JP2002179635A - Electroresponsive complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrode material for a high-performance secondary cell which has a small size and a light weight, has a long life, and exhibits high-speed responsiveness, and a metal catalyst which performs multielectron transfer, exhibits stable oxidation and reduction, and has high heat stability. SOLUTION: An electrically responsive complex comprising a phenylazomethine complex expressed by formula (I) (wherein, Ar is an aromatic π-conjugated molecule, R1 and R2 are each H, or a substituent selected from an alkyl and an aryl group; R and R' are each a substituent selected from an alkyl and an aromatic group; and M is a rare earth metal ion or a metal halide).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electroresponsive complex. More specifically, the invention of this application relates to a phenylazomethine complex and a phenylenediamine complex that effectively act as a cathode material of a secondary battery and a complex catalyst.

[0002]

2. Description of the Related Art In recent years, with the spread of notebook personal computers and mobile phones, or the development and commercialization of electric vehicles, it has been desired to reduce the weight, extend the life and enhance the performance of secondary batteries. .

[0003] Conventional secondary batteries are generally nickel-metal hydride batteries or nickel-cadmium (NiCd) batteries using nickel, a hydrogen storage alloy or the like as an electrode material, but recently have higher energy densities. Lithium secondary batteries are attracting attention, and are expected to be used not only as small batteries for mobile terminals, but also as large batteries for automobiles and space, and are being actively studied.

In such a lithium secondary battery, lithium cobalt oxide is mainly used as a positive electrode material.
Since the reserves of cobalt are extremely small at only 8.4 million tons, there is a problem that the cost of the material is high and the price is liable to fluctuate. Therefore, in order to reduce the cost, positive electrode materials using other metal oxides such as nickel, manganese, and vanadium have been developed and partially adopted.

[0005] However, secondary batteries mainly composed of these metal materials are heavy and heavy in secondary applications such as automobiles and space as well as small applications such as portable electronic devices. Therefore, there is a problem that the size that can be realized is limited.

Further, in terms of the performance of the secondary battery, since the mobile ions of the lithium secondary battery are metal ions, the moving speed is slow, the amount of current that can be charged and discharged is not so large, and the response is low. there were. Further, in a lithium secondary battery, lithium ions are repeatedly inserted (charged) and released (discharged) into and from an electrode material (crystal) during charge and discharge, so that a structural change of the electrode material is large and deterioration easily occurs. As a result, there is a problem that the repetitive life of the battery is shortened. Further, in a general battery including the lithium secondary battery as described above, a liquid electrolyte is used to separate the positive electrode and the negative electrode. Therefore, leakage of the electrolyte solution may occur, and it has been difficult to reduce the thickness.

Therefore, a polymer electrolyte composed of only a polymer and an electrolyte salt and a gel polymer electrolyte obtained by gelling these with an organic solvent have been developed and put into practical use.
However, even in a polymer secondary battery using such a polymer electrolyte, there is a problem that the internal resistance is high and the responsiveness is poor because large ionic species move. Also,
These polymer batteries, like lithium secondary batteries,
Since the main material of the electrode material is a metal material such as lithium cobalt oxide, the above various problems remain without being solved.

In order to effectively solve these problems, a conductive polymer is considered as a suitable electrode material. However, at present, such a conductive polymer material has not been put into practical use, and a high-performance polymer electrode material has been desired.

On the other hand, various types of metal catalysts for chemical reactions have been reported and provided so far. However, as metal catalysts useful in industrial use, they exhibit stable oxidation-reduction and are multi-electron. What can be moved is required. In order for metal catalysts to be used industrially,
Along with further improvement of the catalyst efficiency, thermal stability is also required. However, such metal catalysts have not been known so far.

Therefore, the invention of this application has been made in view of the circumstances described above, and solves the problems of the prior art, which enables a secondary battery to be reduced in size and weight, and has a long life. An object of the present invention is to provide a high-performance secondary battery electrode material exhibiting high-speed response. Another object of the invention of the present application is to provide a metal catalyst having high thermal stability and capable of transferring multiple electrons and exhibiting stable redox.

[0011]

Means for Solving the Problems According to the invention of the present application, as a solution to the above-mentioned problems, firstly, an electrically responsive complex represented by the following general formula (I):

[0012]

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(Where Ar is an aromatic π-conjugated substituent,
R ¹ and R ² are the same or different and each is a hydrogen atom or a hydrocarbon group which may have a substituent; R and R ^a are each the same or different and are an alkyl group or an aromatic group; M represents a rare earth metal or a metal halide).

Secondly, the invention of the present application relates to a complex having an electroresponsive molecule, which has the following general formula (II):

[0015]

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(Where Ar is an aromatic π-conjugated substituent,
R ³ and R ⁴ are the same or different and each is a hydrogen atom or a hydrocarbon group which may have a substituent, and R ^b is
A hydrocarbon group which may have a substituent, M represents a rare earth metal or a metal halide, and n is an integer of 1 or more indicating the degree of polymerization. Thirdly, the invention of this application is, thirdly, a complex having electrical responsiveness, which is represented by the following general formula (II)
I)

[0017]

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(Wherein R ⁵ and R ⁶ are the same or different and each is a hydrogen atom or a hydrocarbon group which may have a substituent, and R ^c may have a substituent. A hydrocarbon group, M is a rare earth metal or a metal halide,
n is an integer of 1 or more indicating the degree of polymerization).

Fourth, the invention of this application provides a polyaniline complex in which polyaniline forms a complex with a rare earth metal ion or a metal halide.

Fifthly, the invention of this application provides a positive electrode material for a secondary battery containing any of the first to fourth complexes.

Sixth, the invention of this application also provides an oxidation-reduction catalyst containing any one of the first to fourth complexes.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies to solve the above-mentioned problems, and have reported a polyphenylazomethine derivative useful as a positive electrode material of a proton electrode (Japanese Patent Application No. 2000-2000). -270712). afterwards,
It has been found that rare earth metal ions have high coordination ability to these phenylazomethine derivatives and phenylenediamine derivatives. And rare earth metal ion and phenylazomethine derivative or phenylenediamine derivative,
They have found that they become electroactive by forming a complex, leading to the invention of this application.

The phenylazomethine complex and phenylenediamine complex of the invention of this application are redox-reduced without ion transfer, and are therefore useful as cathode materials having a much higher energy density than conventional conductive polymers. It is something. In addition, since complex formation can be efficiently performed with metal ions having a catalytic ability, improvement in catalytic efficiency based on smooth electron transfer via a π-conjugated system can be expected.

Accordingly, the invention of this application provides a phenylazomethine complex or a phenylenediamine complex as an electroresponsive complex.

The phenylazomethine complex is represented by the following general formula (IV)

[0026]

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(Where Ar is an aromatic π-conjugated substituent,
R ¹ and R ² are the same or different and each is a hydrogen atom or a hydrocarbon group which may have a substituent; R and R ^a are each the same or different and each represents an alkyl group or an aromatic group; The complex is formed by coordinating a rare earth metal or a metal halide to N of the phenylazomethine derivative represented by the following formula:

In such a phenylazomethine complex, examples of the aromatic π-conjugated substituent represented by Ar include a phenyl group, a biphenyl group and a naphthyl group.
When R ¹ and R ² are a hydrocarbon group, it is preferably an alkyl group or an aromatic group which may have a substituent. Specific examples include a hydrogen atom, an alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl and t-butyl, and an aromatic group such as phenyl, biphenyl and naphthyl. Among them, an aromatic group such as a phenyl group or a naphthyl group that expands the π-conjugated system in the complex is preferable. Also,
R and ^Ra are a hydrocarbon group which may have a substituent, for example, a substituent selected from an alkyl group and an aromatic group. Specifically, methyl, ethyl, propyl,
n-butyl, t-butyl, sec-butyl, phenyl,
Substituents such as naphthyl are exemplified. Among them, an aromatic group, particularly a phenyl group, is preferred. Further, the coordinating M is selected from rare earth metals or metal halides. As the rare earth metal, scandium group selected from scandium (Sc), yttrium (Y), lanthanum (La), and actinium (Ac), cerium (Ce), europium (Eu), terbium (Tb), ytterbium (Yb) And other lanthanoid (Ln) -based metals. Among them, La, Ce, Eu and Tb are preferred. on the other hand,
As the metal halide, various ones are exemplified.
Preferably, tin (II) halides such as SnCl ₂ and SnBr ₂ , vanadium halides such as VCl ₃ , LiCl
And lithium halides such as LiBr.

The phenylazomethine derivative represented by the above general formula (IV) may be synthesized by any method. Various known methods are exemplified,
Specifically, a method in which a diamine and a diketone or an aminophenyl ketone are obtained by a dehydration reaction in the presence of an acid such as titanium tetrachloride or paratoluenesulfonic acid can be considered. The coordination of the rare earth metal or the metal halide (M) to the phenylazomethine derivative thus obtained may be performed by any method. In practice, however, the phenylazomethine derivative and M are dissolved in a solution. Complex formation easily occurs by coexisting with the above. Further, the phenylazomethine complex can be isolated by removing the solvent after coexisting in the solution.

In the invention of this application, the following general formula (V)

[0031]

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(Where Ar is an aromatic π-conjugated substituent,
R ³ and R ⁴ are the same or different and each is a hydrogen atom or a hydrocarbon group which may have a substituent, and R ^b is
A hydrocarbon group which may have a substituent, M represents a rare earth metal or a metal halide, and n is an integer of 1 or more indicating the degree of polymerization. And a polyphenylazomethine complex coordinated by M is provided.

In such a polyphenylazomethine derivative, Ar is as described above. Also, R
^{When 3} and R ⁴ are hydrocarbon groups, they are the same as R ¹ and R ² described above. Among them, an aromatic group such as a phenyl group is preferred. Further, R ^b is a hydrocarbon group which may have a substituent. Such a hydrocarbon group may be chain-like such as an ethylene chain or a propylene chain,
It may be cyclic, such as phenylene. Also,
It may be a substituent having a substituent having S, N, and O atoms, such as amide, imide, ester, and thioether. Preferably, it is a substituent that introduces a heteroatom such as S, N, or O into the main chain of the polyphenylazomethine derivative. Preferable examples of M coordinated to N of such a polyphenylazomethine derivative include the same rare earth metals and metal halides as described above.

The polyphenylazomethine derivative of the general formula (V) may be synthesized by any method, and various known synthesis methods can be applied. For example, a dehydration reaction of diamine and diketone or aminophenylketone in the presence of an acid such as titanium tetrachloride or paratoluenesulfonic acid is considered. The coordination of the rare earth metal or metal halide (M) to the polyphenylazomethine derivative thus obtained may be performed by any method. Complex formation easily occurs by coexisting in a solution.
After coexisting both in a solution, the solvent is removed to isolate the polyphenylazomethine complex.

The invention of this application further provides an electrically responsive molecular complex represented by the following general formula (VI):

[0036]

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(Provided that R ⁵ and R ⁶ are the same or different hydrogen atoms or hydrocarbon groups which may have a substituent, and R ^c and R ^{d each} have a substituent. And n is an integer of 1 or more indicating the degree of polymerization.) A polyphenylenediamine complex in which M is coordinated to the N site of the polyphenylenediamine derivative represented by the formula (1) is provided.

In such a polyphenylenediamine derivative, R ⁵ and R ⁶ are each other than a hydrogen atom.
The same substituents as those described above for R ^{1 to} R ⁴ are exemplified. Preferably, it is an aromatic group such as a phenyl group. R ^c and R ^d are a hydrocarbon group which may have a substituent, and may be a chain-like one such as an ethylene chain or a propylene chain, or a cyclic one such as phenylene. Good. S, such as amide, imide, ester, thioether, etc.
It may have a substituent containing a hetero atom such as N or O. Preferably, it is a substituent that introduces a heteroatom such as S, N, or O into the main chain of polyphenylenediamine. Specific examples of R ^c and R ^d include phenylene sulfide.

The polyphenylenediamine derivative represented by the general formula (VI) may be synthesized by any method, and various known methods are considered. For example, a palladium-catalyzed coupling reaction between a dibrominated phenylenediamine derivative and an aryl distanned or aryl diboronate, or a phenylenediimine derivative having a nucleophilic functional group such as a thiol group or an amino group Methods performed by Michael addition of compounds are contemplated. In order to introduce the metal (M) into the polyphenylenediamine derivative thus obtained, it may be simply made to coexist with a rare earth metal or a metal halide in a solution.

The invention of this application further provides, as a complex having electrical responsiveness, a polyaniline complex formed by forming a complex of polyaniline and a rare earth metal or a halogen metal. At this time, the polyaniline may be any polyaniline in which a substituent is bonded to a carbon atom of the ring structure, for example, various polyanilines in which an appropriate one such as an alkyl group, an aryl group, or an alkoxy group is bonded. Kind is considered. The rare earth metal and halogen metal coordinated to polyaniline are as described above. Of these, rare earth metals are particularly preferred. The method of complex formation is not particularly limited.However, polyaniline and a rare earth metal synthesized by a known method are allowed to coexist in a solution, or a polyaniline solid film is immersed in a solution in which a rare earth metal is dissolved, thereby forming a complex. The polyaniline complex of the invention of the application is obtained.

Each of the above complexes is a compound exhibiting high electrical responsiveness and stable oxidation-reduction potential, and is useful as a positive electrode material of a high energy density secondary battery or a highly stable metal catalyst.

Hereinafter, examples will be shown, and embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail.

[0043]

EXAMPLES Example 1 Synthesis of Bis [(α-phenyl) phenylazomethine] benzene (i) According to the following chemical formula (A), bis [(α-phenyl)
Phenylazomethine] benzene (i) was synthesized.

[0044]

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In a 100 mL three-necked flask, 1,4-dibenzoylbenzene (1.43 g, 5.0 mmol),
Aniline (1.8 mL, 20 mmol) and diazabicyclo [2,2,2] octane (30.0 mmol) were added, and the mixture was placed under a nitrogen atmosphere, and chlorobenzene (50 mL) was added as a solvent. Titanium tetrachloride (0.8 mL,
(7.5 mmol) was added dropwise, and the mixture was heated under reflux at 125 ° C. for 12 hours. After completion of the reaction, the precipitate was filtered, and the filtrate was concentrated.
The target product was obtained in a yield of 97 by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 1/10).
%.

The obtained target substance was analyzed by infrared absorption spectrum,
It was identified by mass spectrometry and elemental analysis. Table 1 shows the results
It was shown to.

[0047]

[Table 1]

Example 2 Complex formation of bis [(α-phenyl) phenylazomethine] benzene and tin (II) chloride and electrochemical measurement In acetonitrile solution containing 0.2 M TBABF ₄ , 2 mM bis [(α -Phenyl) phenylazomethine] cyclic voltammetry measurement of benzene (working electrode: carbon electrode, counter electrode: platinum electrode, reference electrode: A
g / Ag ⁺ , sweep rate: 0.1 V / sec).

When 4 mM of tin (II) chloride was added to the system, a very good oxidation-reduction wave (E _1/2 =
0.65Vvs. Ag / Ag ⁺ ) was observed. <Example 3> Complex formation of bis [(α-phenyl) phenylazomethine] benzene and lithium chloride and electrochemical measurement 2 mM bis [(α-phenyl) phenylazomethine] in an acetonitrile solution containing 0.2 M TBABF ₄ Cyclic voltammetry measurement of benzene (working electrode: carbon electrode, counter electrode: platinum electrode, reference electrode: A
g / Ag ⁺ , sweep rate: 0.1 V / sec).

When 4 mM lithium chloride was added to the system, a very good oxidation-reduction wave (E _1/2 =
0.65Vvs. Ag / Ag ⁺ ) was observed. <Example 4> Complex formation of bis [(α-phenyl) phenylazomethine] and lanthanum (III) ion and electrochemical measurement 2 mM bis [(α-phenyl) phenyl in acetonitrile solution containing 0.2 M TBABF ₄ Azomethine] cyclic voltammetry measurement of benzene (working electrode: carbon electrode, counter electrode: platinum electrode, reference electrode: A
g / Ag ⁺ , sweep rate: 0.1 V / sec).

When 4 mM La (OSO ₂ CF ₃ ) ₃ was added to the system, a very good oxidation-reduction wave (E _1/2 = −0.55 V vs. Ag / Ag ⁺ ) based on complex formation was observed. Was. Example 5 Synthesis of Poly [(α-phenyl) phenylazomethine] (ii) Poly [(α-phenyl) phenylazomethine] (ii) was synthesized according to the following chemical formula (B).

[0052]

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In a 50 mL three-necked flask, 1,4-dibenzoylbenzene (0.286 g, 1.0 mmol),
4,4'-thiodiamine (0.216 g, 1.0 mmol
l), diazabicyclo [2,2,2] octane (8.0
mmol) under a nitrogen atmosphere, chlorobenzene (20 mL) was added, and titanium tetrachloride (2.0 mmol) was added.
l) was added dropwise. The mixture was heated and refluxed at 125 ° C. for 24 hours. After completion of the reaction, the precipitate was filtered, the filtrate was concentrated, and the precipitate was reprecipitated in methanol to give the target compound as a yellow powder in a yield of 96.
%.

The results of product identification are shown in Table 2.

[0055]

[Table 2]

Example 6 Polyphenylene sulfide into which a phenylenediamine derivative was introduced (PPS-PD
A) Synthesis of (v) (a) Synthesis of monomer (TB-2PDI) (iv): According to chemical formula (C), monomer (TB-2PDI) (iv)
Was synthesized.

[0057]

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4,4'-thiobisbenzenethiol (T
B, 0.123 g, 0.5 mmol) in methylene chloride 5
0, and N, N′-diphenyl-1,4-phenylenediamine (PDI, 0.260) dissolved in 100 mL of methylene chloride using a dropping funnel.
g, 1.0 mmol). When the reaction solution was stirred at room temperature for 2 hours, the color of the solution changed from orange to yellow, and the progress of the reaction was confirmed. After the completion of the reaction, the monomer precursor (TB-2PDA) (iii) was isolated by silica gel column chromatography in a yield of 31%.

TB-2PDA (iii) (0.153 g,
0.2 mmol) with N-methylpyrrolidone (NMP, 4
dissolved in calcium hypochlorate (0.1 mL).
72 g, 1.2 mmol) and reacted at room temperature for 4 hours. The color of the solution changed from yellow to orange. The reaction mixture was reprecipitated in water and filtered to obtain the desired monomer (TB-2PDI) (iv) in a yield of 98%.

(B) Polymer (PPS-PDA) (v)
Synthesis of polymer (PPS-P) according to chemical formula (D)
DA) (v) was synthesized.

[0061]

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TB-2 PDI (iv) (0.2 mmol)
Was dissolved in methylene chloride (25 ml) with TB
(50 mg, 0.2 mmol) in methylene chloride (25 m
The solution dissolved in L) was added using a dropping funnel. The reaction was performed at room temperature for 24 hours. After completion of the reaction, PPS-PDA (v) was obtained at a yield of 60% by reprecipitation in methanol.

The obtained PPS-PDA (v) was identified by infrared absorption spectrum and elemental analysis, and the results are shown in Table 3.

[0064]

[Table 3]

Example 7 Synthesis of polyparaphenylene (PPP-PDA) into which phenylenediamine derivative was introduced (a) Synthesis of monomer A (PDA-2Br) (vi): Monomer A was synthesized according to the following chemical formula (E). (PDA-2B
r) (vi) was synthesized.

[0066]

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In a 200 mL three-necked flask, aniline (10.3 g) was dissolved in chlorobenzene (40 mL), and titanium tetrachloride (1.24 mL) was added dropwise from a dropping funnel under a nitrogen atmosphere. Chlorobenzene (20m
L) and then chlorobenzene (100 mL)
2,5-Dibromo-1,4-benzoquinone (2.07 mL) was added dropwise and reacted at 125 ° C. for 12 hours. After the completion of the reaction, the solution was concentrated, and PDA-2Br (vi) was reduced to 65% by silica gel column chromatography.
In a yield of

(B) Synthesis of monomer B (BB) (vii): According to the following chemical formula (F), monomer B (BB)
(Vii) was synthesized.

[0069]

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4,4′-dibromobiphenyl (1.56 g, 5 mmol) was added to a 100 mL three-necked flask.
After drying under reduced pressure, the mixture was placed under nitrogen, and ether (50 mL) and THF (10 mL) were added. After cooling on ice, a 1.14 M methyllithium / ether solution (9.7 mL, 11 mmol
l) and stirred for 30 minutes, then 1.54M at -78 ° C.
t-butyllithium / pentane solution (14.6 mL, 2
2.5 mmol) was added. After further stirring at room temperature for 30 minutes, the mixture was cooled again at -78 ° C, and THF (40 mL),
And tributyltin chloride (7 mL, 25 mmol)
Was added, and the mixture was stirred for 40 minutes, and further stirred at room temperature for 30 minutes. After the completion of the reaction, the reaction solution was poured into water (300 mL),
After extracting the organic layer with ether, the desired monomer (BB) (vii) was isolated by silica gel column chromatography in a yield of 95%.

(C) Polymer (PPP-PDA) (vii
Synthesis of i): Polymer (PPP-PDA) (viii) was synthesized according to the following chemical formula (G).

[0072]

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In a two-necked flask, PDA-2Br (0.1
mmol), BB (0.1 mmol), Pd (PP
h ₃ ) ₄ (5.0 mmol), CuI (5.0 mmol)
Into a nitrogen atmosphere, then NMP (2 mL), T
HF (1 mL) was added. After reacting at 100 ° C. for 24 hours, an aqueous solution of potassium fluoride was added, quenched, and reprecipitated with methanol to quantitatively obtain a target polymer (PPP-PDA).

Table 4 shows the results of identification of the obtained polymer.

[0075]

[Table 4]

Example 8 Complexation of Phenylenediamine Derivative Polymer (PPP-PDA) with Eurobium (III) Ion and Electrochemical Measurement In acetonitrile solution containing 0.2 M TBABF ₄ , 1 mM of PPP-PDA was cyclically applied. Voltammetric measurement (working electrode: carbon electrode, counter electrode: platinum electrode,
Reference electrode: Ag / Ag ⁺ , sweep speed: 0.1 V / se
c) was performed.

In the system, 10 mM Eu (OSO ₂ CF ₃ ) ₃
, A very good oxidation-reduction wave based on complex formation (E _1/2 = 0.28, 0.55 V vs. Ag / Ag ⁺ )
Was observed. <Example 9> polyaniline and lanthanum (III) acetonitrile solution containing ions complexing with electrochemical measuring 0.1 M TBABF _4, cyclic voltammetry measurements of the polyaniline-modified electrode (working electrode: a carbon electrode, counter electrode: platinum electrode , Reference electrode: Ag / Ag ⁺ , sweep speed: 0.1 V / sec)
Was done.

When 5 mM La (OSO ₂ CF ₃ ) ₃ was added to the system, a very good oxidation-reduction wave based on complex formation (E _1/2 = 0.05, 0.60 V vs. Ag / Ag ⁺ ) was obtained. Was observed.

[0079]

As described above, according to the present invention, a phenylazomethine complex, a polyaniline complex, and a phenylenediamine complex useful as a cathode material for a secondary battery having a high energy density and a stable complex catalyst are provided. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07F 5/00 C07F 5/00 D 4J043 7/22 7/22 U 5H029 C08G 61/02 C08G 61/02 5H050 H01M 4/60 H01M 4/60 // C08G 73/02 C08G 73/02 H01M 4/02 H01M 4/02 C 10/40 10/40 Z F term (reference) 4G069 BA27A BA27B BC22B BC38A BC42B BE16A BE16B BE33A BE33B BE37A BE37B CB02 CB07 CC32. CA29 DA02 EA21 HA02

Claims (6)

[Claims] 1. An electrically responsive complex, which is represented by the following general formula (I): (Where Ar is an aromatic π-conjugated substituent, R ¹ and R ²
Is the same or different hydrogen atom or a hydrocarbon group which may have a substituent, R and R ^a are the same or different alkyl group or aromatic group, M is a rare earth metal or A phenylazomethine complex represented by a metal halide). 2. A complex having an electrically responsive molecule,
The following general formula (II) (Where Ar is an aromatic π-conjugated substituent, R ³ and R ⁴
Are the same or different hydrogen atoms or hydrocarbon groups which may have a substituent, R ^b is a hydrocarbon group which may have a substituent, M is a rare earth metal or halogenated Represents a metal, and n is an integer of 1 or more indicating the degree of polymerization). 3. An electrically responsive complex, which is represented by the following general formula (III): (However, R5 and R6 are each the same or different and each is a hydrogen atom or a hydrocarbon group which may have a substituent, and Rc and Rd are each the same or different and each have a substituent. A hydrocarbon group, M is a rare earth metal or a metal halide, and n is an integer of 1 or more indicating the degree of polymerization.) 4. A polyaniline complex having electrical responsiveness, wherein the polyaniline is formed by forming a complex with a rare earth metal ion or a metal halide. 5. A positive electrode material for a secondary battery, comprising the complex according to claim 1. 6. An oxidation-reduction catalyst containing the complex according to claim 1. Description: