JP2002363182A - [3] A monomer based on a rotaxane structure, a method for producing the monomer, and a polymer and a method for producing the polymer. - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a monomer for producing a polymer utilizing a metal coordination interaction and a hydrogen bond interaction, which can be expected to be a molecular electric wire material, and a polymer obtained from the monomer. It is. In addition, since this polymer utilizes a non-covalent bond, it can be expected to be used as a recyclable polymer that can be easily decomposed and recycled. A monomer, a polymer represented by the following (I), and a method for producing the same, which can be converted into a polymer by a metal coordination interaction and a hydrogen bond interaction: (Wherein M represents a transition metal capable of taking two ligands,
P represents a hydrocarbon group having a nitrogen atom capable of coordinating to a metal at the terminal, Q represents a hydrocarbon group, R represents a group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon, and X represents a negative group. Represents an ion atom. n represents an integer of 1 or more. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to [3] a monomer based on a rotaxane structure, a method for producing the monomer, and a polymer and a method for producing the polymer.

[0002]

2. Description of the Related Art Very recently, research results on polymers which are polymerized by hydrogen bonding have been reported [“Science”, 278
Vol. 1601, 1997]. In addition, it is theoretically predicted that there is a limit in the semiconductor technology that depends on the solid state properties of silicon, and it is shown that the technical limit will be reached within 10 years, and then it will be possible to have a function as an electronic component For organic materials and organic macromolecules has been studied, and research on organic molecules and organic polymers has been conducted, and research on the synthesis of molecular electric wires in which a large number of porphyrins are connected by covalent bonds has been proposed. It has also been reported ["Angewante Chemie Int
ernational Edition of English) "Vol. 39, No. 145
8 pages (2000)]. The synthesis of rotaxanes, in which macrocyclic molecules and rod-shaped molecules are mechanically linked, has developed rapidly in recent years, and interest in the synthesis itself has been raised, and the present inventors have also invented the invention (Japanese Patent Application 2000-). 7125
2). In this field, research on application to molecular devices utilizing the characteristic structure has been conducted [Science, Vol. 285, pp. 391, 199].
9 years]. Manufacture of electronic components using a rotaxane in which macrocyclic molecules and rod-shaped molecules are mechanically bonded enables the device to respond to external signals such as electricity, light, and heat without changing its shape. This is a great advantage when assembling electronic components on a nanometer scale. Molecular wires must be routed between electronic components.To do so, it is necessary to construct molecular wires with an arbitrary length between electronic components. It is very difficult to make. Also, it has been difficult to polymerize rotaxane so far, and it cannot be used for molecular electric wires. Based on this background, we thought that a more intelligent molecular machine could be constructed by fusing porphyrin, a promising molecular wire, and rotaxane, a molecular device. Having further developed this idea and came up with the idea of utilizing non-covalent bonds for the fusion of rotaxane and porphyrin, the present inventors hoped that organic compounds could be non-covalently bonded with the hope of approaching the realization of molecular computers. We worked on making polymer.

[0003]

An object of the present invention is to provide a monomer for producing a polymer by utilizing a metal coordination interaction and a hydrogen bond interaction, a polymer obtained from the monomer, and the production of the same. Is to provide a way. The polymer can be a molecular wire material, and is a recyclable polymer that can be easily decomposed and recycled because it is bonded by non-covalent bonds. . All of these properties are materials that are expected to be required in the future, and new applications can be expected.

[0004]

Means for Solving the Problems The present inventors have developed a monomer having a porphyrin metal complex which can form a hydrogen bond with a specific compound, and at the same time, the metal in the monomer is It is capable of forming a specific compound by coordinating from above and below, and this monomer can be polymerized by utilizing the above characteristics, and as a result, a polymer composed of non-covalent bonds can be obtained. And completed the present invention. Since this polymer has conductivity, it can be used as a molecular electric wire. In addition, polymers utilizing this kind of conductive properties can be decomposed and can be used as recycled materials.

The present inventors have conducted intensive studies in order to develop a polymer consisting of non-covalent bonds utilizing metal coordination interaction and hydrogen bond interaction. As a result, the following general formula (III) was obtained. We focused on the compound to be used.

Embedded image (III) (In the formula, M represents a transition metal capable of taking four nitrogens and two ligands, and R represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon.) A novel tetraphenylporphyrin-type compound having a transition metal M at the center and having dibenzo-24-crown-8-ether at the 5th and 15th meso positions and a substituent R at the 10th and 20th meso positions And the compound represented by the general formula (IV)

Embedded image (IV) (Wherein, P represents a group having a nitrogen atom capable of coordinating to a metal at a terminal via a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon, and Q represents an aliphatic hydrocarbon and an aromatic hydrocarbon. A compound represented by the general formula (I), which is obtained by reacting a compound represented by the formula (I):

Embedded image (I) (Wherein, M represents a transition metal capable of taking four nitrogens and two ligands, and P can coordinate to a metal via a hydrocarbon group selected from aliphatic hydrocarbons and aromatic hydrocarbons) Represents a group having a terminal nitrogen atom at the terminal, Q represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon, and R represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon And X represents any anion atom.) The ammonium group in the compound represented by the formula (1) forms a strong hydrogen bond with dibenzo-24-crown-8-ether in the compound; The present inventors have found that a nitrogen atom contained in P coordinates to the central metal of the porphyrin from two directions, upper and lower, and completed the present invention by being able to polymerize this monomer.

That is, according to the present invention, the following inventions are provided. (1) The following general formula (I)

Embedded image (I) (Wherein, M represents a transition metal capable of taking four nitrogens and two ligands, and P can coordinate to a metal via a hydrocarbon group selected from aliphatic hydrocarbons and aromatic hydrocarbons) Represents a group having a terminal nitrogen atom at the terminal, Q represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon, and R represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon Wherein X represents any anion atom), a monomer utilizing a metal coordination interaction and a hydrogen bonding interaction, a method for producing the same, and a compound represented by the general formula (II):

Embedded image (II) (Wherein, M represents a transition metal capable of taking four nitrogens and two ligands, and P can coordinate to a metal via a hydrocarbon group selected from aliphatic hydrocarbons and aromatic hydrocarbons) Represents a group having a terminal nitrogen atom at the terminal, Q represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon, and R represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon , X represents an arbitrary anion atom, and n represents an integer of 1 or more.) Coordination interaction of the nitrogen atom with the central metal and hydrogen bonding between the crown ether and the secondary ammonium salt An object of the present invention is to provide a polymer constructed by interaction and a method for producing the polymer.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The monomer of the present invention, which can be polymerized by a non-covalent bond utilizing metal coordination interaction and hydrogen bond interaction, has a chemical structure represented by the following general formula (I): It has.

Embedded image (I) In the above formula, M represents a transition metal capable of taking four nitrogens and two ligands, and P can be coordinated to a metal via a hydrocarbon group selected from aliphatic hydrocarbons and aromatic hydrocarbons. Represents a group having a terminal nitrogen atom at the terminal, Q represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon, and R represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon And X represents any anion atom. However, either P or Q must be dibenzo-24-
R is an aliphatic hydrocarbon and an aromatic hydrocarbon, and these hydrocarbon groups are substituents selected from ethers, esters and the like. Is a structure that does not hinder the coordination of the substituent P to the transition metal, and X is any anion atom capable of ensuring solubility in a nonpolar organic solvent. It is necessary to be. Any substituent can be employed as long as the above conditions are satisfied.

[0008] Further, the compound represented by formula (I) will be specifically described. The transition metal M is a transition element that has four nitrogen atoms arranged around it as a ligand and can take two more ligands. Metals include cobalt, iron, nickel, manganese, rhodium, iridium,
Gold, silver and platinum can be mentioned. The substituent P is a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon, and directly or through a bond such as an ester bond, an amide bond, and an ether bond, a nitrogen atom that can be coordinated with a transition metal. It is a group formed by bonding with a substituent at the terminal. The substituent having a nitrogen atom at the terminal is an amine, which is a metal-coordinating amine having a lower basicity than a secondary alkylamine. Specific examples of amines include pyridyl, pyridazinyl, phenylamine, imidazolyl, quinolyl, pyrimidyl, pyrrolidyl, indolyl, and indolinyl groups. All of these groups include isomers. For example, in the pyridyl group,
Any of groups such as 2-pyridyl, 3-pyridyl, and 4-pyridyl can be used. In the imidazolyl group, 1
Any of groups such as -imidazolyl, 2-imidazolyl, and 4-imidazolyl can be used. The aliphatic hydrocarbon is a saturated aliphatic hydrocarbon having a straight or branched chain and has 1 to 8 carbon atoms, specifically, methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentyl , Isopentyl, n-hexene, isohexene, n-heptene, isoheptene, n
-Octene, isooctene group. Aromatic hydrocarbons are aromatic hydrocarbons with or without substituents, and aromatic hydrocarbons are phenyl, phenylene, benzyl, benzylidene, tolyl, xylyl, biphenyl, biphenylene, naphthyl, naphthylene, naphthalenyl, anthracenyl groups. Yes, these aromatic hydrocarbons can be replaced by aliphatic hydrocarbons. The substituent Q is a group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon. These hydrocarbon groups can be bonded to the hydrocarbon group directly or via a bond such as an ester bond, an amide bond, and an ether bond. The aliphatic hydrocarbon is a saturated aliphatic hydrocarbon having a straight or branched chain and has 1 to 8 carbon atoms, specifically, methyl, ethyl, propanyl, isopropanyl, n-butyl, i- Butyl, isobutyl, tert-butyl, n-
Pentyl, i-pentyl, tert-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, i-heptyl, tert-heptyl, n-octane, i-octyl and tert-octyl groups. The aromatic hydrocarbon is an aromatic hydrocarbon having or not having a substituent, and is a phenyl, phenylene, benzyl, benzylidene, tolyl, xylyl, biphenyl, biphenylene, naphthyl, naphthalenyl, naphthalenyl, or anthracenyl group. These groups are preferred to use aromatic hydrocarbons rather than aliphatic hydrocarbons because secondary ammonium salts interact more strongly with dibenzo-24-crown-8-ether. Further, one of the substituents P and Q needs to have a size capable of passing through the center of dibenzo-24-crown-8-ether. Specifically,
Since 3,5-dimethylbenzene and 4-tert-butylbenzene are too large to pass through dibenzo-24-crown-8-ether, use these substituents for both P and Q. Can not. More specifically, the molecular size must be smaller than those listed above, and any benzene or toluene can be used. R may be any atom or group selected from a hydrogen atom, an aliphatic hydrocarbon, and an aromatic hydrocarbon. The aliphatic hydrocarbon group is a saturated aliphatic hydrocarbon having a straight or branched chain and has 1 to 8 carbon atoms. Specifically, methyl, ethyl, propanyl, isopropanyl, butyl, isobutyl, tert -Butyl, n-butanyl,
i-butanyl, tert-butanyl, n-pentyl, i
-Pentyl, tert-pentyl, n-hexyl, i-
Hexyl, tert-hexyl, n-octyl, i-octyl and tert-octyl can be mentioned. The aromatic hydrocarbon group is a group consisting of an aromatic hydrocarbon having or not having a substituent, phenyl, phenylene, benzyl, benzylidene, tolyl, xylyl, biphenyl, biphenylene, naphthyl, naphthalenyl, naphthalenyl, anthracenyl, 3, 5-di-tertbutylbenzyl, 3,5-dimethoxybenzyl and 3,5-di-oligoethyleneglycolbenzyl groups. In these groups, in order for hydrogen bonding between molecules to work effectively, it is important to have solubility in a non-polar solvent, such as a long-chain alkyl group (6 to 20 carbon atoms) or a long-chain alkyl group. Esters substituted with an alkyl group, polyalkyl ether chains, and benzene substituted with a tert-butyl group, specifically, tert-butylbenzene, dimethyl isophthalate, and 3,5-dialkoxyl benzene are desirable. X
Is any anion. Since the reaction is carried out in a non-polar organic solvent, anions that dissolve in the non-polar solvent are preferred. Specifically, perchlorate ion, hexafluorophosphate ion and trifluoroacetate ion are desirable.

The monomer for producing the polymer and the polymer obtained therefrom are novel compounds which have not been described in any literature, and are produced as follows. Porphyrin derivative represented by the following general formula (V)

Embedded image (V) (Wherein R has the same meaning as described above) to the dipyrrolemethane derivative (V) represented by the following general formula (VI)

Embedded image (VI) The aldehyde-substituted dibenzo-24-crown-8-ether derivative (VI) and dipyrrolemethane derivative (V) are oxidized with an oxidizing agent in the presence of an acid catalyst. As the acid catalyst, propionic acid, trifluoroacetic acid or the like is generally used. The oxidizing agent is 2,3-dichloro-
5,6-dicyano-p-benzoquinone, chloranil and the like are used. By the above operation, the following general formula (VII)

Embedded image (VII) (R in the formula has the same meaning as described above.)
A 15-dibenzo-24-crown-8-ether-disubstituted porphyrin derivative is synthesized. By reacting the derivative thus obtained with an acetate or chloride of the transition metal M, the following general formula (III)

Embedded image (III) (R and M in the formula have the same meanings as described above.) A transition metal complex (III) of a 5,15-dibenzo-24-crown-8-ether-disubstituted porphyrin derivative represented by the following formula: I can do it. This reaction is carried out at a temperature of 10 to 40 ° C. in the presence of a solvent in the liquid phase.

Next, the part of the secondary ammonium salt is represented by the following general formula (VIII)

(VIII) (Wherein P has the same meaning as described above), and an aldehyde derivative (VIII) represented by the following general formula (IX):

Embedded image (IX) (Wherein Q in the formula has the same meaning as described above) in a solvent (for example, in toluene)
The dehydration reaction is promoted by heating in the following general formula (X)

(X) (Wherein P and Q have the same meanings as described above), and a P, Q-substituted imine derivative (X) is obtained, which is reduced with sodium borohydride and added with an acid to give General formula (IV)

Embedded image (IV) (P and Q in the formula have the same meanings as described above.) Can be produced.

The following general formula (II) obtained by the above operation
I)

Embedded image (III) (R and M in the formula have the same meanings as described above.) A transition metal complex of a 5,15-dibenzo-24-crown-8-ether-disubstituted porphyrin derivative (III)
And the following general formula (IV) obtained by the above operation

Embedded image (IV) (Where P and Q have the same meanings as described above) are reacted in a non-polar solvent. As the non-polar solvent, a non-polar solvent such as methylene chloride or chloroform is used. The ratio of using the compound,
(III): (IV) = 1: 2 at a temperature of 10 ° C. to 40 ° C.
By mixing at ℃, the general formula (I)

Embedded image (I) (Wherein, M represents a transition metal capable of taking four nitrogens and two ligands, and P can coordinate to a metal via a hydrocarbon group selected from aliphatic hydrocarbons and aromatic hydrocarbons) Represents a group having a terminal nitrogen atom at the terminal, Q represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon, and R represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon And X represents any anion atom.). At the same time, the general formula (II)

Embedded image (II) (Wherein, M represents a transition metal capable of taking four nitrogens and two ligands, and P represents a metal via a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon. Represents a group having a nitrogen atom capable of coordinating to a terminal, Q represents a hydrocarbon group selected from aliphatic hydrocarbons and aromatic hydrocarbons, and R is selected from aliphatic hydrocarbons and aromatic hydrocarbons. X represents an anion atom, and n represents an integer of 1 or more.) Coordination interaction of a nitrogen atom to a central metal, and a crown ether and a secondary ammonium salt The properties of the polymer are determined by the number of n, which is usually an integer of 1 or more, and generally about 100.

As can be seen from the structure, the polymer obtained in the present invention has the characteristics of a porphyrin having a large pi-electron system. If this property is used, it has conductivity and can be used as a molecular electric wire. Then, when used as such a conductive material, it can be easily decomposed into a monomer as a structural unit under mild conditions that inhibit coordination to a metal and hydrogen bonding. Therefore, it can be said that the material is recyclable.

[0013]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Under argon atmosphere, 0.500 g of 5-phenyldipyrromethane, (2.25 mmol) and 6,7,9,1
0,12,13,20,21,23,24,26,2
7, -dodecahydrodibenzo [b, n], [1,4,
7,10,13,16,19,22] octaogizacyclotetracosin-2-ylaldehyde 1.61 g,
(3.37 mmol) was dissolved in 300 ml of chloroform, and 0.3 ml of boron trifluoride diethyl ether complex was adjusted to 3.3 mM in the reaction solution in a light-shielded state.
125 ml, (0.986 mmol) was added using a syringe and stirred for 1 hour at room temperature, followed by 0.393 g of 2,3-dichloro-5,6-dicyano-p-benzoquinone,
(1.74 mmol) was added and stirred at room temperature for 1 hour. After washing the reaction mixture with aqueous sodium hydrogen carbonate solution,
The crude product is purified by silica gel column chromatography (elution solvent, ethyl acetate) to give the structural formula

Embedded image (XI) 236 mg (16%) of the porphyrin derivative (XI) were obtained. Mass spectrometry (as C ₈₀ H ₈₂ N ₄ O ₁₆ ) Calculated: 1355 Found: 1357 (M + 2H)

Example 2 75 mg of the porphyrin derivative (XI) obtained in Reference Example 1
(0.055 mmol) was dissolved in 50 ml of chloroform. The chloroform solution was refluxed, and 19 mg (0.076 mmol) of cobalt acetate dissolved in 1 ml of methanol was slowly added. After refluxing for 1 hour, the mixture was allowed to cool to room temperature, washed with a saturated aqueous solution of sodium hydrogencarbonate, purified by chromatography (silica gel, ethyl acetate), and further recrystallized from a mixed solution of methylene chloride and methanol to give a structural formula.

Embedded image (XII) Porphyrin derivative (XII) 37 mg (47
%). Mass spectrometry (as C ₈₀ H ₈₀ CoN ₄ O ₁₆ ) Calculated: 1412 Found: 1435 (M + Na)

EXAMPLE 3 1.1 g (6.4 mmol) of methyl 4-formylbenzoate and 1.0 g of 4-tert-butylbenzylamine
(6.4 mmol) in methylene chloride (100 ml), triethylamine (10 ml) and anhydrous magnesium sulfate (2.3).
2 g (10 mmol) was added and the mixture was heated under reflux for 10 hours, and the solid was filtered off. Purified by column chromatography (silica gel, ethyl acetate)

Embedded image (XIII) 1.6 g (78%) of the ester derivative (XIII) represented by
I got Mass spectrometry value (as C ₂₀ H ₂₃ NO ₂ ) Calculated value: 309 Actual value: 309

Example 4 1.5 g of the ester derivative (XIII) obtained in Example 3
(4.8 mmol) is dissolved by heating in 100 ml of methanol. To this solution was added 1 g of sodium borohydride (26 g
Mmol) and stirred at room temperature for 10 hours. 50 ml of a 2M aqueous hydrochloric acid solution was added to the obtained reaction solution, and the solvent was distilled off.
Add. The aqueous solution was extracted with 100 ml of chloroform, the obtained organic phase was dried over magnesium sulfate, and then the solvent was distilled off to obtain a compound of the structural formula

Embedded image (XIV) 1.4 g (90%) of an ester acid derivative (XIV) represented by
%). Mass analysis (C ₂₀ H ₂₅ as NO ₂₎ Calculated: 311 Found: 311

Example 5 1.2 g of the ester acid derivative (XIV) obtained in Example 4
(3.9 mmol) was dissolved in 50 ml of chloroform,
0.85 g of di-tert-butyl dicarbonate (3.
9 mmol) and 5 mg of dimethylaminopyridine (0.4 mg).
Mmol) and stirred for 5 hours. The reaction solution was washed with 50 ml of 2M hydrochloric acid and 50 ml of distilled water, dried over magnesium sulfate, and evaporated. The resulting oil was purified by column chromatography (silica gel, ethyl acetate / hexane) to give the structural formula

(XV) 1.5 g (93%) of the ester derivative (XV) represented by Mass spectrometry value (C ₂₅ as H ₃₃ NO ₄₎ Calculated: 411 Found: 411

Example 6 1.2 g of the diester derivative (XV) obtained in Example 5
(2.9 mmol) was dissolved in 50 ml of methanol, 50 ml of a 1 M aqueous sodium hydroxide solution was added thereto, and the mixture was heated and stirred for 3 hours, and then the solvent was distilled off to half. Hydrochloric acid was added thereto to adjust the pH to 2, and the precipitated white solid was filtered to obtain the structural formula.

(XVI) 1.0 g of a dicarboxylic acid derivative (XVI) (90
%). Mass spectrometry value (as C ₂₄ H ₃₁ NO ₄ ) Calculated value: 397 Actual value: 397

Example 7 1.0 g of the carboxylic acid derivative (XVI) obtained in Example 6
(2.5 mmol) and 270 mg of 4-aminopyridine
(2.8 mmol) was dissolved in 50 ml of dimethylformamide, and 3-hydroxy-4-oxo-3,4- was added thereto.
490 mg of dihydro-1,2,3-benzotriazine
(3.0 mmol) was added. The solution is cooled to 20 ° C. and, with stirring, 0.55 ml (3.0 mmol) of N-ethyl-N′-3-dimethylaminopropylcarbodiimide are added. After stirring the reaction mixture at room temperature for 6 hours,
The product is precipitated by adding excess cold water. The precipitate is collected by filtration and dried to obtain the structural formula

Embedded image (XVII) 1.0 g (84%) of the amide derivative (XVII) represented by the formula was obtained. Mass spectrometry value (as _{C 29 H 35 N 3 O 3} ) Calcd .: 473 Found: 473

Example 8 1.0 g of the amic acid derivative (XVII) obtained in Example 7
(2.1 mmol), 10 ml of trifluoroacetic acid was added, and the mixture was stirred at room temperature for 1 hour. By removing trifluoroacetic acid under reduced pressure, the structural formula

(XVIII) A secondary amine derivative having a pyridyl group represented by the formula (XVII
I) 980 mg (95%) were obtained. Mass spectrometry value (as _{C 26 H 27 F 3 N 3} O 3) Calcd .: 486 Found: 486

Example 9 5 mg of the porphyrin derivative (XII) obtained in Example 2
(3.5 micromoles) and 4.4 mg (7.0) of the secondary amine derivative (XVIII) having a pyridyl group obtained in Example 8.
Micromol) in chloroform,

Embedded image (XX) At the same time that the monomer (XX) represented by

(XXI) The formation of a polymer (XXI) utilizing the metal coordination interaction and hydrogen bond interaction represented by (1) was confirmed. The number of n is 10
It was 0. Mass spectrometry value (monomer unit is C ₁₃₂ H ₁₃₆ CoF ₅ N ₆ O ₂₂ ) Calculated value: 2387 Actual value: 2387, 4774, 7161, 9548, 1
1935

[0023]

According to the present invention, a monomer capable of producing a polymer by utilizing a metal coordination interaction and a hydrogen bond interaction by a technique based on a new concept of an organic compound, which has not been known at all, is provided. Can be manufactured. By using this monomer to polymerize,
The polymer can be obtained by spontaneous assembly. Since the polymer of the present invention can be easily decomposed by controlling the external environment, it can be used as a recycled green polymer. Further, by utilizing the pi-electron conjugation of the porphyrin ring constituting the polymer, it can be expected to be used as a molecular electric wire material which is a basis of a molecular element which is a component of a molecular computer.

Continued on the front page F term (reference) 4C050 PA05 PA06 PA07 PA20 4J030 CA03 CB01 CC01 CC29 CC30 CD11 CG02

Claims (6)

[Claims] (1) A compound represented by the general formula (I): (Wherein, M represents a transition metal capable of taking four nitrogens and two ligands, and P can coordinate to a metal via a hydrocarbon group selected from aliphatic hydrocarbons and aromatic hydrocarbons) R represents a hydrocarbon group selected from aliphatic hydrocarbons and aromatic hydrocarbons, and Q represents a hydrocarbon group selected from aliphatic hydrocarbons and aromatic hydrocarbons. Represents a group, and X represents any anion atom.) 2. A compound of the general formula (III) (In the formula, M represents a transition metal capable of taking four nitrogens and two ligands, and R represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon.) Compound. (3) a compound represented by the general formula (IV): (Wherein, P represents a group having a nitrogen atom capable of coordinating to a metal at a terminal via a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon, and Q represents an aliphatic hydrocarbon and an aromatic hydrocarbon. Represents a hydrocarbon group selected from group hydrocarbons, and X represents an arbitrary anion atom.) 4. A compound of the general formula (III) (In the formula, M represents a transition metal capable of taking four nitrogens and two ligands, and R represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon.) Compound and general formula (IV) (Wherein, P represents a group having a nitrogen atom capable of coordinating to a metal at a terminal via a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon, and Q represents an aliphatic hydrocarbon and an aromatic hydrocarbon. A hydrocarbon group selected from group hydrocarbons, and X represents an arbitrary anion atom.) In the presence of a solvent to react with a secondary ammonium salt represented by the general formula (I): 6) (I) (Wherein, M represents a transition metal capable of taking four nitrogens and two ligands, and P can coordinate to a metal via a hydrocarbon group selected from aliphatic hydrocarbons and aromatic hydrocarbons) R represents a hydrocarbon group selected from aliphatic hydrocarbons and aromatic hydrocarbons, and Q represents a hydrocarbon group selected from aliphatic hydrocarbons and aromatic hydrocarbons. And X represents an arbitrary anion atom).) A method for producing a monomer, comprising producing a monomer represented by the formula: 5. A compound of the general formula (II) (Wherein, M represents a transition metal capable of taking four nitrogens and two ligands, and P represents a metal via a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon. Represents a group having a terminal coordinable nitrogen atom, Q represents a hydrocarbon group selected from aliphatic hydrocarbons and aromatic hydrocarbons, and R is selected from aliphatic hydrocarbons and aromatic hydrocarbons. X represents an arbitrary anion atom, and n represents an integer of 1 or more. 6. A compound of the general formula (I) (Wherein, M represents a transition metal capable of taking four nitrogens and two ligands, and P can coordinate to a metal via a hydrocarbon group selected from aliphatic hydrocarbons and aromatic hydrocarbons) Represents a group having a terminal nitrogen atom at the terminal, Q represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon, and R represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon Wherein X represents any anion atom.) From the monomer represented by the general formula (II): (Wherein, M represents a transition metal capable of taking four nitrogens and two ligands, and P can coordinate to a metal via a hydrocarbon group selected from aliphatic hydrocarbons and aromatic hydrocarbons) Represents a group having a terminal nitrogen atom at the terminal, Q represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon, and R represents a hydrocarbon group selected from an aliphatic hydrocarbon and an aromatic hydrocarbon Wherein X represents any anion atom, X represents any anion atom, and n represents an integer of 1 or more.) .