JP2007238601A - Polynuclear metal complex modified product and application thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polynuclear metal complex modified product high in reaction activity as a redox catalyst and also high in stability. <P>SOLUTION: [1] The polynuclear metal complex modified product is obtained by modifying treatment such as heating treatment of (a) a polynuclear metal complex having in the molecule at least one macrocyclic ligand having 5-15 coordinating atoms and multiple metal atoms to modify the polynuclear metal complex so as to be 5-90 wt.% in the weight loss percentage after the treatment and 5 wt.% or greater in the carbon content after the modification. Alternatively, [2] the polynuclear metal complex modified product is obtained by modifying treatment such as heating treatment of a mixture of a polynuclear metal complex similar to (a) and a specific organic compound or a carbon carrier to modify the polynuclear metal complex so as to be 5-90 wt.% in the weight loss percentage after the treatment and 5 wt.% or greater in the carbon content after the modification. [3] A redox catalyst comprising the polynuclear metal complex modified product[1] or [2] is also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a modified polynuclear metal complex suitable as a catalyst. Furthermore, this invention relates to the catalyst containing this polynuclear metal complex modified material.

The metal complex acts as a catalyst (redox catalyst) in a redox reaction involving electron transfer such as oxygen addition reaction, oxidative coupling reaction, dehydrogenation reaction, hydrogenation reaction, oxide decomposition reaction, etc. Used in manufacturing. Furthermore, they are also used in various applications such as additives, modifiers, batteries, and sensor materials.

Among these metal complexes, in particular, as a redox catalyst, when a multinuclear complex having a plurality of metal atoms in the molecule and a certain amount of metal atoms accumulated is used, an oxidation-reduction reaction involving multi-electron transfer is possible. Therefore, the reaction rate of the oxidation-reduction reaction can be increased, or side reactions caused by radical species generated by one-electron transfer can be suppressed (for example, see Non-Patent Document 1). In addition, in the oxidative coupling reaction, it is known that radicals of two or more molecules can be generated at the same time, and not only the reaction rate is increased but also the reaction selectivity can be controlled.
Here, as described in Non-Patent Document 2, the polynuclear complex indicates one in which two or more metal atoms are contained as a central atom in one complex.
An example of the redox catalyst is a manganese binuclear complex as a catalyst (hydrogen peroxide decomposition catalyst) that decomposes hydrogen peroxide into water and oxygen while suppressing the generation of free radicals (hydroxyl radical, hydroperoxy radical, etc.) An example of using is known (see, for example, Non-Patent Document 3).

Kenichi Koyanazu, Makoto Yuasa, Surface 2003, 41 (3), 22. Michinori Oki et al., “Chemical Dictionary”, page 1338, Tokyo Kagaku Doujin, 1st edition (7th edition), issued July 1, 2005 A. E. Boelrijk and G. C. Dismukes Inorg. Chem. 2000, 39, 3020.

However, when a manganese binuclear complex as disclosed in Non-Patent Document 3 is used as a hydrogen peroxide decomposition catalyst, the stability of the binuclear complex is insufficient, and the reaction is carried out particularly in the presence of an acid. In some cases or when conducting a heating reaction, the catalyst was insufficiently stable. Thus, in the reaction to which the polynuclear complex catalyst is applied, it has been anxious to further improve the stability to the presence of acid or heat.

An object of the present invention is to provide a modified polynuclear metal complex that is highly reactive as a Redox catalyst, excellent in acid resistance and thermal stability, and suitable as a catalyst.

The inventors of the present invention have intensively studied to find a catalyst having high reaction activity as a redox catalyst and excellent in thermal stability, and as a result, the present invention has been completed.

（式中Ｑは、炭素原子、窒素原子、酸素原子、リン原子及び硫黄原子からなる群より選ばれる配位原子を１つ以上含む二価の有機基であり、ｎは５以上１５以下の整数を示す。）
［６］前記変性処理が、２５０℃以上１０００℃以下の温度での加熱処理であることを特徴とする前記［１］〜［５］の何れかに記載の多核金属錯体変性物
［７］前記変性処理前後の重量減少率が７重量％以上９０重量％以下であることを特徴とする前記［１］〜［６］の何れかに記載の多核金属錯体変性物
［８］多核金属錯体処理物の炭素含有率が１０重量％以上であることを特徴とする前記［１］〜［７］の何れかに記載の多核金属錯体変性物
［９］励起波長５３２ｎｍのレーザーラマン分光測定により求めたスペクトルにおいて、１５５０〜１６００ｃｍ^-1の範囲に吸収極大を有することを特徴とする前記［１］〜［８］の何れかに記載の多核金属錯体変性物
［１０］Ｘ線光電子分光法によるＮ１ｓスペクトルにおいて、３９６ｅＶ〜４０４ｅＶにピーク極大を有する多核金属錯体処理物のシグナルの半値幅が２ｅＶ以上であることを特徴とする前記［１］〜［９］の何れかに記載の多核金属錯体変性物
［１１］Ｘ線光電子分光法によるＮ１ｓスペクトルにおいて、３９６ｅＶ〜４０４ｅＶにピーク極大を有する多核金属錯体処理物のシグナルの半値幅が、処理前の多核金属錯体のシグナルの半値幅の１．３倍以上であることを特徴とする前記［１］〜［１０］の何れかに記載の多核金属錯体変性物
［１２］分子内に、（ａ）５〜１５個の配位原子を有する大環状配位子を１つ以上と、複数の金属原子とを有する多核金属錯体と、（ｂ）カーボン担体、沸点あるいは融点が２５０℃以上の有機化合物、又は熱重合開始温度が２５０℃以下である有機化合物から選ばれる少なくとも１種の有機化合物と、からなる混合物を、加熱処理、放射線照射処理又は放電処理の何れかの変性処理より、処理前後の重量減少率が５重量％以上９０重量％以下まで変性し、変性後の炭素含有率が５重量％以上である多核金属錯体変性物
［１３］前記［１］〜［１２］の何れかに記載の多核金属錯体変性物と、カーボン担体及び／又は導電性高分子とを含む組成物 That is, the present invention provides a polynuclear metal complex-modified product suitable as a catalyst shown in the following [1] to [12].
[1] A polynuclear metal complex having one or more macrocyclic ligands having 5 to 15 coordination atoms in the molecule and a plurality of metal atoms is subjected to heat treatment, radiation irradiation treatment or discharge treatment. The modified polynuclear metal complex modified by any modification treatment until the weight reduction rate before and after the treatment is 5 wt% or more and 90 wt% or less, and the carbon content after modification is 5 wt% or more [2] The metal atom is a transition metal atom belonging to the fourth period to the sixth period of the periodic table, and the modified polynuclear metal complex according to [1] [3] The number of the metal atoms is 2 to 10 The polynuclear metal complex modified product according to any one of [1] or [2], wherein the coordination atom is a carbon atom, a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom. Any one of [1] to [3] above, which is selected from the group consisting of Polynuclear metal complexes modified product according to.
[5] The polynuclear metal complex-modified in any one of [1] to [4], wherein the macrocyclic ligand is a macrocyclic ligand represented by the following general formula (I): object

(In the formula, Q is a divalent organic group containing one or more coordination atoms selected from the group consisting of carbon atom, nitrogen atom, oxygen atom, phosphorus atom and sulfur atom, and n is an integer of 5 or more and 15 or less. Is shown.)
[6] The polynuclear metal complex-modified product according to any one of [1] to [5], wherein the modification treatment is a heat treatment at a temperature of 250 ° C. to 1000 ° C. [7] The polynuclear metal complex modified product according to any one of the above [1] to [6], wherein the weight reduction rate before and after the modification treatment is 7 wt% or more and 90 wt% or less. [9] The polynuclear metal complex-modified product according to any one of [1] to [7] above, wherein the carbon content of [9] is a spectrum determined by laser Raman spectroscopy at an excitation wavelength of 532 nm In the N1s spectrum by the polynuclear metal complex-modified product [10] X-ray photoelectron spectroscopy according to any one of the above [1] to [8], which has an absorption maximum in the range of 1550 to 1600 cm ⁻¹ 396 eV ~ The polynuclear metal complex-modified product [11] X-ray according to any one of [1] to [9] above, wherein the half-value width of the signal of the polynuclear metal complex treated product having a peak maximum at 04 eV is 2 eV or more In the N1s spectrum by photoelectron spectroscopy, the half width of the signal of the polynuclear metal complex treated product having a peak maximum at 396 eV to 404 eV is 1.3 times or more the half width of the signal of the polynuclear metal complex before the treatment. The polynuclear metal complex modified product according to any one of [1] to [10] [12] In the molecule, (a) one or more macrocyclic ligands having 5 to 15 coordination atoms And a polynuclear metal complex having a plurality of metal atoms, and (b) a carbon carrier, an organic compound having a boiling point or melting point of 250 ° C. or higher, or an organic compound having a thermal polymerization start temperature of 250 ° C. or lower. A mixture comprising one kind of organic compound is modified by a heat treatment, a radiation irradiation treatment, or a discharge treatment so that the weight reduction rate before and after the treatment is modified to 5 wt% or more and 90 wt% or less. Polynuclear metal complex modified product having a carbon content of 5% by weight or more [13] The polynuclear metal complex modified product according to any one of [1] to [12], a carbon support and / or a conductive polymer And a composition comprising

Furthermore, the present invention provides [14] a catalyst containing the modified polynuclear metal complex according to any one of [1] to [12] and / or the composition according to [13].

According to the present invention, as a catalyst for redox reactions involving electron transfer such as peroxide decomposition reaction, oxide decomposition reaction, oxygen addition reaction, oxidative coupling reaction, dehydrogenation reaction, hydrogenation reaction, electrode reaction, etc., A catalyst having a high reaction activity can be obtained even in the presence or under heating, and the catalyst is suitable for use in the synthesis of organic compounds and polymer compounds, as well as additives, modifiers, batteries, and sensor materials. It can be used and is extremely useful industrially.

The modified polynuclear metal complex in the present invention is a polynuclear metal complex having one or more macrocyclic ligands having 5 to 15 coordination atoms and a plurality of metal atoms in the molecule, or the polynuclear metal. A mixture comprising a complex and a carbon support or a specific organic compound is modified by a specific modification treatment so that the weight reduction rate before and after the treatment is 5% by weight or more and 90% by weight or less, and the carbon content after the modification treatment is It is a polynuclear metal complex modified product of 5% by weight or more.

In the metal coordination polymers disclosed so far, the present inventors are in a mononuclear state in which only one metal ion is coordinated to the coordination site in the polymer side chain, and the accumulation of metal atoms is unstable. Therefore, it has been found that good reaction activity cannot be obtained, and in order to improve the catalytic activity, the coordination structure in which metal atoms accumulate in this way is obtained by heat treatment of a polynuclear complex. The present inventors have obtained a novel finding that the modification stabilizes the coordination structure.
On the other hand, in the catalyst obtained by heat-treating the polynuclear metal complex disclosed so far, the ligand itself is easily volatilized, so that the coordination structure of the metal atom in the metal complex is impaired in the heat-treatment step. In combination with the above knowledge, the inventors have found that the polynuclear metal complex modified product is useful as a novel catalyst that can solve the problems of the present invention.

The metal atom contained in the polynuclear metal complex applied to the present invention may be an uncharged or charged ion.
Coordinating atoms, as described in Ryogo Kubo et al., “Iwanami Rikagaku Dictionary 4th Edition” (issued January 10, 1991, Iwanami Shoten), page 966, donate electrons to the vacant orbit of the metal atom. An atom having an unshared electron pair and bonded to a metal atom through a coordinate bond.
Furthermore, the macrocyclic ligand having a coordinating atom refers to the “macrocyclic effect” described in pages 133-1324 of Michinori Oki et al., “Chemical Dictionary” (issued July 1, 2005, Tokyo Kagaku Dojin). "Is a cyclic organic compound capable of forming a stable coordination structure. Moreover, the macrocyclic ligand of the present invention includes those having a structure in which a plurality of the above cyclic organic compounds are linked, and the total number of coordination atoms is 5 to 15.

Here, the metal atom is preferably a transition metal belonging to the fourth to sixth periods of the periodic table (long period type).
Specifically, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technesium, ruthenium, rhodium, palladium, silver, lanthanum, cerium, praseodymium, neodymium, promethium And metal atoms selected from the group consisting of samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold.
More preferably scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, silver, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium A metal atom selected from the group consisting of holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum and tungsten,
More preferably, it is a metal atom selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, tantalum and tungsten.
Among these, a metal atom selected from the group consisting of vanadium, chromium, manganese, iron, cobalt, nickel and copper is preferable, and a metal atom selected from the group consisting of manganese, iron, cobalt, nickel and copper is particularly preferable. Metal atom.

The polynuclear metal complex used in the present invention has a plurality of metal atoms selected from the above examples, but the preferred number is 30 or less, more preferably 2 to 5, and still more preferably 2 to 3 And particularly preferably two.

In the polynuclear metal complex, the macrocyclic ligand has 5 to 15 coordination atoms that can be bonded to the metal atom through a coordination bond in the ring, or a plurality of macrocyclic coordinations. It consists of a child, and the total number of coordination atoms is 5-15. The total number of coordinating atoms in the macrocyclic ligand is preferably 5 to 12, more preferably 6 to 10, and particularly preferably 6 to 8.
The coordinating atom may be electrically neutral or a charged ion.

The coordination atom is selected from a carbon atom, a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom, and a plurality of coordination atoms may be the same as or different from each other. More preferred are a nitrogen atom, oxygen atom, sulfur atom and phosphorus atom, still more preferred are a nitrogen atom, oxygen atom and sulfur atom, and particularly preferred are a nitrogen atom and oxygen atom. In particular, when the coordination atom is a macrocycle having a nitrogen atom and / or an oxygen atom, even in the modification treatment described later, the spatial arrangement of a plurality of metal atoms in the polynuclear metal complex before the modification treatment is This is preferable because it is easily retained after modification and maintains an accumulated state of metal atoms suitable as a catalyst.

Furthermore, the molecular weight of the macrocyclic ligand is preferably 160 or more. More preferably, it is 250 or more, More preferably, it is 300 or more, Especially preferably, it is 400 or more. When the molecular weight is less than 160 or the number of coordinating atoms is 4 or less, the boiling point tends to be low, or the complex structure itself tends to be unstable when coordinated with a metal atom. If so, when the above modification treatment is performed, the organic component tends to evaporate, so the weight reduction rate may be significantly increased, and the polynuclear complex structure may be significantly impaired. This is not preferable because the catalytic activity is lowered. Moreover, as an upper limit of molecular weight, 3000 or less is preferable. More preferably, it is 2000 or less, More preferably, it is 1000 or less. When the molecular weight of the macrocyclic ligand is large, the polynuclear complex modification product tends to be heterogeneous.

（式中、Ｑは、炭素原子、窒素原子、酸素原子、リン原子及び硫黄原子からなる群から選ばれる配位原子を一つ以上含む二価の基であり、ｎは５以上１５以下の整数である。複数あるＱは、互いに同一でも異なっていてもよい。）

（式中、Ｑ’、Ｑ’’は式（Ｉ）におけるＱと同義である。ｎ’およびｎ’’は、１以上の整数を表わし、ｎ’＋ｎ’’が５以上１５以下である。Ｚは配位原子を含んでいてもよい二価の基であり、複数あるＱ’の何れかと、複数あるＱ’’の何れかと、を連結する基である。ｍは０以上７以下の整数であり、Ｚが複数ある場合、それらは互いに同一でも異なっていてもよい。） As described above, the macrocyclic ligand is a cyclic organic compound or a compound in which a plurality of cyclic organic compounds are connected. More preferably, the macrocyclic ligand is a cyclic organic compound or a formula (I) represented by the following formula (I): Examples thereof include compounds in which two cyclic organic compounds represented by II) are linked.

(In the formula, Q is a divalent group containing one or more coordination atoms selected from the group consisting of carbon atom, nitrogen atom, oxygen atom, phosphorus atom and sulfur atom, and n is an integer of 5 or more and 15 or less. The plural Qs may be the same or different from each other.)

(In the formula, Q ′ and Q ″ have the same meaning as Q in formula (I). N ′ and n ″ represent an integer of 1 or more, and n ′ + n ″ is 5 or more and 15 or less. Z is a divalent group which may contain a coordinating atom, and is a group connecting any one of a plurality of Q ′ and any one of a plurality of Q ″. M is an integer of 0 or more and 7 or less. And when there are a plurality of Z, they may be the same as or different from each other.)

Specific examples of Q, Q ′ and Q ″ in the general formula (I) or (II) include an oxy group, a thioxy group, an amino group, an imino group (the imino group is an alkyl group having 1 to 50 carbon atoms or Including a tertiary imino group having an aromatic group having 2 to 60 carbon atoms), or an alkylene group, alkenylene group or divalent aromatic group (including an aromatic heterocyclic group) or amino group containing these groups An alkylene group, an alkenylene group, or a divalent aromatic group (including an aromatic heterocyclic group) in which a monovalent group having a coordination atom such as a hydroxyl group or a thiol group is substituted.
The alkylene group, divalent aromatic group and divalent aromatic heterocyclic group may be further substituted with an alkyl group, aryl group, aralkyl group, nitro group, cyano group, halogen atom, or the like. .

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a norbornyl group, and a nonyl group. A linear, branched or cyclic alkyl group having about 1 to 50 carbon atoms, such as decyl group and 3,7-dimethyloctyl group.
Examples of the aryl group include aryl groups having about 6 to 50 carbon atoms such as a phenyl group, a tolyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a terphenyl group.
Examples of the aralkyl group include a phenylmethyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 1-phenyl-1-propyl group, a 1-phenyl-2-propyl group, and a 2-phenyl-2-propyl group. Aralkyl groups having about 6 to 50 carbon atoms such as 1-phenyl-3-propyl group, 1-phenyl-4-butyl group, 1-phenyl-5-pentyl group and 1-phenyl-6-hexyl group. .
The halogen atom is selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

なお、上式において、Ｒ¹⁰は水素原子又は１価の有機基であり、該有機基の典型的なものとしては、前記のとおり炭素数１〜５０のアルキル基又は炭素数２〜６０の芳香族基である。 Among the examples of Q, Q ′ and Q ″ described above, a divalent organic group having a nitrogen atom or an oxygen atom as a coordination atom represented by (Q-1) to (Q-14) shown below. Is preferable.

In the above formula, R ¹⁰ is a hydrogen atom or a monovalent organic group, and typical examples of the organic group include an alkyl group having 1 to 50 carbon atoms or an aromatic group having 2 to 60 carbon atoms as described above. It is a family group.

Moreover, the hydroxyl group in the above (Q-3) and (Q-5) becomes a phenolate group from which a proton has been released, and may be coordinated with a metal atom.

Z in the formula (II) represents an alkylene group which may be substituted, an alkenylene group which may be substituted, an aromatic group which may be substituted, an oxy group, a thioxy group, an imino group (the imino group). Are exemplified by divalent groups such as an alkyl group having 1 to 50 carbon atoms and a tertiary imino group having an aromatic group having 2 to 60 carbon atoms, and a divalent group selected from these groups is linked 2 May be a valent group.

Examples of the alkylene group include methylene group, ethylene group, 1,1-propylene group, 1,2-propylene group, 1,3-propylene group, 2,4-butylene group, 2,4-dimethyl-2, Examples thereof include linear, branched or cyclic alkylene groups having about 1 to 20 carbon atoms, such as 4-butylene group, 1,2-cyclopentylene group and 1,2-cyclohexylene group.
Further, the alkylene group may be substituted with an alkoxy group having 1 to 50 carbon atoms, a nitro group, a cyano group, a halogen atom, or the like.
Examples of the alkoxy group include alkoxy groups having about 1 to 50 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a hexyloxy group, and a decyloxy group. The halogen atom is selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The aromatic group which may be substituted in Z in the general formula (II) is a divalent group which is generated when the aromatic compound loses two hydrogen atoms.
Examples of the aromatic compound include benzene, naphthalene, anthracene, phenanthrene, tetracene, biphenyl, biphenylene, furan, dibenzofuran, thiophene, dibenzothiophene, pyridine, bipyridine, phenanthroline, and xanthene. An aromatic compound is mentioned.
The aromatic group may be substituted with an alkyl group, an aralkyl group, an alkoxy group, a nitro group, a cyano group, a halogen atom, or the like.
Here, examples of the alkyl group, alkoxy group, aralkyl group, and halogen atom include the same groups described as substituents for the alkylene group.

M in general formula (II) represents the integer of 0-7. Preferably it is 1-5, More preferably, it is 1-3. Note that m is 0 means that a cyclic compound composed of a plurality of Q ′ and a cyclic compound composed of a plurality of Q ″ are linked by a direct bond.

なお、式（III―ａ）〜（III―ｈ）において、Ｒ¹、Ｒ²は水素原子又は置換基であり、隣合う２つの原子に結合している２つのＲ¹あるいはＲ¹とＲ²は互いに連結していてもよく、複数あるＲ¹、Ｒ²はそれぞれ同一であっても異なっていてもよい。式（III―ａ）〜（III―ｄ）における、Ｙは大環状配位子を形成する２価の基であり、具体的な例示は、前記式（II）のＺと同様である。また、式（III―ｅ）および式（III―f）中の、Ｚは前記式（II）と同義である。 Examples of the macrocyclic ligand represented by the general formula (I) or (II) include compounds exemplified by the following formulas (III-a) to (III-h). Preferred are compounds represented by formula (III-a) to formula (III-e), more preferred are compounds represented by formula (III-a) to formula (III-d), and particularly preferred It is a compound represented by the formula (III-a).

In the formulas (III-a) to (III-h), R ¹ and R ² are hydrogen atoms or substituents, and two R ¹ or R ¹ and R ² bonded to two adjacent atoms. May be linked to each other, and a plurality of R ¹ and R ² may be the same or different. In formulas (III-a) to (III-d), Y is a divalent group forming a macrocyclic ligand, and specific examples are the same as Z in formula (II). In the formulas (III-e) and (III-f), Z has the same meaning as the formula (II).

R ¹ and R ² in the above formulas (III-a) to (III-h) are hydrogen atoms or substituents, and examples of the substituent include a halogen atom; a hydroxy group; a carboxyl group; a mercapto group; A functional group such as an acid group; a nitro group; a phosphonic acid group; a silyl group having an alkyl group having 1 to 3 carbon atoms;
Examples include an alkyl group having about 1 to 50 carbon atoms; an alkoxy group having about 1 to 50 carbon atoms; and an aromatic group having about 2 to 60 carbon atoms.
Here, examples of the alkyl group and alkoxy group include the same groups as those exemplified as the substituent of Q, Q′Q ″ or Z in the above formula (I) and formula (II).
In addition, the aromatic group includes phenyl, methylphenyl, naphthyl, pyridyl, furadyl, oxazolyl, imidazolyl, pyrazolyl, pyrazyl, pyrimidyl, pyridazyl, benzoimidazolyl, etc. About 2 to 60 aromatic groups;
Etc. are exemplified.
These alkyl groups, alkoxy groups or aromatic groups may be substituted with the above functional groups.

Among R ¹ and R ² in the formulas (III-a) to (III-h), particularly preferred are a hydrogen atom, a methyl group, a phenyl group, a methylphenyl group, a naphthyl group, and a pyridyl group, It is preferable to have such groups as R ¹ and R ² because the catalytic activity of the polynuclear metal complex modified product obtained by performing the modification treatment described later is improved.

Y in the above formulas (III-a) to (III-d) can be specifically exemplified by the same examples as Z in the above formula (II). Among them, an alkylene group which may be substituted, Preferred is a cycloalkylene group or a divalent aromatic group.
An alkylene group is a residue obtained by removing two hydrogen atoms on the same or different carbon from an aliphatic hydrocarbon. Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, A propylene group, an isobutylene group, etc. can be mentioned.
A cycloalkylene group is a residue obtained by removing two hydrogens on the same or different carbon from an alicyclic hydrocarbon, and specific examples thereof include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group. , Cyclopentylidene group, cyclohexylidene group and the like.
A divalent aromatic group is a residue obtained by removing two hydrogen atoms on the same or different carbon from an aromatic compound. Examples of the aromatic compound include benzene, naphthalene, anthracene, tetracene, biphenyl and the like.

Y is more preferably an ethylene group, a propylene group, an isopropylene group, a butylene group, a phenylene group, a naphthylene group, an anthracenylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group, and more preferably an ethylene group, Propylene group, butylene group, phenylene group, cyclohexylene group, naphthylene group, anthracenylene group, cyclohexylene group, particularly preferably ethylene group, propylene group, phenylene group, naphthylene group, and cyclohexylene group, particularly preferably propylene Group or phenylene group.

Here, specific structures of the macrocyclic ligand having the structure of the formula (III-a) are exemplified in the following formulas (III-a-1) to (III-a-6). Of these, formulas (III-a-1) to (III-a-4) are particularly preferred.

Specific structures of the macrocyclic ligand having the structure of the formula (III-b) are exemplified by the following formulas (III-b-1) to (III-b-2).

Specific structures of the macrocyclic ligand having the structure of the formula (III-c) are exemplified by the following formulas (III-c-1) to (III-c-3).

Specific structures of the macrocyclic ligand having the structure of the formula (III-d) are exemplified by the following formulas (III-d-1) to (III-d-2).

Specific structures of the macrocyclic ligand having the structure of the formula (III-e) are exemplified by the following formulas (III-e-1) to (III-e-3).

Specific structures of the macrocyclic ligand having the structure of the formula (III-f) are exemplified by the following formulas (III-f-1) to (III-f-2).

Specific structures of the macrocyclic ligand having the structure of the formula (III-g) are exemplified by the following formulas (III-g-1) to (III-g-2).

Specific structures of the macrocyclic ligand having the structure of the general formula (III-h) are exemplified by the following formulas (III-h-1) to (III-h-2).

The macrocyclic ligand in the polynuclear metal complex of the present invention is preferably a compound represented by the formula (I) or formula (II) specifically exemplified above, particularly the macrocyclic ligand represented by the formula (I). Is preferred.

As the polynuclear metal complex of the present invention, it is essential to have a plurality of metal atoms and one or more macrocyclic ligands, but in addition to the macrocyclic ligand, it has other ligands. It may be. The other ligand may be an ionic or electrically neutral compound, and when it has a plurality of such other ligands, these other ligands may be the same as or different from each other.

Examples of the electrically neutral compound in the other ligand include ammonia, pyridine, pyrrole, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, pyrazole, imidazole, 1,2,3-triazole, and oxazole. , Isoxazole, 1,3,4-oxadiazole, thiazole, isothiazole, indole, indazole, quinoline, isoquinoline, phenanthridine, cinnoline, phthalazine, quinazoline, quinoxaline, 1,8-naphthyridine, acridine, 2,2 '-Bipyridine, 4,4'-bipyridine, 1,10-phenanthroline, ethylenediamine, propylenediamine, phenylenediamine, cyclohexanediamine, pyridine N-oxide, 2,2'-bipyridine N, N'-dioxide, oxamide, dimethyl Compounds containing nitrogen atoms such as luglyoxime and o-aminophenol; water, phenol, oxalic acid, catechol, salicylic acid, phthalic acid, 2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione Oxygen-containing compounds such as hexafluoropentanedione, 1,3-diphenyl-1,3-propanedione and 2,2′-binaphthol; sulfur-containing compounds such as dimethyl sulfoxide and urea; 1,2-bis (dimethylphosphino) Examples thereof include phosphorus-containing compounds such as ethane and 1,2-phenylenebis (dimethylphosphine).
Preferably ammonia, pyridine, pyrrole, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, pyrazole, imidazole, 1,2,3-triazole, oxazole, isoxazole, 1,3,4-oxadiazole, indole , Indazole, quinoline, isoquinoline, phenanthridine, cinnoline, phthalazine, quinazoline, quinoxaline, 1,8-naphthyridine, acridine, 2,2'-bipyridine, 4,4'-bipyridine, 1,10-phenanthroline, ethylenediamine, propylene Diamine, phenylenediamine, cyclohexanediamine, pyridine N-oxide, 2,2'-bipyridine N, N'-dioxide, oxamide, dimethylglyoxime, o-aminophenol, water, phenol, oxalic acid, cateco , Salicylic acid, phthalic acid, 2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, hexafluoropentanedione, 1,3-diphenyl-1,3-propanedione, 2 , 2′-binaphthol,
More preferably ammonia, pyridine, pyrrole, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, pyrazole, imidazole, 1,2,3-triazole, oxazole, isoxazole, 1,3,4-oxadiazole, Indole, indazole, quinoline, isoquinoline, phenanthridine, cinnoline, phthalazine, quinazoline, quinoxaline, 1,8-naphthyridine, acridine, 2,2'-bipyridine, 4,4'-bipyridine, 1,10-phenanthroline, ethylenediamine, Propylenediamine, phenylenediamine, cyclohexanediamine, pyridine N-oxide, 2,2'-bipyridine N, N'-dioxide, o-aminophenol, phenol, catechol, salicylic acid, phthalic acid, 1,3-dipheni Examples include 1,3-propanedione and 2,2′-binaphthol.
Among these, pyridine, pyrrole, pyridazine, pyrimidine, pyrazine, pyrazole, imidazole, oxazole, indole, quinoline, isoquinoline, acridine, 2,2'-bipyridine, 4,4'-bipyridine, 1,10-phenanthroline, phenylenediamine Further, pyridine N-oxide, 2,2′-bipyridine N, N′-dioxide, o-aminophenol, and phenol are more preferable.

Examples of the anionic ligand include hydroxide ions, peroxides, superoxides, cyanide ions, thiocyanate ions, fluoride ions, chloride ions, bromide ions, iodide ions and the like, Sulfate ion, nitrate ion, carbonate ion, perchlorate ion, tetrafluoroborate ion, tetraarylborate ion such as tetraphenylborate ion, hexafluorophosphate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p-toluene Sulfonate ion, benzenesulfonate ion, phosphate ion, phosphite ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate ion, hydroxide ion, metal oxide ion, methoxide ion, etho Side ion, and the like.
Preferably, hydroxide ion, sulfate ion, nitrate ion, carbonate ion, perchlorate ion, tetrafluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p -Toluenesulfonate ion, benzenesulfonate ion, phosphate ion, acetate ion, trifluoroacetate ion are exemplified,
Among these, hydroxide ions, sulfate ions, nitrate ions, carbonate ions, tetraphenylborate ions, trifluoromethanesulfonate ions, p-toluenesulfonate ions, acetate ions, and trifluoroacetic acid are more preferable.

Furthermore, the ion exemplified as the anionic ligand may be a counter ion that electrically neutralizes the polynuclear metal complex itself of the present invention.

Moreover, the polynuclear complex of this invention may have as a counter ion which has cationic property which maintains electrical neutrality. Examples of the counter ion having a cationic property include alkali metal ions, alkaline earth metal ions, tetraalkylammonium ions such as tetra (n-butyl) ammonium ion and tetraethylammonium ion, and tetraarylphosphonium ions such as tetraphenylphosphonium ion. Specifically, lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, magnesium ion, calcium ion, strontium ion, barium ion, tetra (n-butyl) ammonium ion, tetraethylammonium ion, tetraphenyl Phosphonium ion, more preferably tetra (n-butyl) ammonium ion, tetraethylammonium ion, tetraphenylphosphonium Ion, and the like.
Among these, tetra (n-butyl) ammonium ions and tetraethylammonium ions are preferable as the counter ion having a cationic property.

Next, the conditions for the modification treatment of the polynuclear metal complex in the present invention will be described in detail.
As the polynuclear metal complex used for the modification treatment, only one kind of polynuclear metal complex may be used, or two or more kinds of polynuclear metal complexes may be used.
It is particularly preferable that the polynuclear metal complex is dried for 6 hours or more at a temperature of 15 ° C. or more and 200 ° C. or less and a reduced pressure of 10 Torr or less as a pretreatment for the modification treatment. As the pretreatment, a vacuum dryer or the like can be used.

The atmosphere used for the modification treatment of the polynuclear metal complex is preferably in the presence of hydrogen, helium, nitrogen, ammonia, oxygen, neon, argon, krypton, xenon, acetonitrile, and a mixed gas thereof.
Preferably it is in the presence of hydrogen, helium, nitrogen, ammonia, oxygen, neon, argon, and a mixed gas thereof, more preferably in the presence of hydrogen, nitrogen, ammonia, argon, and a mixed gas thereof.
Further, the pressure related to the modification treatment can be appropriately changed in the modification treatment to be selected.

First, the heat treatment will be specifically described.
The temperature at which the polynuclear metal complex is subjected to heat treatment is not particularly limited as long as the weight reduction rate can be 5% by weight or more before and after the heat treatment.
The treatment temperature for the heat treatment is preferably 250 ° C. or higher, more preferably 300 ° C. or higher, further preferably 400 ° C. or higher, and particularly preferably 500 ° C. or higher. Further, the upper limit of the temperature for the baking treatment is not particularly limited as long as the carbon content of the modified product after the treatment can be 5 wt% or more, but is preferably 1200 ° C or less, more preferably 1000 ° C. Below, it is 800 degrees C or less especially preferably.

The processing time required for the heat treatment can be appropriately set depending on the gas used, the temperature, etc. In the sealed or vented state of the gas, the temperature is gradually raised from room temperature and the temperature is lowered immediately after reaching the target temperature. Also good. Among them, it is preferable to gradually modify the polynuclear complex by maintaining the temperature after reaching the target temperature because durability can be further improved. The holding time after reaching the target temperature is preferably 1 to 100 hours, more preferably 1 to 40 hours, further preferably 2 hours to 10 hours, and particularly preferably 2 to 3 hours. .

An apparatus for performing the heat treatment is not particularly limited, and examples thereof include an oven, a furnace, and an IH hot plate. Moreover, if the polynuclear metal complex to be heat-treated is about several tens of mg, the furnace of a thermal analyzer usually used for thermal analysis can be applied. If a thermogravimetric analyzer is used among thermal analyzers, the heat treatment can be stopped when the desired thermogravimetric reduction rate is obtained while confirming the weight reduction rate. Can do.

The polynuclear metal complex modified product of the present invention undergoes weight loss due to low-molecular detachment due to the heat treatment as described above, and the polycyclic metal complex forms a condensate by the reaction between macrocyclic ligands. However, the coordination structure is considered to be stable in the condensate. In the modification treatment instead of the heat treatment, the same effect can be obtained in the treatment capable of setting the weight reduction rate within the above range.

Examples of modification treatments that can replace heat treatment include α rays, β rays, neutron rays, electron rays, γ rays, X rays, vacuum ultraviolet rays, ultraviolet rays, visible rays, infrared rays, microwaves, radio waves, electromagnetic waves such as laser beams, particle rays, etc. It is possible to select from a discharge treatment such as a method of irradiating any radiation selected from the above, corona discharge treatment, glow discharge treatment, plasma treatment (including low temperature plasma treatment).
Among these, a preferable modification treatment includes a treatment of irradiating a radiation selected from X-rays, electron beams, ultraviolet rays, visible rays, infrared rays, microwaves and lasers, or a low-temperature plasma treatment. More preferred is a method of irradiating radiation selected from ultraviolet rays, visible rays, infrared rays, microwaves and lasers.
These methods can be carried out in accordance with the equipment and processing methods usually used for the surface modification treatment of polymer films. For example, the literature (Journal of the Japan Adhesion Society, “Surface Analysis / Modification Chemistry”, daily publication) The method described in Kogyo Shimbun, published on December 19, 2003) can be used.

Here, when performing the radiation irradiation treatment or the discharge treatment, the polynuclear metal complex has a weight reduction rate before and after the treatment of 5% by weight to 90% by weight, and the carbon content of the modified product after the treatment. However, the preferable treatment time is within 10 hours, more preferably within 3 hours, even more preferably within 1 hour, and particularly preferably 30 minutes. Is within.

As described above, any one of the heat treatment, radiation irradiation treatment and discharge treatment is applied, and the weight reduction rate is 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and still more preferably. The polynuclear metal complex-modified product of the present invention can be obtained by performing a modification treatment until it is 20% by weight or more, particularly preferably 25% by weight or more.

On the other hand, when the weight is significantly reduced during the heat treatment, radiation irradiation treatment or discharge treatment, the decomposition of the multinuclear structure of the complex becomes remarkable, which is not preferable. The upper limit of the weight reduction rate is preferably 80% by weight or less, more preferably 70% by weight or less, and particularly preferably 60% by weight or less.

Furthermore, the modified polynuclear metal complex of the present invention has a carbon content of 5% by weight or more in elemental analysis. The carbon content is preferably 10% by weight or more, more preferably 20% by weight or more, further preferably 30% by weight or more, and particularly preferably 40% by weight or more. The higher the carbon content of the treated product, the more stable the multinuclear structure, and the easier it is to improve the accumulation degree of metal atoms in the polynuclear metal complex modified product, which is preferable.

As described above, the modified polynuclear metal complex of the present invention is a reaction between macrocyclic ligands accompanying the modification treatment, that is, the macrocyclic ligands are condensed with low molecular elimination, It is presumed that in the ligand modified product produced by condensation of the cyclic ligand, the metal atom maintains a spatial arrangement substantially equivalent to that of the polynuclear metal complex before modification. Here, it is preferable that the modified body of the macrocyclic ligand is in a graphene-like condensed and connected state, since stability against acid and thermal stability are further improved. Moreover, when the polynuclear metal complex modified product of the present invention is applied to a catalyst layer of a fuel cell, there is also an effect that conductivity is improved. The presence of such a graphene-like structure is confirmed by the presence of a peak (maximum) of 1550 to 1600 cm ⁻¹ representing the presence of the graphene-like structure in a spectrum obtained by laser Raman spectroscopy with an excitation wavelength of 532 nm.
Note that “graphene-like” means a carbon hexagonal network structure in which carbon atoms are chemically bonded by sp ² hybrid orbitals and spread in two dimensions, and some of the carbon atoms constituting the graphene-like structure are nitrogen or the like. It may be replaced by an atom. Moreover, you may take the graphite-like structure on which the above-mentioned graphene-like structure was laminated | stacked.

A polynuclear metal complex modified product in which a macrocyclic ligand is modified into graphene can also be confirmed by measuring an X-ray photoelectron spectrum (hereinafter referred to as “XPS”). That is, in the spectrum obtained by XPS measurement, the C1s peak indicating the photoemission of the 1s orbital of the carbon atom becomes a relatively wide peak and tails to the high binding energy side. The presence of carbon atoms exhibiting a graphene-like structure can also be confirmed.

In addition, when the macrocyclic ligand of the polynuclear metal complex before modification contains a nitrogen atom as a coordination atom, in the spectrum obtained by XPS measurement, an N1s spectrum (396 eV) showing photoemission of the nitrogen atom in the 1s orbital A peak is observed at ˜404 eV). When XPS measurement is performed on a polynuclear metal complex modified product using such a polynuclear metal complex, the N1s peak is often broadened, so the half width of the peak can be used as an index for the modification treatment. . Preferably, the half width of the N1s spectral peak after modification is 2 eV or more, and it is presumed that such a polynuclear metal complex modified product contains a plurality of nitrogen atoms having different chemical bonds, and the modification is sufficiently performed. It is preferable because of progress.

In particular, when the N1s spectrum in the spectrum obtained by XPS measurement is compared before and after the modification treatment, the half-value width (peak half-value width) of the polynuclear metal complex modified product is smaller than the half-value width of the polynuclear metal complex before treatment. If it is 1.3 times or more, the effect of modification is great, and this is preferable from the viewpoint of increasing the amount of nitrogen atoms introduced into the graphene-like structure. The change in the half width of the peak before and after the modification treatment is more preferably 1.4 times or more, and particularly preferably 1.5 times or more.

Next, another embodiment of the modified multinuclear complex of the present invention will be described.
A polynuclear metal comprising (a) a polynuclear metal complex as described above and (b) a carbon support, an organic compound having a boiling point or melting point of 250 ° C. or higher, or an organic compound having a thermal polymerization initiation temperature of 250 ° C. or lower. The complex mixture is subjected to any modification treatment such as heat treatment, radiation irradiation treatment or discharge treatment, and the weight loss rate before and after the treatment is modified to 5 wt% or more and 90 wt% or less, and the carbon content after modification is 5 wt%. % Is a polynuclear metal complex modified product. Here, the weight reduction rate is obtained with respect to the total weight of (a) and (b) in the polynuclear metal complex mixture.

The mixing ratio of (a) and (b) in the polynuclear metal complex mixture is set on the basis of (a) metal atoms contained in the polynuclear metal complex. That is, it is preferable to set the content of the metal atom derived from (a) to 1 to 70% by weight with respect to the total weight of (a) and (b). The content of the metal atom is more preferably 2 to 60% by weight, and particularly preferably 3 to 50% by weight.

Examples of the carbon support include carbon particles such as norit, ketjen black, vulcan, black pearl, and acetylene black, fullerenes such as C60 and C70, carbon nanotubes, carbon nanohorns, and carbon fibers.

Examples of organic compounds having a boiling point or melting point of 250 ° C. or higher include perylene-3,4,9,10-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic diimide, 1,4 , 5,8-Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic diimide, 1,4,5,8-naphthalenetetracarboxylic acid, benzene (pyromellitic acid), dianhydropyro Aromatic compound carboxylic acid derivatives such as merit acid can be mentioned. Here, the boiling point or melting point can be measured using a known method, and can be selected from the measured values, but should be selected using the values described in the literature. You can also.
Moreover, the calculated value calculated | required by computer simulation etc. may be sufficient, for example, you may select using the calculated value of the boiling point or melting | fusing point registered into SciFinder which is the software provided from Chemical Abstract Service. In the compounds shown below, “calc” at the boiling point (b.p.) is a calculated value registered in the SciFinder.

Moreover, the compound which starts thermal polymerization at 250 degrees C or less is an organic compound which has a double bond or a triple bond other than an aromatic ring, for example, organic compounds, such as acenaphthylene and vinyl naphthalene, are illustrated. The numerical value described in the compound shown below is the polymerization start temperature of each organic compound. The numerical values are described in “Basics of Carbonization Engineering” (first edition, second printing, 1982, Ohmsha).

Conditions for modifying such a polynuclear metal complex mixture are the same as the conditions for modifying the polynuclear metal complex.

The polynuclear metal complex-modified product of the present invention can be used in combination with various carriers, additives, etc., and can be processed in shape according to various applications. Applications include peroxide decomposition catalysts, oxidative coupling catalysts for aromatic compounds, exhaust gas / drainage purification catalysts, oxidation-reduction catalyst layers for dye-sensitized solar cells, carbon dioxide reduction catalysts, catalysts for producing reformed hydrogen, oxygen Applications include sensors.

Moreover, when using the polynuclear metal complex modified product of the present invention as a catalyst, it can also be used as a composition containing a carbon support and / or a conductive polymer. This is useful from the viewpoint of increasing the stability of the modified polynuclear metal complex and improving the catalytic activity. Examples of the conductive polymer include polyacetylene, polyaniline, and polypyrrole. Specific examples of the carbon support are the same as described above. In addition, as such a composition, a mixture of a plurality of polynuclear metal complex modified products of the present invention can be used, a plurality of carbon carriers or conductive polymers can be used, and a carbon carrier and a conductive polymer can be used. A combination of functional polymers can also be used.

Below, the preferable use of the polynuclear metal complex modified material of this invention is demonstrated.
The polynuclear metal complex-modified product of the present invention is more preferably used as a peroxide decomposition catalyst, particularly as a hydrogen peroxide decomposition catalyst. When used as a hydrogen peroxide decomposition catalyst, it has a feature that it can be decomposed into water and oxygen while suppressing generation of hydroxyl radicals. Specifically, it can be used for a solid polymer electrolyte fuel cell or water electrolysis ion conductive membrane deterioration preventive, medical agrochemical, food antioxidant, and the like.
Moreover, it is suitable also as an oxidative coupling catalyst of an aromatic compound, and when it is this use, it can be used, for example as a catalyst in connection with polymer manufacture, such as polyphenylene ether and a polycarbonate. Examples of usage forms include a method of directly adding the modified product to the reaction solution, and a method of supporting the modified product on zeolite or silica.

The modified polynuclear metal complex of the present invention can also be used as a desulfurization / denitration catalyst for converting sulfur oxides and nitrogen oxides contained in exhaust gases from various factories and automobiles into sulfuric acid and ammonia. Examples include a method of filling a tower through which exhaust gas from a factory is vented, a method of filling an automobile muffler, and the like.

The polynuclear metal complex-modified product of the present invention can also be used as a catalyst for modifying CO (carbon monoxide) in the reformed hydrogen. The reformed hydrogen contains CO and the like, and when the reformed hydrogen is used as a fuel cell, it is a problem that the fuel electrode is poisoned by CO, and it is desirable to reduce the CO concentration as much as possible. It is. Specific examples of usage include the methods described in Chemical Communications, 2005, p3385.

When the polynuclear metal complex modified product of the present invention is used as a carbon dioxide reduction catalyst, for example, CO ₂ and H ₂ can be reacted to generate CH ₄ and CO together with water. About a concrete usage method, it is equivalent to the method currently disclosed by Unexamined-Japanese-Patent No. 7-68171 and Unexamined-Japanese-Patent No. 2002-104811.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not restrict | limited to an Example. The “polynuclear metal complex” is abbreviated as “polynuclear complex”.

Synthesis Example 1 [Synthesis of polynuclear complex (A)]
A multinuclear complex (A) [binuclear Mn (manganese) complex] represented by the following reaction formula was synthesized according to the method described in Bulletin of Chemical Society of Japan, 68, 1105, (1995).

０．３３ｇの４―メチル−２，６−ジホルミルフェノールと０．４９ｇの酢酸マンガン４水和物を含んだ１０ｍｌのメタノールを５０ｍｌナスフラスコに入れ、室温にて攪拌した。この溶液に０．１５ｇの１，３−プロパンジアミンを５ｍｌのメタノールに溶解させた溶液を徐々に添加した。上記混合物を１時間攪拌後、黄色沈殿が生成した。この沈殿を濾取し、メタノールで洗浄後、真空乾燥することで複核Ｍｎ錯体を得た（収量０．２５ｇ：収率３９％）。なお、上記反応式において、「（ＯＡｃ）₂」とは、２当量の酢酸イオンが対イオンとしてあることを示す。
元素分析値(%)：Ｃａｌｃｄ ｆｏｒ Ｃ₂₈Ｈ₃₂Ｍｎ₂Ｎ₄Ｏ₆；Ｃ，５３．３４；Ｈ，５．１２；Ｎ，８．８９．Ｆｏｕｎｄ：Ｃ，５３．０７；Ｈ，５．１２；Ｎ，８．７２．

10 ml of methanol containing 0.33 g of 4-methyl-2,6-diformylphenol and 0.49 g of manganese acetate tetrahydrate was placed in a 50 ml eggplant flask and stirred at room temperature. A solution prepared by dissolving 0.15 g of 1,3-propanediamine in 5 ml of methanol was gradually added to this solution. After stirring the above mixture for 1 hour, a yellow precipitate was formed. The precipitate was collected by filtration, washed with methanol, and then vacuum-dried to obtain a binuclear Mn complex (yield 0.25 g: yield 39%). In the above reaction formula, “(OAc) ₂ ” indicates that 2 equivalents of acetate ion is used as a counter ion.
Elemental analysis _{(%): Calcd for C 28} H 32 Mn 2 N 4 O 6; C, 53.34; H, 5.12; N, 8.89. Found: C, 53.07; H, 5.12; N, 8.72.

窒素雰囲気下において０．４ｇの塩化鉄４水和物と０．３３gの４―メチル−２，６−ジホルミルフェノールを含んだ２０ｍｌメタノール溶液を５０ｍｌナスフラスコに入れ、室温にて攪拌した。この溶液に０．１５ｇの１，３−プロパンジアミンを１０ｍｌのメタノールに溶解させた溶液を徐々に添加した。上記混合物を３時間攪拌後、赤褐色沈殿が生成した。この沈殿を濾取し、乾燥することで複核Ｆｅ錯体（Ｉ）を得た（収量０．５０ｇ：収率８５％）。なお、上記反応式において、「Ｃｌ₂」とは、２当量の塩素イオンが対イオンとしてあることを示す。
元素分析値(%)：Ｃａｌｃｄ ｆｏｒＣ₂₄Ｈ₂₆Ｃｌ₂Ｆｅ₂Ｎ₄Ｏ₂；Ｃ，４９．２７；Ｈ，４．４８；Ｎ，９．５８．Ｆｏｕｎｄ：Ｃ，４４．９２；Ｈ，４．９４；Ｎ，１０．８６． Synthesis Example 2 [Synthesis of polynuclear complex (B)]
A polynuclear complex (B) [binuclear Fe (iron) complex] represented by the following reaction formula was synthesized according to the method described in Australian Journal of Chemistry, 1970, 23, 2225.

Under a nitrogen atmosphere, 20 ml of a methanol solution containing 0.4 g of iron chloride tetrahydrate and 0.33 g of 4-methyl-2,6-diformylphenol was placed in a 50 ml eggplant flask and stirred at room temperature. A solution prepared by dissolving 0.15 g of 1,3-propanediamine in 10 ml of methanol was gradually added to this solution. After stirring the mixture for 3 hours, a reddish brown precipitate formed. The precipitate was collected by filtration and dried to obtain a binuclear Fe complex (I) (yield 0.50 g: yield 85%). In the above reaction formula, “Cl ₂ ” indicates that 2 equivalents of chlorine ions are present as counter ions.
Elemental analysis _{(%): Calcd forC 24 H} 26 Cl 2 Fe 2 N 4 O 2; C, 49.27; H, 4.48; N, 9.58. Found: C, 44.92; H, 4.94; N, 10.86.

窒素雰囲気下において０．８４ｇの塩化ニッケル６水和物、０．３９ｇの１，３−プロパンジアミンおよび０．５８gの４―t―ブチル−２，６−ジホルミルフェノールを含んだ１０ｍｌのイソプロパノール溶液を１００ｍｌナスフラスコに入れ、攪拌しながら１８時間還流を行った。反応終了後、沈殿をメタノールで洗浄した後、乾燥することで複核Ｎｉ錯体（Ｉ）を得た。なお、上記反応式において、「Ｃｌ₂」とは、２当量の塩素イオンが対イオンとしてあることを示す。
元素分析値(%)：Ｃａｌｃｄ ｆｏｒ Ｃ₃₀Ｈ₃₈Ｃｌ₂Ｆｅ₂Ｎ₄Ｏ₂；Ｃ，５３．８４；Ｈ，５．７２；Ｎ，８．３７．Ｆｏｕｎｄ：Ｃ，５３．３２；Ｈ，５．７４；Ｎ，８．２５． Synthesis Example 3 [Synthesis of polynuclear complex (C)]
A polynuclear complex (C) [binuclear Ni (nickel) complex] represented by the following reaction formula was synthesized according to the method described in Australian Journal of Chemistry, 1970, 23, 2225.

10 ml isopropanol solution containing 0.84 g nickel chloride hexahydrate, 0.39 g 1,3-propanediamine and 0.58 g 4-tert-butyl-2,6-diformylphenol under nitrogen atmosphere Was placed in a 100 ml eggplant flask and refluxed for 18 hours with stirring. After completion of the reaction, the precipitate was washed with methanol and dried to obtain a dinuclear Ni complex (I). In the above reaction formula, “Cl ₂ ” indicates that 2 equivalents of chlorine ions are present as counter ions.
Elemental analysis _{(%): Calcd for C 30} H 38 Cl 2 Fe 2 N 4 O 2; C, 53.84; H, 5.72; N, 8.37. Found: C, 53.32; H, 5.74; N, 8.25.

０．２０ｇの酢酸銅１水和物を含んだ２．５ｍｌのメタノール溶液を２５ｍｌナフフラスコに入れ、０．１ｇの１，２―フェニレンジアミンを１ｍｌのメタノールに溶解させた溶液を攪拌しながら加えた。続いて０．２１gの４―t―ブチル−２，６−ジホルミルフェノールを２ｍｌのメタノールに溶解させた溶液を徐々に添加した後、３時間還流を行った。エバポレーターで溶媒を取り除いた後、残渣を少量のＮ、Ｎ−ジメチルホルムアミドに溶解させ、１０ｍｌのメタノールを加えた後、冷蔵庫で冷却することで褐色の沈殿を得た。この沈殿を濾取し、乾燥することで複核Ｃｕ錯体（Ｉ）を得た（収量０．１６ｇ：収率３１％）。なお、上記反応式において、「（ＯＡｃ）₂」とは、２当量の酢酸イオンが対イオンとしてあることを示し、「３ＤＭＦ」とは、３当量のジメチルホルムアミド（ＤＭＦ）分子が他のは配位子としてあることを示す。
元素分析値(%)：Ｃａｌｃｄ ｆｏｒ Ｃ₄₉Ｈ₆₁Ｃｕ₂Ｎ₇Ｏ₉；Ｃ，５７．７５；Ｈ，６．０３；Ｎ，９．６２．Ｆｏｕｎｄ：Ｃ，５５．１２；Ｈ，５．４２；Ｎ，１０．２２． Synthesis Example 4 [Synthesis of polynuclear complex (D)]
A polynuclear complex (D) represented by the following reaction formula [dinuclear Cu (copper) complex] was synthesized according to the method described in Chemische Berichte 1994, 127, 465.

A 2.5 ml methanol solution containing 0.20 g of copper acetate monohydrate was placed in a 25 ml naphth flask, and a solution of 0.1 g of 1,2-phenylenediamine dissolved in 1 ml of methanol was added with stirring. . Subsequently, a solution prepared by dissolving 0.21 g of 4-t-butyl-2,6-diformylphenol in 2 ml of methanol was gradually added, followed by refluxing for 3 hours. After removing the solvent with an evaporator, the residue was dissolved in a small amount of N, N-dimethylformamide, 10 ml of methanol was added, and then cooled in a refrigerator to obtain a brown precipitate. The precipitate was collected by filtration and dried to obtain a dinuclear Cu complex (I) (yield 0.16 g: yield 31%). In the above reaction formula, “(OAc) ₂ ” means that 2 equivalents of acetate ion is used as a counter ion, and “3DMF” means that 3 equivalents of dimethylformamide (DMF) molecule is distributed in the other way. Indicates that it is a locator.
Elemental analysis _{(%): Calcd for C 49} H 61 Cu 2 N 7 O 9; C, 57.75; H, 6.03; N, 9.62. Found: C, 55.12; H, 5.42; N, 10.22.

窒素雰囲気下において１．９ｇの塩化コバルト６水和物と１．３１gの４―メチル−２，６−ジホルミルフェノールを含んだ５０ｍｌメタノール溶液を１００ｍｌのナスフラスコに入れ、室温にて攪拌した。この溶液に０．５９ｇの１，３−プロパンジアミンを２０ｍｌのメタノールに溶解した溶液を徐々に添加した。上記混合物を３時間還流することにより茶褐色沈殿が生成した。この沈殿を濾取し、乾燥することで多核錯体（Ｆ）を得た（収量１．７５ｇ：収率７４％）。なお、上記反応式において、「Ｃｌ₂」とは、２当量の塩素イオンが対イオンとしてあることを示し、「２ＭｅＯＨ」とは、２当量のメタノール分子が大環状配位子以外の配位子としてあることを示す。
元素分析値(%)：Ｃａｌｃｄ ｆｏｒ Ｃ₂₆Ｈ₃₄Ｃｌ₂Ｃｏ₂Ｎ₄Ｏ₄；Ｃ，４７．６５；Ｈ，５．２３；Ｎ，８．５５．Ｆｏｕｎｄ：Ｃ，４６．６４；Ｈ，５．０２；Ｎ，８．５８． Synthesis Example 5 [Synthesis of polynuclear complex (E)]
A polynuclear complex (E) [binuclear Co (cobalt) complex] represented by the following reaction formula was synthesized according to the method described in Australian Journal of Chemistry, 1970, 23, 2225.

Under a nitrogen atmosphere, 50 ml of a methanol solution containing 1.9 g of cobalt chloride hexahydrate and 1.31 g of 4-methyl-2,6-diformylphenol was placed in a 100 ml eggplant flask and stirred at room temperature. A solution prepared by dissolving 0.59 g of 1,3-propanediamine in 20 ml of methanol was gradually added to this solution. The mixture was refluxed for 3 hours to produce a brown precipitate. The precipitate was collected by filtration and dried to obtain a polynuclear complex (F) (yield 1.75 g: yield 74%). In the above reaction formula, “Cl ₂ ” means that 2 equivalents of chlorine ions are counter ions, and “2MeOH” means that 2 equivalents of methanol molecules are ligands other than macrocyclic ligands. It shows that there is.
Elemental analysis _{(%): Calcd for C 26} H 34 Cl 2 Co 2 N 4 O 4; C, 47.65; H, 5.23; N, 8.55. Found: C, 46.64; H, 5.02; N, 8.58.

窒素雰囲気下において０．４７６ｇの塩化コバルト６水和物と０．４１２gの４―ｔｅｒｔ-ブチル−２，６−ジホルミルフェノールを含んだ１０ｍｌエタノール溶液を５０ｍｌナスフラスコに入れ、室温にて攪拌した。この溶液に０．２１６ｇのｏ−フェニレンジアミンを５ｍｌのエタノールに溶解させた溶液を徐々に添加した。上記混合物を２時間還流することにより茶褐色沈殿が生成した。この沈殿を濾取し、乾燥することで多核錯体（Ｇ）を得た（収量０．４６５ｇ：収率６３％）。なお、上記反応式において、「Ｃｌ₂」とは、２当量の塩素イオンが対イオンとしてあることを示し、「２Ｈ₂Ｏ」とは、２当量の水分子が他の配位子としてあることを示す。
元素分析値(%)：Ｃａｌｃｄ ｆｏｒ Ｃ₃₆Ｈ₃₈Ｃｌ₂Ｃｏ₂Ｎ₄Ｏ₄；Ｃ，５５．４７；Ｈ，４．９１；Ｎ，７．１９．Ｆｏｕｎｄ：Ｃ，５６．３４；Ｈ，４．８３；Ｎ，７．２３． Synthesis Example 6 [Synthesis of polynuclear complex (F)]
A polynuclear complex (F) [binuclear Co complex] represented by the following reaction formula was synthesized by the following method.

Under a nitrogen atmosphere, a 10 ml ethanol solution containing 0.476 g of cobalt chloride hexahydrate and 0.412 g of 4-tert-butyl-2,6-diformylphenol was placed in a 50 ml eggplant flask and stirred at room temperature. . A solution prepared by dissolving 0.216 g of o-phenylenediamine in 5 ml of ethanol was gradually added to this solution. The mixture was refluxed for 2 hours to produce a brown precipitate. This precipitate was collected by filtration and dried to obtain a polynuclear complex (G) (yield 0.465 g: yield 63%). In the above reaction formula, “Cl ₂ ” means that 2 equivalents of chlorine ions are used as counter ions, and “2H ₂ O” means that 2 equivalents of water molecules are used as other ligands. Indicates.
Elemental analysis value (%): Calcd for C ₃₆ H ₃₈ Cl ₂ Co ₂ N ₄ O ₄ ; C, 55.47; H, 4.91; N, 7.19. Found: C, 56.34; H, 4.83; N, 7.23.

窒素雰囲気下において０．４７６ｇの塩化コバルト６水和物と０．３２８gの４―メチル−２，６−ジホルミルフェノールを含んだ１０ｍｌメタノール溶液を５０ｍｌナスフラスコに入れ、室温にて攪拌した。この溶液に０．２２８ｇのシクロヘキシルジアミンを５ｍｌのメタノールに溶解させた溶液を徐々に添加した。上記混合物を２時間還流することにより茶褐色沈殿が生成した。この沈殿を濾取し、乾燥することで多核錯体（Ｈ）を得た（収量０．１４１ｇ：収率２１％）。なお、上記反応式において、「Ｃｌ₂」とは、２当量の塩素イオンが対イオンとしてあることを示し、「２Ｈ₂Ｏ」とは、２当量の水分子が他の配位子としてあることを示す。
元素分析値(％)：Ｃａｌｃｄ ｆｏｒ Ｃ₃₀Ｈ₃₈Ｃｌ₂Ｃｏ₂Ｎ₄Ｏ₄；Ｃ，５０．９３；Ｈ，５．４１；Ｎ，７．９２．Ｆｏｕｎｄ：Ｃ，４９．６０；Ｈ，５．４７；Ｎ，８．０４． Synthesis Example 7 [Synthesis of polynuclear complex (G)]
A polynuclear complex (G) [binuclear Co complex] represented by the following reaction formula was synthesized by the following method.

Under a nitrogen atmosphere, a 10 ml methanol solution containing 0.476 g cobalt chloride hexahydrate and 0.328 g 4-methyl-2,6-diformylphenol was placed in a 50 ml eggplant flask and stirred at room temperature. A solution prepared by dissolving 0.228 g of cyclohexyldiamine in 5 ml of methanol was gradually added to this solution. The mixture was refluxed for 2 hours to produce a brown precipitate. The precipitate was collected by filtration and dried to obtain a polynuclear complex (H) (yield 0.141 g: yield 21%). In the above reaction formula, “Cl ₂ ” means that 2 equivalents of chlorine ions are used as counter ions, and “2H ₂ O” means that 2 equivalents of water molecules are used as other ligands. Indicates.
Elemental analysis _{(%): Calcd for C 30} H 38 Cl 2 Co 2 N 4 O 4; C, 50.93; H, 5.41; N, 7.92. Found: C, 49.60; H, 5.47; N, 8.04.

窒素雰囲気下において１．６３ｇのオキシ硫酸バナジウム水和物と１．６３gの２，６−ジアセチルピリジンを含んだ３０ｍｌメタノール溶液を１００ｍｌナスフラスコに入れ、攪拌しながら８０℃に加熱した。この溶液に０．９０ｇの１，３−ジアミノプロパンを２０ｍｌのメタノールに溶解させた溶液を３０分間かけて滴下した。上記混合溶液を８時間還流することにより濃青紫色沈殿が生成した。この沈殿を濾取し、乾燥することで多核錯体（Ｉ）を得た（収量３．１ｇ：収率４５％）。なお、上記反応式において、「（ＳＯ₄）₂」とは、２当量の硫酸イオンが対イオンとしてあることを示し、「４ＭｅＯＨ」とは、４当量のメタノール分子が他の配位子としてあることを示す。
元素分析値(％)：Ｃａｌｃｄ ｆｏｒ Ｃ₂₈Ｈ₄₄Ｖ₂Ｎ₆Ｏ₁₄Ｓ₂；Ｃ，３９．３５；Ｈ，５．１９；Ｎ，９．８３．Ｆｏｕｎｄ：Ｃ，３９．７３；Ｈ，５．４４；Ｎ，１０．４２． Synthesis Example 8 [Synthesis of polynuclear complex (H)]
A polynuclear complex (H) [binuclear V (vanadium) complex] represented by the following reaction formula was synthesized according to the method described in Journal of Chemical Society, Dalton Transactions, 1996, 1223.

Under a nitrogen atmosphere, a 30 ml methanol solution containing 1.63 g vanadium oxysulfate hydrate and 1.63 g 2,6-diacetylpyridine was placed in a 100 ml eggplant flask and heated to 80 ° C. with stirring. To this solution, 0.90 g of 1,3-diaminopropane dissolved in 20 ml of methanol was added dropwise over 30 minutes. The mixed solution was refluxed for 8 hours to form a deep blue-violet precipitate. The precipitate was collected by filtration and dried to obtain polynuclear complex (I) (yield 3.1 g: yield 45%). In the above reaction formula, “(SO ₄ ) ₂ ” indicates that 2 equivalents of sulfate ion is a counter ion, and “4MeOH” is 4 equivalents of methanol molecules as other ligands. It shows that.
Elemental analysis _{(%): Calcd for C 28} H 44 V 2 N 6 O 14 S 2; C, 39.35; H, 5.19; N, 9.83. Found: C, 39.73; H, 5.44; N, 10.42.

Examples 1 to 8 [heat treatment of polynuclear complex]
Weight during heat treatment of polynuclear complexes (A) to (H) obtained in Synthesis Examples 1 to 8 using a thermogravimetric / differential thermal analyzer (Seiko Instruments EXSTAR-6300, hereinafter referred to as a thermal analyzer) Change (TGA) was measured. The measurement conditions were under a nitrogen atmosphere (temperature increase rate 10 ° C./min), and a platinum dish or an alumina dish was used for the heat treatment.
The analysis results (analysis charts) of the multinuclear complexes (A) to (H) are shown in FIGS.

Based on the knowledge obtained from the thermogravimetric analysis results, the baking treatment was performed so that the weight reduction rate during the heat treatment was 5% by weight or more. That is, the polynuclear complex was heat-treated at a target temperature for 2 hours in a nitrogen atmosphere using a tubular furnace.
The tubular furnace and heat treatment conditions used for the heat treatment are shown below.
Tubular furnace: Program-controlled open / close tubular furnace EPKRO-14R, Isuzu Manufacturing Heat treatment atmosphere: Nitrogen gas flow (200 ml / min)
Temperature increase rate and temperature decrease rate: 200 ° C / h

Table 1 shows the polynuclear complexes and heat treatment temperatures used, and the weight loss rate after treatment. The carbon content (elemental analysis value) after the heat treatment is also shown together with the carbon content before the heat treatment.

Here, the modified complexes obtained by heat-treating the polynuclear complexes (A) to (H) are referred to as modified complexes (A) to (H), respectively.

Example 9 [Measurement of Laser Raman Spectra of Multinuclear Complex (A) and Modified Complex (A)]
FIG. 9 shows laser Raman spectra of the polynuclear complex (A) and the modified complex (A). The measurement was performed under the following conditions.
Equipment used: Microscopic laser Raman spectrometer NSR1000 (JASCO)
Excitation wavelength: 532 nm
Objective lens: 50 × Measurement range: 200-3900 cm ⁻¹
FIG. 9 shows that the modified complex (A) has a maximum peak at 1580 cm ⁻¹ . This indicates that graphene-like carbon is generated by the modification treatment.

Example 10 [Measurement of X-ray photoelectron spectra of polynuclear complex (E) and modified complex (E)]
X-ray photoelectron spectra of the polynuclear complex (E) and the modified complex (E) were measured. For X-ray photoelectron spectroscopy (XPS) measurement, SSX-100 manufactured by SII was used. A monochromated Al Kα ray (1486.6 eV, X-ray spot 1000 μm) was used as the X-ray, and a Ni mesh was placed on the sample for neutralization of the charge during measurement, and a neutralizing electron gun was used. It was measured. The binding energy of the spectrum was calibrated with C1s C—C and C—H bonds as 284.6 eV.
FIG. 10 shows the C1s spectrum, and FIG. 11 shows the N1s spectrum. In FIG. 10, the C1s peak of the modified complex (F) tails on the high binding energy side, suggesting the formation of graphene-like carbon.
In FIG. 11, the half width of the peak of the modified complex (E) is 3.5 eV. Moreover, the half width of the peak of the modified complex (E) was 2.3 times the half width of the peak of the polynuclear complex (E).

Examples 11 to 18 and Comparative Examples 1 to 8 [Evaluation test of metal holding ability of modified complex (A) to modified complex (H)]
10 mg of the modified complex (A) to modified complex (H) obtained in Examples 1 to 8 were immersed in 2 ml of a pH 4 tartrate buffer solution (prepared from a 0.2 mol / L tartaric acid aqueous solution and a 0.1 mol / L sodium tartrate aqueous solution). And stirred for 20 minutes at room temperature. After filtering the solution, the amount of metal contained in the filtrate was quantified by inductively coupled plasma optical emission spectrometry (ICP-AES) or absorptiometry, and the metal retention was calculated.
Moreover, regarding the polynuclear complex (A) to the polynuclear complex (H) not subjected to the heat treatment, an evaluation test of the metal holding ability was performed and compared with Examples 11 to 18. That is, except that the modified complexes (A) to (H) in Examples 11 to 18 were changed to the polynuclear complexes (A) to (H), the same operation was performed, and the amount of metal contained in the filtrate was changed to Example 11. It quantified similarly to -18, and the metal retention was computed. The polynuclear complexes (A) to (H) that were not heat-treated were inferior to the metal-retaining ability as compared with the modified complexes (A) to (H).

Example 19 [hydrogen peroxide decomposition test of modified complex (A)]
1.6 mg (about 8 μmol (per metal atom)) of the modified complex (A) was weighed into a two-necked flask, and a tartaric acid / sodium tartrate buffer solution (1.00 ml (0.20 mol / l tartaric acid aqueous solution and 0%) was used as a solvent. Prepared from a 10 mol / l aqueous sodium tartrate solution, pH 4.0)) and ethylene glycol (1.00 ml) were added and stirred. This was used as a catalyst mixed solution.

A septum was attached to one mouth of the two-necked flask containing the catalyst mixed solution, and the other mouth was connected to a gas burette. After stirring the flask at 80 ° C. for 5 minutes, an aqueous hydrogen peroxide solution (11.4 mol / l, 0.20 ml (2.28 mmol)) was added with a syringe, and a hydrogen peroxide decomposition reaction was performed at 80 ° C. for 20 minutes. It was. The generated oxygen was measured with a gas burette, and the decomposed hydrogen peroxide was quantified.
The amount of hydrogen peroxide decomposed was determined from the volume of oxygen generated in the hydrogen peroxide decomposition test. From the following formula, the actually generated gas volume value v was converted to a gas volume V at 0 ° C. and 101325 Pa (760 mmHg) in consideration of the water vapor pressure.
The results are shown in FIG. The modified complex (A) of the present invention has a higher generated gas volume compared to the blank test described later, and the catalytic effect related to hydrogen peroxide decomposition was confirmed.

（式中、Ｐ：大気圧（ｍｍＨｇ）、ｐ：水の蒸気圧（ｍｍＨｇ）、ｔ：温度（℃）、ｖ：実測の発生気体体積（ｍｌ）、Ｖ：０℃、１０１３２５Ｐａ（７６０ｍｍＨｇ）下の気体体積（ｍｌ）を示す。）

(In the formula, P: atmospheric pressure (mmHg), p: vapor pressure of water (mmHg), t: temperature (° C), v: measured gas volume (ml), V: 0 ° C, 101325 Pa (760 mmHg) Gas volume (ml).

[Blank test]
To a two-necked flask, 1.00 ml of a tartaric acid aqueous solution / sodium tartrate buffer solution (prepared from 0.20 mol / l aqueous tartaric acid solution and 0.10 mol / l aqueous sodium tartrate solution, pH 4.0) and 1.00 ml of ethylene glycol were added as solvents. A septum was attached to one of the two-necked flasks, and the other was connected to a gas burette. After stirring the flask at 80 ° C. for 5 minutes, an aqueous hydrogen peroxide solution (11.4 mol / l, 0.200 ml (2.28 mmol)) was added, and the generated gas was quantified with a gas buret at 80 ° C. for 20 minutes. .
In this blank test, it is considered that air or the like dissolved in the solution is mainly detected.

Comparative Example 9 [hydrogen peroxide decomposition test of polynuclear complex (A)]
A test equivalent to that in Example 19 was performed, except that the modified complex (A) in Example 19 was changed to the polynuclear complex (A). The results are shown in FIG. 12 together with Example 19.
The amount of gas generated was not different from the blank experiment, and the catalytic effect of hydrogen peroxide decomposition was not observed.

Example 20 [Presence or absence of radical generation in the hydrogen peroxide decomposition test using the modified complex (A)]
Modified complex (A) (1.6-2.2 mg, about 8 μmol (per metal atom)), and poly (4-styrenesulfonic acid) sodium salt (Aldrich commercial product, weight average molecular weight: about 70,000) 21.1 mg was weighed into a two-necked flask, and a tartaric acid / sodium tartrate buffer solution (1.00 ml (prepared from 0.2 mol / l aqueous tartaric acid solution and 0.1 mol / l aqueous sodium tartrate solution, pH 4.0)) was used as a solvent. And ethylene glycol (1.00 ml) were added and stirred. This was used as a catalyst mixed solution.

A septum was attached to one mouth of the two-necked flask containing the catalyst mixed solution, and the other mouth was connected to a gas burette. After stirring the flask at 80 ° C. for 5 minutes, an aqueous hydrogen peroxide solution (11.4 mol / l, 0.20 ml (2.28 mmol)) was added with a syringe, and a hydrogen peroxide decomposition reaction was performed at 80 ° C. for 20 minutes. It was. The generated oxygen was measured with a gas burette, and the decomposed hydrogen peroxide was quantified. Thereafter, the reaction solution was diluted with a water / acetonitrile mixed solution (water: acetonitrile = 7: 3 (v / v)) so that the solution amount became 10.0 ml, and this solution was filtered with a syringe filter. This filtrate was subjected to GPC measurement, and a GPC pattern was determined by the following method of poly (sodium 4-styrenesulfonate) after the test, and compared with the poly (4-styrenesulfonic acid) sodium salt itself used in the test.
FIG. 13 shows the GPC pattern.
In the peak of poly (4-styrenesulfonic acid), almost no molecular weight reduction is observed, and a hydroxy radical that decomposes poly (4-styrenesulfonic acid) when the polynuclear complex (A) decomposes hydrogen peroxide. It was confirmed that no radical species were generated. Considering that the decomposition of hydrogen peroxide with a mononuclear metal complex often generates radical species, the results of this test show that the modified complex (A) in the present invention maintains a binuclear structure. It is.

[GPC analysis conditions]
Column: TSKgel α-M manufactured by Tosoh Corporation
(13μm, 7.8mmφ × 30cm)
Column temperature: 40 ° C
Mobile phase: 50 mmol / l ammonium acetate aqueous solution: CH ₃ CN
= 7: 3 (v / v)
Flow rate: 0.6 ml / min
Detector: RI
Injection volume: 50 μl

Example 21 [heat treatment of mixture containing polynuclear complex (A)]
A mixture of 0.053 g of the polynuclear complex (A) obtained in Synthesis Example 1 and 0.20 g of perylene-3, 4, 9, 10-tetracarboxylic dianhydride was uniformly mixed using an agate mortar. This mixture was heat-treated with a thermal analyzer up to 500 ° C. (temperature increase rate: 10 ° C./min). The weight loss after the treatment was 28% based on the initial weight of the entire mixture. The amount of carbon contained in the heat-treated product was calculated from the weight reduction rate and the ratio of coexisting elements, and the lower limit was 57%.

Example 22 [heat treatment of mixture containing polynuclear complex (E)]
15 ml of ethanol was added to a mixture of 20 mg of the polynuclear complex (E) obtained in Synthesis Example 5 and 160 mg of Ketjen Black (Lion, EC300J), and stirred at room temperature for 20 minutes to obtain a slurry. The slurry was dried at room temperature under a reduced pressure of 1.5 Torr for 12 hours. The dried product was heat-treated at 450 ° C. for 2 hours under a nitrogen flow of 200 ml / min using a tubular furnace. The weight loss after the treatment was 5.3% based on the initial weight of the entire mixture. The amount of carbon contained in the heat-treated product was 89.56%.

Example 23 [Heat treatment of mixture containing polynuclear complex (F)]
15 ml of ethanol was added to a mixture of 20 mg of the polynuclear complex (F) obtained in Synthesis Example 6 and 160 mg of Ketjen Black (Lion, EC300J), and stirred at room temperature for 20 minutes to obtain a slurry. The slurry was dried at room temperature under a reduced pressure of 1.5 Torr for 12 hours. The dried product was heat-treated at 500 ° C. for 2 hours under a nitrogen flow of 200 ml / min using a tubular furnace. The weight loss after the treatment was 7.2% with respect to the initial weight of the whole mixture. The amount of carbon contained in the heat-treated product was 85.85%.

Thermogravimetric analysis chart of polynuclear complex (A) Thermogravimetric analysis chart of polynuclear complex (B) Thermogravimetric analysis chart of polynuclear complex (C) Thermogravimetric analysis chart of polynuclear complex (D) Thermogravimetric analysis chart of polynuclear complex (E) Thermogravimetric analysis chart of polynuclear complex (F) Thermogravimetric analysis chart of polynuclear complex (G) Thermogravimetric analysis chart of polynuclear complex (H) Laser Raman spectrum of polynuclear complex (A) and modified complex (A) of Example 9 N1s spectrum by XPS measurement of polynuclear complex (E) and modified complex (E) of Example 10 C1s spectrum by XPS measurement of polynuclear complex (E) and modified complex (E) of Example 10 Results of hydrogen peroxide decomposition test of Example 19 and Comparative Example 9 GPC analysis chart of Example 20

Claims (14)

A polynuclear metal complex having one or more macrocyclic ligands having 5 to 15 coordinating atoms in the molecule and a plurality of metal atoms is any one of heat treatment, radiation irradiation treatment and discharge treatment. A polynuclear metal complex-modified product which is modified by modification treatment until the weight reduction rate before and after the treatment is 5% by weight or more and 90% by weight or less, and the carbon content after modification is 5% by weight or more. 2. The polynuclear metal complex-modified product according to claim 1, wherein the plurality of metal atoms are transition metal atoms belonging to the fourth to sixth periods of the periodic table. The polynuclear metal complex-modified product according to claim 1 or 2, wherein the plurality of metal atoms are 2 to 10 metal atoms. 4. The modified polynuclear metal complex according to claim 1, wherein the coordination atom is selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom. The polynuclear metal complex-modified product according to any one of claims 1 to 4, wherein the macrocyclic ligand is a macrocyclic ligand represented by the following general formula (I).

(In the formula, Q is a divalent organic group containing one or more coordination atoms selected from the group consisting of carbon atom, nitrogen atom, oxygen atom, phosphorus atom and sulfur atom, and n is an integer of 5 or more and 15 or less. .) The polynuclear metal complex-modified product according to any one of claims 1 to 5, wherein the modification treatment is a heat treatment at a temperature of 250 ° C to 1000 ° C. The polynuclear metal complex-modified product according to any one of claims 1 to 6, wherein a weight reduction rate before and after the modification treatment is 7 wt% or more and 90 wt% or less. The polynuclear metal complex-modified product according to any one of claims 1 to 7, wherein the polynuclear metal complex-treated product has a carbon content of 10% by weight or more. The polynuclear metal complex-modified product according to any one of claims 1 to 8, which has a peak in a range of 1550 to 1600 cm ^-1 in a spectrum obtained by laser Raman spectroscopy measurement with an excitation wavelength of 532 nm. 10. The polynuclear according to claim 1, wherein in the N1s spectrum obtained by X-ray photoelectron spectroscopy, the half width of the signal of the polynuclear metal complex treated product having a peak maximum at 396 eV to 404 eV is 2 eV or more. Modified metal complex. In the N1s spectrum obtained by X-ray photoelectron spectroscopy, the half width of the signal of the polynuclear metal complex treated product having a peak maximum at 396 eV to 404 eV is 1.3 times or more the half width of the signal of the polynuclear metal complex before treatment. The modified polynuclear metal complex according to any one of claims 1 to 10. In the molecule, (a) a polynuclear metal complex having one or more macrocyclic ligands having 5 to 15 coordination atoms and a plurality of metal atoms, and (b) a carbon support having a boiling point or melting point Modification of any of heat treatment, radiation irradiation treatment or discharge treatment to a mixture comprising an organic compound of 250 ° C. or higher, or at least one organic compound selected from organic compounds having a thermal polymerization start temperature of 250 ° C. or lower A polynuclear metal complex-modified product in which the weight reduction rate before and after the treatment is modified to 5% by weight or more and 90% by weight or less from the treatment, and the carbon content after the modification is 5% by weight or more. A composition comprising the modified polynuclear metal complex according to any one of claims 1 to 12, and a carbon support and / or a conductive polymer. A catalyst comprising the modified polynuclear metal complex according to any one of claims 1 to 12 and / or the composition according to claim 13.

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