Metal iron carbonyl polymer as well as preparation method and application thereof

Abstract

The invention belongs to the field of metal organic polymers, and particularly relates to a metal iron carbonyl polymer and a preparation method and application thereof. The invention discloses a method for synthesizing an FpC6P (CpFe (CO) 2 (CH2) 6PPh2) monomer by taking a cyclopentadienyl dicarbonyl iron dimer as a raw material, and enabling the monomer to tend to generate a metal iron carbonyl polymer with a linear or cyclic structure in a transfer insertion polymerization reaction by adjusting a solvent. Different from most reported ring molecule synthesis, the transfer-intercalation cyclization can be carried out in quantity, the system is relatively pure, the polymer can be obtained only through precipitation and centrifugation, and extra steps for purifying the macrocyclic polymer are not needed.

Description

Technical Field

[0001] The present invention belongs to the field of metal organic polymers, and in particular relates to a metal iron carbonyl polymer and a preparation method and application thereof. Background Art

[0002] Metallo-organic polymers, due to their combined advantages of metal-centered conductivity, redox properties, polymer chain flexibility, and formability, have found widespread application in conductive materials, luminescent materials, catalysis, and stimuli-responsive materials. Since the synthesis of the first metallo-organic polymer, polyvinylferrocene, they have captivated scientists for nearly a century. Metallo-carbonyl polymers, as an important branch of metallo-organic polymers, possess a range of excellent properties and can be used as precursors for the preparation of magnetic ceramics and metal compound materials, with applications in CO transport, nano-etching, and other fields.

[0003] Liu Ye's team at Dalian University of Technology has developed a novel phosphine-phosphoramide (PNPO) cationic nickel catalytic system for the carbonylation polymerization of ethylene to prepare carbonyl polymer materials with a completely alternating structure. The catalyst maintains high activity even at low pressure (1.0 MPa), with a turnover number as high as 31,150 g (g Ni). -1 , which is comparable to the performance of industrial palladium catalysts. The resulting polymer has an ultra-high molecular weight (Mn = 1470 kg / mol) and a narrow distribution It utilizes low-pressure operation to enhance catalyst stability and reduce energy consumption. However, it is currently primarily targeted at ethylene carbonylation, and its applicability to other monomers remains to be verified. The nickel center is susceptible to impurities, requiring rigorous raw material purification.

[0004] CN114874366A discloses a multi-center loaded metal porphyrin complex and its preparation method and a method for preparing a carbon dioxide-based polymer. By loading a metal porphyrin (such as aluminum, cobalt, etc.) onto a polymer carrier, a multi-center catalyst is prepared for the copolymerization of carbon dioxide and epoxide to produce polycarbonate or polyol. The number of active centers of the catalyst is adjustable, and the catalytic efficiency increases with the increase of active centers. Its multi-center design significantly improves the catalytic efficiency and is suitable for carbon dioxide resource utilization. The catalyst is insoluble in conventional solvents, easy to recycle and reduces pollution. However, the yield of hydroxyporphyrin derivatives is low (<3%), and the synthesis path needs to be optimized. The polymer carrier hinders the diffusion of reactants and affects the mass transfer efficiency.

[0005] Transfer insertion polymerization is a recently developed polymerization method that can be used to prepare carbonylferrocenes-diphenylphosphine polymers. This type of new metal carbonyl polymer shows good application prospects in many fields. Summary of the Invention

[0006] This invention discloses the synthesis of FpC6P (CpFe(CO)2(CH2)6PPh2) monomers using cyclopentadienyl iron dicarbonyl dimer as a raw material. By adjusting the solvent, the monomers are induced to form linear or cyclic metallic iron carbonyl polymers during the transfer-insertion polymerization reaction. Unlike most reported cyclic molecular syntheses, this transfer-insertion cyclization can be performed in large quantities in a relatively pure system. The polymer can be obtained simply by precipitation and centrifugation, without the need for additional purification steps for the macrocyclic polymer.

[0007] In order to solve the above-mentioned technical problems, this application provides the following technical solutions:

[0008] The present invention provides a method for preparing a metal iron carbonyl polymer, comprising the following steps:

[0009] S11: prepare compound FpK and compound Cl(CH2)6PPh2 respectively;

[0010] The compound FpK is prepared by the following steps:

[0011] S21: Under a nitrogen atmosphere, benzophenone and potassium metal were added to an organic solvent and reacted at room temperature (25±5°C) for 8-12 hours to obtain a mixed solution A;

[0012] S22: Add cyclopentadienyl iron dicarbonyl dimer to the mixed solution A, react at room temperature, and remove impurities to obtain the compound FpK; the structural formula of the compound FpK is as follows:

[0013]

[0014] The compound Cl(CH2)6PPh2 is prepared by the following steps:

[0015] S31: Under a nitrogen atmosphere, chlorodiphenylphosphine (ClPPh2) and sodium metal are added to an organic solvent and reacted at 35-45°C for 66-78 hours to obtain NaPPh2;

[0016] S32: Under a nitrogen atmosphere, Cl(CH2)6Br and the compound NaPPh2 are reacted in an organic solvent at room temperature for 2-4 hours, followed by removal of impurities to obtain the compound Cl(CH2)6PPh2; the structural formula of the compound Cl(CH2)6PPh2 is as follows:

[0017]

[0018] S12: The compound FpK and the compound Cl(CH2)6PPh2 are reacted in an organic solvent at room temperature in the dark for 1-3 hours, and impurities are removed to obtain the compound FpC6P (CpFe(CO)2(CH2)6PPh2); the structural formula of the compound FpC6P is as follows:

[0019] Wherein, Ph refers to phenyl;

[0020] S13: polymerizing the compound FpC6P in an organic solvent or an organic mixed solvent at 65-75° C. for 12-16 hours to obtain a reaction mixture;

[0021] S14: Cooling the reaction mixture and adding it into a different solvent to remove impurities, thereby obtaining the metal iron carbonyl polymer; the metal iron carbonyl polymer has the following structural formula:

[0022] Where n is from 1 to 10000.

[0023] Preferably, the organic solvent is tetrahydrofuran, the isosolvent is n-hexane, and the organic mixed solvent is obtained by mixing tetrahydrofuran and n-hexane in a volume ratio of 1:1.

[0024] Preferably, in step S14, after adding a different solvent, centrifugation is performed, and the solid obtained by centrifugation is vacuum-dried at room temperature.

[0025] Preferably, in step S22, the impurity removal method is to remove the solvent in vacuo, add toluene and stand for stratification; repeat the impurity removal step 2-4 times to retain the final solid.

[0026] Preferably, in step S23, the impurity removal method includes the following steps:

[0027] S41: Remove the solvent in vacuo, add dichloromethane to dissolve, and allow to stand for separation;

[0028] S42: After standing and stratifying, the supernatant was vacuum-evacuated at 85-95°C to remove the solvent and unreacted Cl(CH2)6Br;

[0029] S43: adding dichloromethane and mixing, and then using n-hexane as an eluent to pass through a silica gel column to complete the impurity removal.

[0030] Preferably, in step S12, the impurity removal method is to remove the solvent under vacuum, then add a different solvent to dissolve, let it stand to separate the layers, and pass it through a silica gel column.

[0031] Preferably, in step S13, the concentration of compound FpC6P in the organic solvent or organic mixed solvent is 15-25 wt %.

[0032] Preferably, in step S13, the impurity removal method is to add a different solvent, collect the precipitate by centrifugation, and dry it in vacuum at room temperature for 8-12 hours.

[0033] The present invention also provides a metal iron carbonyl polymer prepared by the above preparation method.

[0034] The present invention also provides application of the metal iron carbonyl polymer as a photosensitive material in the biomedical field.

[0035] The technical solution of the present invention has the following advantages over the prior art:

[0036] This invention validates the monomer synthesis route and provides a method for synthesizing linear or cyclic metal carbonyl polymers via monomer transfer insertion polymerization. This transfer insertion cyclization can be performed on a large scale, and the system is relatively pure. The polymer can be obtained simply by precipitation and centrifugation, without the need for additional purification steps for the macrocyclic polymer. Its potential applications cover a wide range of areas, including organometallic medicinal chemistry, catalysis, and materials science. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is the H NMR spectrum of Example 1.

[0038] Figure 2 This is the nuclear magnetic phosphorus spectrum of Example 1.

[0039] Figure 3 This is the H NMR spectrum of Example 2.

[0040] Figure 4 This is the nuclear magnetic phosphorus spectrum of Example 2.

[0041] Figure 5 The test performance diagrams of Example 2 include: (a) circular dichroism spectra of R-FpC6 (red line) and S-FpC6 (blue line) after ultraviolet irradiation; (b) ultraviolet spectrum of the enantiomer FpC6 after ultraviolet irradiation; (c) relationship between circular dichroism intensity at 256 nm and irradiation time; (d) possible degradation of FpC6; concentration: 7.6 (10^-5 M in formonitrile, ultraviolet wavenumber: 365 nm. DETAILED DESCRIPTION

[0042] The present invention will be further described below with reference to the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it. However, the embodiments are not intended to limit the present invention.

[0043] Example 1:

[0044] The preparation method of the metallic iron carbonyl polymer in this embodiment comprises the following steps:

[0045] S1: Preparation of CpFe(CO)2K (FpK): Benzophenone (10.0 g, 55 mmol) was added to a dry Schlenk flask. The flask was evacuated and filled with nitrogen to ensure a nitrogen atmosphere. Sodium-distilled tetrahydrofuran (120 mL) was added via syringe. The nitrogen flow rate was increased, the rubber stopper was removed, and small pieces of potassium (2.15 g, 55 mmol) were added to the flask one by one. Stirring was carried out at room temperature overnight to obtain a dark blue solution. After stirring overnight, cyclopentadienyl iron dicarbonyl dimer (10.7 g, 30.2 mmol, 10% excess) was added to the flask. The reaction was continued at room temperature. After stirring for 3 h, the solution turned reddish-brown. The solvent was removed using a vacuum pump to obtain a brown solid. Sodium-distilled washing solution (toluene) was introduced into the flask via a double-ended needle. The mixture was stirred thoroughly, allowed to separate, and the upper red layer was removed. This procedure was repeated three times to wash the FpK. A yellowish-brown solid was obtained and stored in a glove box. The steps are as follows:

[0046] RT means room temperature and THF means tetrahydrofuran.

[0047] S2: Preparation of NaPPh2: Place ClPPh2 (9.0 mL, 11.03 g, 50 mmol) in a Schlenk flask. Vacuum and refill with nitrogen three times to remove oxygen from the system. Add sodium-distilled tetrahydrofuran (100 mL) via syringe. Increase the nitrogen flow rate, remove the rubber stopper, and add small pieces of sodium (3.45 g, 150 mmol) to the flask. Stir at 40°C for three days to obtain an orange-yellow solution. Wrap the joints with parafilm and store in the refrigerator.

[0048] S3: Preparation of Cl(CH2)6PPh2 (6.0mL, 7.98g, 40mmol): Take Cl(CH2)6Br in a Schlenk bottle, freeze the reagent in the bottle with liquid nitrogen, vacuum, and then dissolve it with ethanol. Repeat the operation three times to remove the air in the bottle and pass nitrogen. Use a syringe to add tetrahydrofuran (40mL) treated with sodium distillation, and add the tetrahydrofuran solution of NaPPh2 prepared in the above steps (48mL, 24mmol) dropwise to the bottle at -40°C. After the addition is complete, gradually return to room temperature and react for three hours. After the reaction is completed, vacuum remove the solvent, add 3.38g of deoxygenated dichloromethane to dissolve (do not add too much, otherwise the system will be relatively stable and turbid and difficult to separate), let it stand for separation, and take the supernatant to remove salt. The solvent and excess Cl(CH2)6Br were removed in vacuo at 90°C, and the product was dissolved in 1.01 g of dichloromethane and passed through a silica gel column with n-hexane as the eluent to remove the oxidized portion, to obtain a translucent oily substance.

[0049] S4: Preparation of CpFe(CO)2(CH2)6PPh2(FpC6P): Place FpK (1.11 g, 5 mmol) in a Schlenk flask, add sodium-distilled tetrahydrofuran, and add Cl(CH2)6PPh2 (1.22 g, 4 mmol) dissolved in tetrahydrofuran dropwise at 0°C. Cover the reaction flask with aluminum foil to block light and allow to react at room temperature for two hours. Remove the solvent under vacuum, add an appropriate amount of n-hexane to dissolve, allow to stand to separate and remove the potassium chloride salt, and pass through a silica gel column to obtain a yellow liquid. The steps are as follows:

[0050]

[0051] Dissolve 50mg of FpC6P in tetrahydrofuran (monomer concentration 20wt%), polymerize at 70°C, and react for 14 hours. After the reaction is complete, cool to room temperature and add the resulting solution dropwise to n-hexane. A flocculent precipitate will form. Collect the precipitate by centrifugation and dry it in a vacuum at room temperature overnight. The synthesis steps are as follows:

[0052] The value of n is 100-10000, and △ means heating.

[0053] The obtained polymer was subjected to nuclear magnetic resonance analysis and its nuclear magnetic hydrogen spectrum ( Figure 1 ), compared to the original monomer FpC6P (CpFe(CO)2(CH2)6PPh2), two new peaks appeared. The coordination of iron with phosphorus causes the cyclopentadienyl group attached to iron to shift upfield, reducing the chemical shift to 4.35 ppm. The presence of the original cyclopentadienyl peak (4.66 ppm) confirms the presence of terminal iron groups not coordinated to phosphorus. Another new peak, shifted to 2.81 ppm, is due to the methylene group attached to the carbonyl group, confirming the insertion of the carbonyl group into the Fe-C bond.

[0054] For this polymer, its NMR phosphorus spectrum shows two peaks ( Figure 2 Since the polymer is exposed to air after preparation, the peaks of oxidized phosphorus in the polymer are all positive, unlike those of unoxidized monomer. The peaks of phosphorus coordinated to iron appear at lower fields, while the peaks appearing at higher fields are those of phosphorus not coordinated to iron, further confirming the presence of terminal diphenylphosphine. This, combined with H-NMR spectroscopy, confirms that the polymer obtained by polymerization in tetrahydrofuran has a linear structure.

[0055] Example 2:

[0056] The preparation method of the metallic iron carbonyl polymer in this embodiment comprises the following steps:

[0057] S1: Preparation of CpFe(CO)2K (FpK): Benzophenone (10.0 g, 55 mmol) was added to a dry Schlenk flask. The flask was evacuated and filled with nitrogen to ensure a nitrogen atmosphere. Sodium-distilled tetrahydrofuran (120 mL) was added via syringe. The nitrogen flow rate was increased, and the rubber stopper was removed. Potassium (2.15 g, 55 mmol) was added to the flask in small pieces. Stirring was continued at room temperature overnight to obtain a dark blue solution. After stirring overnight, cyclopentadienyl iron dicarbonyl dimer (10.7 g, 30.2 mmol, 10% excess) was added to the flask. The reaction was continued at room temperature. After stirring for 3 h, the solution turned reddish-brown. The solvent was removed using a vacuum pump to obtain a brown solid. Sodium-distilled washing solution (toluene) was introduced into the flask via a double-ended needle. The mixture was stirred thoroughly, allowed to separate, and the upper red layer was removed. This procedure was repeated three times to wash the FpK. A yellowish-brown solid was obtained and stored in a glove box. The steps are as follows:

[0058]

[0059] S2: Preparation of NaPPh2: Place ClPPh2 (9.0 mL, 11.03 g, 50 mmol) in a Schlenk flask. Vacuum and fill with nitrogen three times to remove oxygen from the system. Add sodium-distilled tetrahydrofuran (100 mL) via syringe. Increase the nitrogen flow rate, remove the rubber stopper, and add small pieces of sodium (3.45 g, 150 mmol) to the flask piece by piece. Stir and react at 40°C for three days to obtain an orange-yellow solution. Wrap each joint with parafilm and store in the refrigerator.

[0060] S3: Preparation of Cl(CH2)6PPh2 (6.0mL, 7.98g, 40mmol): Take Cl(CH2)6Br in a Schlenk bottle, freeze the reagent in the bottle with liquid nitrogen, vacuum, and then dissolve it with ethanol. Repeat the operation three times to remove the air in the bottle and pass nitrogen. Use a syringe to add tetrahydrofuran (40mL) treated with sodium distillation, and add the tetrahydrofuran solution of NaPPh2 prepared in the above steps (48mL, 24mmol) dropwise to the bottle at -40°C. After the addition is complete, gradually return to room temperature and react for three hours. After the reaction is completed, vacuum remove the solvent, add 3.38g of deoxygenated dichloromethane to dissolve (do not add too much, otherwise the system will be relatively stable and turbid and difficult to separate), let it stand for separation, and take the supernatant to remove salt. The solvent and excess Cl(CH2)6Br were removed in vacuo at 90°C, and the product was dissolved in 1.01 g of dichloromethane and passed through a silica gel column with n-hexane as the eluent to remove the oxidized portion, to obtain a translucent oily substance.

[0061] S4: Preparation of CpFe(CO)2(CH2)6PPh2(FpC6P): Place FpK (1.11 g, 5 mmol) in a Schlenk flask, add sodium-distilled tetrahydrofuran, and add Cl(CH2)6PPh2 (1.22 g, 4 mmol) dissolved in tetrahydrofuran dropwise at 0°C. Cover the reaction flask with aluminum foil to block light and allow to react at room temperature for two hours. Remove the solvent under vacuum, add an appropriate amount of n-hexane to dissolve, allow to stand to separate and remove the potassium chloride salt, and pass through a silica gel column to obtain a yellow liquid. The steps are as follows:

[0062]

[0063] 50 mg of FpC6P was dissolved in a tetrahydrofuran / n-hexane (1:1, v / v) solution (monomer concentration: 20 wt%). The polymerization temperature was 70°C and the reaction time was 14 hours. After the reaction was completed, the solution was cooled to room temperature and added dropwise to n-hexane. A flocculent precipitate was observed. The precipitate was collected by centrifugation and dried in vacuum at room temperature overnight.

[0064] The NMR analysis of the polymer obtained by polymerization in tetrahydrofuran / n-hexane (1:1) showed that its H-NMR spectrum and P-NMR spectrum were more single compared with the linear polymer NMR spectrum obtained in tetrahydrofuran. Figure 3 ), there is only one chemical environment of cyclopentadienyl in the polymer, so there is only one peak at 4.3ppm due to the increase in electron cloud density after phosphorus coordination and the shift to high field. Similarly, for its nuclear magnetic phosphorus spectrum ( Figure 4 ), and the polymer also contains only one type of phosphorus, namely the phosphine coordinated to the iron. The absence of a terminal cyclopentadienyl peak in the hydrogen spectrum and a terminal phosphorus peak in the phosphorus spectrum confirm that the polymer has a ring structure.

[0065] Application Example 1:

[0066] The FPC6P monomer obtained by the synthesis method of Example 2 of the present invention is separated by chiral column chromatography. The chiral iron carbonyl complex FPC6 gradually undergoes decarbonylation reaction under ultraviolet light irradiation. Even at low concentration (7.6×10 - 5 The CO release process can still be monitored in real time by circular dichroism (CD) spectroscopy under low-temperature conditions.

[0067] CO easily coordinates with metal centers, making metal carbonyl complexes ideal therapeutic CO reservoirs. Since the Fe-CO metal-ligand bond is sensitive to light, the decarbonylation process of FpC6 proceeds under ultraviolet light irradiation. With UV irradiation, all circular dichroism (CD) peaks gradually decrease and drop to zero within 15 minutes. Density functional theory (DFT) simulations show that the peak at 256 nm is mainly attributed to CO and COCH3 groups. The attenuation of the 256 nm UV peak indicates that the disappearance of chirality may be related to the dissociation of the Fe-CO bond. The CD intensity at 256 nm is linearly related to the irradiation time, suggesting that there may be controlled release of CO groups in the system. Myoglobin detection and infrared spectroscopy are commonly used methods for detecting CO release rates. For chiral FpC6 complexes, the CD method can sensitively detect low concentrations (7.6×10 -5 M) under CO release. After 5 minutes of UV irradiation, 1 H NMR and 31 New signals appeared in P NMR. 1 H NMR at 4.3 ppm and 31 The new chemical shift at 84.0 ppm in P NMR indicates that new phosphine coordination species are generated by UV irradiation.

[0068] according to 1 HNMR ( Figure 5 In a), the CH2 group connected to the acyl carbonyl group (2.6 and 2.9 ppm) remained unchanged within 60 minutes, indicating that the terminal -CO may be released from Fe first. After 120 minutes of illumination, the 2.6 and 2.9 ppm peaks disappeared, and the peak in the 0.8-1.3 ppm range (corresponding to (CH2)4CH3) shifted to 0.8-1.5 ppm, indicating that the acyl carbonyl group in the system was decarbonylated. The decarbonylation of the CO group generates an unstable Ph3PCpFe species, resulting in 31 The 84 ppm peak in P NMR decreased significantly ( Figure 5 b) in the above example. Figure 5 Figure d shows the proposed decomposition pathway of FpC6. The gradual release of CO groups offers potential biomedical applications. FpC6 undergoes progressive decarbonylation under UV irradiation, and circular dichroism (CD) spectroscopy is an effective tool for monitoring CO release. This suggests that the photoresponsive properties of FpC6 could be applied to photosensitive materials and CO delivery systems in the biomedical field.

[0069] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will appreciate that other variations or modifications can be made based on the above description. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A method for preparing a metal iron carbonyl polymer, characterized in that: The steps include: S11: prepare compound FpK and compound Cl(CH2)6PPh2 respectively; The compound FpK is prepared by the following steps: S21: Under a nitrogen atmosphere, benzophenone and potassium metal are added to an organic solvent and reacted at room temperature for 8-12 hours to obtain a mixed solution A; S22: Add cyclopentadienyl iron dicarbonyl dimer to the mixed solution A, react at room temperature, and remove impurities to obtain the compound FpK; the structural formula of the compound FpK is as follows: The compound Cl(CH2)6PPh2 is prepared by the following steps: S31: Under a nitrogen atmosphere, chlorodiphenylphosphine (ClPPh2) and sodium metal are added to an organic solvent and reacted at 35-45°C for 66-78 hours to obtain NaPPh2; S32: Under a nitrogen atmosphere, Cl(CH2)6Br and the compound NaPPh2 are reacted in an organic solvent at room temperature for 2-4 hours, followed by removal of impurities to obtain the compound Cl(CH2)6PPh2; the structural formula of the compound Cl(CH2)6PPh2 is as follows: S12: The compound FpK and the compound Cl(CH2)6PPh2 are reacted in an organic solvent at room temperature in the dark for 1-3 hours, and impurities are removed to obtain the compound FpC6P (CpFe(CO)2(CH2)6PPh2); the structural formula of the compound FpC6P is as follows: Wherein, Ph refers to phenyl; S13: polymerizing the compound FpC6P in an organic solvent or an organic mixed solvent at 65-75° C. for 12-16 hours to obtain a reaction mixture; S14: Cooling the reaction mixture and adding it into a different solvent to remove impurities, thereby obtaining the metal iron carbonyl polymer; the metal iron carbonyl polymer has the following structural formula: Where n is from 1 to 10000.

2. The preparation method according to claim 1, wherein The organic solvent is tetrahydrofuran, the isosolvent is n-hexane, and the organic mixed solvent is obtained by mixing tetrahydrofuran and n-hexane in a volume ratio of 1:

1.

3. The preparation method according to claim 1, wherein In the step S14, after adding a different solvent, centrifugation is performed, and the solid obtained by centrifugation is vacuum dried at room temperature.

4. The preparation method according to claim 1, wherein In step S22, the impurity removal method is to remove the solvent in vacuo, add toluene and stand for stratification; repeat the impurity removal step 2-4 times to retain the final solid.

5. The preparation method according to claim 1, wherein In step S23, the impurity removal method includes the following steps: S41: Remove the solvent in vacuo, add dichloromethane to dissolve, and allow to stand for separation; S42: After standing and stratifying, the supernatant was vacuum-evacuated at 85-95°C to remove the solvent and unreacted Cl(CH2)6Br; S43: adding dichloromethane and mixing, and then using n-hexane as an eluent to pass through a silica gel column to complete the impurity removal.

6. The preparation method according to claim 1, wherein In step S12, the impurity removal method is to remove the solvent under vacuum, then add a different solvent to dissolve, let it stand and separate, and pass it through a silica gel column.

7. The preparation method according to claim 1, wherein In step S13, the concentration of compound FpC6P in the organic solvent or organic mixed solvent is 15-25 wt %.

8. The preparation method according to claim 1, wherein In step S13, the impurity removal method is to add a different solvent, collect the precipitate by centrifugation, and vacuum dry it at room temperature for 8-12 hours.

9. A metal iron carbonyl polymer prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the metal iron carbonyl polymer according to claim 9 as a photosensitive material in the biomedical field.

Images