A polyacid crystalline material based on modification of zinc porphyrin complex, synthesis method and application thereof

Abstract

The present application relates to a kind of based on purplin zinc complex modification polyacid crystalline material and synthesis method and application, belong to crystalline state color-changing material technical field, the present application is based on purplin zinc complex modification polyacid crystalline material, the molecular formula of its coordination compound is:Zn6 II (pbbd)2(H2O) 20 (TeMo6O 24 )3;Wherein, pbbd is 1,1 '-(1,3-phenyl-m-dimethylene) bis-(4,4 '-bipyridyl-1-oxonium).The present application crystalline material synthesis method is simple, easy to crystallize, and has high synthesis yield, has electrochromic and and ammonia-induced color-changing performance.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of crystalline color-changing materials and synthesis methods, in particular to a zinc complex based on viologen organic ligand and Anderson-type polyacid as well as a synthesis method and application thereof. BACKGROUND

[0002] Viologen organic ligand has been widely concerned due to its adjustable structure, photochromic or thermochromic and electrochromic optical properties. Polyoxometalate is applied in the field of color-changing devices due to its excellent performance in inorganic color-changing materials. The combination of viologen organic molecules and polyoxometalate to prepare organic-inorganic hybrid crystalline materials is a frontier topic in color-changing materials. The main problems in the preparation of such crystalline color-changing materials are as follows: first, the design and synthesis of viologen ligand, which requires the introduction of specific organic groups into the viologen molecule from the perspective of organic tailoring, and a large number of parallel experiments, complicated operation and unsatisfactory performance. Second, the traditional hydrothermal method for preparing viologen polyoxometalate compounds has the advantages of convenience and speed, but has the disadvantage of difficulty in controlling the structure and performance of the compounds. SUMMARY

[0003] The present application provides a polyacid crystalline material based on zinc viologen complex modification with excellent performance to solve the above technical problems in the prior art.

[0004] Another object of the present application is to provide a synthesis method of a polyacid crystalline material based on zinc viologen complex modification with excellent performance.

[0005] The object of the present application also includes an application of a polyacid crystalline material based on zinc viologen complex modification.

[0006] The present application provides a polyacid crystalline material based on zinc viologen complex modification, and the molecular formula of the coordination compound is: Zn6 II (pbbd)2(H2O) 20 (TeMo6O 24 )3; wherein, pbbd is 1,1'-(1,3-phenyl-m-dimethylene) bis-(4,4'-bipyridyl-1-oxonium).

[0007] The present application provides a synthesis method of a polyacid crystalline material based on zinc viologen complex modification, and the specific steps are as follows:

[0008] Zn(NO3)2, TeMo6, viologen organic ligand pbbd are added into deionized water in a molar ratio of Zn(NO3)2:TeMo6:viologen organic ligand pbbd=10:2-5:2-5, and stirred at room temperature for 100-150 min to form a suspension, wherein the viologen organic ligand is 1,1'-(1,3-phenyl-m-dimethylene)bis-(4,4'-bipyridyl-1-oxonium); 0.1-0.5 mol / L of an ammonia solution is used to adjust the pH to 4.0-6.0, and then poured into a high-pressure reactor and heated to 150-190°C, and kept for 8 days, and then cooled to room temperature to obtain block-shaped yellow crystals, which are washed with deionized water and dried to obtain the viologen zinc complex modified heteropoly acid crystalline material.

[0009] Preferably, the molar ratio of Zn(NO3)2, TeMo6, viologen organic ligand pbbd is Zn(NO3)2:TeMo6:viologen organic ligand pbbd=10:3:4.

[0010] Preferably, in the heating step of the high-pressure reactor, the heating rate is 60°C / hour, and the cooling rate is 15°C / hour.

[0011] Preferably, the amount of deionized water added is 70% of the volume of the high-pressure reactor.

[0012] Preferably, the viologen zinc complex modified heteropoly acid crystalline material is a two-dimensional crystalline material formed by connecting the Anderson type polyacid as an inorganic building unit with a viologen zinc complex.

[0013] The application also includes the use of the above-mentioned polyacid crystalline material modified based on a viologen zinc complex as an electrochromic material and an ammonia sensing material.

[0014] The application has the advantages that: the synthesis method is convenient and does not require further purification; the viologen ligand used is a double-sided nitrogen-containing ligand, which has good water solubility, is beneficial to crystallization, and improves the yield; and the synthesized crystalline material is sensitive to electricity and can exhibit electrochromic phenomenon, and can be used as an electrochromic device. BRIEF DESCRIPTION OF DRAWINGS

[0015] Figure 1 is a coordination environment diagram of the heteropoly molybdate crystalline material based on a viologen zinc complex modified by the application;

[0016] Figure 2a is a schematic diagram of the electrochromic performance of the Zn6 II (pbbd)2(H2O) 20 (TeMo6O 24 )3 added in the synthesis of the application;

[0017] Figure 2bZn6 II (pbbd)2(H2O) 20 (TeMo6O 24 )3 under different voltage conditions.

[0018] Figure 2c Zn6 II (pbbd)2(H2O) 20 (TeMo6O 24 )3 under different voltage conditions.

[0019] Figure 3a Zn6 II (pbbd)2(H2O) 20 (TeMo6O 24 )3 under different amino environments.

[0020] Figure 3b Zn6 II (pbbd)2(H2O) 20 (TeMo6O 24 )3 under different ammonia concentrations.

[0021] Figure 3c Zn6 II (pbbd)2(H2O) 20 (TeMo6O 24 )3 under different ammonia concentrations. DETAILED DESCRIPTION

[0022] Embodiment 1

[0023] A polyacid crystalline material based on viologen zinc complex modification, the coordination compound of which has a molecular formula of Zn6 II (pbbd)2(H2O) 20 (TeMo6O 24 )3; wherein pbbd is 1,1'-(1,3-phenyl-methanediyl)bis-(4,4'-bipyridinium-1-ylidene). The preparation method comprises the following steps: mixing 0.2 mmol of 1,1'-(1,3-phenyl-methanediyl)bis-(4,4'-bipyridinium-1-ylidene), 0.15 mmol of H3TeMo6O 24, 0.5 mmol Zn(NO3)2·3H2O and 15 mL H2O were added into a 100 mL beaker in turn, stirred for 120 min at room temperature, pH was adjusted to 4.8 with 0.1 mol / L ammonia solution, poured into a 25 mL high-pressure reaction kettle, heated to 170℃ at a heating rate of 60℃ / h, kept for 8 days under hydrothermal conditions, the temperature was reduced to room temperature at a cooling rate of 15℃ / h, yellow block-shaped crystals were obtained, washed with deionized water for 2 times, naturally air-dried at room temperature, and Zn6 II (pbbd)2(H2O) 20 (TeMo6O 24 )3 with a yield of about 70%, and the coordination environment diagram thereof is shown in Figure 1 .

[0024] Characterization of the heteropoly molybdate crystal state material modified based on zinc porphyrin complex,

[0025] Crystal structure determination,

[0026] Suitable size single crystals were selected by microscope, and diffraction data were collected at room temperature by using a Bruker SMART 1000CCD diffractometer (graphite monochromator, Mo-Ka, ). The scanning mode was w-φ, and the diffraction data were corrected for absorption by using the SADABS program. Data reduction and structure analysis were completed by using the SAINT and SHELXTL programs respectively. The coordinates of all non-hydrogen atoms were determined by least squares method, and the hydrogen atom positions were obtained by theoretical hydrogenation. The crystal structure was refined by least squares method. Figure 1 The basic coordination and stacking mode of the heteropoly molybdate crystal state material modified by zinc porphyrin complex synthesized in Example 1 were shown. Part of the parameters of crystallographic diffraction point data collection and structure refinement are shown in the following table:

[0027]

[0028] Electrochromic experiment, the Zn6 II (pbbd)2(H2O) 20 (TeMo6O 24 )3 (compound 1) synthesized in Example 1 was subjected to electrochromic experiment, and the color change of the crystal material was used as the basis for judging electrochromism, so as to determine the sensitivity of compound 1 to voltage.

[0029]

[0030] The specific experimental steps are as follows:

[0031] ​Two pieces of ITO glass were sequentially placed in deionized water, ethanol and acetone for ultrasonic treatment, and cleaned for 10 minutes. Then, using double-sided transparent tape as a spacer, the electrochromic hydrogel was coated on the ITO glass using the drop casting method (effective working area of 2 cm x 2 cm). In addition, we further tested the electrochromic performance of the compounds 1 by manufacturing integrated electrochromic devices (ECDs) based on the compounds 1. Figure 2a The detailed preparation process of the device is shown. The ECD changes color when a corresponding voltage is applied. The bleaching / coloring photos of the electrochromic device based on the compound 1 are shown in Figure 2b . When the applied voltage is 0 V, it is colorless, when the voltage is -0.12 V, it starts to change color, when the applied voltage is -0.21 V, its color reaches saturated purple, and when the ECD is switched from the optimal voltage to 0 V, it returns to the original state.

[0032] Ammonia-induced color change experiment, Zn6 II (pbbd)2(H2O) 20 (TeMo6O 24 )3 (compound 1);

[0033] Ammonia-induced color change experiments were carried out to determine the sensitivity of compound 1 to amino groups, using the color change of the crystal material as the basis for judging the ammonia-induced color change.

[0034] The specific experimental steps are as follows:

[0035] Under the optical microscope, the compound 1 with regular and complete crystal shape was picked out, and the SAGA electronic ocular lens was installed on the optical microscope. The field focal length was adjusted to be clear, and the photograph was saved. Then, ammonia solutions with concentrations of 1, 2, …, 12 mol / L were prepared, and the compound 1 was placed in an atmosphere of 1 mol / L ammonia solution for 2 min. The compound 1 was photographed again, and the above steps were repeated. When the compound 1 was placed in an atmosphere of other concentrations of ammonia solution, the photograph was saved. Other different amino compounds such as triethylamine (Et3N), ethylenediamine (EN), N,N-dimethylacetamide (DMA), aniline (AN) were selected to repeat the above steps. The color change of the crystal under different amino compounds (3a) and different concentrations of ammonia solution (3b) is shown in the figure. From Figure 3a It can be seen that when different amino compounds are used, the crystal shows different characteristic colors, and in the EN environment and in the 12 mol / L ammonia solution, the color is the darkest, which is dark green. From Figure 3b and 3c It can also be seen that as the concentration of ammonia increases, the color of the crystal gradually deepens, and the characteristic peak of the ultraviolet-visible absorption spectrum changes little, slightly enhanced.

[0036] Example 2

[0037] Zn(NO3)2, TeMo6, viologen organic ligand pbbd were added into deionized water according to the molar ratio, Zn(NO3)2:TeMo6:viologen organic ligand pbbd=10:2:2, and stirred at room temperature for 100 min to form a suspension, the viologen organic ligand was 1,1'-(1,3-phenyl-m-dimethylene) bis-(4,4'-bipyridyl-1-ium); 0.1 mol / L ammonia solution was used to adjust pH=4.0, poured into a high-pressure reactor, heated to 150°C, and kept for 8 days, and then cooled to room temperature to obtain block-shaped yellow crystals, washed with deionized water, dried, and obtained a viologen zinc complex modified heteropoly acid crystalline material, with a yield of about 75%.

[0038] Example 3

[0039] Zn(NO3)2, TeMo6, viologen organic ligand pbbd were added into deionized water according to the molar ratio, Zn(NO3)2:TeMo6:viologen organic ligand pbbd=10:2:2, and stirred at room temperature for 100 min to form a suspension, the viologen organic ligand was 1,1'-(1,3-phenyl-m-dimethylene) bis-(4,4'-bipyridyl-1-ium); 0.1 mol / L ammonia solution was used to adjust pH=4.0, poured into a high-pressure reactor, heated to 150°C, and kept for 8 days, and then cooled to room temperature to obtain block-shaped yellow crystals, washed with deionized water, dried, and obtained a viologen zinc complex modified heteropoly acid crystalline material, with a yield of about 75%.

[0040] The above shows and describes the basic principles, main features and advantages of the present application. Those skilled in the art should understand that the present application is not limited to the above examples, and the above examples and descriptions in the specification are only to illustrate the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection of the present application is defined by the appended claims and their equivalents.

Claims

1. A polyacid crystalline material based on modification of zinc viologen complex, characterized in that, The coordination compound has a molecular formula of: Zn6 II (pbbd)2(H2O) 20 (TeMo6O 24 )3; wherein pbbd is 1,1'-(1,3-phenyl-methylene)bis-(4,4'-bipyridyl-1-ium).

2. Use of the polyacid crystalline material modified with zinc purpurate complex according to claim 1 as electrochromic material and as sensing material for ammonia.

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