy group, dithiocarbamate group, thiocyanate group, isothiocyanate group, cyanate group, isocyanate group, cyano group or arylthio group, or Halogen atom, 1,3-dike Or a thiourea ligand, particularly preferably a ligand coordinated by a group selected from the group consisting of a dithiocarbamate group, a thiocyanate group, an isothiocyanate group, a cyanate group and an isocyanate group, or a halogen atom Or a ligand consisting of a 1,3-diketone, most preferably a ligand coordinated with a group selected from the group consisting of a dithiocarbamate group, a thiocyanate group and an isothiocyanate group, or a 1,3-diketone A ligand consisting of In addition, when the ligand X contains an alkyl group, an alkenyl group, an alkynyl group, an alkylene group or the like, these may be linear or branched, and may be substituted or unsubstituted. Moreover, when an aryl group, a heterocyclic group, a cycloalkyl group, etc. are included, they may be substituted or unsubstituted, and may be monocyclic or condensed.

  When the ligand X is a bidentate ligand, the ligand X is an acyloxy group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, dithio group. A ligand coordinated by a group selected from the group consisting of carbonate group, trithiocarbonate group, acyl group, alkylthio group, arylthio group, alkoxy group and aryloxy group, or 1,3-diketone, carbonamide , A thiocarbonamide, or a thiourea ligand is preferred. When the ligand X is a monodentate ligand, the ligand X is coordinated with a group selected from the group consisting of a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group, and an arylthio group. Or a ligand comprising a halogen atom, carbonyl, dialkyl ketone, or thiourea.

(Counterion CI)
CI in the general formula (2) represents a counter ion when a counter ion is required to neutralize the charge. In general, whether a dye is a cation or an anion, or has a net ionic charge, depends on the metal, ligand and substituent in the dye.

  The dye of the general formula (2) may be dissociated and have a negative charge because the substituent has a dissociable group. In this case, the entire charge of the dye of the general formula (2) is electrically neutralized by the counter ion CI.

  When the counter ion CI is a positive counter ion, for example, the counter ion CI is an inorganic or organic ammonium ion (for example, tetraalkylammonium ion, pyridinium ion, etc.), an alkali metal ion, or a proton.

  When the counter ion CI is a negative counter ion, for example, the counter ion CI may be an inorganic anion or an organic anion. For example, halogen anions (eg, fluoride ions, chloride ions, bromide ions, iodide ions, etc.), substituted aryl sulfonate ions (eg, p-toluene sulfonate ions, p-chlorobenzene sulfonate ions, etc.), aryl disulfones Acid ion (for example, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion, etc.), alkyl sulfate ion (for example, methyl sulfate ion, etc.), sulfate ion, thiocyanate ion Perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion and the like. Further, as the charge balance counter ion, an ionic polymer or another dye having a charge opposite to that of the dye may be used, and a metal complex ion (for example, bisbenzene-1,2-dithiolatonickel (III)) can also be used. is there.

(Bonding group)
The dye having the structure represented by the general formula (1) preferably has at least one suitable interlocking group for the surface of the semiconductor fine particles. It is more preferable to have 1 to 6 bonding groups in the dye, and it is particularly preferable to have 1 to 4 bonding groups. Carboxyl group, sulfonic acid group, hydroxyl group, hydroxamic acid group (for example, —CONHOH, etc.), phosphoryl group (for example, —OP (O) (OH) _2, etc.), phosphonyl group (for example, —P (O) (OH) _2, etc.) It is preferable that the dye has an acidic group (substituent having a dissociable proton).

  The dye represented by the general formula (1) has a maximum absorption wavelength in the solution of preferably 500 to 700 nm, and more preferably 500 to 650 nm.

  The dye represented by the general formula (1) can be prepared by a conventional method with reference to JP-A No. 2001-291534.

  Specific examples of the dye having the structure represented by the general formula (1) used in the present invention are shown below, but the present invention is not limited thereto. In addition, when the pigment | dye in the following specific example contains the ligand which has a proton dissociable group, this ligand may dissociate as needed and may discharge | release a proton.

[Photoelectric conversion element]
A preferred embodiment of the photoelectric conversion element will be described with reference to the schematic cross-sectional view of FIG.
As shown in FIG. 1, the photoelectric conversion element 10 includes a conductive support 1, a photosensitive layer 2, a charge transfer layer 3, and a counter electrode 4 arranged in that order on the conductive support 1. The conductive support 1 and the photoreceptor layer 2 constitute a light receiving electrode 5. The photoreceptor layer 2 has semiconductor fine particles 22 and a sensitizing dye (hereinafter also simply referred to as a dye) 21. At least a part of the sensitizing dye 21 is adsorbed on the semiconductor fine particles 22 (the sensitizing dye 21 is in an adsorption equilibrium state and may be partially present in the charge transfer layer 3). The charge transfer body layer 3 functions as, for example, a hole transport layer that transports holes. The conductive support 1 on which the photoreceptor layer 2 is formed functions as a working electrode in the photoelectric conversion element 10. The photoelectric conversion element 10 can be operated as the photoelectrochemical cell 100 by causing the external circuit 6 to work.

  The light receiving electrode 5 is an electrode composed of a conductive support 1 and a photosensitive layer 2 (semiconductor film) of semiconductor fine particles 22 adsorbed by a sensitizing dye 21 coated on the conductive support 1. Light incident on the photoreceptor layer 2 (semiconductor film) excites the dye. The excited dye has high energy electrons. Therefore, the electrons are transferred from the sensitizing dye 21 to the conduction band of the semiconductor fine particles 22 and reach the conductive support 1 by diffusion. At this time, the molecule of the sensitizing dye 21 is an oxidant. The electrons on the electrode return to the oxidant while working in the external circuit 6, thereby acting as the photoelectrochemical cell 100. At this time, the light receiving electrode 5 functions as a negative electrode of the battery.

  The photoreceptor layer 2 is composed of a porous semiconductor layer composed of a layer of semiconductor fine particles 22 to which a dye described later is adsorbed. This dye may be partially dissociated in the electrolyte. The photoreceptor layer 2 is designed according to the purpose and has a multilayer structure.

  As described above, since the photosensitive layer 2 includes the semiconductor fine particles 22 on which a specific dye is adsorbed, the light receiving sensitivity is high, and when used as the photoelectrochemical cell 100, high photoelectric conversion efficiency can be obtained. Furthermore, it has high durability.

(Charge transfer body)
The electrolyte composition used for the photoelectric conversion element 10 of the present invention includes, for example, a combination of iodine and iodide (for example, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, etc.) as an oxidation-reduction pair, alkyl Combinations of viologens (for example, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate) and reduced forms thereof, combinations of polyhydroxybenzenes (for example, hydroquinone, naphthohydroquinone, etc.) and oxidized forms thereof, bivalent and trivalent And a combination of iron complexes (for example, red blood salt and yellow blood salt). Of these, a combination of iodine and iodide is preferred.

  The cation of the iodine salt is preferably a 5-membered or 6-membered nitrogen-containing aromatic cation. In particular, when the compound represented by the general formula (1) is not an iodine salt, republished WO95 / 18456, JP-A-8-259543, Electrochemistry, Vol.65, No.11, p.923 (1997) It is preferable to use iodine salts such as pyridinium salts, imidazolium salts, and triazolium salts described in the above.

  The electrolyte composition used for the photoelectric conversion element 10 of the present invention preferably contains iodine together with the heterocyclic quaternary salt compound. The iodine content is preferably 0.1 to 20% by mass, and more preferably 0.5 to 5% by mass with respect to the entire electrolyte composition.

  The electrolyte composition used for the photoelectric conversion element 10 of the present invention may contain a solvent. The content of the solvent in the electrolyte composition is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 10% by mass or less based on the entire composition.

  As the solvent, those having a low viscosity and high ion mobility, a high dielectric constant and capable of increasing the effective carrier concentration, or both are preferable because they can exhibit excellent ion conductivity. As such a solvent, carbonate compounds (ethylene carbonate, propylene carbonate, etc.), heterocyclic compounds (3-methyl-2-oxazolidinone, etc.), ether compounds (dioxane, diethyl ether, etc.), chain ethers (ethylene glycol dialkyl ether, Propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc.), alcohols (methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, etc.), Polyhydric alcohols (ethylene glycol, propylene glycol, polyethylene glycol Nitrile compounds (acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, biscyanoethyl ether, etc.), esters (carboxylic esters, phosphate esters, phosphonates, etc.) , Cyclic esters such as lactone, sultone, sultin, etc.), aprotic polar solvent (dimethyl sulfoxide (DMSO), sulfolane, etc.), water, hydrous electrolyte described in JP-A No. 2002-110262, JP-A No. 2000-36332, Examples thereof include electrolyte solvents described in JP 2000-243134 A and republished WO / 00-54361. These solvents may be used as a mixture of two or more.

  Further, as the electrolyte of the present invention, a charge transport layer containing a hole conductor material may be used. As the hole conductor material, a 9,9'-spirobifluorene derivative or the like can be used.

  In addition, an electrode layer, a photoreceptor layer (photoelectric conversion layer), a charge transfer layer (hole transport layer), a conductive layer, and a counter electrode layer can be sequentially stacked. A hole transport material that functions as a p-type semiconductor can be used as the hole transport layer. As a preferred hole transport layer, for example, an inorganic or organic hole transport material can be used. Examples of the inorganic hole transport material include CuI, CuO, and NiO. Examples of the organic hole transport material include high molecular weight materials and low molecular weight materials, and examples of the high molecular weight materials include polyvinyl carbazole, polyamine, and organic polysilane. Moreover, as a low molecular weight thing, a triphenylamine derivative, a stilbene derivative, a hydrazone derivative, a phenamine derivative etc. are mentioned, for example. Among these, organic polysilanes are preferable because, unlike conventional carbon-based polymers, σ electrons delocalized along the main chain Si contribute to photoconductivity and have high hole mobility (Phys. Rev.). B, 35, 2818 (1987)).

(Conductive support)
As shown in FIG. 1, in the photoelectric conversion element of the present invention, a photosensitive layer 2 in which a sensitizing dye 21 is adsorbed on porous semiconductor fine particles 22 is formed on a conductive support 1. As will be described later, for example, the photoreceptor layer 2 can be produced by immersing the dispersion of semiconductor fine particles in the dye solution of the present invention after coating and drying on a conductive support.

As the conductive support 1, glass or a polymer material having a conductive film on the surface can be used as the support itself, such as metal. The conductive support 1 is preferably substantially transparent. Substantially transparent means that the light transmittance is 10% or more, preferably 50% or more, particularly preferably 80% or more. As the conductive support 1, a glass or polymer material coated with a conductive metal oxide can be used. The coating amount of the conductive metal oxide at this time is preferably 0.1 to 100 g per 1 m ² of the support of glass or polymer material. When a transparent conductive support is used, light is preferably incident from the support side. Examples of polymer materials that are preferably used include tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), Examples include polyarylate (PAR), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin, and brominated phenoxy. On the conductive support 1, the surface may be provided with a light management function. For example, an antireflection film in which high refractive films and low refractive index oxide films described in JP-A-2003-123859 are alternately laminated, The light guide function described in JP-A-2002-260746 is improved.

  In addition to this, a metal support can also be preferably used. Examples thereof include titanium, aluminum, copper, nickel, iron, stainless steel, gold, and silver. These metals may be alloys. More preferably, titanium, aluminum, and copper are preferable, and titanium and aluminum are particularly preferable.

(Semiconductor fine particles)
As shown in FIG. 1, in the photoelectric conversion element 10 of the present invention, a photosensitive layer 2 in which a sensitizing dye 21 is adsorbed on porous semiconductor fine particles 22 is formed on a conductive support 1. As will be described later, for example, the photoreceptor layer 2 can be produced by immersing the dispersion of the semiconductor fine particles 22 on the conductive support 1 and then immersing it in the above dye solution.

  As the semiconductor fine particles 22, metal chalcogenides (for example, oxides, sulfides, selenides, etc.) or perovskite fine particles are preferably used. Preferred examples of the metal chalcogenide include titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, tantalum oxide, cadmium sulfide, cadmium selenide, and the like. . Preferred perovskites include strontium titanate and calcium titanate. Of these, titanium oxide, zinc oxide, tin oxide, and tungsten oxide are particularly preferable.

In semiconductors, there are an n-type in which carriers involved in conduction are electrons and a p-type in which carriers are holes. In the element of the present invention, n-type is preferable in terms of conversion efficiency. In n-type semiconductors, in addition to intrinsic semiconductors (for example, intrinsic semiconductors) having no impurity level and equal carrier concentration due to conduction band electrons and valence band holes, the electron carrier concentration is reduced by structural defects derived from impurities. There are high n-type semiconductors. The n-type inorganic semiconductor preferably used in the present invention is TiO ₂ , TiSrO ₃ , ZnO, Nb ₂ O ₃ , SnO ₂ , WO ₃ , Si, CdS, CdSe, V ₂ O ₅ , ZnS, ZnSe, SnSe, KTaO. ₃ , FeS ₂ , PbS, InP, GaAs, CuInS ₂ , CuInSe ₂ and the like. Of these, the most preferred n-type semiconductors are TiO ₂ , ZnO, SnO ₂ , WO ₃ , and Nb ₂ O ₃ . A semiconductor material in which a plurality of these semiconductors are combined is also preferably used.

  The particle size of the semiconductor fine particles 22 is preferably such that the average particle size of the primary particles is 2 nm or more and 50 nm or less for the purpose of keeping the viscosity of the semiconductor fine particle dispersion high, and the average particle size of the primary particles is 2 nm or more and 30 nm or less. More preferably, it is an ultrafine particle. Two or more kinds of fine particles having different particle size distributions may be mixed. In this case, the average size of the small particles is preferably 5 nm or less. In addition, for the purpose of scattering incident light and improving the light capture rate, large particles having an average particle size exceeding 50 nm can be added to the ultrafine particles at a low content, or another layer can be applied. In this case, the content of the large particles is preferably 50% or less, more preferably 20% or less of the mass of particles having an average particle size of 50 nm or less. The average particle size of the large particles added and mixed for the above purpose is preferably 100 nm or more, and more preferably 250 nm or more. By controlling the average particle size as described above, the haze ratio can be 60% or more.

(Semiconductor fine particle dispersion)
In the present invention, the semiconductor fine particle dispersion having a solid content other than the semiconductor fine particles of 10% by mass or less of the whole of the semiconductor fine particle dispersion is applied to the conductive support 1 and heated appropriately. Quality semiconductor fine particle coating layer can be obtained.

  In addition to the sol-gel method described above, a method of preparing a semiconductor fine particle dispersion is a method of depositing fine particles in a solvent and using them as they are when synthesizing a semiconductor. Ultrafine particles are irradiated with ultrasonic waves. Or a method of mechanically pulverizing and grinding using a mill or a mortar. As the dispersion solvent, one or more of water and various organic solvents can be used. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, citronellol and terpineol, ketones such as acetone, esters such as ethyl acetate, dichloromethane, acetonitrile and the like.

The preferred thickness of the entire semiconductor fine particle layer is 0.1 μm to 100 μm. The thickness of the semiconductor fine particle layer is further preferably 1 μm to 30 μm, and more preferably 2 μm to 25 μm. The amount of the semiconductor fine particles supported per 1 m ² of the support is preferably 0.5 g to 400 g, and more preferably 5 g to 100 g. The method for forming the film by applying the fine particle dispersion is not particularly limited, and a known method may be applied as appropriate.

The coating amount of the semiconductor fine particles 22 per 1 m ² of the support is preferably 0.5 g to 500 g, more preferably 5 g to 100 g.

  In order to adsorb the sensitizing dye 21 to the semiconductor fine particles 22, it is preferable to immerse the well-dried semiconductor fine particles 22 in a dye adsorbing dye solution comprising the solution and the dye according to the present invention for a long time. The solution used for the dye solution for dye adsorption can be used without particular limitation as long as it can dissolve the sensitizing dye 21 according to the present invention. For example, ethanol, methanol, isopropanol, toluene, t-butanol, acetonitrile, acetone, n-butanol, dimethylformamide, dimethylacetamide and the like can be used. Among these, ethanol and toluene can be preferably used.

The total amount of the sensitizing dye 21 used is preferably from 0.01 mmol to 100 mmol, more preferably from 0.1 mmol to 50 mmol, and particularly preferably from 0.1 mmol to 10 mmol, per 1 m ² of the support. . In this case, the amount of the sensitizing dye 21 according to the present invention is preferably 5 mol% or more.

  Further, the adsorption amount of the sensitizing dye 21 to the semiconductor fine particles 22 is preferably 0.001 mmol to 1 mmol, more preferably 0.1 to 0.5 mmol, with respect to 1 g of the semiconductor fine particles.

  By using such a dye amount, a sensitizing effect in a semiconductor can be sufficiently obtained. On the other hand, when the amount of the dye is small, the sensitizing effect is insufficient, and when the amount of the dye is too large, the dye not attached to the semiconductor floats and causes the sensitizing effect to be reduced.

  The counter electrode 4 functions as a positive electrode of the photoelectrochemical cell. The counter electrode 4 is usually synonymous with the conductive support 1 described above, but a support for the counter electrode is not necessarily required in a configuration in which the strength is sufficiently maintained. However, having a support is advantageous in terms of hermeticity. Examples of the material for the counter electrode 4 include platinum, carbon, and conductive polymer. Preferable examples include platinum, carbon, and conductive polymer.

  The structure of the counter electrode 4 is preferably a structure having a high current collecting effect. Preferable examples include JP-A-10-505192.

  The light receiving electrode 5 may be a tandem type in order to increase the utilization rate of incident light. Preferred examples of the tandem type configuration include those described in JP-A Nos. 2000-90989 and 2002-90989.

  A light management function for efficiently performing light scattering and reflection inside the layer of the light receiving electrode 5 may be provided. Preferably, the thing of Unexamined-Japanese-Patent No. 2002-93476 is mentioned.

  It is preferable to form a short-circuit prevention layer between the conductive support 1 and the porous semiconductor fine particle layer in order to prevent a reverse current due to direct contact between the electrolyte and the electrode. Preferable examples include Japanese Patent Application Laid-Open No. 06-507999.

  In order to prevent contact between the light receiving electrode 5 and the counter electrode 4, it is preferable to use a spacer or a separator. A preferable example is JP-A No. 2001-283941.

  Cell and module sealing methods include polyisobutylene thermosetting resin, novolak resin, photo-curing (meth) acrylate resin, epoxy resin, ionomer resin, glass frit, method using aluminum alkoxide for alumina, low melting point glass paste It is preferable to use a laser melting method. When glass frit is used, powder glass mixed with acrylic resin as a binder may be used.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these.

<Example 1-1>
4,4′-bis {2- [5- (1-heptynyl) -2-thienyl] vinyl} -2,2′-bipyridine (1.38 g, 2.45 mmol) and dichloro (p-cymene) ruthenium (II ) A 100 ml solution of DMF (0.747 g, 1.22 mmol) in DMF was heated at 60 ° C. for 10 minutes under microwave (200 W) in a dark nitrogen atmosphere. Subsequently, 2,2′-bipyridine-4,4′-dicarboxylic acid (0.6 g, 2.46 mmol) and a base species: sodium acetate anhydride (1 g, 12.19 mmol) were added, and the mixture was stirred at 150 ° C. for 10 minutes. Heated. The temperature was cooled to 100 ° C., ammonium thiocyanate (8 g) was added, and the mixture was reacted at 120 ° C. for 10 minutes. The temperature was lowered to room temperature and DMF was removed in vacuo. 500 ml of water was added to the residue and immersed for 30 minutes. The insoluble material was collected and washed with water and diethyl ether. The crude product was dissolved in methanol together with TBAOH (tetrabutylammonium hydroxide), and purified with a column of Sephadex LH-20 (trade name, manufactured by Pharmacia Fine Chemicals) using methanol as the effluent. The product of the main layer was collected and concentrated, and 0.2M nitric acid was added to obtain a precipitate. The product was collected and dried in vacuum at room temperature, and then the exemplified dye Ru-7 (1.46 g, yield = 47.4%, HPLC purity = 98.6 area%) having the structure represented by the general formula (1). )

<Example 1-2>
4,4′-bis {2- [5- (1-heptynyl) -2-thienyl] vinyl} -2,2′-bipyridine (1.38 g, 2.45 mmol) and dichloro (p-cymene) ruthenium (II ) A 100 ml solution of DMF (0.747 g, 1.22 mmol) in DMF was heated at 60 ° C. for 10 minutes under microwave (200 W) in a dark nitrogen atmosphere. Subsequently, 2,2′-bipyridine-4,4′-dicarboxylic acid (0.6 g, 2.46 mmol) and base species: sodium hydroxide (0.197 g, 4.92 mmol) were added, and the mixture was stirred at 150 ° C. for 10 minutes. Heated. The temperature was cooled to 100 ° C., ammonium thiocyanate (8 g) was added, and the mixture was reacted at 120 ° C. for 10 minutes. The temperature was lowered to room temperature, 500 ml of water from which DMF was distilled off under vacuum was added to the residue, and the mixture was immersed for 30 minutes. The insoluble material was collected and washed with water and diethyl ether. The crude product was dissolved in methanol together with TBAOH (tetrabutylammonium hydroxide), and purified with a column of Sephadex LH-20 (trade name, manufactured by Pharmacia Fine Chemicals) using methanol as the effluent. The product of the main layer was collected and concentrated, and 0.2M nitric acid was added to obtain a precipitate. The product was collected, dried in vacuum at room temperature, and the exemplified dye Ru-7 (1.24 g, yield = 40.3%, HPLC purity = 98.2 area%) having the structure represented by the general formula (1). )
Examples carried out in the same manner except that the base species were changed are summarized in Table 1 below.

<Example 2-1>
Under a yellow light, 4,4′-bis (5-hexyl-2-thienyl) -2,2′-bipyridine (0.865 g, 1.77 mmol) and osmium hexaammonium diammonium (0.384 g, 0.87 mmol) Was dissolved in 20 ml of ethylene glycol and stirred at 170 ° C. for 3 hours under a nitrogen atmosphere. After cooling to room temperature, 20 ml of an aqueous solution of sodium hyposulfite (0.4 g, 2.2 mmol) was added and stirred. The deposited precipitate was separated by filtration, washed well with water and diethyl ether, and then vacuum-dried in the dark (osmium dichloroform, 0.75 g).
Triethylamine (0.269 g, 2.65 mmol), 2,2′-bipyridine-4,4′-dicarboxylic acid (0.213 g, 0.87 mmol), osmium dichloro-form (3013 ml) in 30 ml of ethanol under a light-shielded and nitrogen atmosphere 0.939 g, 0.74 mmol) was added, and the mixture was heated to reflux for 6 hours. A solution of ammonium hexafluorophosphate (0.3 g, 1.8 mmol) dissolved in 5 ml of water was added and cooled. Thereafter, ethanol was distilled off under reduced pressure, 0.25M hexafluorophosphoric acid was added to adjust the pH of the system to 2 or less, and the mixture was allowed to stand at 0 ° C. for 20 hours. The precipitated crystals were separated by filtration and washed with an aqueous solution adjusted to pH 1.5 with hexafluorophosphoric acid and diethyl ether. The crude product was dissolved in methanol together with TBAOH (tetrabutylammonium hydroxide), and purified with a column of Sephadex LH-20 (trade name, manufactured by Pharmacia Fine Chemicals) using methanol as the effluent. The product of the main layer was collected and concentrated, and 0.2M nitric acid was added to obtain a precipitate. The product was collected, dried in vacuum at room temperature, and then the exemplified dye Os-2 having a structure represented by the general formula (1) (0.527 g, yield = 40.1%, HPLC purity = 97.2 area%). )

<Comparative Example 1>
4,4′-bis {2- [5- (1-heptynyl) -2-thienyl] vinyl} -2,2′-bipyridine (1.38 g, 2.45 mmol) and dichloro (p-cymene) ruthenium (II ) A 100 ml solution of DMF (0.747 g, 1.22 mmol) in DMF was heated at 60 ° C. for 10 minutes under microwave (200 W) in a dark nitrogen atmosphere. Subsequently, 2,2′-bipyridine-4,4′-dicarboxylic acid (0.6 g, 2.46 mmol) was added and heated at 150 ° C. for 10 minutes. The temperature was cooled to 100 ° C., ammonium thiocyanate (8 g) was added, and the mixture was reacted at 120 ° C. for 10 minutes. The temperature was lowered to room temperature and DMF was removed in vacuo. 500 ml of water was added to the residue and immersed for 30 minutes. The insoluble material was collected and washed with water and diethyl ether. The crude product was dissolved in methanol together with TBAOH (tetrabutylammonium hydroxide), and purified with a column of Sephadex LH-20 (trade name, manufactured by Pharmacia Fine Chemicals) using methanol as the effluent. The product of the main layer was collected and concentrated, and 0.2M nitric acid was added to obtain a precipitate. The product was collected and dried under vacuum at room temperature, and then the exemplified dye Ru-7 (1.02 g, yield = 33.1%, HPLC purity = 88.3 area%) having the structure represented by the general formula (1). )

<Identification of by-products>
By-product in Example 1-1: Ru (LL ¹ ) (LL ² ) (CH ₃ COO) (NCS) (where LL ¹ is 4,4′-bis {2- [5- (1-heptynyl) 2-thienyl] vinyl} -2,2′-bipyridine, LL ² represents 2,2′-bipyridine-4,4′-dicarboxylic acid.) Was confirmed by HPLC / MS. The results were as follows.
Mass measured value (m / z); M ⁺ : 1023.1735 /
Mass calculated value (m / z); M ⁺ : 1023.1732 (C ₅₁ H ₄₇ N ₅ O ₆ RuS ₃ )
This result shows that it is a metal complex composition containing the compound which contains the base added by reaction as a ligand.

<Evaluation of battery characteristics>
1. Preparation of Titanium Dioxide Dispersion 15 g of titanium dioxide fine particles (Nippon Aerosil Co., Ltd., Degussa P-25), water 45 g, dispersant (Aldrich, Triron X −100) 1 g and 30 g of zirconia beads having a diameter of 0.5 mm (manufactured by Nikkato Co., Ltd.) were added, and dispersion treatment was performed at 1500 rpm for 2 hours using a sand grinder mill (manufactured by Imex). Zirconia beads were filtered off from the resulting dispersion. The average particle diameter of the titanium dioxide fine particles in the obtained dispersion was 2.5 μm. The particle size was measured with a master sizer (trade name) manufactured by MALVERN.

2. Preparation of Titanium Oxide Fine Particle Layer (Electrode A) Adsorbed with Dye 20 mm × 20 mm conductive glass plate coated with fluorine doped tin oxide (Asahi Glass Co., Ltd., TCO glass-U, surface resistance: about 30Ω / m ² ) was prepared, and an adhesive tape for spacers was applied to both ends (a portion having a width of 3 mm from the end) on the conductive layer side, and then the dispersion was applied onto the conductive layer using a glass rod. After application of the dispersion, the adhesive tape was peeled off and air-dried at room temperature for 1 day. Next, this semiconductor-coated glass plate was placed in an electric furnace (muffle furnace FP-32 type manufactured by Yamato Scientific Co., Ltd.) and baked at 450 ° C. for 30 minutes. The semiconductor-coated glass plate was taken out and cooled, and then immersed in an ethanol solution (concentration: 3 × 10 ⁻⁴ mol / L) of a pigment prepared using the base species shown in Table 1 at 40 ° C. for 3 hours. The semiconductor-coated glass plate on which the dye was adsorbed was immersed in 4-tert-butylpyridine for 15 minutes, then washed with ethanol and naturally dried to obtain a titanium oxide fine particle layer (electrode A) on which the dye was adsorbed. The thickness of the dye-sensitized titanium oxide fine particle layer of the electrode A was 10 μm, and the coating amount of the titanium oxide fine particles was 20 g / m ² . Moreover, the adsorption amount of the pigment | dye was in the range of 0.1-10 mmol / m < ² > according to the kind.

3. Production of Dye-Sensitized Solar Cell Dye-sensitized electrode A (20 mm × 20 mm) produced as described above was superimposed on platinum-deposited glass having the same size. Next, the electrolyte composition was impregnated into the gap between the two glasses using a capillary phenomenon, and the electrolyte was introduced into the titanium oxide electrode. Thus, as shown in FIG. 1, a conductive support 1 made of conductive glass (a conductive layer formed on a glass transparent substrate), a photoreceptor 2, a charge transfer body 3, and a counter electrode made of platinum. 4 and a glass transparent substrate (not shown) are laminated in order, and a glass sphere having a diameter of 25 μm is almost formed in a resin composition comprising Epicoat 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), a curing agent and a plastic paste. A dye-sensitized solar cell sealed with a uniformly dispersed sealant was produced. However, if the electrolyte composition has a high viscosity and it is difficult to impregnate the electrolyte composition using capillary action, the electrolyte composition is heated to 50 ° C. and applied to the titanium oxide electrode. After the electrode was placed under reduced pressure and the electrolyte composition sufficiently penetrated and the air in the electrode escaped, platinum-deposited glass (counter electrode) was overlaid to produce a dye-sensitized solar cell.

A dye-sensitized solar cell was manufactured by changing the dye and performing the above-described steps. As the electrolyte composition used for each dye-sensitized solar cell, a composition containing 98% by mass of the following heterocyclic quaternary salt compound and 2% by mass of iodine was used.

4). Measurement of photoelectric conversion efficiency Simulated sunlight that does not contain ultraviolet rays by passing light from a 500 W xenon lamp (manufactured by USHIO ELECTRIC CO., LTD.) Through an AM1.5 filter (manufactured by Oriel) and a sharp cut filter (Kenko L-37) Was generated. The intensity of this light was 70 mW / cm ² . This simulated sunlight was irradiated to a dye-sensitized solar cell at 50 ° C., and the generated electricity was measured with a current-voltage measuring device (Keutley SMU238 type). Further, the rate of decrease in conversion efficiency after storage at 85 ° C. for 1000 hours in a dark place was also measured. These results are shown in Table 1.
In addition, the fresh performance of the battery characteristics was evaluated as ◎ for those with 6% or more, ◯ for 5% or more and less than 6%, △ for 3% or more and less than 5%, and × for those with less than 3%. The rate of decrease in conversion efficiency after storage in the dark is less than 15% for ◎, 15% to less than 25% ○, 25% to less than 35% △, 35% or more × evaluated.

From the above results, the target metal complex compound can be obtained with good yield and purity according to the production method of the present invention. And when the preparation raw material is used as a coloring material for photoelectric conversion elements, it turns out that a very favorable performance is exhibited in a battery characteristic.

DESCRIPTION OF SYMBOLS 1 Conductive support body 2 Photosensitive layer 21 Sensitizing dye 22 Semiconductor fine particle 3 Charge transfer body layer 4 Counter electrode 5 Photosensitive electrode 6 External circuit 10 Photoelectric conversion element 100 Photoelectrochemical cell

Claims (9)

In the production of the metal complex represented by the following general formula (1), a base having a pKa of a conjugate acid of 3 or more is added after the step of introducing a ligand containing an acidic group among LL ¹ and LL ^2. The manufacturing method of the metal complex characterized by these.

M (LL ¹ ) _m1 (LL ² ) _m2 (X) _m3 · CI (1)

M represents a metal atom,
LL ¹ is a bidentate ligand represented by the following general formula (2), and LL ² is a bidentate ligand represented by the following general formula (3) , LL ¹ and LL ² represent different structures, at least one of LL ¹ and LL ² has an acidic group,
X is acyloxy group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, dithiocarbonate group, trithiocarbonate group, acyl group, thiocyanate group A monodentate or bidentate ligand coordinated by a group selected from the group consisting of an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a halogen atom Represents a monodentate or bidentate ligand consisting of an atom, carbonyl, dialkyl ketone, 1,3-diketone, carbonamide, thiocarbonamide, or thiourea;
· M1 represents an integer of 1 to 3, LL ¹ when m1 is 2 or more may be the same or different,
· M2 represents an integer of 0 to 2, LL ² when m2 is 2 may be the same or different,
M3 represents an integer of 0 to 3, and when m3 is 2, Xs may be the same or different, and Xs may be linked together,
CI represents a counter ion when a counter ion is required to neutralize the charge.

^{(R 101} and ^{R 102} are each independently a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, represents a phosphoryl group or a phosphonyl ^{group, R 103} and ^{R 104} each independently represents a ^{substituent, R 105} and R ¹⁰⁶ independently represents an alkyl group, an aryl group and / or a heterocyclic group, L ¹ and L ² each independently represent a conjugated chain composed of an ethenylene group and / or an ethynylene group, and a 1 and a 2 each independently represents 0 Or an integer of 1, b1 and b2 each independently represents an integer of 0 to 3, and when b1 is 2 or more, R ¹⁰³ may be the same or different and may be linked together to form a ring; When b2 is 2 or more, R ¹⁰⁴ may be the same or different and may be connected to each other to form a ring. Preliminary b2 are both 1 or more when linked is ^{R 103} and ^{R 104} may form a ring, d1 and d2 each independently represents an integer of 0 to 5, d3 represents 0 or 1.)

(Za and Zb each independently represents a nonmetallic atom group capable of forming a 5- or 6-membered ring.) Comprising a second step of introducing a ligand containing a first step, the other acidic group of LL ¹ and LL ² for introducing one of said LL ¹ and LL ^2, adding the base in the second step The method for producing a metal complex according to claim 1.   The method for producing a metal complex according to claim 1 or 2, wherein the base does not substantially contain water or does not generate water in the system. The method for producing a metal complex according to any one of claims 1 to 3, wherein the base is 6.7 _CH3I or less in _ηCH3I .   The method for producing a metal complex according to any one of claims 1 to 4, wherein the ligand represented by the general formula (3) has an acidic group. The method for producing a metal complex according to any one of claims 2 to 5, wherein the LL ¹ is introduced in a first step and the LL ² is introduced in a second step.   The manufacturing method of the photoelectric conversion element characterized by preparing the composition containing a metal complex through the process of any one of Claims 1-6, and applying without refine | purifying this component. A metal complex composition comprising a compound represented by the following general formula (1) and a compound represented by the following general formula (4).

M (LL ¹ ) _m1 (LL ² ) _m2 (X) _m3 · CI (1)
M (LL ¹ ) _m1 (LL ² ) _m2 (Y ¹ ) (Y ² ) · CI (4)

M represents a metal atom,
LL ¹ is a bidentate ligand represented by the following general formula (2), and LL ² is a bidentate ligand represented by the following general formula (3) , LL ¹ and LL ² represent different structures, at least one of LL ¹ and LL ² has an acidic group,
X is acyloxy group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, dithiocarbonate group, trithiocarbonate group, acyl group, thiocyanate group A monodentate or bidentate ligand coordinated by a group selected from the group consisting of an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a halogen atom Represents a monodentate or bidentate ligand consisting of an atom, carbonyl, dialkyl ketone, 1,3-diketone, carbonamide, thiocarbonamide, or thiourea;
· M1 represents an integer of 1 to 3, LL ¹ when m1 is 2 or more may be the same or different,
· M2 represents an integer of 1 or 2, LL ² when m2 is 2 may be the same or different,
M3 represents an integer of 0 to 3, and when m3 is 2, Xs may be the same or different, and Xs may be linked together,
CI represents a counter ion when a counter ion is required to neutralize the charge.

^{(R 101} and ^{R 102} are each independently a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, represents a phosphoryl group or a phosphonyl ^{group, R 103} and ^{R 104} each independently represents a ^{substituent, R 105} and R ¹⁰⁶ independently represents an alkyl group, an aryl group and / or a heterocyclic group, L ¹ and L ² each independently represent a conjugated chain composed of an ethenylene group and / or an ethynylene group, and a 1 and a 2 each independently represents 0 Or an integer of 1, b1 and b2 each independently represents an integer of 0 to 3, and when b1 is 2 or more, R ¹⁰³ may be the same or different and may be linked together to form a ring; When b2 is 2 or more, R ¹⁰⁴ may be the same or different and may be connected to each other to form a ring. Preliminary b2 are both 1 or more when linked is ^{R 103} and ^{R 104} may form a ring, d1 and d2 each independently represents an integer of 0 to 5, d3 represents 0 or 1.)

(Za and Zb each independently represents a nonmetallic atom group capable of forming a 5- or 6-membered ring.)
(Y ¹ represents A when the conjugate acid of the base is H-A. Y ² is the same as Y ¹ or the same as X.)   The photoelectric conversion element which applied the compound represented by the said General formula (1) contained in the said metal complex composition of Claim 8 and the compound represented by the said General formula (4) as a sensitizing dye.

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