JP6007650B2 - Photofunctional material, water-splitting photocatalyst, and method for producing photofunctional material - Google Patents

Description

  The present invention relates to a photofunctional material, a redox reaction photocatalyst and a water splitting photocatalyst using the photofunctional material, a metal complex suitable for producing the photofunctional material, and a method for producing the same.

  In recent years, solar energy has attracted attention as a clean energy resource in place of fossil fuels that have depletion problems and environmental problems, and it is expected that light energy will be used effectively by using various optical functional materials. Yes. As one of such utilization techniques of light energy, for example, a technique for decomposing water using light energy and converting it into hydrogen useful for extraction of chemical energy is known. As a functional material, research on water-splitting photocatalyst has been actively conducted.

  Conventionally, an oxide semiconductor has been used as a water-splitting photocatalyst. A water-splitting photocatalyst using an oxide semiconductor absorbs light having energy greater than the band gap, whereby electrons in the valence band are excited to the conduction band, and hydrogen is generated by reduction by electrons in the generated conduction band. Then, oxygen is generated by oxidation by holes in the valence band, and water is decomposed. At this time, since an oxide semiconductor usually has a large band gap, ultraviolet light is required to excite electrons in the valence band to the conduction band. For example, Non-Patent Document 1 discloses an oxide semiconductor that exhibits a high quantum yield when irradiated with ultraviolet light.

J. et al. Am. Chem. Soc. 2003, 125, 3082-3089

  However, since only a small amount of ultraviolet light is contained in sunlight, a water-splitting photocatalyst that responds to visible light, which accounts for about half of sunlight, has been demanded. Here, a water-splitting photocatalyst is cited as an example of a photofunctional material. Similarly, in the field of other photofunctional materials, a material that responds to visible light has been demanded from the viewpoint of effective use of light energy. .

  The present invention has been made in view of the above circumstances, and is a novel photofunctional material capable of responding to visible light, a redox reaction catalyst such as a water-splitting photocatalyst using the photofunctional material, and the light. It is an object of the present invention to provide a novel metal complex suitable for the production of a functional material and a production method thereof.

To solve the above problem,
In a first aspect of the present invention, a coordination polymer in which a compound represented by the following formula (1) is coordinated to a titanium atom , metal particles or other metal complexes other than the coordination polymer, Is an optical functional material.

（式中、Ｐは、Ｒ^ａ及びＲ^ｂ以外に置換基を有していてもよい、ベンゼン、ナフタレン、アズレン、アントラセン、テトラセン又はペンタセンから、「ｍ＋ｎ」個の水素原子を除いてなる芳香族炭化水素基、あるいはマンガン、鉄、コバルト、ニッケル、ルテニウム及び白金の原子から選ばれる１種の金属原子と単環芳香族複素環式基及び／又はフェニル基が１以上の単結合で連結された配位子とで構成された金属錯体部位を有する基であり、前記芳香族炭化水素基が１以上の単結合で連結された基であってもよく；
Ｒ^ａは式「−ＣＯ _２ ⁻ 」又は「−ＣＯ _２ Ｈ」で表される基であり；ｍは２以上の整数であり、Ｐが前記金属錯体部位を有する基である場合、ｍは４以下であり、複数あるＲ^ａは互いに同一であっても異なっていてもよく；
Ｒ^ｂは、ハロゲン原子、又は式「−ＯＨ」、「−ＯＲ^Ｂ」、「−ＮＨ_２」、「−ＮＲ^Ｂ _２」もしくは「−ＮＯ_２」で表される基（ここで、Ｒ^Ｂは炭素数１〜４のアルキル基、又は炭素数６〜１０のアリール基であり、式「−ＮＲ^Ｂ _２」において２個のＲ^Ｂは、互いに同一であっても異なっていてもよい。）であり；ｎは、Ｐが炭素数６の芳香族炭化水素基である場合には１以上の整数であり、それ以外の場合には０以上の整数であり、ｎが２以上の整数である場合、複数あるＲ^ｂは互いに同一であっても異なっていてもよい。）

(In the formula, P is an aromatic group obtained by removing “m + n” hydrogen atoms from benzene, naphthalene, azulene, anthracene, tetracene or pentacene, which may have a substituent other than R ^a and R ^b. hydrocarbon group, Oh Rui manganese, iron, cobalt, nickel, connected by one metal atom and a monocyclic aromatic heterocyclic group and / or a phenyl group selected from the atoms of ruthenium and platinum one or more single bond A group having a metal complex site composed of a ligand formed, and the aromatic hydrocarbon group may be a group linked by one or more single bonds;
R ^a formula "-CO ₂ ^-" is a group represented by or "-CO ₂ H"; m is an integer of 2 or more, if P is a group having the metal complex sites, m is 4 And a plurality of R ^a may be the same or different from each other;
R ^b is a halogen atom or a group represented by the formula “—OH”, “—OR ^B ”, “—NH ₂ ”, “—NR ^B ₂ ” or “—NO ₂ ” (where R ^B is alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, two ^{R B} in the formula ^"-NR _{B 2"} may being the same or different.) in Yes; n is an integer of 1 or more when P is an aromatic hydrocarbon group having 6 carbon atoms; otherwise, it is an integer of 0 or more; and n is an integer of 2 or more The plurality of R ^b may be the same as or different from each other. )

A first aspect of an optical functional material of the present invention, the P may have a substituent other than R ^a and R ^b, benzene, naphthalene, azulene, anthracene, from Te anthracene or pentacene, " It is preferably an aromatic hydrocarbon group formed by removing m + n ”hydrogen atoms.
In the photofunctional material according to the first aspect of the present invention, the P may have a substituent other than R ^a and R ^b , 2-phenylpyridine, 2,2′-bipyridine, 5 , 5′-bisphenyl-2,2′-bipyridine, 1,3-bis (2-pyridyl) benzene, 2,2 ′: 6 ′, 2 ″ -terpyridine, 4-phenyl-2,2 ′: 6 Metal Complex Site Containing a Group Excluding “m + n” Hydrogen Atoms from “, 2 ″ -Terpyridine or 2,2 ′: 6 ′, 2 ″: 6 ″, 2 ′ ″-Quarterpyridine It is preferable that it is group which has.

Also, a second aspect of the present invention is a water splitting photocatalyst obtained by using the optical functional material of the first aspect.

The third aspect of the present invention is a method for producing the optical functional material, wherein the compound represented by the formula (1), one or more metal salts containing a titanium atom, And a step of mixing the obtained coordination polymer with metal particles or other metal complexes other than the coordination polymer. This is a method for producing a functional material .

In the method for producing a photofunctional material according to the third aspect of the present invention, the compound represented by the formula (1) and the metal salt are reacted by heating in the range of 60 to 250 ° C. Is preferred.

  According to the present invention, a novel photofunctional material capable of responding to visible light, a redox reaction catalyst such as a water-splitting photocatalyst using the photofunctional material, and a novel novel suitable for production of the photofunctional material The metal complex and its production method can be provided.

4 is a graph showing an adsorption isotherm of nitrogen at 77K of the metal complex (A) obtained in Example 1. 4 is a graph showing a powder X-ray diffraction pattern of the metal complex (B) obtained in Example 2. 4 is a graph showing a powder X-ray diffraction pattern of the metal complex (C) obtained in Example 3. It is a graph which shows the adsorption | suction isotherm of nitrogen in 77K of the optical functional material (A1) obtained in Example 4.

  The optical functional material of the present invention includes a compound represented by the following formula (1) (hereinafter sometimes referred to as “compound (1)”), magnesium, aluminum, calcium, scandium, titanium, vanadium, chromium, Manganese, iron, cobalt, nickel, copper, gallium, strontium, yttrium, niobium, molybdenum, ruthenium, palladium, silver, cadmium, barium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, One or more metal salts containing one or more metal atoms selected from the group consisting of erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold; , A mixture comprising, containing a metal complex obtained by reacting.

（式中、Ｐは、Ｒ^ａ及びＲ^ｂ以外に置換基を有していてもよい、芳香族炭化水素基、π電子共役系を有する縮環複素環式基、あるいは周期表第２族〜第１２族から選ばれる１種の金属原子と単環芳香族複素環式基及び／又はフェニル基が１以上の単結合で連結された配位子とで構成された金属錯体部位を有する基であり、前記芳香族炭化水素基及び／又はπ電子共役系を有する縮環複素環式基が１以上の単結合で連結された基であってもよく；
Ｒ^ａは式「−ＣＯ_２Ｒ^Ａ」、「−ＳＯ_３Ｒ^Ａ」、「−ＰＯ_４Ｒ^Ａ _２」、「−ＣＯ_２ ⁻」、「−ＳＯ_３ ⁻」、「−ＰＯ_４（Ｒ^Ａ）⁻」又は「−Ｃ≡Ｎ」で表される基（ここで、Ｒ^Ａは水素原子、アルカリ金属原子又は炭素数１〜４のアルキル基である。）であり；ｍは２以上の整数であり、Ｐが前記金属錯体部位を有する基である場合、ｍは４以下であり、複数あるＲ^ａは互いに同一であっても異なっていてもよく；
Ｒ^ｂは、ハロゲン原子、又は式「−ＯＨ」、「−ＯＲ^Ｂ」、「−ＮＨ_２」、「−ＮＲ^Ｂ _２」もしくは「−ＮＯ_２」で表される基（ここで、Ｒ^Ｂは炭素数１〜４のアルキル基、又は炭素数６〜１０のアリール基であり、式「−ＮＲ^Ｂ _２」において２個のＲ^Ｂは、互いに同一であっても異なっていてもよい。）であり；ｎは、Ｐが炭素数６の芳香族炭化水素基である場合には１以上の整数であり、それ以外の場合には０以上の整数であり、ｎが２以上の整数である場合、複数あるＲ^ｂは互いに同一であっても異なっていてもよい。）

(Wherein P is an aromatic hydrocarbon group which may have a substituent other than R ^a and R ^b , a condensed heterocyclic group having a π-electron conjugated system, or Group 2 of the periodic table) A group having a metal complex site composed of one kind of metal atom selected from Group 12 and a monocyclic aromatic heterocyclic group and / or a ligand in which a phenyl group is linked by one or more single bonds. And the aromatic hydrocarbon group and / or the condensed heterocyclic group having a π-electron conjugated system may be a group connected by one or more single bonds;
R ^a formula _"-CO 2 ^{R A",} "- _SO 3 ^{R A",} _"- PO ^{4 R} _{A 2",} "- CO ₂ ^-", "- SO ₃ ^-", _"- PO 4 ^{(R A} ) ^- "Or" -C≡N "(wherein R ^A is a hydrogen atom, an alkali metal atom or an alkyl group having 1 to 4 carbon atoms); m is an integer of 2 or more And when P is a group having the metal complex moiety, m is 4 or less, and a plurality of ^Ra may be the same or different from each other;
R ^b is a halogen atom or a group represented by the formula “—OH”, “—OR ^B ”, “—NH ₂ ”, “—NR ^B ₂ ” or “—NO ₂ ” (where R ^B is alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, two ^{R B} in the formula ^"-NR _{B 2"} may being the same or different.) in Yes; n is an integer of 1 or more when P is an aromatic hydrocarbon group having 6 carbon atoms; otherwise, it is an integer of 0 or more; and n is an integer of 2 or more The plurality of R ^b may be the same as or different from each other. )

  In the present specification, a plurality of "may be the same or different from each other" means that a plurality of "may be all the same or all different, only a part of It may be the same. "

First, the compound (1) will be described. The compound (1) is represented by the formula (1).
In the formula (1), P represents an aromatic hydrocarbon group, a condensed heterocyclic group having a π electron conjugated system, or one metal atom selected from Groups 2 to 12 of the periodic table and a monocyclic aromatic group. Group having a metal complex site composed of a group heterocyclic group and / or a ligand in which a phenyl group is linked by one or more single bonds.
The aromatic hydrocarbon group may be monocyclic or condensed, and preferable examples include benzene, naphthalene, azulene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, picene, perylene, Examples include groups obtained by removing “m + n” hydrogen atoms from an aromatic hydrocarbon compound such as acridine and coronene. The aromatic hydrocarbon compound is preferably benzene, naphthalene, azulene, anthracene, phenanthrene, tetracene, chrysene from the viewpoint that the synthesis of the compound (1) is easy and the visible light absorption property of the optical functional material is more excellent. , Triphenylene, pyrene, pentacene, picene, perylene or acridine, more preferably benzene, naphthalene, azulene, anthracene, tetracene or pentacene.

  The condensed heterocyclic group is a group having a π-electron conjugated system in which two or more rings are condensed, and at least one of the two or more rings has a hetero atom as an atom constituting the ring structure. If it is. Here, preferred examples of the “hetero atom” include an oxygen atom, a nitrogen atom, and a sulfur atom. The hetero ring may have only one hetero atom, or two or more hetero atoms, and in the case of two or more hetero atoms, these hetero atoms may be the same as or different from each other.

  Preferred examples of the condensed heterocyclic group include indole, isoindole, benzimidazole, purine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, acridine, phenazine, carbazole, dibenzofuran, dibenzothiophene, porphyrin, phthalocyanine and the like. Examples include a group formed by removing “m + n” hydrogen atoms from a ring heterocyclic compound. The condensed heterocyclic compound is preferably indole, isoindole, benzimidazole, purine, quinoline from the viewpoint that the compound (1) can be easily synthesized and the optical functional material has better visible light absorption characteristics. , Isoquinoline, quinoxaline, cinnoline, pteridine, acridine, phenazine, carbazole, dibenzofuran or dibenzothiophene. In addition, porphyrin and phthalocyanine may contain any element from Group 1 to Group 14 of the periodic table at the center thereof.

  In the group having the metal complex part, one type of metal atom selected from Groups 2 to 12 of the periodic table is preferably one type of atom selected from Groups 5 to 11 of the periodic table and lanthanoids. . Among these, vanadium, chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, ruthenium, rhodium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, cerium, praseodymium, neodymium, promethium , Samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium or ytterbium atoms, more preferably vanadium, chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, ruthenium, rhodium, iridium or Platinum atom, more preferably manganese, iron, cobalt, nickel, ruthenium, rhodium, osmium, iridium or platinum atom, particularly preferably manganese, iron, Barth, nickel, an atom of ruthenium or platinum, most preferably atoms ruthenium or platinum.

The ligand site constituting the metal complex site is a group in which a monocyclic aromatic heterocyclic group and / or a phenyl group are linked by one or more single bonds, and at most “m + n” hydrogen atoms are excluded. The monocyclic aromatic heterocyclic group is a nitrogen-containing monocyclic aromatic heterocyclic group (a group having a nitrogen atom as an atom constituting the ring structure of the monocyclic aromatic heterocyclic ring). It is preferable.
The ligand part constituting the metal complex part is preferably a group formed by removing at most “m + n” hydrogen atoms from at least monocyclic aromatic heterocyclic groups linked. , Phenylpyridine, bipyridine, bisphenylbipyridine, bisphenylphenanthroline, bispyridylbenzene, terpyridine, 4-phenylterpyridine, 4 ′, 4 ″ -bisphenylterpyridine, quarterpyridine, bipyrazine, 2,2′-bipyrimidine, 2,6-bis (pyrazin-2-yl) pyridine, 2,6-bis (pyrimidin-2-yl) pyridine, 4-phenyl-2,6-bispyrazinylpyridine, 4-phenyl-2,6- Bis (pyrimidin-2-yl) pyridine, 2,4,6-tris (pyridin-2-yl) -1,3,5-triazine or 2,4 , 6-tris (pyrimidin-2-yl) -1,3,5-triazine, etc., from a compound in which a monocyclic aromatic heterocyclic group and / or a phenyl group are linked by one or more single bonds, And a group formed by removing “m + n” hydrogen atoms.

  As a compound in which a monocyclic aromatic heterocyclic group and / or a phenyl group are connected by one or more single bonds, preferably phenylpyridine, bipyridine, bisphenylbipyridine, bisphenylphenanthroline, bispyridylbenzene, terpyridine, 4-phenyl Terpyridine or 2,2′-bipyrimidine is preferable, and 2-phenylpyridine, 2,2′-bipyridine, 5,5′-bisphenyl-2,2′-bipyridine, 1,3-bis (2 -Pyridyl) benzene, 2,2 ': 6', 2 "-terpyridine, 4-phenyl-2,2 ': 6', 2" -terpyridine, 2,2 ': 6', 2 ": 6 '', 2 '' '-quarterpyridine.

  Further, as a compound in which a monocyclic aromatic heterocyclic group and / or a phenyl group are linked by one or more single bonds, 2,2′-bipyridine, 5,5′-bisphenyl-2,2 ′ is more preferable. -Bipyridine, 2,2 ′: 6 ′, 2 ″ -terpyridine, 4-phenyl-2,2 ′: 6 ′, 2 ″ -terpyridine, particularly preferably 2,2′-bipyridine, 4- Phenyl-2,2 ′: 6 ′, 2 ″ -terpyridine.

The number of ligand sites constituting the metal complex site may be one, or two or more. That is, the group having the metal complex part may be composed of one metal atom and one ligand part, or one metal atom and two or more ligand parts. It may be composed of
And when there are two or more ligand moieties, both m R ^a and n R ^b described later may have only one ligand moiety, or two The above ligand sites may be dispersed, and when two or more ligand sites are dispersed, all the ligand sites may have.
The number of ligand sites constituting the metal complex site is limited by the type of metal atom and ligand site combined.

  In the group having the metal complex part, the metal atom may have an auxiliary ligand in addition to the ligand part. The auxiliary ligand may be one type or two or more types.

Examples of the auxiliary ligand include halide ions (fluoride ions, chloride ions, bromide ions, iodide ions), oxide ions, sulfide ions, hydroxide ions, hydride ions, cyanide ions. Inorganic ligands such as thiocyanate ion and carbonyl.
Examples of the auxiliary ligand include trialkylamine compounds (triethylamine, diethylpropylamine, tripropylamine, triisopropylamine, triethylenediamine, etc.), alkoxide ions (methoxide ions, ethoxide ions, isopropoxy ions). Ion), acetate ion, acetylacetonate ion, optionally substituted cyclopentadienyl anion (cyclopentadienyl anion, indenyl anion, fluorenyl anion, etc.), organic substituted Phosphorus compounds (triphenylphosphine, 1,2-bisdiphenylphosphinoethane, 1,3-bisdiphenylphosphinopropane, etc.), optionally substituted nitrogen-containing heterocyclic compounds (pyrazine, pyridazine, pyrimidine, 2, 2'-bipyridine , Phenanthroline, etc.), optionally substituted 2-phenylpyridine radical anion, optionally substituted carboxylic acid anion (oxalate ion, malonate ion, succinate ion, phthalate ion, benzoic acid anion, Salicylic acid anion, etc.), optionally substituted dioxolenes (catecholate, ortho-semiquinonate, ortho-benzoquinone, etc.), optionally substituted dithiolenes (ortho-benzenedithiolate, 3,5-cyclohexadiene-1) , 2-dithione) and the like. Here, “may be substituted” means that one or more hydrogen atoms may be substituted with atoms or groups other than hydrogen atoms, and the number of substituted hydrogen atoms is particularly limited. Not.

  The optionally substituted cyclopentadienyl anion, the optionally substituted organic phosphorus compound, the optionally substituted nitrogen-containing heterocyclic compound, the optionally substituted 2-phenylpyridine radical anion, The substituent in the anion of an optionally substituted carboxylic acid, an optionally substituted dioxolene, an optionally substituted dithiolene, etc. is preferably a halogen atom, a chain carbonization having 4 or less carbon atoms. Phenyl optionally substituted by a hydrogen group (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, etc.) or a methyl group or a halogen atom It is a group.

  The auxiliary ligand is preferably a chloride ion, an oxide ion, a hydroxide ion, a thiocyanate ion, a carbonyl, an optionally substituted cyclohexane from the viewpoint of the stability of the metal complex site and the performance of the optical functional material. Pentadienyl anions, optionally substituted organophosphorus compounds, optionally substituted nitrogen-containing heterocyclic compounds, optionally substituted dioxolenes, more preferably chloride ions, hydroxides Ion, thiocyanate ion, carbonyl, optionally substituted nitrogen-containing heterocyclic compound, optionally substituted dioxolene, more preferably chloride ion, thiocyanate ion, optionally substituted Nitrogen heterocyclic compounds and optionally substituted dioxolenes, most preferably chloride ions, thiocyanate ions, Is a nitrogen-containing heterocyclic compound be.

In the group having the metal complex part, water, methanol, ethanol, propanol, ethylene glycol, diethyl ether, tetrahydrofuran, dimethoxyethane, 1,4-dioxane, pyridine, acetone, acetonitrile, N, N-dimethylformamide, Solvent molecules such as N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, benzene, toluene and xylene may be coordinated.
The solvent molecule to be coordinated depends on the type of solvent used in the production of the complex, but is preferably water, methanol, acetonitrile from the stability of the complex, reactivity during complex production, safety in handling during reaction, etc. N, N-dimethylformamide or N, N-dimethylacetamide, more preferably water or methanol.

  The P may be a group in which the aromatic hydrocarbon group and / or a condensed heterocyclic group having a π electron conjugated system is connected by one or more single bonds.

  In the group in which the aromatic hydrocarbon group and / or the condensed heterocyclic group having a π-electron conjugated system is connected by one or more single bonds, the number of the single bonds is the compound ( From the point that the solubility of 1) is good, it is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4.

  Examples of the group in which the aromatic hydrocarbon group and / or the condensed heterocyclic group having a π electron conjugated system are linked by one or more single bonds include biphenyl, terphenyl, 2,4,6-tri Examples include groups obtained by removing “m + n” hydrogen atoms from an aromatic compound such as phenylbenzene and 5,10,15,20-tetraphenylporphyrin.

The P may have a substituent other than R ^a and R ^b described later, and when the number of substituents is 2 or more, these substituents may be the same or different from each other. May be. Examples of the substituent include a silyl group in which one or more hydrogen atoms are substituted with an alkyl group having 1 to 4 carbon atoms; and an alkyl group having 1 to 30 carbon atoms.

  The alkyl group having 1 to 4 carbon atoms in the silyl group may be linear, branched or cyclic, but is preferably linear or branched, and examples thereof include a methyl group, Examples include ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. When the alkyl group is 2 to 3 (when the substitution number of the silyl group with the alkyl group is 2 to 3), these alkyl groups may be the same as or different from each other.

The alkyl group having 1 to 30 carbon atoms may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic.
The alkyl group having 1 to 30 carbon atoms preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Examples thereof 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, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3- Methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethyl Pentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl , Isooctyl group, nonyl group, decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2- Examples include an adamantyl group and a tricyclodecyl group.

The substituent other than R ^a and R ^b possessed by P is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group or an ethyl group, from the viewpoint of easy synthesis of the compound (1). N-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, and tert-butyl group.

In the formula (1), R ^a is represented by the formula “—CO ₂ R ^A ”, “—SO ₃ R ^A ”, “—PO ₄ R ^A ₂ ”, “—CO ₂ ^— ”, “—SO ₃ ^— ”, It is a group represented by “—PO ₄ (R ^A ) ^— ” or “—C≡N”. Here, ^RA is a hydrogen atom, an alkali metal atom, or an alkyl group having 1 to 4 carbon atoms.
Examples of the alkali metal atom in ^RA include a lithium atom, a sodium atom, a potassium atom, a rubidium atom, and a cesium atom.
The C1-C4 alkyl group in ^RA is the same as the C1-C4 alkyl group as substituents other than R ^<a> and R ^{<b > which} P has.

Since Ra interacts with a cation as described later, R ^a is represented by the formula “—CO ₂ R ^A ”, “—SO ₃ R ^A ” or “—PO ₄ R ^A ₂ ” which can be an anion. Or a group represented by the formula “—CO ₂ ^— ”, “—SO ₃ ^— ” or “—PO ₄ (R ^A ) ^— ” which is an anion, and interaction with a cation From the viewpoint of the strength, it is more preferably a group represented by the formula “—CO ₂ R ^A ” or “—CO ₂ ^— ”.
In addition, from the viewpoint of easily becoming an anion, R ^A is preferably a hydrogen atom or an alkali metal atom. R ^A is more preferably a hydrogen atom because the removal of the inorganic salt produced during the interaction with the cation can be omitted.

In the formula (1), m is an integer of 2 or more. And since the said compound (1) acts as a ligand bridge | crosslinking between metals, m becomes like this. Preferably it is 2-8, More preferably, it is 2-6, More preferably, it is 2-4. However, when P is a group having the metal complex part, m is 4 or less.
A plurality of ^Ra may be the same as or different from each other. And from the point that the synthesis | combination of a compound (1) is easy, it is preferable that all ^Ra is the same.

In the formula (1), R ^b is a halogen atom or a group represented by the formula “—OH”, “—OR ^B ”, “—NH ₂ ”, “—NR ^B ₂ ” or “—NO ₂ ”. It is. Here, ^{R B} is an alkyl group, or an aryl group having 6 to 10 carbon atoms having 1 to 4 carbon atoms, two ^{R B} in the formula ^"-NR _{B 2"} is not being the same or different May be.

Examples of the halogen atom in R ^b include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Alkyl group having 1 to 4 carbon atoms in R ^B are the same as the alkyl group having 1 to 4 carbon atoms as a substituent other than ^{R a} and ^{R b} wherein P has.

Aryl group having 6 to 10 carbon atoms in R ^B may be either monocyclic and fused-ring, and examples thereof include phenyl, 1-naphthyl, 2-naphthyl group in which one or more hydrogen atoms And a phenyl group having a substituent substituted with an alkyl group having 1 to 4 carbon atoms. Here, the C1-C4 alkyl group as a substituent in a phenyl group is the same as the C1-C4 alkyl group as substituents other than R ^<a> and R ^<b > which said P has, and this alkyl When the number of groups is 2 or more (when the number of substituents in the phenyl group is 2 or more), these alkyl groups may be the same as or different from each other. Examples of the phenyl group having the substituent include toluene, o-xylene (1,2-dimethylbenzene), m-xylene (1,3-dimethylbenzene) or p-xylene (1,4-dimethylbenzene). And a group formed by removing one hydrogen atom from an aromatic ring.

In the formula (1), n is an integer of 1 or more when the P is an aromatic hydrocarbon group having 6 carbon atoms (a group obtained by removing a hydrogen atom from benzene), and otherwise. Is an integer of 0 or more. ^Rb has the effect of lengthening the absorption wavelength of P in formula (1). And by setting n in this way, the response sensitivity to visible light can be improved in the metal complex described later.
And when P is a C6 aromatic hydrocarbon group, n becomes like this. Preferably it is 1-4, More preferably, it is 1-3. When P is other than an aromatic hydrocarbon group having 6 carbon atoms, n is preferably 0 to 4, more preferably 0 to 3, and further preferably 0 to 2. When n is an integer of 2 or more, a plurality of R ^b may be the same as or different from each other.

  In the optical functional material of the present invention, the compound (1) may be used alone or in combination of two or more. That is, the said mixture for obtaining the metal complex contained in the said optical functional material may contain only 1 type of the said compound (1), and may contain 2 or more types.

Examples of preferred compounds (1) are shown below. In the compound (1) shown below, for example, “—COOH” may be “—SO ₃ H”, “—PO ₄ H ₂ ” or “—CN”, or “—COO ⁻ ” "-SO ₃ ^-" or ^- may be _"-PO 4 H".

Next, the metal salt will be described.
Metal salts include magnesium, aluminum, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, gallium, strontium, yttrium, niobium, molybdenum, ruthenium, palladium, silver, cadmium, barium, lanthanum, One selected from the group consisting of cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold Contains two or more metal atoms.
Among these, from the viewpoint of easy handling, the metal atom is preferably scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, gallium, yttrium, niobium, molybdenum, cadmium, lanthanum, cerium, Praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, more preferably scandium, titanium, vanadium, manganese, iron, cobalt, nickel, yttrium , Niobium, hafnium, and tantalum, and more preferably scandium, titanium, vanadium, manganese, iron, cobalt, and nickel.
And since the stability of the structure formed is higher, the metal atom is particularly preferably scandium or titanium, and most preferably titanium.

  The metal salt usually has the metal atom as a cation. And since this cation needs to form a metal complex with several said compound (1), it is preferable that the valence is 2-7, and it is more preferable that it is 2-6, 2 Is more preferably -4, and most preferably 3-4.

The metal salt usually has the metal atom as a cation and an anion as a counter ion so that the entire metal salt is electrically neutral. Preferred examples of such anions include fluoride ions, chloride ions, bromide ions, iodide ions, oxide ions, sulfide ions, hydroxide ions, hydride ions, sulfite ions, phosphate ions, Cyanide ion, acetate ion, carbonate ion, sulfate ion, nitrate ion, bicarbonate ion, trifluoroacetate ion, thiocyanate ion, trifluoromethanesulfonate ion, tetrafluoroborate ion, hexafluorophosphate ion, tetraphenylboron And acid ions, tetrakis (3,5-bis (trifluoromethyl) phenyl) borate ions, acetylacetonate ions, alkoxide ions (methoxide ions, ethoxide ions, isopropoxide ions, etc.).
Among these, anions are more preferably chloride ions, bromide ions, iodide ions, acetate ions, sulfate ions, nitrate ions, and alkoxide ions, and further preferably chloride ions, nitrate ions, and alkoxide ions. .
When the metal salt has a plurality of anions, the plurality of anions may be the same as or different from each other.

In addition to the cation and the anion, the metal salt may have as a ligand a molecule that solvates to form a solvated salt.
Examples of molecules that solvate to form solvated salts include water, methanol, ethanol, 2-propanol (isopropyl alcohol), ethylene glycol, N, N-dimethylformamide, N, N-diethylformamide, N, N -Dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, acetone, chloroform, acetonitrile, benzonitrile, triethylamine, pyridine, pyrazine, diazabicyclo [2,2,2] octane, 4,4'-bipyridine, tetrahydrofuran, diethyl Examples include ether, dimethoxyethane, methyl ethyl ether, 1,4-dioxane, and among these, water, methanol, ethanol, 2-propanol, ethylene glycol, N, N-dimethylformamide, N, N-diethylformamide.
When the metal salt has a plurality of molecules that solvate to form a solvated salt, the plurality of molecules may be the same or different.

  In the optical functional material of the present invention, the metal salt may be used alone or in combination of two or more. That is, the said mixture for obtaining the metal complex contained in the said optical functional material may contain only 1 type of the said metal salt, and may contain 2 or more types.

  The optical functional material of the present invention is an optical functional material containing a metal complex obtained by reacting a mixture containing the compound (1) and the metal salt.

  The metal complex is preferably produced by, for example, blending the compound (1), the metal salt, and a solvent, and reacting the obtained liquid. The liquid may be a solution in which the compound (1) and the metal salt are dissolved, or may be a suspension in which at least a part of the compound (1) and / or the metal salt is not dissolved.

The solvent is preferably a polar solvent, and examples thereof include N, N-dimethylformamide, N, N-diethylformamide, water, methanol, ethanol, 2-propanol, dimethyl sulfoxide, N, N-dimethylacetamide. N-methyl-2-pyrrolidone and the like. Among these, it is more preferable that the solvent is N, N-dimethylformamide, N, N-diethylformamide, water, methanol, or ethanol because the compound (1) and the metal salt are more easily dissolved.
The said solvent to be used may be only 1 type, and 2 or more types may be sufficient as it.

  The molar ratio (compound (1) / metal salt) between the compound (1) and the metal salt used in the production of the metal complex is preferably 0.5 to 3.0, more preferably 0.8 to 2.5. It is. By doing in this way, the yield of a metal complex improves more.

  The concentration of the compound (1) in the liquid is preferably 0.05 to 1000 mmol / L, more preferably 0.07 to 500 mmol / L. By doing in this way, the solubility of a compound (1) can be improved and the yield of a metal complex improves more.

  The concentration of the metal salt in the liquid is preferably 0.01 to 1000 mmol / L, more preferably 0.05 to 500 mmol / L. By doing in this way, the solubility of a metal salt can be improved and the yield of a metal complex improves more.

  The reaction conditions of the mixture may be appropriately adjusted according to the types of the compound (1), the metal salt, and the solvent, but the reaction is preferably performed by heating in the range of 60 to 250 ° C. It is more preferable to heat the reaction in the range of ° C, and it is more preferable to heat the reaction in the range of 100 to 200 ° C. This is because the yield of the metal complex is further improved.

  When heating the liquid material, it may be heated in an air atmosphere or may be heated under normal pressure, but the reaction vessel is under a high pressure of 0.1 to 100 MPa due to volatilization of the solvent during heating. In such a case, it is preferable to use a sealed reaction vessel such as an autoclave. Moreover, an oil bath, oven, etc. may be used for a heating, and you may heat by irradiation of a microwave or an ultrasonic wave.

  The heating time of the liquid material may be appropriately adjusted according to the types of the compound (1), the metal salt and the solvent, but is usually 1 minute to 1 week, preferably 1 to 120 hours, More preferably, it is 2 to 72 hours.

  Since the metal complex tends to precipitate after completion of the reaction under the above production conditions, it can be easily separated by, for example, filtration after completion of the reaction. The separated metal complex may be subjected to post-treatment operations such as washing and drying as necessary.

  The optical functional material of the present invention may be obtained by using other components in addition to the compound (1) and the metal salt. The optical functional material using other components can be obtained by blending other components when the liquid material is prepared.

Preferable examples of the other components include auxiliary ligands used when forming a metal complex.
Examples of auxiliary ligands include compounds having two nitrogen atoms, such as pyridazine, pyrimidine, pyrazine, 2,2'-bipyridyl, 3,3'-bipyridyl, 4,4'-bipyridyl, triethylenediamine; Acid (ethanedioic acid), malonic acid (propanedioic acid), succinic acid (butanedioic acid), phthalic acid (benzene-1,2-dicarboxylic acid), isophthalic acid (benzene-1,3-dicarboxylic acid), terephthalic acid Examples thereof include compounds having two carboxyl groups, such as acid (benzene-1,4-dicarboxylic acid).
Among these, the auxiliary ligand is preferably pyrazine, 4,4′-bipyridyl, triethylenediamine, oxalic acid, or terephthalic acid, and more preferably pyrazine, 4,4′- from the viewpoint of excellent handleability. Bipyridyl and triethylenediamine.

  As a preferable example of the metal complex, a mixture containing a compound represented by the following formula (2) (hereinafter sometimes referred to as “compound (2)”) and a metal salt containing a titanium atom is reacted. Can be obtained.

（式中、Ｐ^１は、Ｒ^ａ１及びＲ^ｂ１以外に置換基を有していてもよい、芳香族炭化水素基、π電子共役系を有する縮環複素環式基、あるいは周期表第２族〜第１２族から選ばれる１種の金属原子と単環芳香族複素環式基及び／又はフェニル基が１以上の単結合で連結された配位子とで構成された金属錯体部位を有する基であり、前記芳香族炭化水素基及び／又はπ電子共役系を有する縮環複素環式基が１以上の単結合で連結された基であってもよく；
Ｒ^ａ１は式「−ＣＯ_２Ｒ^Ａ１」、「−ＳＯ_３Ｒ^Ａ１」、「−ＰＯ_４Ｒ^Ａ１ _２」、「−ＣＯ_２ ⁻」、「−ＳＯ_３ ⁻」、「−ＰＯ_４（Ｒ^Ａ１）⁻」又は「−Ｃ≡Ｎ」で表される基（ここで、Ｒ^Ａ１は水素原子、アルカリ金属原子又は炭素数１〜４のアルキル基である。）であり；ｍ１は２以上の整数であり、Ｐ^１が前記金属錯体部位を有する基である場合、ｍ１は４以下であり、複数あるＲ^ａ１は互いに同一であっても異なっていてもよく；
Ｒ^ｂ１は、ハロゲン原子、又は式「−ＯＨ」、「−ＯＲ^Ｂ１」、「−ＮＨ_２」、「−ＮＲ^Ｂ１ _２」もしくは「−ＮＯ_２」で表される基（ここで、Ｒ^Ｂ１は炭素数１〜４のアルキル基、又は炭素数６〜１０のアリール基であり、式「−ＮＲ^Ｂ１ _２」において２個のＲ^Ｂは、互いに同一であっても異なっていてもよい。）であり；ｎ１は、Ｐ^１が炭素数６の芳香族炭化水素基である場合には１以上の整数であり、それ以外の場合には０以上の整数であり、ｎ１が２以上の整数である場合、複数あるＲ^ｂ１は互いに同一であっても異なっていてもよい。）

(In the formula, P ¹ is an aromatic hydrocarbon group which may have a substituent other than R ^a1 and R ^b1 , a condensed heterocyclic group having a π electron conjugated system, or Group 2 of the periodic table) A group having a metal complex site composed of one metal atom selected from Group 12 and a monocyclic aromatic heterocyclic group and / or a ligand in which a phenyl group is linked by one or more single bonds And the aromatic hydrocarbon group and / or the condensed heterocyclic group having a π-electron conjugated system may be a group connected by one or more single bonds;
R ^a1 formula _"-CO 2 ^{R A1",} _"- SO ^{3 R A1",} _"- PO ^{4 R A1} _2", "- CO ₂ ^-", "- SO ₃ ^-", _"- PO 4 ^{(R A1} ) ^- "Or" -C≡N "(wherein R ^A1 is a hydrogen atom, an alkali metal atom or an alkyl group having 1 to 4 carbon atoms); m1 is an integer of 2 or more And when P ¹ is a group having the metal complex moiety, m1 is 4 or less, and a plurality of R ^a1 may be the same or different from each other;
R ^b1 is a halogen atom or a group represented by the formula “—OH”, “—OR ^B1 ”, “—NH ₂ ”, “—NR ^B1 ₂ ” or “—NO ₂ ” (where R ^B1 is alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, two ^{R B} in the formula ^{"-NR B1} _2" may being the same or different.) in There; n1 is an integer of 1 or more in the case P ¹ is an aromatic hydrocarbon group of 6 carbon atoms, and otherwise an integer of 0 or more, n1 is 2 or more integer In this case, a plurality of R ^b1 may be the same as or different from each other. )

In the formula (2), P ¹ , R ^a1 , R ^A1 , m1, R ^b1 , R ^B1 , n1 are respectively P, R ^a , R ^A , m, R ^b , in the formula (1). R ^B, same ones exemplified as n.
Therefore, for example, a plurality of R ^a1 may be the same or different from each other, and in the formula “—NR ^B1 ₂ ”, two R ^B1 may be the same or different from each other, and n1 is When it is an integer of 2 or more, a plurality of R ^b1 may be the same as or different from each other.

P ¹ may have a substituent other than R ^a1 and R ^b1 , and when the number of substituents is 2 or more, these substituents may be the same or different from each other. It may be.
Examples of the substituent other than R ^a1 and R ^b1 possessed by P ¹ include the same substituents as those other than R ^a and R ^b possessed by P in the formula (1).

  When the metal complex is a coordination polymer, such a metal complex is preferable because it can be easily used as a heterogeneous catalyst. In this specification, the coordination polymer means a metal complex that forms an integrated structure through at least one type of bond selected from the group consisting of a coordination bond and an ionic bond.

The metal complex preferably forms a porous structure. The metal complex forming the porous structure preferably has a BET specific surface area of 100 m ² g ⁻¹ or more, and more preferably 300 m ² g ⁻¹ or more. By forming a porous structure and increasing the specific surface area, the number of active sites per unit weight of the metal complex is increased, and thus an improvement in catalytic activity is expected.

As described above, the metal complex is obtained by reacting the mixture containing the compound (1) and the metal salt containing the metal atom. On the other hand, a metal complex having a specific structure can also be obtained by other production methods described below.
Here, the metal complex having a specific structure is, for example, a group having the metal complex part, in which P may have a substituent other than ^Ra , and a coordination constituting the metal complex part. has a R ^a of 2 or more per child site, the a one in which the metal atom is selected from group 5 to 11 and group lanthanide periodic table for the metal complex sites, n is 0, R ^a is formula _"-CO 2 ^{R A",} "- _SO 3 ^{R A",} _"- PO ^{4 R} _{A 2",} "- CO ₂ ^-", "- SO ₃ ^-" or _"-PO 4 ^{(R A} ) ⁻ ”And one or more metal salts containing one or more metal atoms selected from the group consisting of scandium, titanium, gallium and yttrium. And are obtained by using.

  The other production method means that in the compound (1), P is not a group having the metal complex portion, but a metal atom (one metal atom selected from Groups 5 to 11 and lanthanoid of the periodic table). A compound that does not include a monocyclic aromatic heterocyclic group and / or a group in which a phenyl group is connected to one or more single bonds from a maximum of m hydrogen atoms. After using and reacting the mixture containing this and the metal salt to obtain a reaction product, the reaction product obtained contains one metal atom selected from Groups 5 to 11 of the periodic table and lanthanoids. In this method, a metal salt is reacted to obtain the metal complex. This method uses a compound containing a structure in which one metal atom selected from Group 5 to Group 11 of the periodic table and lanthanoid is removed from the metal complex, and from Group 5 to Group 11 of the periodic table and lanthanoid. One selected metal atom is finally introduced and reacted.

  Such a metal complex is a structure represented by the following formula (3) (hereinafter sometimes referred to as “structure (3)”) and one or more selected from the group consisting of scandium, titanium, gallium, and yttrium. A metal complex containing ions of two or more metals (preferably titanium) (hereinafter sometimes referred to as “precursor metal complex”) is selected from Group 5 to Group 11 of the periodic table and lanthanoid 1 It can be produced by reacting with a metal salt containing a seed metal atom. In the obtained metal complex, the ligand in the precursor metal complex is coordinated to one metal atom selected from Group 5 to Group 11 of the periodic table and lanthanoid.

（式中、Ｐ^２は、Ｒ^ａ２以外に置換基を有していてもよい、単環芳香族複素環式基及び／又はフェニル基が１以上の単結合で連結された基からなる有機部位を有する基であり、単環芳香族複素環式基が連結されている場合、前記単環芳香族複素環式基の環構造を構成するヘテロ原子が、前記金属のイオン又はその他の金属のイオンに配位しておらず；
Ｒ^ａ２は式「−ＣＯ_２ ⁻」、「−ＳＯ_３ ⁻」又は「−ＰＯ_４（Ｒ^Ａ２）⁻」で表される基（ここで、Ｒ^Ａ２は水素原子又は炭素数１〜４のアルキル基である。）であり；
ｍ２は２以上の整数であり、複数あるＲ^ａ２は互いに同一であっても異なっていてもよい。）

(In the formula, P ² is an organic moiety comprising a monocyclic aromatic heterocyclic group and / or a group in which a phenyl group is linked by one or more single bonds, which may have a substituent other than R ^a2. And when the monocyclic aromatic heterocyclic group is linked, the hetero atom constituting the ring structure of the monocyclic aromatic heterocyclic group is an ion of the metal or other metal ion Not coordinated to;
R ^a2 is a group represented by the formula “—CO ₂ ^— ”, “—SO ₃ ^— ” or “—PO ₄ (R ^A2 ) ^— ” (wherein R ^A2 is a hydrogen atom or an alkyl having 1 to 4 carbon atoms). A group);
m2 is an integer of 2 or more, and a plurality of R ^a2 may be the same as or different from each other. )

In the formula (3), P ² may have a substituent other than R ^a2 , and may be a monocyclic aromatic heterocyclic group and / or a group in which a phenyl group is linked by one or more single bonds. The organic part is the same as that obtained by removing the metal atom from the metal complex part in P in the formula (1).
However, when a monocyclic aromatic heterocyclic group is linked in the organic moiety, when reacted with a metal salt containing one type of metal atom selected from Groups 5 to 11 and lanthanoids of the periodic table In addition, the hetero atom constituting the ring structure of the monocyclic aromatic heterocyclic group connected so as to be able to coordinate to the metal atom is composed of the metal ion (scandium, titanium, gallium and yttrium). One or two or more metal ions selected from the group) or other metal ions are not coordinated. Here, examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. The other metal ions mean ions of metals other than scandium, titanium, gallium and yttrium.

  The monocyclic aromatic heterocyclic group is preferably a nitrogen-containing monocyclic aromatic heterocyclic group (a group having a nitrogen atom as an atom constituting the ring structure of the monocyclic aromatic heterocyclic ring), and a pyridyl group It is more preferable that

The organic moiety is preferably one having at least a monocyclic aromatic heterocyclic group linked thereto, and may have a substituent other than R ^a2 , 2-phenylpyridine, 2,2′-bipyridine, 5 , 5′-bisphenyl-2,2′-bipyridine, 1,3-bis (2-pyridyl) benzene, 2,2 ′: 6 ′, 2 ″ -terpyridine, 4-phenyl-2,2 ′: 6 It is more preferably a group formed by removing m2 hydrogen atoms from ', 2 ″ -terpyridine or 2,2 ′: 6 ′, 2 ″: 6 ″, 2 ′ ″-quarterpyridine.
The organic moiety is also preferably a group formed by removing m2 hydrogen atoms from a phenylcyclopentadienide anion or a 1,3-bisphenylcyclopentadienide anion.

In the formula (3), R ^a2 is a group represented by the formula “—CO ₂ ^— ”, “—SO ₃ ^— ” or “—PO ₄ (R ^A2 ) ^— ”. Here, R ^A2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and examples of the alkyl group are the same as those of the alkyl group having 1 to 4 carbon atoms in ^RA in the formula (1). it can.

In the formula (3), m2 is the same as m in the formula (1). Therefore, for example, a plurality of R ^a2 may be the same as or different from each other.

  In the precursor metal complex, the molar ratio of the structure (3) to the metal ion (structure (3) / metal ion) is preferably 0.5 to 3.

In the precursor metal complex, R ^a2 is coordinated to the metal ion.

As the precursor metal complex, for example, instead of the compound (1), a compound that is a raw material of the structure (3) is used, and one or two kinds selected from the group consisting of scandium, titanium, gallium, and yttrium as a metal salt It can be produced by the same method as in the case of the metal complex except that one containing the above metal atoms is used. For example, the reaction temperature is preferably 60 to 250 ° C.
As an example of a compound which is a raw material of the structure (3), in the structure (3), an anion of R ^a2 is bonded to a hydrogen ion, an alkali metal ion or an alkyl cation having 1 to 4 carbon atoms, that is, R ^a2 The thing substituted by ^Ra in the said compound (1) is mentioned.

Preferred examples of one metal atom selected from Groups 5 to 11 of the periodic table and lanthanoids are the same as the preferred examples of the metal atom in the group having the metal complex moiety.
The metal salt containing one metal atom selected from Groups 5 to 11 of the periodic table and lanthanoids is preferably a metal salt containing a titanium atom.

  The said metal complex which the optical functional material of this invention contains may be only 1 type, and 2 or more types may be sufficient as it.

  In the other production method, for example, a precursor metal complex and a metal salt containing one metal atom selected from Group 5 to Group 11 of the periodic table and a lanthanoid are mixed and reacted in a solvent. .

The metal salt used in the other production method usually has the metal atom as a cation and an anion as a counter ion so that the entire metal salt is electrically neutral. Preferred examples of such anions include fluoride ions, chloride ions, bromide ions, iodide ions, oxide ions, sulfide ions, hydroxide ions, hydride ions, sulfite ions, phosphate ions, Cyanide ion, acetate ion, carbonate ion, sulfate ion, nitrate ion, bicarbonate ion, trifluoroacetate ion, thiocyanate ion, trifluoromethanesulfonate ion, tetrafluoroborate ion, hexafluorophosphate ion, tetraphenylboron An acid ion is mentioned.
Among these, the anions are more preferably chloride ions, bromide ions, iodide ions, acetate ions, sulfate ions, and nitrate ions, and further preferably chloride ions and nitrate ions.
When the metal salt used in the other production method has a plurality of anions, the plurality of anions may be the same as or different from each other.

The reaction temperature in the other production method may be adjusted as appropriate according to the type of the precursor metal complex, metal salt, and solvent to be used, but is preferably -20 to 100 ° C, and has the effect of preventing side reactions. Since it is high, it is more preferable that it is 0-80 degreeC.
The reaction pressure is not particularly limited and is usually normal pressure, but is preferably 0.01 to 10 MPa, more preferably 0.05 to 1 MPa.

The solvent used in the other production method is preferably a solvent capable of dissolving at least a part of a metal salt containing one type of metal atom selected from Group 5 to Group 11 of the periodic table and a lanthanoid. N, N-dimethylformamide, N, N-diethylformamide, water, methanol, ethanol, 2-propanol, dimethyl sulfoxide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, acetone, chloroform, dichloromethane, tetrahydrofuran, Examples include acetonitrile.
Among these, since the drying treatment after the reaction is easy, the solvent is more preferably methanol, ethanol, acetone, chloroform, dichloromethane, tetrahydrofuran, or acetonitrile.
The said solvent to be used may be only 1 type, and 2 or more types may be sufficient as it.

  In the metal complex obtained by the other production method, when one metal atom selected from Group 5 to Group 11 of the periodic table and a lanthanoid further has an auxiliary ligand, the other production method further includes: You may have the process of introduce | transducing an auxiliary ligand. By introducing a suitable auxiliary ligand, the photocatalytic performance of the metal complex is expected to be improved. The auxiliary ligand here is preferably chloride ion, thiocyanate ion, 2,2′-bipyridine and 2,2 ′: 6 ′, 2 ″ -terpyridine, more preferably thiocyanate ion, Examples include 2,2′-bipyridine and 2,2 ′: 6 ′, 2 ″ -terpyridine.

  Since the metal complex can respond to visible light (for example, a wavelength band of 380 to 780 nm), an optical functional material obtained using the metal complex is also capable of responding to visible light. .

  The optical functional material of the present invention includes the metal complex, and may be composed of only the metal complex or may include components other than the metal complex. Preferable examples of components other than the metal complex include metal particles and other metal complexes, and metal particles are more preferable. In the present specification, unless otherwise specified, the description of mere “metal complex” means a metal complex obtained by reacting the mixture, and “other metal complexes” and The “precursor metal complex” is different from the above.

  Examples of the material of the metal particles include manganese, iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold. Among these, more excellent photocatalytic ability. Is preferable, ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold, and more preferably ruthenium, rhodium, palladium, osmium, iridium, and platinum.

The optical functional material containing metal particles can be produced by, for example, the following photodeposition method or impregnation method.
The photo-deposition method is to reduce the metal ions by irradiating a liquid containing a reducing agent, a metal ion that is a precursor for forming metal particles, the metal complex, and a solvent, In this method, the produced metal particles are attached to the metal complex and the solvent is removed.
The impregnation method is a method of immersing the metal complex in a metal-containing colloid, impregnating the metal complex with the metal complex, and removing the solvent.

The content of the metal particles in the optical functional material is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less.
The content of the metal particles of the optical functional material is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, further preferably 0.1% by mass or more, and particularly preferably 0.2% by mass. % Or more.

Examples of preferable other metal complexes include those represented by the following formula.
In other metal complexes represented by the following formula, for example, X ¹ means ^one selected from BF ₄ ⁻ , PF ₆ ⁻ , NO ₃ ⁻ and ClO ₄ ⁻ , X ⁶ and ^{X 8} is similar. X ² means one or two selected from BF ₄ ⁻ , PF ₆ ⁻ , NO ₃ ⁻ and ClO ₄ ^— , and this means that X ³ , X ⁴ , X ⁵ , X ⁷ And X ⁹ are the same. M means Mn, Fe or Ru. Further, M ² is Fe or Co, which means that all three M ² may be the same or only two may be the same.

The optical functional material containing the other metal complex can be produced by, for example, an impregnation method shown below.
Here, the impregnation method is to immerse the metal complex (not other metal complex) in a colloid or solution containing other metal complex, impregnate the metal complex with the metal complex, and remove the solvent. Is the method.

The content of the other metal complex of the optical functional material is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.
Further, the content of other metal complexes of the optical functional material is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 1.0% by mass or more.

  Among the other metal complexes exemplified above, those containing 2,2′-bipyridine or 2,2 ′: 6 ′, 2 ″ -terpyridine as a ligand are as follows: 2 ′: 6 ′, 2 ″ -terpyridine obtained by introducing a carboxyl group may be used.

  The components other than the metal complex contained in the optical functional material may be only one type or two or more types.

  The content of the metal complex in the optical functional material is preferably 85% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 97% by mass or more.

  The optical functional material according to the present invention exhibits a photocatalytic effect, a sensitizing effect, a photoelectric conversion effect, a heat generation effect, a magneto-optical effect, an optical recording effect, a radical generation effect, etc. by absorbing light, particularly visible light. For example, photocatalysts, redox reaction photocatalysts (water decomposition photocatalysts, organic redox photocatalysts, carbon dioxide reduction photocatalysts, etc.), redox photocatalyst sensitizing dyes (water decomposition photocatalyst sensitizing dyes, organic redox photocatalysts Sensitizing dye, sensitizing dye for carbon dioxide reduction photocatalyst, etc.), photoelectric conversion material, sensitizing dye for photoelectric conversion, light emitting material, photoconductive material, light absorbing material and the like.

  The water-splitting photocatalyst expresses photocatalytic ability by absorbing light, exerts a redox action on water, and generates hydrogen and / or oxygen. The water-splitting photocatalyst can be distinguished by calling it an oxygen-generating photocatalyst when it only shows an oxidizing action and a hydrogen-generating photocatalyst when it shows only a reducing action.

  The organic redox photocatalyst expresses photocatalytic ability by absorbing light, exerts at least one action selected from the group consisting of reducing action and oxidizing action on the organic substance, and gives different compounds. The organic redox photocatalyst can be distinguished by calling it an organic redox photocatalyst when it shows only an oxidizing action on the organic matter, and an organic redox photocatalyst when it shows only a reducing action on the organic matter.

  The organic redox photocatalyst can exert at least one action selected from the group consisting of a reducing action and an oxidizing action on various substrates. Examples of the reducing action include reduction of a nitro compound, reduction of a carbonyl compound, halogenation of a halogenated compound, and hydrogenation of a double bond. Preferred reduction actions include reduction of a nitro compound and reduction of a carbonyl compound. is there. Examples of the oxidizing action include oxidation of amine compounds, oxidation of alcohols, and oxidation of aldehydes.

For example, when the oxidation-reduction reaction photocatalyst exerts a reducing action, the oxidation-reduction reaction photocatalyst temporarily enters a high oxidation state. By being reduced by a substance other than the product, it returns to the oxidized state before absorbing light. The substance that reduces the oxidation-reduction reaction photocatalyst in a highly oxidized state is not particularly limited as long as it can reduce the oxidized oxidation-reduction reaction photocatalyst. However, since it is easily available and relatively inexpensive, Methanol or triethanolamine is preferable, and triethanolamine is more preferable because of its relatively high reducing ability.
Further, for example, when the oxidation-reduction reaction photocatalyst exerts an oxidizing action, the oxidation-reduction reaction photocatalyst is temporarily in a low oxidation state. And by being oxidized by a substance other than the product, it returns to the oxidation state before absorbing light. The substance that oxidizes the redox reaction photocatalyst in the low oxidation state is not particularly limited as long as it can oxidize the reduced redox reaction photocatalyst, but silver nitrate is easy to obtain and relatively inexpensive. Silver compounds such as silver oxide are preferred.

  Since the optical functional material of the present invention comprises the metal complex, it can exhibit various excellent functions by absorbing visible light. And solar light energy can be utilized more effectively than before.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples. In this example, measurement of powder X-ray diffraction (hereinafter referred to as “XRD”) of a metal complex and creation of an adsorption isotherm, analysis by gas chromatography in the test of water splitting photocatalytic ability of the photofunctional material, In addition, the analysis by gas chromatography in the test of the organic redox photocatalytic ability of the photofunctional material was performed under the following conditions.

(Measurement conditions of powder XRD of metal complex)
Apparatus: “LabX XRD-6100” manufactured by Shimadzu Corporation
X-ray tube: Cu-Kα
X-ray output: 40kV-30mA
Exposure time: 3300 seconds Resolution: 0.02 °
Angular measuring range: 5-60 °

(Conditions for creating adsorption isotherms for metal complexes)
Equilibrium time: Nitrogen 10 minutes (P / P ₀ : _{0 to} 0.17, P represents the equilibrium pressure, and P ₀ represents the saturated vapor pressure)

(Analysis conditions of gas chromatography in water-decomposing photocatalytic activity test of photofunctional materials)
Apparatus: “GC-12A” manufactured by Shimadzu Corporation
Detector: Thermal conductivity detector (TCD)
Carrier gas: Argon Column: MS-5A
Detector temperature: 150 ° C
Column temperature: 60 ° C
Detector current value: 60 mA

(Analysis conditions of gas chromatography in the test of organic redox photocatalytic activity of photofunctional materials)
Equipment: “GC-14B” manufactured by Shimadzu Corporation
Detector: Hydrogen flame ionization detector (FID)
Carrier gas: Helium Column: InertCap 1
Vaporization chamber temperature: 200 ° C
Detector temperature: 200 ° C
Column temperature: 120 ° C

<Manufacture of metal complexes>
[Example 1]
Into a crucible made of polytetrafluoroethylene, 2.0 g of 2-aminoterephthalic acid, 2.4 mL of tetraisopropyl orthotitanate, 36 mL of N, N-dimethylformamide (hereinafter referred to as “DMF”) and 4 mL of methanol were added. And the crucible was sealed with a stainless steel jacket. At this time, the molar ratio of 2-aminoterephthalic acid to tetraisopropyl orthotitanate (2-aminoterephthalic acid: tetraisopropyl orthotitanate) was 1.3: 1, and the concentration of 2-aminoterephthalic acid was 2. The concentration of 8 × 10 ² mmol / L and tetraisopropyl orthotitanate is 2.0 × 10 ² mmol / L.
Next, the stainless steel jacket was heated for 48 hours in an oven adjusted to 150 ° C. At this time, since the crucible was sealed, the liquid material as the contents was heated under pressure. After heating, the mixture was cooled to room temperature (25 ° C.), and the yellow powder generated during the reaction was filtered and washed with DMF. Furthermore, after adding DMF to the obtained filtrate and stirring at room temperature (25 ° C.) for 1 minute, filtering this and washing with DMF was repeated twice, it was dried overnight at room temperature (25 ° C.), Furthermore, the metal complex (A) was obtained by making it vacuum-dry at 150 degreeC for 1 hour (yield 1.9g).

  When XRD was measured for the obtained metal complex (A), peaks were observed at 6.7 degrees, 9.8 degrees, 11.7 degrees, and 16.6 degrees (2θ), and the document “J. Am. Chem. Soc. 2009, 131, 10857-10859 ”was suggested to be a metal complex having a structure very similar to MIL-125. In addition, no peak derived from titanium oxide (anatase type or rutile type) was observed.

Further, an adsorption isotherm of nitrogen at 77K was prepared for the obtained metal complex (A). The results are shown in FIG. In FIG. 1, the horizontal axis shows the relative pressure obtained by dividing the equilibrium pressure (P) by the saturated vapor pressure (P ₀ ), and the vertical axis shows the adsorption of nitrogen converted to the volume in the standard state (0 ° C., 1 atm). Indicates the amount.
The BET specific surface area of the metal complex (A) calculated from the adsorption isotherm was 1101 m ² g ⁻¹ .

[Example 2]
The Ru complex (1) represented by the following formula (5) is synthesized according to the contents described in documents “Dalton Trans., 2007, 4323-4332” and “Eur. J. Inorg. Chem., 2010, 3040-3050”. did.

300 mg of the Ru complex (1), 0.1 mL of tetraisopropyl orthotitanate, 4.5 mL of DMF and 0.5 mL of methanol were placed in a polytetrafluoroethylene crucible, and the crucible was sealed with a stainless steel jacket. At this time, the molar ratio of Ru complex (1) to tetraisopropyl orthotitanate (Ru complex (1): tetraisopropyl orthotitanate) was 1: 1, and the concentration of Ru complex (1) was 0.10 mmol / L. The concentration of tetraisopropyl orthotitanate is 0.07 mmol / L.
Next, the stainless steel jacket was heated in an oven adjusted to 150 ° C. for 15 hours. At this time, since the crucible was sealed, the liquid material as the contents was heated under pressure. After heating, the mixture was cooled to room temperature (25 ° C.), and the red powder generated during the reaction was filtered and washed with acetone. Furthermore, after adding acetone to the obtained filtrate and stirring at room temperature (25 ° C) for 1 minute, filtering this and washing with acetone twice, it was dried overnight at room temperature (25 ° C), Furthermore, the metal complex (B) was obtained by making it vacuum-dry at 100 degreeC for 1 hour (yield 250 mg).

  XRD was measured about the obtained metal complex (B). The powder X-ray diffraction pattern obtained at this time is shown in FIG. As shown here, peaks were observed at 6.1 degrees, 10.3 degrees, 12.3 degrees, and 14.7 degrees (2θ). In addition, no peak derived from titanium oxide (anatase type or rutile type) was observed.

[Example 3]
300 mg of 2,2′-bipyridine-5,5′-dicarboxylic acid, 0.25 mL of tetraisopropyl orthotitanate, 4.5 mL of DMF and 0.5 mL of methanol are placed in a polytetrafluoroethylene crucible, The crucible was sealed with a stainless steel jacket. At this time, the molar ratio of 2,2′-bipyridine-5,5′-dicarboxylic acid to tetraisopropyl orthotitanate (2,2′-bipyridine-5,5′-dicarboxylic acid: tetraisopropyl orthotitanate) is 1.3: 1, the concentration of 2,2′-bipyridine-5,5′-dicarboxylic acid is 1.6 × 10 ² mmol / L, and the concentration of tetraisopropyl orthotitanate is 1.2 × 10 ² mmol. / L.
Next, the stainless steel jacket was heated for 48 hours in an oven adjusted to 150 ° C. At this time, since the crucible was sealed, the liquid material as the contents was heated under pressure. After heating, the mixture was cooled to room temperature (25 ° C.), and the white powder generated during the reaction was filtered and washed with DMF. Furthermore, after adding DMF to the obtained filtrate and stirring at room temperature (25 ° C.) for 1 minute, filtering this and washing with DMF was repeated twice, it was dried overnight at room temperature (25 ° C.), Further, the Ti complex (1) was obtained by vacuum-drying at 150 ° C. for 1 hour (yield 280 mg).
Under a nitrogen gas atmosphere, 60 mg of Ti complex (1) and 35 mg of K ₂ PtCl ₄ were added to a mixed solvent obtained by adding 5 mL of water to 45 mL of acetone, and stirred at 60 ° C. for 5 hours. After cooling to room temperature (25 ° C.), the resulting red-yellow powder was filtered and washed with acetone and water. Furthermore, after adding acetone to the obtained filtrate and stirring at room temperature (25 ° C) for 1 minute, filtering this and washing with acetone twice, it was dried overnight at room temperature (25 ° C), Furthermore, the metal complex (C) was obtained as a precursor metal complex by vacuum-drying at 100 degreeC for 1 hour (yield 50 mg).

  XRD was measured about the obtained metal complex (C). The powder X-ray diffraction pattern obtained at this time is shown in FIG. As shown here, the peaks are 6.2 degrees, 12.4 degrees, 16.2 degrees, 17.5 degrees, 18.7 degrees, 25.0 degrees, 25.8 degrees, 28.0 degrees (2θ). Observed. In addition, no peak derived from titanium oxide (anatase type or rutile type) was observed.

<Production of comparative metal complex>
[Comparative Example 1]
According to the method described in the document “J. Am. Chem. Soc. 2009, 131, 10857-10859”, a metal complex was produced by the following procedure.
2.0 g terephthalic acid, 2.4 mL tetraisopropyl orthotitanate, 36 mL DMF and 4 mL methanol were placed in a polytetrafluoroethylene crucible and the crucible was sealed with a stainless steel jacket.
Next, the stainless steel jacket was heated in an oven adjusted to 150 ° C. for 15 hours, then cooled to room temperature (25 ° C.), and the white powder generated during the reaction was filtered and washed with DMF. Furthermore, after adding DMF to the obtained filtrate and stirring at room temperature (25 ° C.) for 1 minute, filtering this and washing with DMF was repeated twice, it was dried overnight at room temperature (25 ° C.), Furthermore, the metal complex (RA) for a comparison was obtained by making it vacuum-dry at 150 degreeC for 1 hour (yield 2.0g).

  When XRD was measured for the obtained metal complex (RA), peaks were observed at 6.7 degrees, 9.8 degrees, 11.7 degrees, and 16.6 degrees (2θ), and the document “J. Am. Chem. Soc. 2009, 131, 10857-10859 ”. In addition, no peak derived from titanium oxide (anatase type or rutile type) was observed.

<Manufacture of optical functional materials>
[Example 4]
400 mg of the metal complex (A) and a methanol solution of chloroplatinic acid prepared so that the amount of platinum charged is 0.5% by mass are put in a quartz glass container, and 20 mL of DMF and 20 mL of methanol are further added thereto. Added and mixed. The resulting suspension mixture was subjected to argon bubbling for 10 minutes, and then irradiated with ultraviolet light at 5 mWcm ⁻² for 3 hours using a 100 W high-pressure mercury lamp “SHL-100UV” manufactured by Toshiba Corporation. Subsequently, centrifugation was performed and the supernatant was removed. Further, DMF was added to the residue, and the mixture was stirred at room temperature (25) ° C. for 1 minute, centrifuged, and the operation of removing the supernatant was repeated twice, followed by drying at room temperature (25 ° C.) overnight, and further at 150 ° C. By vacuum-drying for 1 hour, a photofunctional material (A1) in which platinum particles were supported on the metal complex (A) by a photo-deposition method was obtained (yield 362 mg).

  When XRD was measured about the obtained optical functional material (A1), the XRD pattern was the same as that of the metal complex (A).

Further, with respect to the obtained optical functional material (A1), an adsorption isotherm of nitrogen at 77 K was prepared in the same manner as in Example 1. The results are shown in FIG. The horizontal and vertical axes in FIG. 4 are the same as in FIG.
In the same manner as in Example 1, the BET specific surface area of the optical functional material (A1) calculated from the adsorption isotherm was 910 m ² g ⁻¹ .

[Examples 5 to 7]
In the same manner as in Example 4 except that the amount of platinum charged was changed to 0.5% by mass, and 1.0% by mass, 1.5% by mass, or 2.0% by mass, an optical functional material ( A2) to (A4) were obtained. Table 1 shows the correspondence between the amount of platinum charged (the amount of platinum supported in the optical functional material) and the optical functional material in Examples 4 to 7.

[Example 8]
A reaction cell made of Pyrex (registered trademark) (Corning) was charged with 10 mg of the metal complex (B), 5.5 μL of 0.02 M chloroplatinic acid aqueous solution, and 2 mL of 0.01 M triethanolamine aqueous solution. , Freeze degassed.
Next, as a light source, a 500 W xenon lamp “Super Bright 500, XEF-501S” manufactured by Mitsunaga Electric Mfg. Co., Ltd., to which a cut filter that blocks light with a wavelength of 420 nm or less was attached, was used for the sample after freeze degassing. Light was irradiated to obtain a suspension mixed solution (B) containing the photofunctional material (B) and triethanolamine.

[Example 9]
A reaction cell made of Pyrex (registered trademark) (Corning) was charged with 10 mg of the metal complex (C), 5.5 μL of 0.02 M chloroplatinic acid aqueous solution, and 2 mL of 0.01 M triethanolamine aqueous solution. , Freeze degassed.
Next, as a light source, a 500 W xenon lamp “Super Bright 500, XEF-501S” manufactured by Mitsunaga Electric Mfg. Co., Ltd., to which a cut filter that blocks light with a wavelength of 420 nm or less was attached, was used for the sample after freeze degassing. Light was irradiated to obtain a suspension mixed solution (C) containing the photofunctional material (C) and triethanolamine.

<Manufacture of optical functional materials for comparison>
[Comparative Example 2]
400 mg of the metal complex (RA) and a methanol solution of chloroplatinic acid prepared so that the amount of platinum charged is 0.5% by mass are put in a quartz glass container, and further 20 mL of DMF and 20 mL of methanol are added thereto. Added and mixed. The resulting suspension mixture was subjected to argon bubbling for 10 minutes, and then irradiated with ultraviolet light at 5 mWcm ⁻² for 3 hours using a 100 W high-pressure mercury lamp “SHL-100UV” manufactured by Toshiba Corporation. Subsequently, centrifugation was performed and the supernatant was removed. Further, DMF was added to the residue, and the mixture was stirred at room temperature (25 ° C.) for 1 minute, centrifuged, and the operation of removing the supernatant was repeated twice, followed by drying at room temperature (25 ° C.) overnight, and further at 150 ° C. By vacuum-drying for 1 hour, a comparative photofunctional material (RA) in which platinum particles were supported on the metal complex (RA) by a photo-deposition method was obtained (yield 370 mg).

  When XRD was measured about the obtained optical functional material (RA), the XRD pattern was the same as that of a metal complex (RA).

<Test of water splitting photocatalytic activity (1)>
In the optical functional material (A1) obtained in Example 4, the optical functional material (B) obtained in Example 8, the optical functional material (C) obtained in Example 9, and the comparative example 2 The obtained photofunctional material (RA) for comparison was tested for water splitting catalytic ability during light irradiation in the presence of a sacrificial reducing agent (triethanolamine). Specifically, it is as follows.
Pyrex (registered trademark) (Corning Co., Ltd.) reaction cell was charged with 10 mg of photofunctional material (A1) or (RA) and 2 mL of 0.01 M triethanolamine aqueous solution as a sacrificial reducing agent. did.
Next, using a 500 W xenon lamp “Super Bright 500, XEF-501S” manufactured by Mitsunaga Electric Co., Ltd., to which a cut filter was attached, as a light source, the sample after freeze degassing was irradiated with light.
As the light irradiation condition (1), a cut filter that shields light with a wavelength of 390 nm or less was attached to the xenon lamp, and light irradiation was performed (irradiation light wavelength> 390 nm). As the light irradiation condition (2), a cut filter that shields light with a wavelength of 420 nm or less was attached to the xenon lamp, and light irradiation was performed (irradiation light wavelength> 420 nm). The amount of light irradiated was 100 mWcm ⁻² .
Then, the amount of hydrogen generated by the decomposition of water was quantified by gas chromatography. The results are shown in Table 2.
In addition, the suspension mixture (B) containing the photofunctional material (B) and triethanolamine obtained in Example 8 and the photofunctional material (C) and triethanolamine obtained in Example 9 were used. The suspension mixture (C) was tested for water splitting catalytic ability during light irradiation in the presence of a sacrificial reducing agent (triethanolamine) (the suspension mixture (B) was removed in Example 8). The suspension mixture (C) has been degassed in Example 9). Specifically, it is as follows.
Using a 500 W xenon lamp “Super Bright 500, XEF-501S” manufactured by Mitsunaga Electric Mfg. Co., Ltd. with a cut filter as a light source, the light irradiation condition (2) is applied to the suspension mixture (B) or (C). We irradiated with light. The amount of light irradiated was 100 mWcm ⁻² . Then, the amount of hydrogen generated by the decomposition of water was quantified by gas chromatography. The results are shown in Table 2.

As is clear from the above results, when the photofunctional material (A1) is used, a sufficient amount of hydrogen is generated by light irradiation under the light irradiation condition (1), and the light irradiation condition (2). The generation of hydrogen was clearly observed even when irradiated with light on the longer wavelength side. Even when the optical functional materials (B) and (C) were used, generation of a sufficient amount of hydrogen was observed by light irradiation under the light irradiation condition (2) on the long wavelength side. Thus, the photofunctional materials (A1), (B), and (C) had visible light responsiveness and had excellent water-decomposing photocatalytic ability.
On the other hand, when the optical functional material (RA) is used, the peak indicating the generation of hydrogen is not confirmed in the light irradiation under the light irradiation conditions (1) and (2), and the amount of hydrogen generated Was less than the detection limit (<0.01 μmol / h). Thus, it was suggested that the optical functional material (RA) has almost no response to visible light.

<Test of water-splitting photocatalytic activity (2)>
For the metal complex (A) obtained in Example 1 and the optical functional materials (A1) to (A4) obtained in Examples 4 to 7, light in the presence of a sacrificial reducing agent (triethanolamine) The water decomposition catalytic ability at the time of irradiation was tested. Specifically, it is as follows.
In a reaction cell made of Pyrex (registered trademark) (Corning), 10 mg of the metal complex (A), or the optical functional material (A1), (A2), (A3) or (A4), and 2 mL as a sacrificial reducing agent And 0.01M triethanolamine aqueous solution were added and freeze degassed.
Next, using a 500 W xenon lamp “Super Bright 500, XEF-501S” manufactured by Mitsunaga Electric Mfg. Co., Ltd., to which a cut filter is attached, as a light source, the sample after freezing and degassing is subjected to the light irradiation condition (2). Light was irradiated for 3 hours. The amount of light irradiated was 100 mWcm ⁻² .
Then, the amount of hydrogen generated by the decomposition of water was quantified by gas chromatography. The results are shown in Table 3.

  As is clear from the above results, a sufficient amount of hydrogen can be obtained by light irradiation under the light irradiation condition (2) in any case using the metal complex (A) and the photofunctional materials (A1) to (A4). The water decomposition photocatalytic ability was excellent.

<Test of water splitting photocatalytic activity (3)>
The photofunctional material (A1) obtained in Example 4 was tested for water splitting catalytic ability during light irradiation in the presence of a sacrificial reducing agent (triethanolamine). Specifically, it is as follows.
A reaction cell made of Pyrex (registered trademark) (Corning) was charged with 10 mg of the optical functional material (A1) and 2 mL of 0.01 M triethanolamine aqueous solution as a sacrificial reducing agent, and freeze-deaerated.
Next, using a 500 W xenon lamp “Super Bright 500, XEF-501S” manufactured by Mitsunaga Electric Manufacturing Co., Ltd., to which a cut filter is attached, as the light source, the light irradiation condition (1) and In addition to (2), light was irradiated under the following light irradiation conditions (3) to (5). As the light irradiation condition (3), a cut filter for blocking light having a wavelength of 450 nm or less was attached to the xenon lamp, and light irradiation was performed (irradiation light wavelength> 450 nm). As light irradiation condition (4), a cut filter that shields light having a wavelength of 480 nm or less was attached to the xenon lamp, and light irradiation was performed (irradiation light wavelength> 480 nm). As the light irradiation condition (5), a cut filter that shields light having a wavelength of 500 nm or less was attached to the xenon lamp, and light irradiation was performed (irradiation light wavelength> 500 nm). The amount of light irradiated was 100 mWcm ⁻² .
Then, the amount of hydrogen generated by the decomposition of water was quantified by gas chromatography. The results are shown in Table 4.

  As is clear from the above results, the photofunctional material (A1) has a sufficient amount of hydrogen generated by light irradiation under any of the light irradiation conditions (1) to (5). And had excellent water splitting photocatalytic activity.

<Test of water-splitting photocatalytic activity (4)>
The metal complex (B) obtained in Example 2 was tested for water splitting catalytic ability during light irradiation in the presence of a sacrificial reducing agent (triethanolamine). Specifically, it is as follows.
A reaction cell made of Pyrex (registered trademark) (Corning) was charged with 10 mg of the metal complex (B) and 2 mL of a 0.01 M triethanolamine aqueous solution as a sacrificial reducing agent, followed by freeze degassing.
Next, using a 500 W xenon lamp “Super Bright 500, XEF-501S” manufactured by Mitsunaga Electric Mfg. Co., Ltd., to which a cut filter is attached, as the light source, the light irradiation conditions (2) to In addition to (4), light was irradiated under the following light irradiation conditions (6) and (7). As the light irradiation condition (6), a cut filter that shields light having a wavelength of 550 nm or less was attached to the xenon lamp, and light irradiation was performed (irradiation light wavelength> 550 nm). As the light irradiation condition (7), a cut filter that shields light having a wavelength of 620 nm or less was attached to the xenon lamp, and light irradiation was performed (irradiation light wavelength> 620 nm). The amount of light irradiated was 100 mWcm ⁻² .
Then, the amount of hydrogen generated by the decomposition of water was quantified by gas chromatography. The results are shown in Table 5.

  As is clear from the above results, the metal complex (B) has a sufficient amount by light irradiation under any of the light irradiation conditions (2) to (4), (6), and (7). Generation of hydrogen was observed, and it had excellent water splitting photocatalytic ability.

<Test of organic redox photocatalytic activity>
The photofunctional material (A1) obtained in Example 4 was tested for organic substance (nitrobenzene) reduction catalytic ability during light irradiation in the presence of a sacrificial reducing agent (triethanolamine). Specifically, it is as follows.
A reaction cell manufactured by Pyrex (registered trademark) (Corning) was charged with 25 mg of photofunctional material (A1), 4 mL of acetonitrile (solvent), 0.1 mmol of nitrobenzene (reaction substrate), and 1.0 mmol of trimethylamine. Ethanolamine (sacrificial reducing agent) was added and argon bubbling was performed for 15 minutes.
Next, using a 500 W xenon lamp “Super Bright 500, XEF-501S” manufactured by Mitsunaga Electric Mfg. Co., Ltd., to which a cut filter is attached, as a light source, the sample after argon bubbling is irradiated with light under the light irradiation condition (2). Irradiated. The amount of light irradiated was 100 mWcm ⁻² .
The yields (%) of nitrosobenzene and aminobenzene produced by the photoreduction reaction of nitrobenzene were quantified by gas chromatography. The results are shown in Table 6.

  As is clear from the above results, the photofunctional material (A1) reduces nitrobenzene to aminobenzene by light irradiation under the light irradiation condition (2), and has excellent organic redox photocatalytic ability. It was.

  The present invention is useful as an optical functional material having responsiveness to visible light.

Claims (6)

A photofunctional material comprising a coordination polymer in which a compound represented by the following formula (1) is coordinated to a titanium atom , and metal particles or other metal complexes other than the coordination polymer .

(In the formula, P is an aromatic group obtained by removing “m + n” hydrogen atoms from benzene, naphthalene, azulene, anthracene, tetracene or pentacene, which may have a substituent other than R ^a and R ^b. hydrocarbon group, Oh Rui manganese, iron, cobalt, nickel, connected by one metal atom and a monocyclic aromatic heterocyclic group and / or a phenyl group selected from the atoms of ruthenium and platinum one or more single bond A group having a metal complex site composed of a ligand formed, and the aromatic hydrocarbon group may be a group linked by one or more single bonds;
R ^a formula "-CO ₂ ^-" is a group represented by or "-CO ₂ H"; m is an integer of 2 or more, if P is a group having the metal complex sites, m is 4 And a plurality of R ^a may be the same or different from each other;
R ^b is a halogen atom or a group represented by the formula “—OH”, “—OR ^B ”, “—NH ₂ ”, “—NR ^B ₂ ” or “—NO ₂ ” (where R ^B is alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, two ^{R B} in the formula ^"-NR _{B 2"} may being the same or different.) in Yes; n is an integer of 1 or more when P is an aromatic hydrocarbon group having 6 carbon atoms; otherwise, it is an integer of 0 or more; and n is an integer of 2 or more The plurality of R ^b may be the same as or different from each other. ) Wherein P may have a substituent other than R ^a and R ^b, benzene, naphthalene, azulene, anthracene, from Te anthracene or pentacene, "m + n" number of aromatic hydrocarbons obtained by removing a hydrogen atom The optical functional material according to claim 1, which is a group. The P may have a substituent other than R ^a and R ^b , 2-phenylpyridine, 2,2′-bipyridine, 5,5′-bisphenyl-2,2′-bipyridine, 1, 3-bis (2-pyridyl) benzene, 2,2 ′: 6 ′, 2 ″ -terpyridine, 4-phenyl-2,2 ′: 6 ′, 2 ″ -terpyridine or 2,2 ′: 6 ′, The optical functional material according to claim 1, which is a group having a metal complex site containing a group formed by removing “m + n” hydrogen atoms from 2 ″: 6 ″, 2 ′ ″-quaterpyridine. . A water-splitting photocatalyst using the photofunctional material according to any one of claims 1 to 3 . It is a manufacturing method of the optical functional material according to any one of claims 1 to 3,
Reacting the compound represented by the formula (1) with one or more metal salts containing a titanium atom to obtain the coordination polymer;
And a step of mixing the obtained coordination polymer with metal particles or other metal complex other than the coordination polymer. The method for producing an optical functional material according to claim 5, wherein the compound represented by the formula (1) is reacted with the metal salt by heating in the range of 60 to 250 ° C.

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