A variable-valence metal mercapto two-dimensional coordination polymer, its preparation method and application

Abstract

The present invention discloses a variable-valence metal mercapto two-dimensional coordination polymer, its preparation method and application. The method comprises the following steps: S1. Mix an inorganic metal salt and 4,4'-thiobis(phenethyl alcohol) in a mixed solvent of an ionic liquid, an organic amine, N,N-dimethylformamide and isopropanol. After complete dissolution, carry out an ionothermal reaction; S2. Separate the mixture after the ionothermal reaction, and then wash and dry the separated solid phase with an alcohol until a pure-phase colored or colorless octahedral crystal is obtained, namely, a variable-valence metal mercapto two-dimensional coordination polymer is obtained; the variable-valence metal mercapto two-dimensional coordination polymer is an organic-inorganic hybrid compound, which is a colored or colorless octahedral crystal and can be applied to catalytic, electrical conductance, and photothermal conversion devices.

Description

Technical Field

[0001] The present invention belongs to the technical field of crystal materials, and particularly relates to a variable-valence metal mercapto two-dimensional coordination polymer, a preparation method thereof and an application thereof. Background Art

[0002] Coordination polymers are formed by the self-assembly of metal ions and inorganic / organic ligands through coordination bonds. They have the characteristics of both inorganic and organic compounds, and have good structural tunability and easy functionalization. In recent years, the design, synthesis, structure and properties of coordination polymer molecular materials have attracted more and more attention from scientific researchers. Its research has important academic significance for the development of basic concepts and basic theories of synthetic chemistry, structural chemistry and materials chemistry. At the same time, it has important application value for the development of new high-performance functional molecular materials and devices. Therefore, it is necessary to find new synthesis methods for coordination polymers to obtain coordination polymer materials with novel structures and suitable properties. Summary of the Invention

[0003] To solve the above problems, the present invention provides a variable-valence metal mercapto two-dimensional coordination polymer, a preparation method thereof and an application thereof. The method uses an inorganic metal salt and 4,4'-thiobis(benzyl alcohol) as raw materials, and adopts an ionothermal synthesis method using an ionic liquid, an organic amine, DMF and isopropanol as solvents to prepare a variable-valence metal mercapto two-dimensional coordination polymer. The variable-valence metal mercapto two-dimensional coordination polymer is an organic-inorganic hybrid compound, which is a colored or colorless octahedral crystal and can be applied to catalysts, electrical conductivity, and photothermal conversion devices.

[0004] The present invention adopts the following technical solutions:

[0005] A preparation method of a variable-valence metal mercapto two-dimensional coordination polymer, comprising the following steps:

[0006] S1. Mix an inorganic metal salt and 4,4'-thiobis(benzyl alcohol) in a mixed solvent of an ionic liquid, an organic amine, N,N-dimethylformamide and isopropanol. After complete dissolution, perform an ionothermal reaction;

[0007] S2. Separate the mixture after the ionothermal reaction, and then wash and dry the separated solid phase with alcohol until a pure-phase colored or colorless octahedral crystal is obtained, that is, a variable-valence metal mercapto two-dimensional coordination polymer is obtained.

[0008] Preferably, the inorganic metal salt in step S1 is FeSO4·7H2O or Co(NO3)2·6H2O.

[0009] Preferably, the variable-valence metal mercapto two-dimensional coordination polymer obtained in step S2 is C 42 H 50 N4S6Fe or C42 H 50 N4S6Co; C containing guest molecules 42 H 50 N4S6Fe, Mr is 859.07, the structure is monoclinic system, the space group is P21 / n, the unit cell parameter a is b is c is α is 90°, β is 116.751(6)°, γ is 90°, V is C without guest molecules 42 H 50 N4S6Co, Mr is 862.22, the structure is monoclinic system, the space group is P21 / n, the unit cell parameter a is b is c is α is 90°, β is 116.574(3)°, γ is 90°, V is

[0010] Preferably, the ionic liquid in step S1 is 1-butyl-2,3-dimethylimidazolium chloride.

[0011] Preferably, the organic amine in step S1 is one or a mixture of more than one of 4-(2-aminoethyl)morpholine, N-aminoethylpiperazine, dimethylpiperazine and dimethylpiperidine.

[0012] Preferably, the dissolution process of the inorganic metal salt in step S1 is carried out by ultrasonic dissolution; the reaction temperature of the ionothermal reaction is 60-150 °C, and the reaction time is 72-480 hours.

[0013] Preferably, in step S2, a monohydric alcohol is used to wash the separated solid phase, and the monohydric alcohol is one or a mixture of more than one of methanol, ethanol, propanol and isopropanol.

[0014] A variable-valence metal thiol two-dimensional coordination polymer, which is prepared by the preparation method of the variable-valence metal thiol two-dimensional coordination polymer.

[0015] An application of a variable-valence metal thiol two-dimensional coordination polymer, which is applied to catalytic, conductance, and photothermal conversion devices.

[0016] After adopting the above technical solution, compared with the background art, the present invention has the following advantages: The present invention uses inorganic metal salts and 4,4'-thiobis(benzyl alcohol) as raw materials, and adopts an ionothermal synthesis method with ionic liquids, organic amines, DMF and isopropanol as solvents to prepare a variable-valence metal mercapto two-dimensional coordination polymer. The variable-valence metal mercapto two-dimensional coordination polymer is a variable-valence new material, namely an organic-inorganic hybrid metal mercapto two-dimensional coordination polymer; the process requirements are simple, the purity requirements for raw materials are low, the raw materials are easily obtained and inexpensive, which is convenient for large-scale production, and the post-treatment is simple and easy. Only simple alcohol washing and separation are required, and pure-phase crystalline products can be obtained by air drying indoors. The pollution during the synthesis process of this process is small, meeting the requirements of green environmental protection; in addition, the metal in the metal mercapto two-dimensional coordination polymer prepared by this synthesis method has variable valence, and the yield can reach more than 75%. The variable-valence metal mercapto two-dimensional coordination polymer is a compound that can be used in fields such as catalysis, conductivity, and photothermal conversion. Description of the Drawings

[0017] Figure 1 Schematic diagram of the crystal structure of the crystalline product prepared in Example 1 of the present invention;

[0018] Figure 2 X-ray powder diffraction pattern of the crystalline product prepared in Example 1 of the present invention, where the lower line is the theoretical value and the upper line is the experimental value;

[0019] Figure 3 Infrared spectrum of the crystalline product prepared in Example 1 of the present invention;

[0020] Figure 4 X-ray photoelectron spectroscopy (XPS) of the crystalline product prepared in Example 1 of the present invention. Detailed Description of the Invention

[0021] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0022] Example 1

[0023] Mix FeSO4·7H2O (64.5 mg, 0.232 mmol), 4,4′-thiobis(benzyl alcohol) (37.5 mg, 0.15 mmol), 1-butyl-2,3-dimethylimidazolium chloride (500.0 mg, 2.65 mmol), 4-(2-aminoethyl)morpholine (0.5 mL), N,N-dimethylformamide (1 mL), isopropanol (0.5 mL) and H2O (0.5 mL) in a 20 mL glass bottle, ultrasonicate for 30 minutes until completely dissolved, and then heat to 100 °C for 7 days. Naturally cool the reaction mixture to room temperature, wash it several times with ethanol, and collect brown octahedral crystals with a yield of 76%.

[0024] The brown octahedral crystals (C 42 H 50 N4S6Fe) prepared in this example have the following crystal parameters: Mr is 859.07, the structure is monoclinic, the space group is P21 / n, the unit cell parameter a is b is c is α is 90°, β is 116.751(6)°, γ is 90°, V is

[0025] The schematic diagram of the crystal structure of the brown octahedral crystal (C 42 H 50 N4S6Fe) is shown in Figure 1 as follows. The X-ray powder diffraction pattern of the brown octahedral crystal (C 42 H 50 N4S6Fe) is shown in Figure 2 as follows. The lower line is the theoretical value and the upper line is the experimental value. The infrared spectrum of the brown octahedral crystal (C 42 H 50 N4S6Fe) is shown in Figure 3 as follows. The X-ray photoelectron spectrum of the brown octahedral crystal (C 42 H 50 N4S6Fe) is shown in Figure 4 as follows.

[0026] Example 2

[0027] Co(NO3)2·6H2O (45.5 mg, 0.156 mmol), 4,4′-thiodiphenylethanol (37.5 mg, 0.15 mmol), 1-butyl-2,3-dimethylimidazolium chloride (500.0 mg, 2.65 mmol), N-aminoethylpiperazine (0.5 mL), N,N-dimethylformamide (1 mL), isopropanol (0.5 mL) and H2O (0.5 mL) were mixed in a 20 mL glass bottle and sonicated for 30 minutes until completely dissolved, then heated to 100 °C for 7 days. The reaction mixture was naturally cooled to room temperature, washed several times with ethanol, and brown octahedral crystals were collected with a yield of 75%.

[0028] The brown octahedral crystals (C 42 H 50 N4S6Co) prepared in this example have the following crystal parameters: Mr is 862.22, the structure is monoclinic, the space group is P21 / n, the unit cell parameter a is b is c is α is 90°, β is 116.574(3)°, γ is 90°, V is

[0029] As mentioned above, the above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A preparation method of a variable-valence metal mercapto two-dimensional coordination polymer, characterized in that, It includes the following steps: S1. Mix an inorganic metal salt and 4,4′-thiobis(benzyl alcohol) in a mixed solvent of an ionic liquid, an organic amine, N,N-dimethylformamide and isopropanol. After complete dissolution, carry out an ionothermal reaction; The inorganic metal salt described in step S1 is FeSO4·7H2O or Co(NO3)2·6H2O; The ionic liquid described in step S1 is 1-butyl-2,3-dimethylimidazolium chloride; The organic amine described in step S1 is one or a mixture of more than one of 4-(2-aminoethyl)morpholine, N-aminoethylpiperazine, dimethylpiperazine and dimethylpiperidine; During the dissolution process of the inorganic metal salt in step S1, ultrasonic dissolution is adopted; the reaction temperature of the ionothermal reaction is 60-150 °C, and the reaction time is 72-480 hours; S2. Separate the mixture after the ionothermal reaction, and then use an alcohol to wash and dry the separated solid phase until a pure-phase colored or colorless octahedral crystal is obtained, that is, a variable-valence metal mercapto two-dimensional coordination polymer is obtained; The variable-valence metal mercapto two-dimensional coordination polymer obtained in step S2 is C 42 H 50 N4S6Fe or C 42 H 50 N4S6Co.

2. The preparation method of the variable-valence metal mercapto two-dimensional coordination polymer according to claim 1, characterized in that, C with guest molecules 42 H 50 N4S6Fe, Mr is 859.07, the structure is monoclinic, the space group is P21 / n, the unit cell parameters are a = 16.9805(8) Å, b = 16.3895(5) Å, c = 17.0828(8) Å, α = 90 o , β = 116.751(6) o , γ = 90 o , V = 4245.3(4) Å 3 ; C with guest molecules 42 H 50 N4S6Co, Mr is 862.22, the structure is monoclinic, the space group is P21 / n, the unit cell parameters are a = 16.9834(3) Å, b = 16.3415(2) Å, c = 17.0437(3) Å, α = 90 o , β = 116.574(3) o , γ = 90 o , V = 4230.50(16) Å 3 .

3. The preparation method of the variable-valence metal mercapto two-dimensional coordination polymer according to claim 1, characterized in that, In step S2, a monohydric alcohol is used to wash the separated solid phase, and the monohydric alcohol is one or a mixture of more than one of methanol, ethanol, propanol and isopropanol.

4. A variable-valence metal mercapto two-dimensional coordination polymer, characterized in that, The variable-valence metal mercapto two-dimensional coordination polymer is prepared by the preparation method of the variable-valence metal mercapto two-dimensional coordination polymer according to any one of claims 1-3.

5. Use of a variable-valence metal mercapto two-dimensional coordination polymer as described in claim 4, characterized in that: The variable-valence metal mercapto two-dimensional coordination polymer is applied to a photothermal conversion device.

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