JP2012062256A - Ditetraazaporphyrin-based compound, and dye-sensitized solar cell using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound having the absorption maximum in a near infrared region, and allowing high photoelectric conversion efficiency as a sensitizing dye, and to provide a dye-sensitized solar cell using the compound as the sensitizing dye.SOLUTION: There is provided the ditetraazaporphyrin-based compound containing a substituent having an acrylic acid residue at the terminal. Furthermore, there is provided the dye-sensitized solar cell using the compound as the sensitizing dye.

Description

The present invention relates to a novel ditetraazaporphyrin-based compound having an absorption maximum in the near infrared region, and a dye-sensitized solar cell using this compound as a sensitizing dye. Specifically, in a dye-sensitized solar cell, the present invention relates to a novel ditetraazaporphyrin-based compound that efficiently absorbs solar energy over the near-infrared region and a dye-sensitized solar cell having high photoelectric conversion efficiency using the same.

In recent years, interest in energy problems has increased, and research on solar cells that can efficiently convert sunlight into electricity has become active as clean alternative energy. Some have already been put into practical use, and silicon-based solar cells using amorphous silicon or polycrystalline silicon have begun to spread. However, these silicon-based solar cells are expensive to manufacture, and it is difficult to supply high-purity silicon inexpensively and in large quantities. Accordingly, research on a new type of solar cell that replaces a silicon-based solar cell is underway, and one of them is a dye-sensitized solar cell.
Dye-sensitized solar cells are silicon-based solar cells that have a relatively low manufacturing cost, that oxide semiconductors such as titanium oxide can be used as raw materials without being purified with high purity, and that equipment used for manufacturing can be inexpensive. Has many advantages. In addition, dye-sensitized solar cells can be applied to fields with high design that make use of the color tone of dyes, and are expected to be put to practical use in various fields such as exteriors of mobile electronic devices, clothing, and walls of buildings. It is expected to spread as a next-generation solar cell (Patent Document 1).
The dye-sensitized solar cell includes an anode, a cathode, and an electrolyte, as in a normal battery. The cathode is a base material made of transparent conductive glass, and an oxide thin film formed on the surface thereof. And a structure in which a specific sensitizing dye is adsorbed to the oxide thin film electrode.
In the dye-sensitized solar cell, it is known that the photoelectric conversion efficiency largely depends on the sensitizing dye. As the sensitizing dye, for example, a dye called “N719” or a ruthenium complex called “black dye” Is known (Non-Patent Documents 1 and 2).
Although such a dye-sensitized solar cell using a ruthenium complex exhibits high photoelectric conversion efficiency, the photoelectric conversion efficiency is low compared to a silicon-based solar cell, durability is not sufficient, and the ruthenium complex is Since it is an expensive and rare metal, there is a problem to be solved such as an increase in cost.

In order to solve such a problem, a search for a new sensitizing dye that achieves both a photoelectric conversion efficiency higher than that of a ruthenium complex and a low cost has been actively conducted. For example, having a wide absorption region, having a high extinction coefficient, having a carboxyl group for adsorption to titanium oxide, that the LUMO level of the dye is on the higher energy side than the conduction band of titanium oxide, the dye There is a demand for a sensitizing dye having characteristics such as that the HOMO level of this is on the lower energy side than the redox potential of iodine.
In particular, coumarin dyes, indoline dyes and the like have been actively developed as sensitizing dyes, and photoelectric conversion characteristics comparable to ruthenium complexes have been reported (Patent Document 2 and Non-Patent Document 3). However, the main absorption band of these sensitizing dyes is in the visible light region between 400 and 700 nm, and there is a problem that light in the near infrared region exceeding 700 nm is hardly utilized.

For this problem, for example, a dye-sensitized solar cell using a squarylium-based dye or a dye-sensitized solar cell using a heptamethine-cyanine-based dye has been disclosed in order to more efficiently use light in the long wavelength region. (Non-Patent Documents 4 and 5). Furthermore, from the viewpoint of efficiently using sunlight, as a sensitizing dye based on a long conjugated system having absorption in the visible region and a skeleton having appropriate solubility in a solvent, absorption called the Q band is increased to 750 nm. A dye-sensitized solar cell using a phthalocyanine-based dye is also disclosed (Non-patent Document 6 and Patent Document 3).
As an example, a phthalocyanine dye is proposed that introduces three tert-butyl groups with large steric hindrance into the phthalocyanine skeleton to improve the solubility and suppress the recombination of charges while suppressing the association and aggregation of the dyes. (Non-Patent Document 6). However, these phthalocyanine dyes only sensitize absorption in the region between 600 and 750 nm and cannot be said to have an efficient sensitizing action in the near-infrared region. In terms of conversion efficiency and durability, it was not sufficient.
As described above, various sensitizing dyes as constituent materials of the dye-sensitized solar cell have been studied. However, the sensitizing dye has an effective sensitizing action in the near infrared region of 700 nm or more and also has durability. The pigment has not been developed yet.

U.S. Pat. No. 4,927,721 JP 2007-287694 A JP 9-199744 A

J. Am. Chem. Soc., 115, 1993, 6382 J. Am. Chem. Soc., 123, 2001, 1613 Angew.Chem.Int.Ed., 47,1923,2008 J. Am. Chem. Soc., 129, 2007, 10320 Chem. Lett., 2008, 37, 176 Angew.Chem., Int.Ed., 46,313,2007

An object of the present invention is to provide a novel compound having an absorption maximum in the near infrared region and enabling high photoelectric conversion efficiency as a sensitizing dye. Another object is to provide a dye-sensitized solar cell using the compound as a sensitizing dye.

［式中、Ｍ１及びＭ２はそれぞれ独立に金属原子、金属化合物または２個の水素原子を表し、Ｑ０は無置換のベンゼン環または無置換のナフタレン環を表し、Ｑ１〜Ｑ６は、それぞれ独立に置換基を有しても良いベンゼン環または置換基を有しても良いナフタレン環を表す。但し、Ｑ1〜Ｑ６上の置換基の１又は２個は一般式（１−１）で表される置換基を有する。］

［式中、Ｙは酸素原子又は硫黄原子を表し、Ｘ１〜Ｘ２はそれぞれ独立に水素原子、未置換のアルキル基を表し、Ｘ３〜Ｘ４はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、カルボキシル基、置換または未置換のアルキル基、置換または未置換のアリール基を表し、ｌは０〜２の整数を表し、ｍは０または１の整数を表す。ただし、ｌが１又は２のいずれかの整数である場合は、ｍは１の整数を表す。］
As a result of intensive studies to solve the above problems, the present inventors have found that a ditetraazaporphyrin-based compound having a substituent having a specific structure having an acrylic acid residue at the terminal can solve the above problems. Thus, the present invention has been completed.

That is, the present invention
(I) It relates to a ditetraazaporphyrin-based compound represented by the following general formula (1).

[Wherein, M1 and M2 each independently represent a metal atom, a metal compound or two hydrogen atoms, Q0 represents an unsubstituted benzene ring or an unsubstituted naphthalene ring, and Q1 to Q6 each independently represents a substituent. A benzene ring which may have a group or a naphthalene ring which may have a substituent is represented. However, one or two of the substituents on Q1 to Q6 have a substituent represented by the general formula (1-1). ]

[Wherein Y represents an oxygen atom or a sulfur atom, X1 to X2 each independently represent a hydrogen atom or an unsubstituted alkyl group, and X3 to X4 each independently represent a hydrogen atom, a halogen atom, a nitro group or a cyano group. , A carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, l represents an integer of 0 to 2, and m represents an integer of 0 or 1. However, when l is an integer of 1 or 2, m represents an integer of 1. ]

The present invention also provides:
(Ii) In the above formula (1), the substituent of Q1 to Q6 is a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted The ditetraazaporphyrin-based compound according to (i), which is an aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, or a substituted amino group.

(Iii) The ditetraazaporphyrin-based compound according to (i) or (ii), wherein Q1 to Q6 in Formula (1) are the same.

further,

(Iv) The present invention relates to a dye-sensitized solar cell, wherein the ditetraazaporphyrin-based compound according to any one of (i) to (iii) is used as a sensitizing dye.

By using the ditetraazaporphyrin-based compound of the present invention as a sensitizing dye, it becomes possible to provide a dye-sensitized solar cell having superior photoelectric conversion efficiency and wavelength absorption characteristics as compared with conventional sensitizing dyes. It was.

The best mode for carrying out the present invention will be described below.

The ditetraazaporphyrin-based compound of the present invention is a ditetraazaporphyrin-based compound represented by the following general formula (1), and a ditetraazaporphyrin-based compound having a substituent having a specific structure having an acrylic acid residue at the terminal. A compound.
The ditetraazaporphyrin-based compound constituting the structural unit of the present invention has a broad absorption band in the near infrared region due to exciton interaction because the tetraazaporphyrin-based compound has a planar binuclear structure.

［式中、Ｍ１及びＭ２はそれぞれ独立に金属原子、金属化合物または２個の水素原子を表し、Ｑ０は無置換のベンゼン環または無置換のナフタレン環を表し、Ｑ１〜Ｑ６は、それぞれ独立に置換基を有しても良いベンゼン環または置換基を有しても良いナフタレン環を表す。但し、Ｑ1〜Ｑ６上の置換基の１又は２個は一般式（１−１）で表される置換基を有する。］

［式中、Ｙは酸素原子又は硫黄原子を表し、Ｘ１〜Ｘ２はそれぞれ独立に水素原子、未置換のアルキル基を表し、Ｘ３〜Ｘ４はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、カルボキシル基、置換または未置換のアルキル基、置換または未置換のアリール基を表し、ｌは０〜２の整数を表し、ｍは０または１の整数を表す。ただし、ｌが１又は２のいずれかの整数である場合は、ｍは１の整数を表す。］
Hereinafter, the ditetraazaporphyrin-based compound in the present invention will be described more specifically.

[Wherein, M1 and M2 each independently represent a metal atom, a metal compound or two hydrogen atoms, Q0 represents an unsubstituted benzene ring or an unsubstituted naphthalene ring, and Q1 to Q6 each independently represents a substituent. A benzene ring which may have a group or a naphthalene ring which may have a substituent is represented. However, one or two of the substituents on Q1 to Q6 have a substituent represented by the general formula (1-1). ]

[Wherein Y represents an oxygen atom or a sulfur atom, X1 to X2 each independently represent a hydrogen atom or an unsubstituted alkyl group, and X3 to X4 each independently represent a hydrogen atom, a halogen atom, a nitro group or a cyano group. , A carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, l represents an integer of 0 to 2, and m represents an integer of 0 or 1. However, when l is an integer of 1 or 2, m represents an integer of 1. ]

In the present specification, the aryl group represents a carbocyclic aromatic group such as a phenyl group or a naphthyl group, for example, a heterocyclic aromatic group such as a furyl group, a thienyl group or a pyridyl group.

In the ditetraazaporphyrin-based compound represented by the general formula (1), Q1 to Q6 each independently represent a benzene ring that may have a substituent or a naphthalene ring that may have a substituent.

As the substituent in the above, each independently, a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 24 carbon atoms, or 4 to 30 carbon atoms. Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group having 4 to 30 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 24 carbon atoms, substituted or unsubstituted arylthio group having 4 to 30 carbon atoms Group, a substituted amino group having 1 to 20 carbon atoms, and the like.

More preferably, each independently, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 16 carbon atoms, or a carbon number A substituted or unsubstituted aryl group having 6 to 26 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 26 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 16 carbon atoms, a substituted or unsubstituted group having 6 to 26 carbon atoms Examples thereof include a substituted arylthio group and a substituted amino group having 1 to 14 carbon atoms.

More preferably, each independently, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a carbon number A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted group having 6 to 20 carbon atoms Examples thereof include a substituted arylthio group and a substituted amino group having 1 to 12 carbon atoms.

Specific examples of the substituents of Q1 to Q6 in the general formula (1) are not particularly limited, but each independently represents a hydrogen atom or a halogen atom, for example, a fluorine atom, a chlorine atom, or a bromine atom Are mentioned,

Examples of the unsubstituted alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, Neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group, 1 -Methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, 1-ethyloctyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-hexylheptyl group N-tetradecyl group, n-pentadecyl group, 1-heptyloctyl group, n-hexadecyl group, n-heptadecyl group, 1-octylnonyl group, n-octadecyl group, 1-nonyldecyl group, 1-decylundecyl group, n- Examples thereof include linear, branched or cyclic alkyl groups consisting of only carbon atoms and hydrogen atoms such as eicosyl group, n-docosyl group, n-tetracosyl group, 1-adamantyl group, cyclopentyl group, cyclohexyl group and norbornyl group.

  Specific examples of the alkyl group having a substituent include, for example, methoxymethyl group, ethoxymethyl group, n-butoxymethyl group, n-hexyloxymethyl group, (2-ethylbutyloxy) methyl group, and n-octyl. Oxymethyl group, n-decyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxyethyl group, 2-n- Pentyloxyethyl group, 2-n-hexyloxyethyl group, 2- (2′-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2- (2 ′ -Ethylhexyloxy) ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group, 2-n-tetradecyloxyethyl group 2-cyclohexyloxyethyl group, 2-methoxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3- (n-butoxy) propyl group, 3- (n-pentyloxy) propyl group, 3- (n-hexyloxy) propyl group, 3- (2′-ethylbutoxy) propyl group, 3- (n-octyloxy) propyl group, 3- (2 ′ -Ethylhexyloxy) propyl group, 3- (n-decyloxy) propyl group, 3- (n-dodecyloxy) propyl group, 3- (n-tetradecyloxy) propyl group, 3-cyclohexyloxypropyl group, 4-methoxy Butyl group, 4-ethoxybutyl group, 4-n-propoxybutyl group, 4-isopropoxybutyl group, 4-n-butoxyb Group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 4-n-decyloxybutyl group, 4-n-dodecyloxybutyl group, 5-methoxypentyl group, 5-ethoxypentyl group 5-n-propoxypentyl group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyloxyhexyl group, 6-n-decyloxyhexyl group, 4- Methoxycyclohexyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group, 10-methoxydecyl group, 10-n-butoxydecyl group, 12-ethoxydodecyl group, 12-isopropoxidedecyl group, An alkyl group having an alkyloxy group, such as a tetrahydrofurfuryl group;

For example, (2-methoxyethoxy) methyl group, (2-ethoxyethoxy) methyl group, (2-n-butyloxyethoxy) methyl group, (2-n-hexyloxyethoxy) methyl group, (3-methoxypropyloxy) ) Methyl group, (3-ethoxypropyloxy) methyl group, (3-n-butyloxypropyloxy) methyl group, (3-n-pentyloxypropyloxy) methyl group, (4-methoxybutyloxy) methyl group, (6-methoxyhexyloxy) methyl group, (10-ethoxydecyloxy) methyl group, 2- (2′-methoxyethoxy) ethyl group, 2- (2′-ethoxyethoxy) ethyl group, 2- (2′-) n-butoxyethoxy) ethyl group, 3- (2′-ethoxyethoxy) propyl group, 3- (2′-methoxypropyloxy) propyl group, Alkyl groups having an alkyloxyalkyloxy group, such as-(2'-isopropyloxypropyloxy) propyl group, 3- (3'-methoxypropyloxy) propyl group, and 3- (3'-ethoxypropyloxy) propyl group .
For example, benzyloxymethyl group, 2-benzyloxyethyl group, 2-phenethyloxyethyl group, 2- (4′-methylbenzyloxy) ethyl group, 2- (2′-methylbenzyloxy) ethyl group, 2- ( 4′-fluorobenzyloxy) ethyl group, 2- (4′-chlorobenzyloxy) ethyl group, 3-benzyloxypropyl group, 3- (4′-methoxybenzyloxy) propyl group, 4-benzyloxybutyl group, Alkyl groups having an aralkyloxy group, such as a 2- (benzyloxymethoxy) ethyl group and a 2- (4′-methylbenzyloxymethoxy) ethyl group;
For example, phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-methoxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 4-chlorophenyl Oxymethyl group, 2-chlorophenyloxymethyl group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′- Methoxyphenyloxy) ethyl group, 2- (4′-chlorophenyloxy) ethyl group, 2- (4′-bromophenyloxy) ethyl group, 2- (1′-naphthyloxy) ethyl group, 2- (2′-) Naphthyloxy) ethyl group, 3-phenyloxypropyl group, 3- (2′-naphthyloxy) propyl group, 4-phenyl Nyloxybutyl group, 4- (2′-ethylphenyloxy) butyl group, 5- (4′-tert-butylphenyloxy) pentyl group, 6- (2′-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl Group, 10-phenyloxydecyl group, 10- (3′-chlorophenyloxy) decyl group, 2- (2′-phenyloxyethoxy) ethyl group, 3- (2′-phenyloxyethoxy) propyl group, 4- ( An alkyl group having an aryloxy group, such as a 2'-phenyloxyethoxy) butyl group;

  For example, n-butylthiomethyl group, n-hexylthiomethyl group, 2-methylthioethyl group, 2-ethylthioethyl group, 2-n-butylthioethyl group, 2-n-hexylthioethyl group, 2-n -Octylthioethyl group, 2-n-decylthioethyl group, 3-methylthiopropyl group, 3-ethylthiopropyl group, 3-n-butylthiopropyl group, 4-ethylthiobutyl group, 4-n-propylthio Alkylthio groups such as butyl group, 4-n-butylthiobutyl group, 5-ethylthiopentyl group, 6-methylthiohexyl group, 6-ethylthiohexyl group, 6-n-butylthiohexyl group, and 8-methylthiooctyl group An alkyl group having

For example, fluoromethyl group, 3-fluoropropyl group, 6-fluorohexyl group, 8-fluorooctyl group, trifluoromethyl group, 1,1-dihydro-perfluoroethyl group, 1,1-dihydro-perfluoro-n -Propyl group, 1,1,3-trihydro-perfluoro-n-propyl group, 2-hydro-perfluoro-2-propyl group, 1,1-dihydro-perfluoro-n-butyl group, 1,1- Dihydro-perfluoro-n-pentyl group, 1,1-dihydro-perfluoro-n-hexyl group, 6-fluorohexyl group, 4-fluorocyclohexyl group, 1,1-dihydro-perfluoro-n-octyl group, 1,1-dihydro-perfluoro-n-decyl group, 1,1-dihydro-perfluoro-n-dodecyl group, 1,1-dihydro-perf group O-n-tetradecyl group, 1,1-dihydro-perfluoro-n-hexadecyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, 2 , 2-bis (trifluoromethyl) propyl group, dichloromethyl group, 2-chloroethyl group, 3-chloropropyl group, 4-chlorocyclohexyl group, 7-chloroheptyl group, 8-chlorooctyl group, 2,2,2 An alkyl group having a halogen atom, such as a trichloroethyl group;
For example, fluoromethyloxymethyl group, 3-fluoro-n-propyloxymethyl group, 6-fluoro-n-hexyloxymethyl group, trifluoromethyloxymethyl group, 1,1-dihydro-perfluoroethyloxymethyl group, 1,1-dihydro-perfluoro-n-propyloxymethyl group, 2-hydro-perfluoro-2-propyloxymethyl group, 1,1-dihydro-perfluoro-n-butyloxymethyl group, 1,1- Dihydro-perfluoro-n-pentyloxymethyl group, 1,1-dihydro-perfluoro-n-hexyloxymethyl group, 1,1-dihydro-perfluoro-n-octyloxymethyl group, 1,1-dihydride Rhoperfluoro-n-decyloxymethyl group, 1,1-dihydro-perfluoro-n-tetradecylo Cymethyl group, 2,2-bis (trifluoromethyl) propyloxymethyl group, 3-chloro-n-propyloxymethyl group, 2- (8-fluoro-n-octyloxy) ethyl group, 2- (1,1 -Dihydro-perfluoroethyloxy) ethyl group, 2- (1,1,3-trihydro-perfluoro-n-propyloxy) ethyl group, 2- (1,1-dihydro-perfluoro-n-pentyloxy) An ethyl group, a 2- (6-fluoro-n-hexyloxy) ethyl group, a 2- (1,1-dihydro-perfluoro-n-octyloxy) ethyl group, a 3- (4-fluorocyclohexyloxy) propyl group, 3- (1,1-dihydro-perfluoroethyloxy) propyl group, 3- (1,1-dihydro-perfluoro-n-dodecyloxy) propyl group, 4- (par Fluoro-n-hexyloxy) butyl group, 4- (1,1-dihydro-perfluoroethyloxy) butyl group, 6- (2-chloroethyloxy) hexyl group, 6- (1,1-dihydro-perfluoro group) An alkyl group having a halogenoalkyloxy group, such as an ethyloxy) hexyl group;

For example, phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-ethylphenyloxymethyl group, 4-n-propylphenyloxymethyl group, 4 -N-butylphenyloxymethyl group, 4-tert-butylphenyloxymethyl group, 4-n-hexylphenyloxymethyl group, 4-n-octylphenyloxymethyl group, 4-n-decylphenyloxymethyl group, 4 -Methoxyphenyloxymethyl group, 4-ethoxyphenyloxymethyl group, 4-butoxyphenyloxymethyl group, 4-n-pentyloxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 3-fluorophenyloxymethyl group, 2-Fluorophenyloxymethyl 3,4-difluorophenyloxymethyl group, 4-chlorophenyloxymethyl group, 2-chlorophenyloxymethyl group, 4-phenylphenyloxymethyl group, 1-naphthyloxymethyl group, 2-naphthyloxymethyl group, 2-furyl Oxymethyl group, 1-phenyloxyethyl group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′- n-hexylphenyloxy) ethyl group, 2- (4′-methoxyphenyloxy) ethyl group, 2- (4′-n-butoxyphenyloxy) ethyl group, 2- (4′-fluorophenyloxy) ethyl group, 2- (4′-chlorophenyloxy) ethyl group, 2- (4′-bromophenyloxy) ethyl group, 2- (1′-naphthyloxy) Til group, 2- (2'-naphthyloxy) ethyl group, 2-phenyloxypropyl group, 3-phenyloxypropyl group, 3- (4'-methylphenyloxy) propyl group, 3- (2'-naphthyloxy) ) Propyl group, 4-phenyloxybutyl group, 4- (2′-ethylphenyloxy) butyl group, 4-phenyloxypentyl group, 5-phenyloxypentyl group, 5- (4′-tert-butylphenyloxy) Pentyl group, 6-phenyloxyhexyl group, 6- (2′-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 10- (3′-methylphenyloxy) decyl group, etc. And an alkyl group having an aryloxy group.

The substituted or unsubstituted alkoxy group is an alkoxy group which may have a substituent similar to the alkyl group listed above, and an alkoxy group derived from the alkyl group shown as a specific example of the alkyl group is Can be mentioned.

Examples of the unsubstituted aryl group include a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 1-pyrenyl group, 2- A pyrenyl group, a 2-perylenyl group, a 3-perylenyl group, a 2-fluoranthenyl group, a 3-fluoranthenyl group, a 7-fluoranthenyl group, and an 8-fluoranthenyl group.

Specific examples of the aryl group having a substituent include, for example, 1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4- (4′-tert-butylcyclohexyl) phenyl group. , Aryl groups having an alkyl group such as a 3-cyclohexylphenyl group, a 2-cyclohexylphenyl group, a 4-ethyl-1-naphthyl group, a 6-n-butyl-2-naphthyl group, and a 2,4-dimethylphenyl group.
For example, 4-methoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 3-isopropoxyphenyl group, Such as 2-isopropoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-methyl-5-methoxyphenyl group, 2-phenyloxyphenyl group, etc. An aryl group having an alkoxy group and an aryloxy group;
For example, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 2,6-diphenylphenyl group, 4- (2′-naphthyl) phenyl group, 2-phenyl-1-naphthyl group, 1- Aryl groups having an aryl group such as a phenyl-2-naphthyl group and a 7-phenyl-1-pyrenyl group;
For example, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group Aryl groups having a halogen atom such as 2-methyl-3-chlorophenyl group, 2-methoxy-4-fluorophenyl group, 2-fluoro-4-methoxyphenyl group.
Furthermore, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-perfluoroethylphenyl group, 4-methylthiophenyl Group, 4-ethylthiophenyl group, 4-cyanophenyl group, 3-cyanophenyl group and the like.

The substituted or unsubstituted aryloxy group is an aryloxy group which may have the same substituent as the above-mentioned aryl group, and is shown as a specific example of the above-mentioned substituted aryl group. Examples thereof include a substituted or unsubstituted aryloxy group derived from a substituent.

The substituted or unsubstituted alkylthio group is an alkylthio group which may have a substituent similar to the alkyl group listed above, and an alkylthio group derived from the alkyl group shown as a specific example of the alkyl group is Can be mentioned.

The substituted or unsubstituted arylthio group is an arylthio group which may have the same substituent as the above-mentioned aryl group, and is derived from the substituents shown as specific examples of the substituted aryl groups listed above. Substituted or unsubstituted arylthio groups.

Examples of the substituted amino group include N-methylamino group, N-ethylamino group, Nn-butylamino group, N-cyclohexylamino group, Nn-octylamino group, Nn-decylamino group and the like. An amino group having an alkyl group.
For example, N-benzylamino group, N-phenylamino group, N- (3-methylphenyl) amino group, N- (4-methylphenyl) amino group, N- (4-n-butylphenyl) amino group, N -(4-methoxyphenyl) amino group, N- (3-fluorophenyl) amino group, N- (4-chlorophenyl) amino group, N- (1-naphthyl) amino group, N- (2-naphthyl) amino group An amino group having an aralkyl group or an aryl group, such as
For example, N, N-dimethylamino group, N, N-diethylamino group, N, N-di-n-butylamino group, N, N-di-n-hexylamino group, N, N-di-n-octyl Amino group, N, N-di-n-decylamino group, N, N-di-n-dodecylamino group, N-methyl-N-ethylamino group, N-ethyl-Nn-butylamino group, N- Alkyl groups or aralkyl groups such as methyl-N-phenylamino group, N-ethyl-N-phenylamino group, Nn-butyl-N-phenylamino group, or disubstituted amino groups;
For example, N, N-diphenylamino group, N, N-di (3-methylphenyl) amino group, N, N-di (4-methylphenyl) amino group, N, N-di (4-ethylphenyl) amino Group, N, N-di (4-tert-butylphenyl) amino group, N, N-di (4-n-hexylphenyl) amino group, N, N-di (4-methoxyphenyl) amino group, N, N-di (4-ethoxyphenyl) amino group, N, N-di (4-n-butoxyphenyl) amino group, N, N-di (4-n-hexyloxyphenyl) amino group, N, N-di (1-naphthyl) amino group, N, N-di (2-naphthyl) amino group, N-phenyl-N- (3-methylphenyl) amino group, N-phenyl-N- (4-methylphenyl) amino group N-phenyl-N- (4-octylphenyl) Mino group, N-phenyl-N- (4-methoxyphenyl) amino group, N-phenyl-N- (4-ethoxyphenyl) amino group, N-phenyl-N- (4-n-hexyloxyphenyl) amino group N-phenyl-N- (4-fluorophenyl) amino group, N-phenyl-N- (1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) amino group, N-phenyl-N— An amino group disubstituted by an aryl group such as (3-phenylphenyl) amino group and N-phenyl-N- (4-phenylphenyl group) can be used.

［式中、Ｙは酸素原子又は硫黄原子を表し、Ｘ１〜Ｘ２はそれぞれ独立に水素原子、未置換のアルキル基を表し、Ｘ３〜Ｘ４はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、カルボキシル基、置換または未置換のアルキル基、置換または未置換のアリール基を表し、ｌは０〜２の整数を表し、ｍは０または１の整数を表す。ただし、ｌが１又は２のいずれかの整数である場合は、ｍは１の整数を表す。］ However, in the general formula (1), one or two of the substituents on Q1 to Q6 are groups represented by the following general formula (1-1) having an acrylic acid residue at the end (hereinafter referred to as “ The specific substituent L ”is referred to as a substituent.

[Wherein Y represents an oxygen atom or a sulfur atom, X1 to X2 each independently represent a hydrogen atom or an unsubstituted alkyl group, and X3 to X4 each independently represent a hydrogen atom, a halogen atom, a nitro group or a cyano group. , A carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, l represents an integer of 0 to 2, and m represents an integer of 0 or 1. However, when l is an integer of 1 or 2, m represents an integer of 1. ]

In the specific substituent L represented by the general formula (1-1), examples of X1 to X2 include a hydrogen atom and an unsubstituted alkyl group having 1 to 24 carbon atoms.
More preferably, a hydrogen atom and a C1-C18 unsubstituted alkyl group are mentioned each independently.
More preferably, a hydrogen atom and a C1-C16 unsubstituted alkyl group are mentioned each independently.

Specific examples of X1 to X2 in the general formula (1-1) are not particularly limited, but each independently represents a hydrogen atom or an unsubstituted alkyl group, for example, the general formula (1) The linear, branched or cyclic alkyl group which consists only of the carbon atom and the hydrogen atom which were shown as a specific example of the substituent of Q1-Q6 in is mentioned.
In the specific substituent L represented by the general formula (1-1), X3 to X4 are each independently a hydrogen atom, a nitro group, a cyano group, a carboxyl group, a halogen atom, a substituted or non-substituted group having 1 to 24 carbon atoms. Examples thereof include a substituted alkyl group and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
More preferably, each independently, a hydrogen atom, a nitro group, a cyano group, a carboxyl group, a fluorine atom, a chlorine atom, a bromine atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substitution having 4 to 24 carbon atoms Or an unsubstituted aryl group is mentioned.
More preferably, each independently, a hydrogen atom, a nitro group, a cyano group, a carboxyl group, a fluorine atom, a chlorine atom, a bromine atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substitution having 6 to 16 carbon atoms. Or an unsubstituted aryl group is mentioned.
Specific examples of X3 to X4 in the general formula (1-1) are not particularly limited, but independently, as the hydrogen atom and the halogen atom, for example, a fluorine atom, a chlorine atom, and a bromine atom are Named,

Examples of the unsubstituted alkyl group include linear, branched or cyclic alkyl groups composed of only carbon atoms and hydrogen atoms, which are shown as specific examples of the substituents Q1 to Q6 in the general formula (1). It is done.

Specific examples of the alkyl group having a substituent include, for example, methoxymethyl group, ethoxymethyl group, n-butoxymethyl group, n-hexyloxymethyl group, (2-ethylbutyloxy) methyl group, and n-octyl. Oxymethyl group, n-decyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxyethyl group, 2-n- Pentyloxyethyl group, 2-n-hexyloxyethyl group, 2- (2′-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2- (2 ′ -Ethylhexyloxy) ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group, 2-n-tetradecyloxyethyl group 2-cyclohexyloxyethyl group, 2-methoxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3- (n-butoxy) propyl group, 3- (n-pentyloxy) propyl group, 3- (n-hexyloxy) propyl group, 3- (2′-ethylbutoxy) propyl group, 3- (n-octyloxy) propyl group, 3- (2 ′ -Ethylhexyloxy) propyl group, 3- (n-decyloxy) propyl group, 3- (n-dodecyloxy) propyl group, 3- (n-tetradecyloxy) propyl group, 3-cyclohexyloxypropyl group, 4-methoxy Butyl group, 4-ethoxybutyl group, 4-n-propoxybutyl group, 4-isopropoxybutyl group, 4-n-butoxyb Group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 4-n-decyloxybutyl group, 4-n-dodecyloxybutyl group, 5-methoxypentyl group, 5-ethoxypentyl group 5-n-propoxypentyl group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyloxyhexyl group, 6-n-decyloxyhexyl group, 4- Methoxycyclohexyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group, 10-methoxydecyl group, 10-n-butoxydecyl group, 12-ethoxydodecyl group, 12-isopropoxidedecyl group, An alkyl group having an alkyloxy group, such as a tetrahydrofurfuryl group;

For example, fluoromethyl group, 3-fluoropropyl group, 6-fluorohexyl group, 8-fluorooctyl group, trifluoromethyl group, 1,1-dihydro-perfluoroethyl group, 1,1-dihydro-perfluoro-n -Propyl group, 1,1,3-trihydro-perfluoro-n-propyl group, 2-hydro-perfluoro-2-propyl group, 1,1-dihydro-perfluoro-n-butyl group, 1,1- Dihydro-perfluoro-n-pentyl group, 1,1-dihydro-perfluoro-n-hexyl group, 6-fluorohexyl group, 4-fluorocyclohexyl group, 1,1-dihydro-perfluoro-n-octyl group, 1,1-dihydro-perfluoro-n-decyl group, 1,1-dihydro-perfluoro-n-dodecyl group, 1,1-dihydro-perf group O-n-tetradecyl group, 1,1-dihydro-perfluoro-n-hexadecyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, 2 , 2-bis (trifluoromethyl) propyl group, dichloromethyl group, 2-chloroethyl group, 3-chloropropyl group, 4-chlorocyclohexyl group, 7-chloroheptyl group, 8-chlorooctyl group, 2,2,2 -Alkyl groups having a halogen atom such as a trichloroethyl group.

As an unsubstituted aryl group, the unsubstituted aryl group shown as a specific example of the substituent of Q1-Q6 in the said General formula (1) is mentioned, for example.

Specific examples of the aryl group having a substituent include, for example, 1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4- (4′-tert-butylcyclohexyl) phenyl group. , Aryl groups having an alkyl group such as a 3-cyclohexylphenyl group, a 2-cyclohexylphenyl group, a 4-ethyl-1-naphthyl group, a 6-n-butyl-2-naphthyl group, and a 2,4-dimethylphenyl group.
For example, 4-methoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 3-isopropoxyphenyl group, Such as 2-isopropoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-methyl-5-methoxyphenyl group, 2-phenyloxyphenyl group, etc. An aryl group having an alkoxy group and an aryloxy group;
For example, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group Aryl groups having a halogen atom such as 2-methyl-3-chlorophenyl group, 2-methoxy-4-fluorophenyl group, 2-fluoro-4-methoxyphenyl group.
Furthermore, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-perfluoroethylphenyl group, 4-methylthiophenyl Group, 4-ethylthiophenyl group, 4-cyanophenyl group, 3-cyanophenyl group and the like.

In the general formula (1-1), when l is 2, Y may be the same or different.

Hereinafter, specific examples of the specific substituent L represented by the general formula (1-1) include the following compounds, but the present invention is not limited thereto.
In the formulas (L-1) to (L-24), (+) represents a bonding position.

一般式（１）において、Ｍ１及びＭ２は、好ましくはそれぞれ独立に、金属原子、金属化合物または２個の水素原子などが挙げられ、金属原子または金属化合物としては、錯体を形成可能な金属原子または金属化合物であればいずれであってもよく、例えば、２価の金属原子、金属酸化物、金属水酸化物、または金属塩化物である。なお、２個の水素原子を表す場合は、２つの水素原子が異なる２つの窒素原子にそれぞれ結合している。

一般式（１）における、Ｍ１及びＭ２の具体例を以下に示す。

In the general formula (1), M1 and M2 are preferably each independently a metal atom, a metal compound, or two hydrogen atoms, and the metal atom or metal compound includes a metal atom or a metal atom capable of forming a complex or Any metal compound may be used, for example, a divalent metal atom, metal oxide, metal hydroxide, or metal chloride. When two hydrogen atoms are represented, the two hydrogen atoms are bonded to two different nitrogen atoms, respectively.

Specific examples of M1 and M2 in the general formula (1) are shown below.

Examples of the divalent metal atom include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, Pb, and Sn. Examples of the metal oxide include VO and TiO. Examples of the metal hydroxide include MnOH and Si (OH) ₂ . The metal chlorides may be for example _AlCl, InCl, _FeCl, be mentioned _{TiCl 2, SnCl 2, SiCl 2} , GeCl 2.

More preferably, they are each independently Mg, AlCl, FeCl, Co, Ni, Cu, Zn, Pd, SnCl2, InCl, VO, MnOH, TiO, and Ru.

More preferably, each independently, a Cu, Co, Ni, Pd, MnOH, AlCl, FeCl, InCl, SnCl 2, VO, TiO, Zn, Ru.

Particularly preferably, they are each independently VO, Pd, Cu, and Zn.

［式（２−１ａ）及び式（２−１ｂ）中のＭ１１及びＭ１２は、一般式（１）におけるＭ１及びＭ２の例と同義であり、その好ましい態様も同様である。さらに、式（２−１ａ）中のＲ１１〜Ｒ３４、及び式（２−１ｂ）中のＲ５０〜Ｒ８６は、一般式（１）におけるＱ１〜Ｑ６の置換基で表される例と同義であり、その好ましい態様も同様である。］
Preferred forms of the ditetraazaporphyrin-based compound of the present invention are represented by general formula (2-1a), general formula (2-1b), general formula (2-2a), and general formula (2-2b). The invention is not limited to these.

[M11 and M12 in the formula (2-1a) and the formula (2-1b) have the same meanings as the examples of M1 and M2 in the general formula (1), and the preferred embodiments thereof are also the same. Furthermore, R11 to R34 in the formula (2-1a) and R50 to R86 in the formula (2-1b) are synonymous with the examples represented by the substituents of Q1 to Q6 in the general formula (1). The preferable aspect is also the same. ]

［式（２−２ａ）及び式（２−２ｂ）中のＭ２１及びＭ２２は、一般式（１）におけるＭ１及びＭ２の例と同義であり、その好ましい態様も同様である。さらに、式（２−２ａ）中のＲ１１〜Ｒ３４、及び式（２−２ｂ）中のＲ５０〜Ｒ８６は、一般式（１）におけるＱ１〜Ｑ６の置換基で表される例と同義であり、その好ましい態様も同様である。］

以下、一般式（１）で表わされるジテトラアザポルフィリン系化合物の具体例としては、例えば以下の化合物を挙げることができるが、本発明はこれらに限定されるものではない。

[M21 and M22 in the formulas (2-2a) and (2-2b) have the same meanings as the examples of M1 and M2 in the general formula (1), and preferred embodiments thereof are also the same. Furthermore, R11 to R34 in the formula (2-2a) and R50 to R86 in the formula (2-2b) are synonymous with the examples represented by the substituents of Q1 to Q6 in the general formula (1). The preferable aspect is also the same. ]

Hereinafter, specific examples of the ditetraazaporphyrin-based compound represented by the general formula (1) include, for example, the following compounds, but the present invention is not limited thereto.

＜製造方法＞
一般式（１）で表わされるジテトラアザポルフィリン系化合物は、それ自体公知の方法を参考にして製造することができる。例えば、一般式（１）において、Ｑ１〜Ｑ６の置換基として臭素原子を有する化合物と、下記一般式（Ｂ）で表されるボロン酸化合物とを、鈴木−宮浦反応でカップリングした反応化合物に、下記一般式（Ｃ）で表される化合物を、脱水縮合反応させることによって製造することができる。

（式中、Ｙ、ｌ、Ｘ１、Ｘ２およびＸ３は、既述の一般式（１−１）中のＹ、ｌ、Ｘ１、Ｘ２、およびＸ３と同じ意味を表す）

（式中、Ｘ４は、既述の一般式（１−１）中のＸ４と同じ意味を表す）

<Manufacturing method>
The ditetraazaporphyrin-based compound represented by the general formula (1) can be produced with reference to a method known per se. For example, in the general formula (1), a reaction compound obtained by coupling a compound having a bromine atom as a substituent of Q1 to Q6 and a boronic acid compound represented by the following general formula (B) by the Suzuki-Miyaura reaction. The compound represented by the following general formula (C) can be produced by a dehydration condensation reaction.

(In the formula, Y, l, X1, X2 and X3 represent the same meaning as Y, l, X1, X2 and X3 in the general formula (1-1) described above)

(In the formula, X4 represents the same meaning as X4 in the general formula (1-1) described above).

In addition, about a manufacture example, it describes with reference to the case of the above-mentioned exemplary compound A-1.

Exemplified Compound A-1 is first composed of a compound represented by Formula (D), a compound represented by Formula (E), and a compound represented by Formula (F) with zinc chloride as a metal halide. Optionally base (eg ammonium molybdate, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, trialkylamine, ammonia) The intermediate compound represented by the following formula (A-1-1) can be produced by reacting in the presence of [for example, Chemistry-A
Eur. J. et al. , 12.1468 (2006), J. et al. Am. Chem. Soc. , 1144.475 (1992), International Publication No. 01/50199, can be produced].

The intermediate compound represented by the formula (A-1-1) is, for example, a subphthalocyanine boron complex produced by reacting a compound represented by the formula (D) and a boron compound (for example, boron trichloride). A compound represented by the formula (D), a compound represented by the formula (E), and a boron compound (for example, can be prepared according to the method described in JP-A-2005-289854). The compound represented by the formula (A-1-1) by further reacting the compound represented by the formula (F) with the halide of the subphthalocyanine boron complex produced by the same action of the boron trichloride) [For example, it can be produced according to the method described in JP-A-02-9882], and further, the metal-free body and a metal oxide such as zinc or zinc oxide are converted into a salt. (E.g., triethylamine, sodium hydride) may be prepared by reacting in the presence of [for example, be prepared according to the method described in JP 2005-290282.

In addition, when the intermediate compound represented by the formula (A-1-1) is produced by the above method, generally, a plurality of structural isomers having different positions to which substituents are bonded may exist.

For example, the compound represented by the formula (A-1-1) is actually selected from compounds represented by the formula (A-1-1a), the formula (A-1-1b), and the like. It represents a mixture of one compound or two or more structural isomers. For the description of the structure of such a mixture composed of a plurality of structural isomers, for example, in this specification, for example, one structural formula represented by the formula (A-1-1) is described. is there.

本明細書においては、本発明のジテトラアザポルフィリン系化合物について例外ではなく、例示化合物Ａ−１〜Ａ−６８で示した構造式も、あるひとつの構造異性体を示すものであり、この構造に限定はされない。

なお、本発明のジテトラアザポルフィリン系化合物においては、単一の化合物形態として用いてもよいし、２種以上の構造異性体からなる混合物として用いることもできる。
構造異性体からなる混合物として用いる場合には、構造異性体の混合比率はいかなるものでもよい。

次に、式（Ａ−１−１）で表される中間体化合物と、式（Ｂ）で表されるボロン酸化合物として、５‘−ホルミル−２，２’−ビチオフェン−５’−ボロン酸を、塩基およびリガンドの存在下又は非存在下、遷移金属触媒の存在下、好ましくは溶媒を用いて鈴木−宮浦カップリング反応により、一般式（Ａ−１−２）で表される前駆体化合物を製造する。

In the present specification, the ditetraazaporphyrin-based compound of the present invention is not an exception, and the structural formulas shown as exemplary compounds A-1 to A-68 also show one structural isomer. It is not limited to.

In addition, in the ditetraazaporphyrin-type compound of this invention, it may be used as a single compound form, and can also be used as a mixture which consists of 2 or more types of structural isomers.
When used as a mixture of structural isomers, the mixing ratio of the structural isomers may be any.

Next, as an intermediate compound represented by the formula (A-1-1) and a boronic acid compound represented by the formula (B), 5′-formyl-2,2′-bithiophene-5′-boronic acid In the presence or absence of a base and a ligand, in the presence of a transition metal catalyst, and preferably by a Suzuki-Miyaura coupling reaction using a solvent, a precursor compound represented by the general formula (A-1-2) Manufacturing.

鈴木−宮浦カップリング反応に用いる溶媒としては、本反応を阻害しないものであれば特に限定されず、例えばベンゼン、トルエン、キシレン等の芳香族炭化水素類、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、クロロホルム、ジクロロメタン等のハロゲン化炭化水素類、酢酸メチル、酢酸エチル等のエステル類、１，２−ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル類、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン、１，３-ジメチル−２−イミダゾリジノン等のアミド類、アセトニトリル、ジメチルスルホキシド、ピリジン等を挙げることができる。

これらの溶媒は反応の起こりやすさにしたがって適宜選択され、１種単独で又は２種以上混合して用いることができる。なお、必要に応じて適当な脱水剤や乾燥剤により水分を除去し、非水溶媒として用いてもよい。

溶媒を用いる場合、一般に、溶媒の量が多くなると反応の効率が低下し、反対に少なくなると、均一に加熱・撹拌するのが困難になったり、副反応が起り易くなる。したがって、溶媒の量を重量比で中間体化合物全体の１００倍まで、好ましくは５〜５０倍にするのが望ましい。

The solvent used in the Suzuki-Miyaura coupling reaction is not particularly limited as long as it does not inhibit this reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. , Halogenated hydrocarbons such as chloroform and dichloromethane, esters such as methyl acetate and ethyl acetate, ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, N, N-dimethylformamide, N, N-dimethyl Examples include amides such as acetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, dimethyl sulfoxide, pyridine and the like.

These solvents are appropriately selected according to the ease of reaction, and can be used singly or in combination of two or more. If necessary, water may be removed with a suitable dehydrating agent or desiccant and used as a non-aqueous solvent.

In the case of using a solvent, generally, when the amount of the solvent increases, the efficiency of the reaction decreases. On the other hand, when the amount of the solvent decreases, it becomes difficult to uniformly heat and stir or a side reaction tends to occur. Therefore, it is desirable that the amount of the solvent is up to 100 times, preferably 5 to 50 times that of the whole intermediate compound by weight ratio.

Examples of the base used in the reaction include alkali metal hydrides such as sodium hydride, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, and carbonate. Examples thereof include alkali metal carbonates such as cesium, and organic bases such as pyridine and triethylamine.

What is necessary is just to select the usage-amount of a base suitably in the range of 1.0-10.0 times mole with respect to the intermediate compound represented by Formula (A-1-1).

Examples of the transition metal catalyst used in the reaction include palladium compounds such as palladium acetate, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and tris (dibenzylacetone) palladium, and bis (triphenylphosphine). ) Nickel compounds such as nickel chloride and tetrakis (triphenylphosphine) nickel.

The amount of the transition metal catalyst used may be appropriately selected within the range of 0.0001 to 0.2 times the molar amount of the intermediate compound represented by the formula (A-1-1), but is preferably 0.00. It is the range of 001-0.15 times mole.

Examples of the ligand used in the reaction include phosphines such as triphenylphosphine, 1,2-bisdiphenylphosphinoethane, 1,3-bisdiphenylphosphinopropane, 1,4-bisdiphenylphosphinobutane, and the like. Can be mentioned.

The amount of the ligand used may be appropriately selected in the range of 0.5 to 100-fold mol with respect to the transition metal catalyst, but is preferably in the range of 1.0 to 10.0-fold mol, even in the absence. good.

The reaction temperature may be appropriately selected in the range of 0 to 200 ° C., but is preferably in the range of room temperature to solvent reflux temperature.

The reaction time is not constant depending on the reaction scale and reaction temperature, but may be appropriately selected within the range of 1 to 48 hours.

Since this reaction is an equimolar reaction, the intermediate compound represented by the formula (A-1-1) and the boronic acid compound represented by the general formula (B) may be reacted in an equimolar amount. The amount of the boronic acid compound used may be appropriately selected within the range of 0.5 to 5.0 times the number of the intermediate compound represented by the formula (A-1-1), preferably It is the range of 1.0-3.0 times mole.

When a solvent that dissolves in water is used after completion of the reaction, the reaction solution is discharged into water, and the precipitate is filtered off and washed with methanol. When a solvent insoluble in water is used, the solvent is distilled off under reduced pressure, water is added, the precipitate is filtered off and washed with methanol. If necessary, the precipitate can be purified by a method such as column chromatography.

Next, as a precursor compound represented by the general formula (A-1-2) produced by the Suzuki-Miyaura coupling reaction described above, and cyanoacetic acid as a compound represented by the general formula (C), The ditetraazaporphyrin-based compound of the present invention can be produced by a dehydration condensation reaction in the presence of a base, preferably using a solvent.

The solvent used in the dehydration condensation reaction is not particularly limited as long as it does not inhibit the reaction. For example, hydrocarbons such as pentane, hexane, cyclohexane, octane, benzene, toluene, xylene, carbon tetrachloride, Chloroform, 1,2-dichloroethane, 1,2-dibromoethane, trichloroethylene, tetrachloroethylene, chlorobenzene, bromobenzene, α-dichlorobenzene and other halides, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2 -Butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, phenol, benzyl alcohol, cresol, Alcohols and phenols such as ethylene glycol, triethylene glycol, glycerin, diethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, dicyclohexyl-18-crown -6, ethers such as methyl carbitol and ethyl carbitol, acetic acid, acetic anhydride, trichloroacetic acid, trifluoroacetic acid, propionic anhydride, ethyl acetate, butyl carbonate, ethylene carbonate, propylene carbonate, formamide, N-methylformamide, Acids and acid derivatives such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, hexamethylphosphoric triamide, Examples thereof include nitriles such as tolyl, propionitrile, succinonitrile and benzonitrile, nitro compounds such as nitromethane and nitrobenzene, and sulfur-containing compounds such as dimethyl sulfoxide and sulfolane.

These solvents are appropriately selected according to the ease of reaction, and can be used singly or in combination of two or more. If necessary, water may be removed with a suitable dehydrating agent or desiccant and used as a non-aqueous solvent.
In the case of using a solvent, generally, when the amount of the solvent is increased, the efficiency of the reaction is decreased. On the other hand, when the amount is decreased, it becomes difficult to uniformly heat and stir, or a side reaction is likely to occur. Therefore, the amount of the solvent is up to 100 times, preferably 5 to 50 times that of the whole precursor compound represented by the general formula (A-1-2) produced by the Suzuki-Miyaura coupling reaction by weight ratio. It is desirable to do.

Examples of the base used in the reaction include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, ammonia, triethylamine, piperidine, pyridine, pyrrolidine, aniline, N, N-dimethylaniline, N, N-diethylaniline and the like can be mentioned.
What is necessary is just to select the usage-amount of a base suitably in the range of 1-10 times mole with respect to the precursor compound represented by general formula (A-1-2) manufactured by Suzuki-Miyaura coupling reaction.

The reaction temperature may be appropriately selected in the range of 0 to 200 ° C., but is preferably in the range of room temperature to solvent reflux temperature.

The reaction time is not constant depending on the reaction scale and reaction temperature, but may be appropriately selected within the range of 1 to 48 hours.

Since this reaction is an equimolar reaction, the compound produced by the Suzuki-Miyaura coupling reaction and the compound represented by the general formula (C) may be reacted in an equimolar amount. The amount of the compound represented is 0.5 to the number of —CHO groups of the precursor compound represented by the general formula (A-1-2) produced by the Suzuki-Miyaura coupling reaction. What is necessary is just to select suitably in the range of -30 times mole, Preferably it is the range of 1-15 times mole.

When a solvent that dissolves in water is used after completion of the reaction, the reaction solution is discharged into water, and the precipitate is filtered off and washed with water. When a solvent insoluble in water is used, the solvent is distilled off under reduced pressure, water is added, the precipitate is filtered off and washed with water. If necessary, the precipitate can be purified by a method such as column chromatography.

Moreover, as a manufacturing method other than the above-mentioned of the ditetraazaporphyrin type compound represented by General formula (1), when it describes with reference to the case of the above-mentioned exemplary compound A-10, for example, it represents with Formula (F). And a compound represented by formula (G), zinc chloride as a metal halide, and optionally a base (for example, ammonium molybdate, 1,8-diazabicyclo [5.4.0] -7-undecene, Intermediate compounds prepared by reacting in the presence of 1,5-diazabicyclo [4.3.0] -5-nonene, trialkylamine, ammonia) [e.g. Chemistry-A
Eur. J. et al. , 12.1468 (2006), J. et al. Am. Chem. Soc. , 1144.475 (1992), WO 01/50199] can be formylated with Vilsmeier reagent [for example, described in WO 98/14520 The intermediate reactant represented by the formula (A-10-1) can be obtained.

次に、下記式（Ａ−１０−１）で表される反応中間体と一般式（Ｃ）で表される化合物として、シアノ酢酸を、塩基の存在下、好ましくは溶媒を用いて脱水縮合反応させることにより、本発明のジテトラアザポルフィリン系化合物を製造することができる。

又、式（Ａ−１０−１）で表される反応中間体をビルスマイヤー試薬によるホルミル化後、アセトン中、亜塩素酸ナトリウム水で酸化することにより、例示化合物Ａ−１１を製造することができる。

Next, as a reaction intermediate represented by the following formula (A-10-1) and a compound represented by the general formula (C), dehydration condensation reaction is performed using cyanoacetic acid in the presence of a base, preferably using a solvent. By doing so, the ditetraazaporphyrin-based compound of the present invention can be produced.

Alternatively, exemplary compound A-11 can be produced by formylating a reaction intermediate represented by formula (A-10-1) with a Vilsmeier reagent and then oxidizing with sodium chlorite water in acetone. it can.

The ditetraazaporphyrin-based compound of the present invention can be advantageously used in various fields that require an organic compound that absorbs visible light. Further, since it has a carboxyl group, it is extremely useful as a material for a dye-sensitized solar cell, such that a compound can be fixed on the surface of titanium oxide.

In the dye-sensitized solar cell of the present invention, the ditetraazaporphyrin-based compound of the present invention may be used alone or in combination. The ditetraazaporphyrin-based compound of the present invention includes not only crystals but also amorphous (amorphous).
Considering the required characteristics of the dye-sensitized solar cell of the present invention, the ditetraazaporphyrin-based compound of the present invention is preferably a compound having a maximum absorption wavelength at 550 nm to 1200 nm, more preferably 600 nm to It is a compound having a maximum absorption at 1100 nm.

<Dye-sensitized solar cell>
Embodiments of the dye-sensitized solar cell of the present invention include, for example, an anode, a cathode, and an electrolyte. The cathode includes a base material made of transparent conductive glass or polymer, and an oxidation formed on the surface thereof. A thin film electrode. The ditetraazaporphyrin-based compound of the present invention is adsorbed on the oxide thin film electrode. Such a dye-sensitized solar cell exhibits excellent photoelectric conversion efficiency as compared with a conventional dye-sensitized solar cell, and has excellent durability such as weather resistance and heat resistance.

The anode need only be composed of a conductive material, and there are no particular restrictions on the type of constituent material. For example, a material in which a trace amount of platinum or conductive carbon is attached to the surface of a substrate made of transparent conductive glass can be suitably used. As the transparent conductive glass, for example, glass made of tin oxide or indium-tin oxide (ITO) can be used.

The cathode has a substrate made of transparent conductive glass and an oxide thin film electrode formed on the surface thereof, and the ditetraazaporphyrin-based compound of the present invention described above is adsorbed on the oxide thin film electrode. It is what. As the transparent conductive glass, glass made of the material exemplified in the section of the anode can be used. There is no restriction | limiting in particular about the shape of a base material, For example, a plate-shaped thing etc. can be used.

The oxide thin film electrode is a thin film made of an oxide. Examples of the oxide constituting the oxide thin film electrode include a metal oxide, more specifically, titanium oxide, niobium oxide, zinc oxide, and tin oxide. , Tungsten oxide, indium oxide, and the like. Among these oxides, titanium oxide, niobium oxide and tin oxide are preferable, and titanium oxide is particularly preferable. The oxide thin film electrode is used in a state where the ditetraazaporphyrin-based compound of the present invention is adsorbed.

As the electrolyte, a liquid or solid made of an electrolyte, a solution containing the electrolyte, or the like can be used. Among these, it is preferable to use a redox electrolyte. A redox electrolyte is a solution containing a substance (oxidizing agent, reducing agent) that constitutes a redox system. For example, the redox electrolyte forms a redox system (I ⁻ / I ^{3 −} system) represented by the following formula (I). A solution containing iodine and an imidazolium salt of iodine can be preferably used. As the solvent of this solution, an electrochemically inert substance such as acetonitrile or propionitrile can be suitably used.
I ₃ ⁻ + 2e ⁻ ← → 3I ⁻ + I ₂ : (A)

What is necessary is just to comprise a dye-sensitized solar cell so that electrolyte may fill between an anode and a cathode. For example, a configuration in which the container is filled with the electrolyte solution, and the anode and the cathode are disposed so as to face each other in the electrolyte solution.

The ditetraazaporphyrin-based compound of the present invention is a compound that efficiently absorbs sunlight energy. Therefore, when the ditetraazaporphyrin-based compound of the present invention is used as a sensitizing dye, a dye-sensitized solar cell having superior photoelectric conversion efficiency and wavelength absorption characteristics can be provided as compared with conventional sensitizing dyes. .

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
In the following production examples and examples, the physical properties of each compound were measured by the following methods.
Absorption spectrum: An N, N-dimethylformamide solution having a concentration of 0.01 g / L was measured with an optical path length of 10 mm using a U-3500 self-recording spectroscopic clock manufactured by Hitachi, Ltd. as a measuring instrument.
Mass spectrometry spectrum (MASS): Measured by infusion analysis using a Quatro micro API system Masslynx manufactured by Japan Waters and using a syringe pump by an electrospray ionization method.

Example 1 Synthesis of Exemplary Compound A-1
20 ml of 1-amyl alcohol, 1.00 g of benzobis (1,3-diiminopyrroline), 1.06 g of 5-bromoisoindoline-1,3-diimine, 5-tert-butylisoindoline-1,3-diimine 4 .74 g and zinc chloride 1.28 g were added, and the mixture was stirred at 120 to 125 ° C. for 6 hours. Thereafter, the reaction solution was cooled to room temperature, 100 ml of water was added, and further stirred for 1.5 hours, and then the precipitate was collected by filtration and washed with 50 ml of methanol four times. After drying at 60 ° C., separation was performed by column chromatography using silica gel (developing solvent: toluene / hexane = 4/1), and 150 mg of intermediate compound represented by the above formula (A-1-1) Yield 2.2%) as green crystals.
MASS spectrum (M + 1) + = 1437

Next, 7.5 mg of 1,3-dimethyl-2-imidazolidinone was added to 150 mg of the above intermediate compound, 49.7 mg of 5′-formyl-2,2′-bithiophene-5-boronic acid, and 43.3 mg of potassium carbonate. , Tetrakis (triphenylphosphine) palladium (6.03 mg) was added, and the mixture was stirred at 80 to 85 ° C. for 8 hours. Thereafter, the reaction solution was cooled to room temperature, 15 ml of water was added, and the mixture was further stirred for 1.5 hours, and then the precipitate was collected by filtration and washed 4 times with 10 ml of methanol. The above formula (A-1-2) 101 mg of a precursor compound represented by

Furthermore, 101 mg of the above precursor compound, 33.3 mg of cyanoacetic acid, 30.1 mg of ammonium acetate were added to 10 ml of acetic acid, and the mixture was stirred at 90 to 95 ° C. for 8 hours. Thereafter, the reaction solution was cooled to room temperature, 20 ml of water was added, and the mixture was further stirred for 1.5 hours, and then the precipitate was collected by filtration and washed 4 times with 20 ml of water. After drying at 60 ° C., the obtained crude product was separated and purified by column chromatography using silica gel (developing solvent: toluene / ethyl acetate = 1/1) to give 99 mg (yield 94%) of the exemplified compound. A-1 was obtained as green crystals.
Absorption maximum wavelength in N, N-dimethylformamide solution 720 nm
Gram extinction coefficient in N, N-dimethylformamide solution 6.2 × 10 ⁴ ml / gcm
MASS spectrum (M + 1) + = 1618

Example 2 Synthesis of Exemplified Compound A-2 50.0 mg of Exemplified Compound A-1 was dissolved in 5 ml of sulfuric acid, stirred for 10 minutes, and then discharged into 100 ml of a saturated aqueous solution of sodium bicarbonate. The precipitate was filtered and dried at 60 ° C., and the obtained crude product was separated by column chromatography using silica gel (developing solvent: toluene / ethyl acetate = 1/1) to give 40.0 mg (yield) 87%) of Exemplified Compound A-2 was obtained as green crystals.
Absorption maximum wavelength in N, N-dimethylformamide solution 724 nm
Gram extinction coefficient in N, N-dimethylformamide solution 4.8 × 10 ⁴ ml / gcm
MASS spectrum (M + 1) + = 1491

Example 3 Synthesis of Exemplary Compound A-3
In Example 1, 109 mg (yield 55%) of Exemplified Compound A-3 was obtained as green crystals by the same method as in Example 1 except that vanadyl trichloride was used instead of zinc chloride.
Absorption maximum wavelength in N, N-dimethylformamide solution 764 nm
Gram extinction coefficient in N, N-dimethylformamide solution 7.1 × 10 ⁴ ml / gcm
MASS spectrum (M + 1) + = 1621

Example 4 Synthesis of Exemplary Compound A-4
In Example 1, except that palladium chloride was used in place of zinc chloride, 99 mg (yield 48%) of Exemplified Compound A-4 was obtained as green crystals in the same manner as in Example 1.
Absorption maximum wavelength in N, N-dimethylformamide solution 720 nm
Gram extinction coefficient in N, N-dimethylformamide solution 7.0 × 10 ⁴ ml / gcm
MASS spectrum (M + 1) + = 1700

Example 5 Synthesis of Exemplified Compound A-5 In Example 1, 129 mg (yield 62%) of Exemplified Compound A- was obtained in the same manner as in Example 1 except that copper chloride was used instead of zinc chloride. 4 was obtained as green crystals.
Absorption maximum wavelength in N, N-dimethylformamide solution 719 nm
Gram extinction coefficient in N, N-dimethylformamide solution 6.9 × 10 ⁴ ml / gcm
MASS spectrum (M + 1) + = 1616

(Example 6) Synthesis of exemplary compound A-7 In Example 1, 5- (2,4-dimethylpentan-3-yl) oxy instead of 4.74 g of 5-bromoisoindoline-1,3-diimine) Except for using 6.11 g of isoindoline-1,3-diimine, 84.2 mg (yield 63%) of Exemplified Compound A-7 was obtained as green crystals in the same manner as in Example 1.
Absorption maximum wavelength in N, N-dimethylformamide solution 742 nm
Gram extinction coefficient in N, N-dimethylformamide solution 1.11 × 10 ⁵ ml / gcm
MASS spectrum (M + 1) + = 1908

Example 7 Synthesis of Exemplary Compound A-8 In Example 1, instead of 4.74 g of 5-bromoisoindoline-1,3-diimine, 6-butyl-1H-benzo [f] isoindole-1,3 Except that 5.92 g of (2H) -diimine was used, 223 mg (yield 50%) of exemplary compound A-8 was obtained as green crystals in the same manner as in Example 1.
Absorption maximum wavelength in N, N-dimethylformamide solution 791 nm
Gram extinction coefficient in N, N-dimethylformamide solution 1.01 × 10 ⁵ ml / gcm
MASS spectrum (M + 1) + = 1868

Example 8 Synthesis of Exemplary Compound A-10 To 50 ml of 1-amyl alcohol, 1.00 g of benzobis (1,3-diiminopyrroline), 4,9-dibutoxy-1H-benzo [f] isoindole-1, 3 (2H) -diimine (16.0 g) and zinc chloride (1.93 g) were added, and the mixture was stirred at 130 to 135 ° C. for 24 hours. Thereafter, the reaction solution was cooled to room temperature, 100 ml of water was added, and further stirred for 1.5 hours, and then the precipitate was collected by filtration and washed with 50 ml of methanol four times. After drying at 60 ° C., separation and purification were performed by column chromatography using silica gel (developing solvent: toluene) to obtain 788 mg of an intermediate of green crystals.
Under cooling, 323 mg of phosphoryl chloride was added dropwise to 5 ml of dimethylformamide, followed by stirring at room temperature for 30 minutes. Next, 788 mg of intermediate and 5 ml of toluene were added and stirred at 95 ° C. for 10 hours, and then the reaction solution was cooled to room temperature, and 8 ml of water and 1.04 g of sodium acetate were added and stirred for 30 minutes. Furthermore, 50 ml of ethyl acetate was added and the mixture was allowed to stand, and the organic layer was separated and washed twice with 50 ml of 10% aqueous sodium hydrogen carbonate solution. Subsequently, after washing 3 times with 50 ml of water, the organic layer was concentrated. The obtained concentrate was separated and purified by column chromatography using a silica gel column (developing solvent: toluene / ethyl acetate = 4/1), and 335 mg of the compound represented by the formula (A-10-1) ( Yield 41%) was obtained as green crystals.
MASS spectrum (M + 1) + = 2287

335 mg of the obtained compound, 75.3 mg of cyanoacetic acid, and 77.1 mg of ammonium acetate were added to 34 ml of acetic acid, and the mixture was stirred at 90 to 95 ° C. for 8 hours. Thereafter, the reaction solution was cooled to room temperature, 20 ml of water was added, and the mixture was further stirred for 1.5 hours, and then the precipitate was collected by filtration and washed 4 times with 20 ml of water. After drying at 60 ° C., the obtained crude product was separated and purified by column chromatography using silica gel (developing solvent: toluene / ethyl acetate = 1/1), and 254 mg (74% yield) of the exemplified compound. A-10 was obtained as green crystals.
Absorption maximum wavelength in N, N-dimethylformamide solution 870 nm
Gram extinction coefficient in N, N-dimethylformamide solution 9.5 × 10 ⁴ ml / gcm
MASS spectrum (M + 1) + = 2338

Example 9 Synthesis of Exemplified Compound A-11 Under cooling, 30 mg of acetone was added 300 mg of the compound represented by the formula (A-10-1), 23.9 mg of sodium chlorite, and 1 ml of water. Stir at 5 ° C. for 30 minutes. Next, 25.7 mg of sulfamic acid and 1 ml of water were added, and the mixture was stirred at room temperature for 2 hours. The aqueous solution was washed twice with toluene, 20 ml of 5% hydrochloric acid was added to the aqueous layer, and the resulting precipitate was filtered to obtain 185 mg (yield 61%) of exemplary compound A-11 as brown crystals.
Absorption maximum wavelength in N, N-dimethylformamide solution 878 nm
Gram extinction coefficient in N, N-dimethylformamide solution 8.8 × 10 ⁴ ml / gcm
MASS spectrum (M + 1) + = 2287

Example 10 Synthesis of Exemplified Compound A-13 In Example 6, 5-formyl-2-thiopheneboronic acid was replaced by 21 instead of 33.5 mg of 5′-formyl-2,2′-bithiophene-5-boronic acid. Except for using .9 mg, 63.1 mg (yield 49%) of Exemplified Compound A-13 was obtained as green crystals in the same manner as in Example 6.
Absorption maximum wavelength in N, N-dimethylformamide solution 737 nm
Gram extinction coefficient in N, N-dimethylformamide solution 1.1 × 10 ⁵ ml / gcm
MASS spectrum (M + 1) + = 1826

Example 11 Synthesis of Exemplary Compound A-14 In Example 6, 74.3 mg (yield) was obtained in the same manner as in Example 6 except that 56.5 mg of trifluoroacetic acid was used instead of 26.4 mg of cyanoacetic acid. 54%) of Exemplified Compound A-14 was obtained as green crystals.
Absorption maximum wavelength in N, N-dimethylformamide solution 741 nm
Gram extinction coefficient in N, N-dimethylformamide solution 1.2 × 10 ⁵ ml / gcm
MASS spectrum (M + 1) + = 1951

Example 12 Synthesis of Exemplary Compound A-15 In Example 6, 251 mg (yield 51%) was exemplified in the same manner as in Example 6 except that 102 mg of malonic acid was used instead of 49.7 mg of cyanoacetic acid. Compound A-15 was obtained as green crystals.
Absorption maximum wavelength in N, N-dimethylformamide solution 738 nm
Gram extinction coefficient in N, N-dimethylformamide solution 1.3 × 10 ⁵ ml / gcm
MASS spectrum (M + 1) + = 1927

Example 13 Synthesis of Exemplified Compound A-16 In Example 6, 55.8 mg (yield 54) was obtained in the same manner as in Example 6 except that 39.0 mg of nitroacetic acid was used instead of 33.3 mg of cyanoacetic acid. %) Of Exemplified Compound A-16 as green crystals.
Absorption maximum wavelength in N, N-dimethylformamide solution 743 nm
Gram extinction coefficient in N, N-dimethylformamide solution 1.2 × 10 ⁵ ml / gcm
MASS spectrum (M + 1) + = 1928

(Example 14) Production of dye-sensitized solar cell In a mixed medium of 0.4 ml of acetylacetone and 20 ml of ion-exchanged water, 12 g of titanium oxide fine particles and a dispersant (trade name “Triton X-100”, manufactured by Aldrich) 2 g was added to prepare an oxide slurry. This oxide slurry was applied to the surface of a substrate made of transparent conductive glass (having fluorine doped SnO ₂ as a conductive layer) washed with ethanol, and heated in an air atmosphere at 500 ° C. for 0.5 hour. As a result, an oxide thin film electrode made of titanium oxide was formed on the surface of the base material made of transparent conductive glass to obtain a member for cathode.
Subsequently, Exemplified Compound A-1 produced in Example 1 and chenodeoxycholic acid (3.0 × 10 ⁻⁴ M) as a co-adsorbent were dissolved in ethanol, and the concentration of Compound A-1 was 0.5 mmol / L. A solution was prepared. And the cathode by which the compound A-1 was carry | supported by the oxide thin film electrode was manufactured by immersing the said member for cathodes in this solution at 23 degreeC for 24 hours.
Further, a platinum electrode obtained by sintering platinum on the surface of a base material (thickness 4 mm, made of tin oxide, resistance value = 10 Ω / cm ² ) made of transparent conductive glass is used as an anode, and the platinum sintered surface of the anode and the cathode A general ionomer resin spacer was attached to an appropriate position in the cell container so that the oxide thin film electrode formation surface was opposed and the distance between both electrodes was 25 μm.
Thereafter, a redox electrolyte solution (acetonitrile solution containing 0.45 mM iodine and 30 mM lithium iodide) was injected into the cell container to produce a dye-sensitized solar cell.

(Example 15)
Example compound A-2 produced in Example 2 instead of Example compound A-1 produced in Example 1 was the same as Example 14 except that the concentration was 0.5 mmol / L. The operation was performed to prepare a dye-sensitized solar cell.

(Example 16)
Except for Exemplified Compound A-1 produced in Example 1, Exemplified Compound A-3 produced in Example 3 was the same as Example 14 except that it was dissolved so as to have a concentration of 0.5 mmol / L. The operation was performed to prepare a dye-sensitized solar cell.

(Example 17)
Example compound A-4 produced in Example 4 was used instead of Example Compound A-1 produced in Example 1 except that it was dissolved so that the concentration was 0.5 mmol / L. The operation was performed to prepare a dye-sensitized solar cell.

(Example 18)
Except for Example Compound A-1 produced in Example 1, Example Compound A-5 produced in Example 5 was the same as Example 14 except that the concentration was 0.5 mmol / L. The operation was performed to prepare a dye-sensitized solar cell.

(Example 19)
Except for Example Compound A-1 produced in Example 1, Example Compound A-7 produced in Example 6 was dissolved in the same concentration as in Example 14 except that the concentration was 0.5 mmol / L. The operation was performed to prepare a dye-sensitized solar cell.

(Example 20)
Except for Example Compound A-1 produced in Example 1, Example Compound A-8 produced in Example 7 was the same as Example 14 except that the concentration was 0.5 mmol / L. The operation was performed to prepare a dye-sensitized solar cell.

(Example 21)
Except for Example Compound A-1 produced in Example 1, Example Compound A-10 produced in Example 8 was the same as Example 14 except that it was dissolved so as to have a concentration of 0.5 mmol / L. The operation was performed to prepare a dye-sensitized solar cell.

(Example 22)
Except for Example Compound A-1 produced in Example 1, Example Compound A-11 produced in Example 9 was the same as Example 14 except that the concentration was 0.5 mmol / L. The operation was performed to prepare a dye-sensitized solar cell.

(Example 23)
Example compound A-13 produced in Example 10 instead of Example compound A-1 produced in Example 1 was the same as Example 14 except that the concentration was 0.5 mmol / L. The operation was performed to prepare a dye-sensitized solar cell.

(Example 24)
Example compound A-14 produced in Example 11 instead of Example compound A-1 produced in Example 1 was the same as Example 14 except that the concentration was 0.5 mmol / L. The operation was performed to prepare a dye-sensitized solar cell.

(Example 25)
Except for Exemplified Compound A-1 produced in Example 1, Exemplified Compound A-15 produced in Example 12 was dissolved so that the concentration was 0.5 mmol / L. The operation was performed to prepare a dye-sensitized solar cell.

(Example 26)
Example compound A-16 produced in Example 13 instead of Example compound A-1 produced in Example 1 was the same as Example 14 except that the concentration was 0.5 mmol / L. The operation was performed to prepare a dye-sensitized solar cell.

(Comparative Example 1)
Instead of Example Compound A-1 produced in Example 1, a ruthenium complex (trade name: N3, manufactured by Solaronix) was dissolved in the same manner as in Example 14 except that the concentration was 0.5 mmol / L. Thus, a dye-sensitized solar cell was produced.

(Example 27) Photoelectric conversion characteristic evaluation of a dye-sensitized solar cell The photoelectric conversion characteristic of the dye-sensitized solar cell was implemented by the following operations. For this test, an IPCE (Incident Photon to Current Conversion Efficiency) measuring device (manufactured by Nippon Optel) was used, and the photoelectric conversion pole absorption wavelength and wavelength of 800 nm of the dye-sensitized solar cells obtained in Examples 14 to 22 were used. The external quantum yield was determined. The results are shown in Table 1.

表から明らかなように、本発明のジテトラアザポルフィリン系化合物を用いた色素増感太陽電池は近赤外領域において高い光電変換効率を示すことがわかった。 (Comparative Example 2)
The dye-sensitized solar cell produced in Comparative Example 1 was evaluated in the same manner as in Example 19. The results are shown in Table 1.

As is apparent from the table, it was found that the dye-sensitized solar cell using the ditetraazaporphyrin-based compound of the present invention exhibits high photoelectric conversion efficiency in the near infrared region.

  By using the ditetraazaporphyrin-based compound of the present invention as a sensitizing dye, it is possible to provide a dye-sensitized solar cell having excellent photoelectric conversion efficiency and wavelength absorption characteristics.

Claims (4)

Ditetraazaporphyrin-based compound represented by the following general formula (1)

[Wherein, M1 and M2 each independently represent a metal atom, a metal compound or two hydrogen atoms, Q0 represents an unsubstituted benzene ring or an unsubstituted naphthalene ring, and Q1 to Q6 each independently represents a substituent. A benzene ring which may have a group or a naphthalene ring which may have a substituent is represented. However, one or two of the substituents on Q1 to Q6 have a substituent represented by the general formula (1-1). ]

[Wherein Y represents an oxygen atom or a sulfur atom, X1 to X2 each independently represent a hydrogen atom or an unsubstituted alkyl group, and X3 to X4 each independently represent a hydrogen atom, a halogen atom, a nitro group or a cyano group. , A carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, l represents an integer of 0 to 2, and m represents an integer of 0 or 1. However, when l is an integer of 1 or 2, m represents an integer of 1. ]
In the formula (1), the substituent of Q1 to Q6 is a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group. The ditetraazaporphyrin compound according to claim 1, which is a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, or a substituted amino group.
The ditetraazaporphyrin-based compound according to claim 1 or 2, wherein in formula (1), Q1 to Q6 are the same.
A dye-sensitized solar cell, wherein the acrylic acid-based compound according to claim 1 is used as a sensitizing dye.