A solar photostimulation-responsive metal coordination polymer, its preparation method and applications

Abstract

This invention discloses a solar photoresponsive metal coordination polymer, its preparation method, and its applications, belonging to the field of coordination polymer technology. This invention synthesizes four structurally similar coordination polymers by reacting the ligand (E)-4-(4-(pyridin-4-yl)styryl)pyridine with isophthalic acid derivatives and CdSO4·8 / 3H2O via a solvothermal reaction. These four coordination polymers undergo a [2+2] cycloaddition reaction under solar irradiation. The resulting series of single crystals exhibit photoresponsive behavior under sunlight, with crystals of different sizes and shapes producing different mechanical movements. The composite film prepared by combining this coordination polymer with PVA exhibits mechanical movement under ultraviolet light, displaying mechanical behaviors not found in single crystals, and holds promise for applications in photo-actuators. Furthermore, this invention also extracts cyclobutane products based on the photoreaction of this series of coordination polymers, a simple and environmentally friendly process.

Description

Technical Field

[0001] This invention belongs to the field of coordination polymer technology, specifically relating to a metal coordination polymer that is responsive to sunlight stimulation, its preparation method, and its application. Background Technology

[0002] Stimulus-responsive materials are a class of smart materials that can reconstruct their physical and chemical properties in response to changes in the external environment. They have attracted considerable attention due to their significant application value in sensors, optical devices, information storage, and artificial intelligence. Through proper design, these materials can respond to a variety of external physical and chemical stimuli, such as heat, electric fields, magnetic fields, humidity, and light. Among these external stimuli, light energy is particularly attractive. It can not only remotely trigger molecular motion in a non-contact and non-invasive manner but also has the characteristic of being able to adjust its irradiation angle, wavelength, position, and duration. Furthermore, light energy is readily available and has advantages such as being green, clean, low-cost, and highly efficient.

[0003] Coordination polymers (CPs), as novel inorganic-organic hybrid functional materials formed by the coordination bonds between metal ions and organic ligands, play an important role in stimulus-responsive materials due to their combination of the advantages of inorganic and organic materials and their ease of structural modulation. Many photoresponsive materials based on photosensitive functional groups such as azobenzene, diaryl, and anthracene have been reported. The basic deformation mechanisms of these photosensitive functional groups can be divided into two categories: chemical reactions (such as the [2+2] photocycloaddition reaction of olefins) and changes in molecular configuration (such as the cis-trans isomerization of azobenzene). The material absorbs photon energy, triggering nanoscale molecular structural motion, and the release of stress generated by this molecular structural motion ultimately leads to macroscopic mechanical motion. For example, patent publication number CN 113999402 A discloses a photostimulation-responsive coordination polymer and its preparation and application. A photoactuator prepared using this photostimulation-responsive coordination polymer can perform various behaviors according to its specific shape under 365nm wavelength ultraviolet light irradiation. Because of the adjustable and precise uniformity of the structure of coordination polymers, they can be used as raw materials for synthesizing photoresponsive materials. Summary of the Invention

[0004] To address the above problems, this invention provides a solar photostimulation-responsive metal coordination polymer, its preparation method, and its application. The coordination polymer is synthesized by solvothermal reaction of ligand (E)-4-(4-(pyridin-4-yl)styryl)pyridine with isophthalic acid derivative and CdSO4·8 / 3H2O. This coordination polymer can undergo a [2+2] photocycloaddition reaction under sunlight irradiation.

[0005] This invention is achieved through the following technical solution:

[0006] A solar-stimulated metal coordination polymer, the molecular formula of which includes C 104 H 72 N8O 18 Cd4F4 or C 52 H 34 N4O8Cd2Cl2 belongs to the triclinic crystal system, space group P-1, and its unit cell parameters are: α=76.241(4)~83.07310°, β=84.16610(6)~81.260(4)°, γ=77.27460(5)~77.459(4)°, Z = 2.

[0007] A method for preparing a solar-stimulated responsive metal coordination polymer as described above includes the following steps:

[0008] (1) Synthesis of ligand: 4-(4-bromophenyl)pyridine, 4-vinylpyridine, bis(triphenylphosphine)palladium dichloride and anhydrous potassium carbonate were dissolved in N,N-dimethylformamide. The mixture was heated in an oil bath under an inert gas atmosphere and reacted at a constant temperature. After the reaction was completed, the mixture was filtered, washed and dried to obtain the ligand (E)-4-(4-(pyridin-4-yl)styryl)pyridine.

[0009] (2) Synthesis of coordination polymer: CdSO4·8 / 3H2O, isophthalic acid derivative and (E)-4-(4-(pyridin-4-yl)styryl)pyridine were mixed with N,N-diethylformamide, water and acetonitrile. The resulting solution was adjusted to acidity, sealed and reacted at a constant temperature. After the reaction was completed, it was cooled to room temperature to obtain a metal coordination polymer that responds to sunlight stimulation.

[0010] Further, in step (1), the mass ratio of 4-(4-bromophenyl)pyridine, 4-vinylpyridine, bis(triphenylphosphine)palladium dichloride and potassium carbonate is 258:0.1-0.2:10-12:0.15-0.3.

[0011] Further, in step (1), the mass-to-volume ratio of 4-(4-bromophenyl)pyridine to N,N-dimethylformamide is 258 mg: 25-30 mL.

[0012] Furthermore, in step (1), the reaction temperature is 100-120°C and the time is 45-48h.

[0013] Further, in step (2), the isophthalic acid derivative is any one of 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 5-bromoisophthalic acid, and 5-methylisophthalic acid.

[0014] Further, in step (2), the mass ratio of CdSO4·8 / 3H2O, isophthalic acid derivative and (E)-4-(4-(pyridin-4-yl)styryl)pyridine is 250-280:85-100:65.

[0015] Further, in step (2), the mass-to-volume ratio of (E)-4-(4-(pyridin-4-yl)styryl)pyridine to water is 65 mg: 1 to 1.2 mL; the volume ratio of N,N-diethylformamide, water and acetonitrile is 3:10 to 12:3.

[0016] Furthermore, in step (2), the reaction temperature is 130–150°C and the time is 10–12 h; the pH of the solution is adjusted to 3–4 using nitric acid.

[0017] The application of a solar-stimulated metal coordination polymer as described in claim 1 in composite films made by combining it with PVA or in the preparation of cyclobutane compounds under sunlight irradiation.

[0018] The synthesis principle of the solar-stimulated responsive metal coordination polymer of the present invention:

[0019] This invention involves mixing 4-(4-bromophenyl)pyridine and 4-vinylpyridine and reacting them under the catalysis of bis(triphenylphosphine)palladium dichloride to synthesize the ligand (E)-4-(4-(pyridin-4-yl)styryl)pyridine. This ligand contains one carbon-carbon double bond and two pyridine groups, exhibiting numerous coordination sites and strong coordination ability. Four structurally similar coordination polymers were synthesized from this ligand via a solvothermal reaction with isophthalic acid derivatives and CdSO4·8 / 3H2O. The synthesized coordination polymers are spatially ordered, ensuring that the distance between the parallel carbon-carbon double bonds is within the range where [2+2] cycloaddition reactions can occur. When the coordination polymer synthesized from this ligand is exposed to sunlight, the double bonds of adjacent molecules spontaneously polymerize into a four-membered ring after receiving energy from the light, and this coordination polymer exhibits photoresponsive behavior.

[0020] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows:

[0021] 1. This invention synthesizes a coordination polymer by reacting the ligand (E)-4-(4-(pyridin-4-yl)styryl)pyridine with an isophthalic acid derivative and CdSO4·8 / 3H2O via a solvothermal reaction. This coordination polymer undergoes a [2+2] photocycloaddition reaction under sunlight irradiation, accompanied by crystal mechanical movement. This mechanical movement can be regulated by the auxiliary carboxylic acid ligands involved in the coordination. This invention alters the mechanical behavior of the coordination polymer by combining it with a membrane. Such composite membranes hold promise for applications in photo-actuators. Furthermore, this invention provides a simple and low-pollution method for synthesizing cyclobutane based on the photoreaction of this series of coordination polymers.

[0022] 2. This invention obtained four structurally similar coordination polymers by changing the substituents on the auxiliary carboxylic acid. These four coordination polymers underwent a [2+2] cycloaddition reaction under sunlight irradiation. The single crystals of this series exhibit photoresponsive behavior under sunlight, with crystals of different sizes and shapes producing different mechanical movements. However, since the coordination polymers are mostly large, ordered crystals, their flexibility is severely limited, and they are easily broken under light irradiation. Therefore, this invention combines these coordination polymers with PVA to create a composite film that exhibits mechanical movement under ultraviolet light irradiation, displaying mechanical behaviors not found in single crystals. Furthermore, this invention also extracts cyclobutane products based on the photoreaction of these coordination polymers, a simple and environmentally friendly process.

[0023] 3. The preparation method of the coordination polymer of this invention is simple, the reaction conditions are mild, and the light conversion efficiency is high. The target product has stable chemical properties, the reagents used are relatively common and have low pollution, and the method is safe and reliable. The intermediate ligands and final products involved in this invention are stable, requiring no harsh reaction or storage conditions, and the operation is simple and does not require complex processing. The irradiation source used in this invention is mainly sunlight, with ultraviolet light as an auxiliary radiation source, making it suitable for widespread application. Attached Figure Description

[0024] Figure 1 The image shows the proton NMR spectrum of the ligand in Example 2.

[0025] Figure 2 The image shows the 1H NMR spectrum of the coordination polymer CP2 in Example 2.

[0026] Figure 3 The image shows the single-crystal X-ray diffraction pattern of the coordination polymer CP1 in Example 1.

[0027] Figure 4 This is the single-crystal X-ray diffraction pattern of the coordination polymer CP2 in Example 2.

[0028] Figure 5The diagram shows the structure of the coordination polymers CP1 and CP2 crystals in Examples 1-2.

[0029] Figure 6 The following are powder X-ray diffraction patterns of coordination polymers CP1, CP2, CP3, and CP4 in Examples 1-4.

[0030] Figure 7 Thermogravimetric analysis (TGA) diagrams of coordination polymers CP1, CP2, CP3, and CP4 in Examples 1-4 are shown.

[0031] Figure 8 The diagram shows the photoresponse behavior of the coordination polymer CP1 in Example 1 under sunlight.

[0032] Figure 9 The diagram shows the photoresponse behavior of the coordination polymer CP2 in Example 2 under sunlight.

[0033] Figure 10 The diagram shows the photoresponse behavior of the coordination polymer CP3 in Example 3 under sunlight.

[0034] Figure 11 This is a graph showing the photoresponse behavior of the coordination polymer CP4 in Example 4 under sunlight.

[0035] Figure 12 The diagram shows the mechanical motion behavior of single crystals of different shapes and sizes of coordination polymer CP1 in Example 1 under ultraviolet light.

[0036] Figure 13 The graph shows the calculated photoreaction rates of coordination polymers CP1, CP2, CP3, and CP4 in Examples 1-4.

[0037] Figure 14 The image shows the deformation behavior of the composite film in Application Example 1 under ultraviolet light irradiation.

[0038] Figure 15 This is a comparison of the proton NMR spectra of the coordination polymer CP1 in Application Example 2 before and after sunlight exposure. Detailed Implementation

[0039] The present invention will be further described in detail below through embodiments. These embodiments are only used to illustrate the present invention and do not limit the scope of protection of the present invention.

[0040] Example 1

[0041] Preparation of solar photostimulation-responsive metal coordination polymers:

[0042] (1) Synthesis of ligand: (1) Take 0.258g of 4-(4-bromophenyl)pyridine, 0.126mg of 4-vinylpyridine, 10mg of bis(triphenylphosphine)palladium dichloride, and 0.207mg of anhydrous potassium carbonate, and add them to a 250mL eggplant-shaped reaction flask. Then add 25mL of N,N-dimethylformamide (DMF) solvent, purge with nitrogen, and stir in an oil bath at a constant temperature of 110℃ for 48h. After filtration, washing and drying, the intermediate product ligand (E)-4-(4-(pyridin-4-yl)styryl)pyridine is obtained.

[0043] (2) Synthesis of coordination polymer: 65 mg of ligand (E)-4-(4-(pyridin-4-yl)styryl)pyridine, 95 mg of 5-fluoroisophthalic acid, and 265 mg of CdSO4·8 / 3H2O were added to a glass tube. 0.3 mL of N,N-diethylformamide (DEF), 1.1 mL of water, and 0.3 mL of acetonitrile were added to the glass tube. The pH was adjusted to 3 with nitric acid. After sealing the glass tube, it was transferred to a constant temperature reaction chamber and reacted at 140 °C for 12 h. After the reaction was completed, it was cooled to room temperature to obtain a metal coordination polymer (denoted as CP1) that responds to sunlight stimulation.

[0044] Example 2

[0045] Preparation of solar photostimulation-responsive metal coordination polymers:

[0046] (1) Synthesis of ligands: (1) Take 0.258 g of 4-(4-bromophenyl)pyridine, 0.131 mg of 4-vinylpyridine, 10 mg of bis(triphenylphosphine)palladium dichloride, and 0.225 mg of anhydrous potassium carbonate, and add them sequentially to a 250 mL eggplant-shaped reaction flask. Then add 25 mL of N,N-dimethylformamide (DMF) solvent, purge with nitrogen, and stir the reaction in an oil bath at a constant temperature of 110 °C for 48 h. After filtration, washing, and drying, the intermediate ligand (E)-4-(4-(pyridin-4-yl)styryl)pyridine is obtained. Its 1H NMR spectrum is shown below. Figure 1 As shown;

[0047] (2) Synthesis of the coordination polymer: 65 mg of ligand (E)-4-(4-(pyridin-4-yl)styryl)pyridine, 90 mg of 5-chloroisophthalic acid, and 270 mg of CdSO4·8 / 3H2O were added to a glass tube. 0.3 mL of N,N-diethylformamide (DEF), 1.0 mL of water, and 0.3 mL of acetonitrile were added to the glass tube. The pH was adjusted to 3 with nitric acid. After sealing the glass tube, it was transferred to a constant temperature reaction chamber and reacted at 140 °C for 12 h. After the reaction was completed and cooled to room temperature, a metal coordination polymer with a solar photostimulation response (denoted as CP2) was obtained. Its 1H NMR spectrum is shown below. Figure 2 As shown.

[0048] Example 3

[0049] Preparation of solar photostimulation-responsive metal coordination polymers:

[0050] (1) Synthesis of ligand: (1) Take 0.258g of 4-(4-bromophenyl)pyridine, 0.140mg of 4-vinylpyridine, 11mg of bis(triphenylphosphine)palladium dichloride, and 0.225mg of anhydrous potassium carbonate, and add them to a 250mL eggplant-shaped reaction flask. Then add 30mL of N,N-dimethylformamide (DMF) solvent, purge with nitrogen, and stir in an oil bath at a constant temperature of 120℃ for 45h. After filtration, washing and drying, the intermediate product ligand (E)-4-(4-(pyridin-4-yl)styryl)pyridine is obtained.

[0051] (2) Synthesis of coordination polymer: 65 mg of ligand (E)-4-(4-(pyridin-4-yl)styryl)pyridine, 85 mg of 5-bromoisophthalic acid, and 275 mg of CdSO4·8 / 3H2O were added to a glass tube. 0.3 mL of N,N-diethylformamide (DEF), 1.2 mL of water, and 0.3 mL of acetonitrile were added to the glass tube. The pH was adjusted to 3 with nitric acid. After sealing the glass tube, it was transferred to a constant temperature reaction chamber and reacted at 130 °C for 12 h. After the reaction was completed, it was cooled to room temperature to obtain a metal coordination polymer (denoted as CP3) that responds to sunlight stimulation.

[0052] Example 4

[0053] Preparation of solar photostimulation-responsive metal coordination polymers:

[0054] (1) Synthesis of ligand: (1) Take 0.258g of 4-(4-bromophenyl)pyridine, 0.145mg of 4-vinylpyridine, 12mg of bis(triphenylphosphine)palladium dichloride, and 0.260mg of anhydrous potassium carbonate, and add them to a 250mL eggplant-shaped reaction flask. Then add 25mL of N,N-dimethylformamide (DMF) solvent, purge with nitrogen, and stir in an oil bath at 100℃ for 48h. After filtration, washing and drying, the intermediate product ligand (E)-4-(4-(pyridin-4-yl)styryl)pyridine is obtained.

[0055] (2) Synthesis of coordination polymer: 65 mg of ligand (E)-4-(4-(pyridin-4-yl)styryl)pyridine, 100 mg of 5-methylisophthalic acid, and 280 mg of CdSO4·8 / 3H2O were added to a glass tube. 0.3 mL of N,N-diethylformamide (DEF), 1.2 mL of water, and 0.3 mL of acetonitrile were added to the glass tube. The pH was adjusted to 3 with nitric acid. After sealing the glass tube, it was transferred to a constant temperature reaction chamber and reacted at 150 °C for 10 h. After the reaction was completed, it was cooled to room temperature to obtain a metal coordination polymer (denoted as CP4) that responds to sunlight stimulation.

[0056] Material characterization analysis

[0057] (I) Single-crystal X-ray diffraction analysis

[0058] Single-crystal X-ray diffraction analysis was performed on the coordination polymers CP1 and CP2 in Examples 1-2, and the results are as follows: Figure 3 and 4 As shown in Table 1, the main crystal data and correction parameters of coordination polymers CP1 and CP2 are shown in Table 1 below, and their crystal structures are as follows. Figure 5 As shown.

[0059] Table 1 Crystal data and structural optimization parameters of coordination polymers CP1 and CP2

[0060]

[0061]

[0062] (III) Powder X-ray Diffraction Analysis

[0063] Powder X-ray diffraction analysis was performed on the coordination polymers CP1, CP2, CP3, and CP4 in Examples 1-4, and the results are as follows: Figure 6 As shown. By Figure 6 It can be seen that the experimental powder X-ray diffraction patterns of coordination polymers CP1, CP2, CP3, and CP4 demonstrate the similarity of the structures of this series of coordination polymers.

[0064] (iv) Thermogravimetric analysis

[0065] Thermogravimetric analysis (TGA) was performed on the coordination polymers CP1, CP2, CP3, and CP4 in Examples 1-4, and the results are as follows: Figure 7 As shown. By Figure 7 It can be seen that the four coordination polymers CP1, CP2, CP3 and CP4 have good thermal stability under N2 atmosphere, with no weight loss below 300℃, after which thermal decomposition occurs.

[0066] (V) Analysis of Photoresponse Behavior

[0067] Single crystals of coordination polymers CP1, CP2, CP3, and CP4 with different shapes from Examples 1-4 were exposed to sunlight. It was found that the complexes exhibited varying degrees of light response under sunlight. With increasing exposure time, all complexes developed cracks of varying degrees. For example, CP1 showed crystal splitting at the crystal ends after 45 minutes of sunlight exposure. Figure 8-11 As shown. By Figure 12 It is known that when single crystals of coordination polymer CP1 with different shapes are illuminated, narrower and thicker single crystals are more prone to cracking, flipping, and jumping phenomena in a short period of time, while thinner single crystals are more prone to cracking. This may be because larger crystals have a higher Young's modulus, resulting in greater photogenerated stress accumulated during the photo-addition reaction within the crystal. The release of this photogenerated stress in a short time leads to more severe deformation of the crystal, such as cracking and jumping. Furthermore, calculations of the photoreaction rates of coordination polymers CP1, CP2, CP3, and CP4 show that… Figure 13 When the substituent is a halogen atom, the rate of response of the coordination polymer to photoresponse behavior under sunlight increases with the increase of atomic radius.

[0068] Application Example 1

[0069] The coordination polymer CP1 crystals from Example 1 were ground into a uniform powder in an agate mortar. The powder was then mixed with a PVA aqueous solution and stirred to obtain a uniform viscous liquid. The viscous liquid was dropped onto a clean, dry glass substrate and placed in a constant temperature oven at 60°C to dry. After drying, the substrate was cooled to room temperature and the composite film of coordination polymer CP1 was peeled off from the glass substrate.

[0070] Application Example 2

[0071] The coordination polymer CP1 powder from Example 1 was irradiated under sunlight for 3 hours, then mixed with 5 mL of 4 mol / L sodium hydroxide solution, 10 mL of water and 20 mL of dichloromethane, and stirred at room temperature for 2 hours. The reaction mixture was separated and the organic layer was retained. Anhydrous sodium sulfate was added to the organic layer and dried to obtain the cyclobutane compound.

[0072] Materials Application Analysis

[0073] (I) Photoresponse Analysis of Composite Films

[0074] The composite film from Application Example 1 was cut into small, curved rectangles and then exposed to an ultraviolet light source. The composite film exhibited mechanical behavior not found in single crystals: bending. Furthermore, the degree of bending gradually increased under continuous ultraviolet irradiation. Its deformation behavior under ultraviolet light irradiation is as follows: Figure 14As shown. Because the flexibility of large single crystals is easily restricted and they are prone to breakage when undergoing the [2+2] photocycloaddition reaction, this invention combines coordination polymers with PVA films to compensate for this defect. The composite film can produce mechanical behaviors that coordination polymers do not have and is not easily broken, and is expected to be used in optical actuators.

[0075] (II) Cyclobutane Extraction Analysis

[0076] In Application Example 2, when a single crystal of the coordination polymer CP1 was exposed to sunlight for a period of time, obvious cracks appeared on its surface, indicating that the coordination polymer may have undergone a photochemical reaction under sunlight irradiation. The proton NMR spectra of the samples before and after irradiation were analyzed, and the comparison is shown in the figure below. Figure 15 As shown. By Figure 15 It is evident that the 1H NMR spectra of the samples before and after single-crystal irradiation are completely different. The peak of the carbon-carbon double bond disappears completely, and an equal amount of cyclobutane peak appears. This indicates that the signal peak representing the H atom on the carbon atom of the olefin disappears, while the signal peak of the H atom on the carbon atom of cyclobutane appears, demonstrating that the coordination polymer did indeed undergo a [2+2] cycloaddition photochemical reaction after sunlight irradiation. The appearance of the cyclobutane peak (around 4.7 ppm) and the migration of the pyridine peak (8.68 to 8.57 ppm) can be observed in its NMR spectrum, thus confirming that the coordination polymer underwent a cycloaddition reaction.

[0077] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A metal coordination polymer that is responsive to sunlight, characterized in that, The molecular formula of the coordination polymer includes C 104 H 72 N8O 18 Cd4F4 or C 52 H 34 N4O8Cd2Cl2 belongs to the triclinic crystal system and has a space group of P-1. The coordination polymer C 104 H 72 N8O 18 The crystal structure parameters of Cd₄F₄ are: a = 10.38907(7) Å, b = 16.12166(12) Å, c = 18.26864(12) Å, α = 83.07310°, β = 84.16610(6)°, γ = 77.27460(5)°, V = 2953.95(4) Å. 3 Z=2; The coordination polymer C 52 H 34 The crystal structure parameters of N4O8Cd2Cl2 are: a=10.3418(6)Å, b=16.9311(9)Å, c=18.2618(9)Å, α=76.241(4)°, β=81.260(4)°, γ=77.459(4)°, V=3014.7(3) Å. 3 Z=2.

2. A method for preparing a solar-stimulated responsive metal coordination polymer, characterized in that, Includes the following steps: (1) Synthesis of ligands: 4-(4-bromophenyl)pyridine, 4-vinylpyridine, bis(triphenylphosphine)palladium dichloride and anhydrous potassium carbonate were dissolved in N,N-dimethylformamide. The mixture was heated in an oil bath under an inert gas atmosphere and reacted at a constant temperature. After the reaction was completed, the mixture was filtered, washed and dried to obtain ligand A. The structural formula of ligand A is: ; (2) Synthesis of coordination polymer: Take CdSO4·8 / 3H2O, isophthalic acid derivative and ligand A, add N,N-diethylformamide, water and acetonitrile and mix. Adjust the resulting solution to acidity, seal it and react at a constant temperature. After the reaction is completed, cool to room temperature to obtain a metal coordination polymer that responds to sunlight stimulation.

3. The method for preparing a solar-stimulated responsive metal coordination polymer according to claim 2, characterized in that, In step (1), the mass ratio of 4-(4-bromophenyl)pyridine, 4-vinylpyridine, bis(triphenylphosphine)palladium dichloride and potassium carbonate is 258:0.1-0.2:10-12:0.15-0.

3.

4. The method for preparing a solar-stimulated responsive metal coordination polymer according to claim 3, characterized in that, In step (1), the mass-to-volume ratio of 4-(4-bromophenyl)pyridine to N,N-dimethylformamide is 258 mg: 25-30 mL.

5. The method for preparing a solar-stimulated responsive metal coordination polymer according to claim 2, characterized in that, In step (1), the reaction temperature is 100-120°C and the time is 45-48h.

6. The method for preparing a solar-stimulated responsive metal coordination polymer according to claim 2, characterized in that, In step (2), the isophthalic acid derivative is any one of 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 5-bromoisophthalic acid, and 5-methylisophthalic acid.

7. The method for preparing a solar-stimulated responsive metal coordination polymer according to claim 6, characterized in that, In step (2), the mass ratio of CdSO4·8 / 3H2O, isophthalic acid derivative and ligand A is 250-280:85-100:

65.

8. The method for preparing a solar-stimulated responsive metal coordination polymer according to claim 7, characterized in that, In step (2), the mass-to-volume ratio of ligand A to water is 65 mg: 1 to 1.2 mL; the volume ratio of N,N-diethylformamide, water, and acetonitrile is 3:10 to 12:

3.

9. The method for preparing a solar-stimulated responsive metal coordination polymer according to claim 2, characterized in that, In step (2), the reaction temperature is 130-150℃ and the time is 10-12h; the pH of the solution is adjusted to 3-4 using nitric acid.

10. The use of the solar-stimulated metal coordination polymer as described in claim 1 in composite films made by combining with PVA or in the preparation of cyclobutane compounds under sunlight irradiation.

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