JPS6256162B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polymeric metal complex and a method for producing the same, and particularly relates to a polymeric metal complex having two axially coordinating groups and a method for producing the same. Conventionally, as a type of polymer metal complex in which a ligand is bonded to a polymer chain by a covalent bond, a homopolymer of a low molecular weight ligand monomer having a vinyl group or a copolymer with an appropriate comonomer is used. etc. are known. However, it is only known that conventional polymeric metal complexes can be used to a limited extent for industrial catalysts and the like. On the other hand, Angew.Chem.Int.Ed.Engl. 16 , 117
(1977) and West German Patent Application Publication No. 2645079
No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, March 2006, describes a covalently bonded polymeric metal complex in which a metal complex is bonded to polyethylene glycol esterified with glycine at both ends, and a stepwise production method thereof as shown in the following formula. That is, However, the process of the above reaction is complicated, and the reaction does not necessarily proceed completely at each stage. Moreover, since the obtained polymeric metal complex also has metal complexes bonded only to both ends, interaction between the complexes cannot be expected. This invention was made in view of the above circumstances,
The object of the present invention is to provide a novel covalent-bonded polymer-metal complex having two axial bases, which has further improved various properties of conventional covalent-bonded polymer-metal complexes, and a method for producing the same. That is, in the covalently bonded polymer metal complex of the present invention, a macrocyclic tetradentate planar ligand is bonded as a pendant to a polymer chain, and the ring of the planar ligand and this ring are bonded to the polymer chain. It is a type of polymer metal complex in which one axially coordinating group is covalently bonded to each group, and the general formula is (Here, is a metal complex having a porphyrin skeleton having iron or cobalt as a coordination center metal, R ¹ is a coordination group having coordination ability to the center metal, and has the formula (Here, R is hydrogen or a methyl group), R ² is a coordinating group whose coordination ability to the central metal is weaker than that of R ¹ and is of the formula The group represented by R ³ is

[Formula] - CH ₂ CH ₂ - or -CH ₂ CH ₂ CH ₂ -, m and n
are positive integers, and m/(m+n) is
0.03 to 0.19). The polymer metal complex of the present invention represented by the formula () has the general formula (Here, m, n and R ³ are as described for formula ()) is a polymer compound represented by the general formula (Here, R ¹ and R ² are as described for formula ()) by reacting with a metal complex compound. The metal complex compound of formula () is a metal complex P' (for example,
Co or Fe-protoporphyrin, Co or
Fe-chlorophyllin, Co or Fe-saponified chlorophyll, Co or Fe-saponified chlorophyll, etc.) and the formula (Here, R is hydrogen or methyl group) and the imidazole compound represented by the formula It can be obtained by reacting with histidine shown in Both of the compounds represented by formulas (1) and (2) above react with the carboxyl group in P' to form an amide bond through dehydration condensation, producing a metal complex represented by formula (). That is, first, P' and an equivalent amount of ethyl chloroformate and a tertiary amine (e.g., trimethylamine) are uniformly mixed in a solvent such as dimethylformamide (DMF) at 0°C to 5°C, and the carboxyl group equivalent of P' is mixed. The compound of formula () is added so that the amino group equivalent is in slight excess of 1:1, and the mixture is reacted at about 0° C. for several tens of minutes to about 2 hours, and then at room temperature for several hours.
Thereafter, the monoamide compound is separated by development using a silica gel column. To the monoamide obtained in this way, ethyl chloroformate and a tertiary amine (e.g. triethylamine) are added in an amount equal to or slightly in excess of the remaining carboxyl group equivalent, and to this is also added the same amount of the formula
Add the compound (2) and perform the reaction and column separation in the same manner as above to obtain the metal complex of formula ().
At this time, dicyclohexylcarbodiimide (DCCI) and 1-hydroxybenzotriazole may be used instead of ethyl chloroformate and triethylamine, and when using histidine, free carboxyl groups may be esterified (for example, alkyl esterification). ) and react. When such an ester is used, after the above reaction is completed, add 1N-NaOH aqueous solution and DMF (50/50).
By dissolving the product in a mixed solution with and stirring for several hours to hydrolyze it, and neutralizing it with hydrochloric acid to pH 4.5 to 5.0 and allowing the product to settle, a complex of formula () can be obtained. Can be done. Also, the metal complex of formula () has no central metal.
It can also be derived from P′. In this case, the macrocyclic planar ligand is reacted with the compound of formula (1) in the same manner as above, and the resulting product is then treated in DMF or tetrahydrofuran (THF) under pure nitrogen with a large excess of a metal salt (e.g. FeBr). ₂ etc.) and react under boiling for several hours. Then, the solvent was distilled off under reduced pressure, and 0.1N−
An intermediate into which a central metal has been introduced after thorough washing with HCl and water (equivalent to the monoamide described above)
is obtained. Thereafter, the metal complex of formula () is obtained by reacting with the compound of formula (2) in the same manner as described above. In addition, it can also be synthesized, for example, by the following route. The metal complex of formula () thus obtained reacts with the polymer compound of formula () in one step to form an amide bond, thereby producing a covalent polymer metal complex of formula (). That is, the polymer compound of formula () and the formula ()
A metal complex of formula () and the same amount of ethyl chloroformate or DCCI and 1-hydroxybenzotriazole are dissolved at 0°C to 20°C in a solvent other than water that uniformly dissolves the metal complex, An appropriate amount of the polymer compound of formula () is added and reacted at 0°C to 20°C for several hours and then at room temperature for more than ten hours to several days. This reaction mixture is developed in a Sephadex column and the unreacted metal complex is separated to obtain the polymeric metal complex of formula (). This reaction is easy and the introduction rate of the metal complex is also good. The polymer metal complex of this invention is of a type in which a metal complex is bonded pendantly to a polymer chain, and interaction between the metal complex parts can be expected.
It is advantageous in carrying out catalytic reactions such as electron transfer, redox, oxygen (substance) adsorption and desorption. For example, column separation methods using resins containing metal complexes are sometimes used to separate amino acids, but these methods suffer from (1) outflow of metal ions, (2) low exchange capacity, and (3) poor separation efficiency. There are drawbacks such as bad. By using the covalently bonded polymeric metal complex of this invention, a column with a large exchange capacity can be provided without the outflow of metal ions, and in terms of separation efficiency, the balance between R ¹ and R ² can be varied depending on the purpose. can exert any desired effect. It is also used as a carrier that can adsorb and desorb oxygen reversibly. As mentioned above, since the polymeric metal complex of the present invention has a coordinating axial base R ¹ bonded to a macrocyclic tetradentate planar ligand, there is no need to separately add a basic ligand. In addition, when oxygen is coordinated to the 6th position, the oxygenated complex is stabilized by the interaction between R ² and oxygen in the vicinity, which has the advantage that side reactions such as oxidation of the central metal ion do not occur. It exhibits superior properties compared to conventional polymer metal complexes. The present invention will be further explained below based on Examples, but prior to that, a synthesis example of a metal complex of general formula () will be shown. Synthesis of metal complex Synthesis example 1 (A) Dissolve 10 g of protoporphyrin disodium salt in 300 ml of chloroform to obtain about 5.5 g of phosphorus pentachloride.
was added, and the mixture was stirred and reacted at room temperature for about 1 hour. Add 100 ml of a chloroform solution containing 0.8 g of ethanol and 1 ml of triethylamine to this solution for about 30 minutes.
The mixture was added dropwise over a period of time, and the mixture was further reacted at room temperature for 2 hours. After the reaction, the pH was adjusted to 5 with triethylamine, 900 ml of chloroform was added, and the mixture was washed 7 times with the same amount of water to separate the layers. Filter out insoluble components,
Separate the chloroform layer and add 20g of silica gel powder.
(80-130 meshes) and the solvent was distilled off under reduced pressure. Next, the silica gel powder was added onto a column made of the same silica gel (360 g of silica gel, chloroform/methanol = 20/1) and developed with a solvent to obtain protoporphyrin monoethyl ester monocarboxylic acid as the second component. Ta. (Yield 50% approx. 4.85g, infrared absorption spectrum ν _C=0
1740cm ^-1 , 1710cm ^-1 ). (B) Add 3.2 g of this monocarboxylic acid to 150 g of chloroform.
ml of triethylamine, cooled to 0°C,
0.8 ml and 0.54 ml of ethyl chloroformate were added dropwise, and the mixture was stirred and reacted for 3 minutes. 1- for this
0.814 g of (aminopropyl)imidazole/10 ml of chloroform were added, and the mixture was stirred and reacted at 0° C. for 1 hour and then at room temperature for 2 hours. This solution was shaken twice with about twice the amount of water, separated, and then 12 g of the same silica gel as described above was added to the chloroform layer, and the solvent was distilled off under reduced pressure. Separate this using a column (300 g of silica gel, chloroform/methanol = 15/1) as described above; the second component contains 2.55 g of the reaction product.
(Yield 67.5%, infrared absorption spectrum ν _C=0 1735
cm ^-1 , amide 1650 cm ^-1 , amide 1550 cm
^-1 ). (C) 1.84 g of this reaction product was dissolved in 70 ml of THF and placed under a pure nitrogen atmosphere. Next, 1g
Add FeBr ₂ 2H ₂ O, stir at room temperature, and gradually
The temperature was raised to 60°C and the reaction was continued for about 2 hours. The solvent was distilled off under reduced pressure and a small amount of chloroform/methanol = 2/
1 Dissolved in mixed solvent, 6g of basic alumina powder
was added and the solvent was distilled off again under reduced pressure. This sample was loaded onto a column of about 90 g of basic alumina (φ8 mm x 400 mm, chloroform/methanol = 10/1), developed with a solvent, and all the eluate was collected and evaporated under reduced pressure. Dissolved in a small amount of DMF and diluted with hydrochloric acid/
Adjust the pH to 6 with THF and reprecipitate into ether 3 to obtain 1.2 g (yield 55%) of the desired product (infrared absorption spectrum ν _{C = 0} 1730 cm ^-1 , amide number 1660 cm ^-1 , Amide no. 1540 cm ^-1 ). (D) 1.2 g of the product obtained in (C) above was dissolved in 20 ml of DMF, 1.5 ml of 20% KOH water was added, and the mixture was allowed to react at room temperature all day and night. After adjusting the pH to 4 with hydrochloric acid, it was concentrated under reduced pressure. Next, dissolve in a mixed solvent of butanol/acetic acid/water/methanol/pyridine = 20/2/14/6/3, add about 5 times the amount of water, adjust the pH to 4 again with hydrochloric acid, and collect the precipitate by filtration. The target product was isolated by washing with a large amount of water. Yield: 0.9 g (yield 87%, infrared absorption spectrum ν _{C = 0} 1720 cm ^-1 , amide number 1650 cm ^-1 , amide number 1550 cm ^-1 ). (E) Dissolve 0.8 g of the product obtained in (D) above in 8 ml of DMF, and add 1.0 g of histidine-o-methyl ester.
Add a solution dissolved in 5 ml of DMF, then add 0.3 g of 1-hydroxybenzotriazole and bring to 0°C.
It was cooled to A solution of 0.5 g of dicyclohexylcarbodiimide dissolved in 5 ml of DMF was added to this, and the mixture was stirred at 0° C. for 2 hours and at room temperature overnight for reaction. After distilling off the solvent under reduced pressure, it is dissolved in DMF and insoluble components are filtered off. The filtrate was poured into a 3/2 mixed solvent of ether/ethyl acetate, reprecipitated, collected by filtration, and thoroughly washed. This was dissolved in chloroform/methanol=5/1, 5 g of the same silica gel powder as above was added, and the solution was distilled off under reduced pressure. This sample was developed on a column of 100 g of silica gel (φ20 mm x 600 mm, butanol/acetic acid/water/methanol = 12/3/5/3), the first fraction was collected, and the solvent was distilled off under reduced pressure.
Dissolve this in the minimum amount of methanol and dissolve approximately 30g of neutral alumina (φ10mm x 300mm chloroform/
The target product was obtained by developing with a methanol = 1/1) column. Yield 475 mg/(yield 46.5%, infrared absorption spectrum ν _C=0 1740 cm ^-1 , amide 1650 cm
^-1 , amide No. 1550cm ^-1 , visible absorption spectrum
412, 534, 565 nm, FD mass spectrometry spectrum parent peak 888). The above reaction is shown in the flowchart below. However, for convenience, protoporfuphyrin

It is abbreviated as [Formula] (the same applies below). Synthesis Example 2 The same procedure as in Synthesis Example 1 was carried out except that 2.0 g of CoCl ₂ 6H ₂ O was used in (C) of Synthesis Example 1 to obtain 510 mg of the compound of formula (B) (infrared absorption spectrum ν _C=0
1740cm ^-1 , amide 1650cm ^-1 , amide 1550
cm ^-1 , visible absorption spectrum 404 nm FD mass spectrometry spectrum parent peak 889). Synthesis Example 3 5.2 g of hemin (protoporphyrin-Fe()・Cl), 1.0 ml of 1-(aminopropyl)imidazole and 200 ml of DMF were placed in a 500 ml Erlenmeyer flask, and 0.6 ml of ethyl chloroformate was added at 0°C. The mixture was stirred and reacted at room temperature for 2 hours, and then for about 20 hours at room temperature. After removing insoluble components by filtration, reprecipitate in ether,
Filter and dry. Add this to Wakogel C-100 (φ
50mm×300mm, butanol/methanol/acetic acid/
The mixture was developed in a column of water (2/2/2/1), the first component was collected, and the solvent was distilled off under reduced pressure. Yield 0.8g (yield approx.
12%) This product was reacted in the same manner as (E) in Synthesis Example 1 to yield 490 mg (yield 48%, infrared absorption spectrum ν _{C = 0} 1740 cm ^-1 , amide number 1650 cm ^-1 , amide number 1550cm ^-1 , visible absorption spectrum 412,
534, 565 nm) to obtain a compound of formula (A). Synthesis Example 4 The reaction was carried out in the same manner as in Synthesis Example 3 except that 1.0 ml of 1-(aminopropyl)-2-methylimidazole was used instead of 1-(aminopropyl)imidazole to obtain the product of the following formula. Yield 510 mg (yield 47
%) Infrared absorption spectrum ν _C=0 1740cm ^-1 , amide number
1650 cm ^-1 , amide number 1550 cm ^-1 , visible absorption spectrum 402 nm, 500 nm, 630 nm Synthesis Example 5 9.4 g of 2-aminopyridine and 20.4 g of dicyclohexylcarbonimide were dissolved in 100 ml of DMF and kept at 0°C. Add this to 10ml of triethylamine
and N-(t-butoxycarbonyl)glycine
50 ml of DMF in which 20 g of DMF was dissolved was added dropwise over about 3 hours, and the mixture was stirred at 0° C. for 2 hours and then stirred at room temperature overnight for reaction. After removing insoluble matter by filtration, the solvent was distilled off under reduced pressure, and the product was purified by recrystallization twice from ethanol to obtain the following structure. Yield: 9.2g (yield 61%). Next, Synthesis Example 3 except that 2.0g of the compound of formula (D) was used.
The reaction was carried out in the same manner as above to obtain the product of the following formula. yield
465 mg (yield 42%). Infrared absorption spectrum ν _C=0 1735cm ^-1 , amide number
1650 (1647) cm ^-1 , amide number 1550 cm ^-1 , visible absorption spectrum 411, 533, 566 nm Synthesis Example 6 1.0 g of methionine-o-methyl ester and 0.8 g of the product of Synthesis Example 1 (D) were used. , Synthesis Example 1 (E)
The reaction was carried out in the same manner as above to obtain a product with the following structure. Yield 490 mg (yield 47%). Infrared absorption spectrum ν _C=0 1737cm ^-1 , amide number
1650 cm ^-1 , amide number 1550 cm ^-1 , visible absorption spectrum 415, 539, 561 nm Example 1 (A) 6.0 g of dextran (average molecular weight 5800) and about 5 g of nitrobenzyl chloride were added to a 0.1N NaOH aqueous solution 60 nm
ml and stirred at 95°C for 3 hours. After cooling, it was reprecipitated in methanol, collected by filtration, thoroughly washed with acetone and ether, and dried under reduced pressure. Yield 5.8g.
The introduction rate of nitrobenzyl groups was determined by elemental analysis and ultraviolet absorption spectrum (ε=1.0×10 ⁵ /mol・cm, λ
max=252 nm), it was 4% per dextran unit. 3g of this nitrobenzylated dextran
Dissolved in 30ml of 0.1N-NaOH aqueous solution and heated at 70℃ under nitrogen.
1.0 g of Na ₂ S ₂ O ₄ was added thereto, and the mixture was stirred for 30 minutes. This was concentrated under reduced pressure, reprecipitated in methanol, washed with acetone and ether, and dried under reduced pressure. This was made into an aqueous solution again and Sephadex G-25 (Medium, φ
The ultraviolet absorption spectrum of aminobenzyl group (λmax=
230 nm) was collected and dried under reduced pressure. Yield 2.3g. Absorption of aniline (ε=8600/mol・
Quantitation using the standard (cm, λmax = 230 nm) confirmed that all nitrobenzyl groups were reduced to aminobenzyl groups. 0.8 g of compound (A) obtained in Synthesis Example 1 or 3 was dissolved in 5 ml of DMF, 0.5 ml of 1N-NaOH was added, and the mixture was reacted for 2 hours. The pH was adjusted to a range of 5 to 4.5 with hydrochloric acid, a large amount of water was added, and the precipitated material was collected by filtration and dried under reduced pressure. All the obtained substances were dissolved in 10 ml of dimethyl sulfoxide (DMSC), and 10 ml of DMSO containing 0.6 g of dicyclohexylcarbodiimide and 0.6 g of 1-hydroxybenzotriazole was dissolved.
was added dropwise to the solution over a period of 30 minutes at 18°C. After stirring for an additional 30 minutes, 2 g of the above-mentioned aminobenzylated dextran was added, stirred at 18° C. for 3 hours, and further reacted at room temperature for 12 hours. Filter off the insoluble part and reprecipitate with methanol until the collected liquid becomes clear.
Washed with DMF, then acetone and ether. This was dissolved in water and divided using a Cephadex G-25 column (φ20 mm x 300 mm), and a brownish-colored first fraction was collected and dried under reduced pressure. Yield 2.1g. The infrared absorption spectrum of dextran into which this complex is introduced is the same as that specific to dextran, and the visible absorption spectrum in water shows absorption maxima of 410, 534, and 560 nm, and when reduced with Na ₂ S ₂ O ₄ , 423, When carbon monoxide was further introduced at 528 and 557 nm, absorption maximums were observed at 418, 538 and 564 nm. This absorption at 418 nm is unique to the heme-(imidazole)-CO complex, and the molecular extinction coefficient at 418 ^nm of the heme-(imidazole)-CO complex prepared separately is set as a standard. The rate of introduction of the complex portion of this polymeric metal complex was determined to be 4%. Example 2 2.2 g of the target compound was obtained in exactly the same manner as in Example 1 (A), except that 0.8 g of compound (B) obtained in Synthesis Example 2 was used. This polymeric metal complex exhibits an absorption characteristic of Co()protoporphyrin-(imidazole) at 412nm, and a separately prepared Co()protoporphyrin-(imidazole) aqueous solution at 412nm
From the absorption intensity of , the introduction rate of compound (B) residue was calculated to be 4%. Example 3 6 g of dextran (average molecular weight 5800)
It was dissolved in 10 ml of DMSO, 1 ml of ethyleneimine was added, and the mixture was reacted in an autoclave at 60°C for 24 hours.
This was reprecipitated into methanol. Yield: 5.7g.
Quantification of the primary amine with copper(ethylenedinitro)tetraacetic acid and elemental analysis revealed that the primary amino group is 2
%, and the introduction rate of secondary amino groups was 10% (each based on dextran units). 2g of this ethyleneimine-added dextran
Complex introduction was carried out in the same manner as in Example 1, except that . Yield: 1.7g. The introduction rate of the residue of the complex portion represented by formula (A) was determined to be 2% by the same method as described in Example 1. Example 4 6.48g of dextran (average molecular weight 5800)
Acrylonitrile dissolved in 20 ml of DMSO at room temperature
ml dropwise and 0.2 ml of 2% NaOH-methanol solution was added under nitrogen. After stirring for 10 minutes, the mixture was stirred at 55°C for 1 hour. After cooling, 20 ml of DMSO was added, reprecipitated in acetone, collected by filtration, and dried under reduced pressure. Yield: 6.3g. The infrared absorption spectrum of this cyanoethylated dextran was the same as that of dextran, except that absorption based on C≡N was observed at 2250 nm ^-1 . Dissolve 3 g of this cyanoethylated dextran in 30 ml of water in an autoclave, and dissolve 1 ml of concentrated ammonia water.
ml, and further added 0.1 g of Raney nickel, and the mixture was stirred and reacted at a hydrogen pressure of 50 atm and 60° C. for 3 hours.
After cooling, the insoluble portion was filtered off, and the filtrate was poured into acetone again, collected by filtration, and dried under reduced pressure. Yield 2.5g. This aminated dextran aqueous solution was titrated with hydrochloric acid using a congo red indicator to quantify amino groups, and as a result, it was confirmed that 4% of amino groups were contained per dextran unit. Next, a complex was introduced in the same manner as in Example 2 except that 2 g of this aminated dextran was used, and as in Example 2, from the absorbance at 412 nm, the introduction rate of the residue of the complex shown in formula (B) was 4. %. Example 5 6 g of dextran (average molecular weight 40,000)
It was dissolved in 10 ml of DMSO, 1 ml of triethylamine and 10 ml of dioxane were added, and the mixture was cooled to 8°C. 10 ml of dioxane solution containing 1 ml of ethyl chloroformate was added dropwise and stirred for 3 minutes to react. Add this solution to 8
While maintaining the temperature at °C, 10 ml of DMSO solution in which 7 ml of ethylenediamine was dissolved was added dropwise, stirred and reacted for 1 hour, and further reacted for 2 hours at room temperature. After appropriately concentrating under reduced pressure, it was reprecipitated in ethanol, collected by filtration, thoroughly washed with ethanol and ether, and then dried under reduced pressure. Yield: 5.9g. From elemental analysis, the introduction rate of ethylenediamine units was calculated to be approximately 20% per dextran unit. Next, a complex introduction reaction was carried out in the same manner as in Example 1 except that 0.8 g of this aminated dextran was used. Yield: 0.69g. The introduction rate of the residue of the complex represented by formula (A) was determined in the same manner as in Example 1, and was calculated to be about 19%. Example 6 A complex was introduced into aminated dextran in the same manner as in Example 5, except that 0.2 g of the compound of formula (C) was used. Yield 0.7g. The introduction rate of the complex portion was calculated in the same manner as in Example 1, and was confirmed to be about 19%. Example 7 A complex was introduced into aminated dextran in the same manner as in Example 5, except that 0.15 g of the compound of formula (E) was used. Yield 0.65g. The introduction rate of the complex moiety was determined using the absorbance of the substance of formula (E) in DMSO (at 411 nm, ε=1.2×10 ⁴ ) as a reference, and was calculated to be about 17%. Example 8 A complex was introduced into aminated dextran in the same manner as in Example 5, except that 0.17 g of the compound of formula (F) was used. Yield 0.68g. The introduction rate of the complex moiety was determined using the absorbance of the substance of formula (F) in DMSO (at 415 nm, ε=0.9×10 ⁴ ) as a reference, and was calculated to be about 19%. Example 9 0.8 g of compound (A) obtained in Synthesis Example 1 or 3 was treated with an alkali in the same manner as in Example 1 to hydrolyze the ester. All of the obtained substances were dissolved in 10 ml of DMSO, and added dropwise over 30 minutes at 18° C. to 10 ml of DMSO in which 0.6 g of dicyclohexylcarbodiimide and 0.6 g of 1-hydroxybenzotriazole were dissolved. After stirring for an additional 30 minutes, 2 g of dextran (average molecular weight: 5800) was added, and the mixture was reacted at 18° C. for 3 hours and at room temperature for 1 day. Thereafter, the same treatment as in Example 1 was carried out to obtain a polymer metal complex. Yield: 1.8g. The infrared absorption spectrum of dextran into which the complex has been introduced is exactly the same as that of dextran, and the visible absorption spectrum has an absorption maximum of 410, 534, and 560 nm (in water).
showed that. When the introduction rate of the complex moiety was determined by the same method as in Example 1, it was found that
It was 0.3%.

Claims (1)

[Claims] 1. General formula (Here, is a metal complex having a porphyrin skeleton having iron or cobalt as a coordination center metal, R ¹ is a coordination group having coordination ability to the center metal, and has the formula (Here, R is hydrogen or a methyl group), R ² is a coordinating group whose coordination ability to the central metal is weaker than that of R ¹ and is of the formula The group represented by R ³ is [Formula] -CH ₂ - CH ₂ - or -CH ₂ CH ₂ CH ₂ -, m and n are each positive integers, and m/(m+n) is 0.03 to 0.19). A polymeric metal complex having two axially coordinating groups as shown. 2 General formula (Here, m and n are each positive integers, m/(m+n) is 0.03 to 0.19, and R ³ is represented by [Formula] -CH ₂ CH ₂ - or - CH ₂ CH ₂ CH ₂ -) General formula for polymer compounds (Here, is a metal complex having a porphyrin skeleton having iron or cobalt as a coordination center metal, R ¹ is a coordination group having coordination ability to the center metal, and has the formula (Here, R is hydrogen or a methyl group), R ² is a coordinating group whose coordination ability to the central metal is weaker than that of R ¹ and is of the formula A general formula characterized by reacting with a metal complex compound represented by a group represented by (Here, R ¹ , R ² , R ³ , m and n are as described above.) A method for producing a polymeric metal complex having two axially coordinating groups.