Crystal material based on viologen cadmium complex, preparation method and application thereof
By preparing zero-dimensional crystalline CdII(Btybipy)Cl4 material, the synthesis problem in the existing technology was solved, and high-purity, high-yield cadmium vizimon complexes were achieved for the visualization of mercury ion sensing.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- BOHAI UNIV
- Filing Date
- 2023-10-11
- Publication Date
- 2026-06-26
AI Technical Summary
Existing technologies make it difficult to easily synthesize high-performance violet metal complex crystalline materials, and it is also difficult to prepare compounds with specific properties. Aqueous solution and solvothermal synthesis methods present challenges in achieving the desired synthesis.
A clear solution was formed by stirring CdCl2∙2H2O and viologen organic ligand in deionized water. The solution was then slowly evaporated to obtain blocky yellow crystals, which were then dried at room temperature to prepare CdII(Btybipy)Cl4 zero-dimensional crystalline material.
The synthesis method is simple, with high purity and high yield. The synthesized crystalline material is sensitive to mercury ions and can change color, which can be used to visualize mercury ion sensing.
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Figure CN117384191B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to crystalline catalytic materials, specifically to a crystalline material based on cadmium vizigon complex, its preparation method, and its application. Background Technology
[0002] Metal complexes constructed from viologen-based organic ligands are inorganic-organic hybrid crystalline functional materials with diverse structures and optical properties such as photochromism or electrochromism. However, the main challenges in designing and synthesizing these crystalline materials are: first, the design and synthesis of high-performance viologen ligands, as these organic molecules are relatively rare, and obtaining crystalline materials with novel structures and excellent properties is difficult; second, the preparation of compounds with specific properties using molecular tailoring methods. The main synthetic methods for viologen metal complexes are conventional aqueous solution evaporation, hydrothermal methods, and solvothermal methods. A common problem with these methods is the difficulty in achieving targeted synthesis. Summary of the Invention
[0003] The purpose of this invention is to provide a crystalline material based on cadmium vizimon complex and its preparation method, which has a simple synthesis method, high purity and yield of the target product, and good visual response to mercury ions. It can effectively solve the problems existing in the background art.
[0004] This invention also provides an application of crystalline materials based on cadmium vizigon complexes in visual mercury ion sensing materials.
[0005] To solve the above-mentioned technical problems, the present invention is implemented as follows:
[0006] Based on crystalline materials of cadmium vitreoretin complexes, the molecular formula of which is: Cd II (Btybipy)Cl4; where 4cbbp is bis-1-(thienyl)-3-methyl-4,4'-bipyridyl-1-onium.
[0007] The preparation method of the crystalline material based on cadmium vizigon complex includes the following steps: (1) adding CdCl2∙2H2O and vizigon organic ligand to deionized water and stirring to form a clear solution; (2) filtering the obtained clear solution and slowly evaporating it to obtain blocky yellow crystals; washing the blocky yellow crystals with deionized water and air-drying them at room temperature to obtain the target product, crystalline material based on cadmium vizigon complex.
[0008] As a preferred embodiment, the viologen organic ligand described in this invention is bis-1-(thienyl)-3-methyl-4,4'-bipyridyl-1-onium.
[0009] Furthermore, in step (1) of the present invention, a clear solution is formed by stirring at 80°C for 40 minutes.
[0010] The above-mentioned applications of crystalline materials based on cadmium vizigon complexes in visual mercury ion sensing materials.
[0011] Due to the adoption of the above technical solutions, this invention has the following beneficial effects: This invention uses chlorine as a counter anion, linked with a cobalt complex to form a zero-dimensional crystalline material. Wherein: Cd II (Btybipy) Cl4 is a zero-dimensional structure with the following advantages: simple synthesis method and convenient purification; the use of viologen-type compounds as nitrogen-containing ligands, which have good water solubility, are conducive to the crystallization of crystalline materials and improve the synthesis yield; the synthesized crystalline materials are sensitive to mercury ions and can undergo mercury ion-induced color change, which can be used as a visual mercury ion sensing material. Attached Figure Description
[0012] To illustrate the present invention more clearly, the embodiments will be briefly described below with reference to the accompanying drawings.
[0013] Figure 1 This is a coordination environment diagram of the crystalline material based on cadmium vizigon complex synthesized in this invention;
[0014] Figure 2 The Cd synthesized in this invention II (Btybipy) Photoluminescence and chromatograms of Cl4 in methanol solution and crystals;
[0015] Figure 3 The Cd synthesized in this invention II Fluorescence spectra of (Btybipy) Cl4 in different solutions;
[0016] Figure 4 It is the Cd synthesized by adding the present invention II (Btybipy) Fluorescence spectrum of Cl4 after fluorescence quenching following the addition of mercury ions;
[0017] Figure 5 It is the Cd synthesized by adding the present invention II (Btybipy) Fluorescence spectrum of interfering ions of Cl4;
[0018] Figure 6 It is the Cd synthesized by adding the present invention II (Btybipy) Photographs showing the color change after fluorescence quenching following the addition of mercury ions to Cl4. Detailed Implementation
[0019] To make the technical means, creative features, objectives and effects of the present invention easy to understand, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings.
[0020] Example 1
[0021] The preparation method of crystalline materials based on cadmium vizimon complexes includes the following steps:
[0022] (1) Add CdCl2∙2H2O and viologen organic ligand to deionized water and stir at 80℃ for 40 min to form a clear solution. The viologen organic ligand is bis-1-(thienyl)-3-methyl-4,4'-bipyridyl-1-onium.
[0023] (2) After filtering the above solution, the blocky yellow crystals obtained by the slow evaporation of the solution are washed with deionized water and air-dried at room temperature to obtain the crystalline material of cadmium violet complex.
[0024] Characterization of crystalline materials based on cadmium vizigon complexes
[0025] Crystal structure determination
[0026] Select a single crystal of appropriate size using a microscope, and then use a Bruker SMART 1000 CCD diffractometer (graphite monochromator, Mo-K) at room temperature. a , l Diffraction data were collected at 0.71069 Å. Scanning method w-φ Diffraction data were analyzed using the SADABS program for absorption correction. Data reconstruction and structure analysis were performed using the SAINT and SHELLXTL programs, respectively. The coordinates of all non-hydrogen atoms were determined using the least squares method, and the positions of hydrogen atoms were obtained using the theoretical hydrogenation method. The crystal structure was then refined using the least squares method. Figure 1 The basic coordination and packing configuration of the crystalline vizigon cadmium complex synthesized in Example 1 are shown. Some parameters for crystallographic diffraction point data collection and structural refinement are shown in the table below:
[0027]
[0028] Cd synthesized in Example 1 II (Btybipy) Cl4 (compound 1); Photochemical sensing experiments were conducted using aqueous solutions of heavy metal ions to detect the synthesized Cd. II The attenuation of fluorescence intensity of (Btybipy) Cl4 is used as a basis for determining the type of ion and for detecting mercury ions.
[0029] The specific experimental steps are as follows:
[0030] 1) Preparation of test solution
[0031] Prepare a 0.022 mol / L solution of compound 1 (5 mg) using solvents such as methanol, and allow it to stand for 5 minutes by sonication. The solution will produce blank fluorescence if no other metal ions are added.
[0032] 2) Fluorescence spectral characteristics test
[0033] First, solutions of compound 1 in different solvents were tested, and the spectra were analyzed. Figure 1 The study found that compound 1 exhibited the highest fluorescence intensity in its methanol solution, and subsequent tests used methanol as a dispersant for ion sensing detection of the crystalline material. Fluorescence spectra after adding mercury ions and other different metal ions to the test solutions are shown below. Figure 2 As shown, the fluorescence spectra of compound 1 after the addition of different concentrations of mercury ions show that the emission peak is located at 505 nm. With increasing mercury ion concentration, the fluorescence intensity of compound 1 gradually decreases, but the position of the emission peak remains unchanged, with a sensitivity of 12.54. Furthermore, it exhibits a good linear relationship, with R... 2 =0.9954. When other different metal ions were added to the methanol solution of Compound 1, only mercury ions weakened the fluorescence of the compound, demonstrating excellent selectivity in the crystalline material. Compound 1, due to the introduction of viologen units, exhibits photochromic properties. During mercury ion detection, the sensing system treated with different mercury ion concentrations showed different color changes, achieving visualized mercury ion sensing performance, such as... Figure 6 As shown, the fluorescence intensity and color changes of the sensing system were recorded.
Claims
1. A crystalline material based on cadmium vizimon complex, characterized in that, The molecular formula of the crystalline material based on cadmium vizimon complex is: Cd II (Btybipy)Cl4; where Btybipy is bis(thienyl)-3-methyl-4,4'-bipyridyl-1-onium.
2. The preparation method of crystalline materials based on cadmium vitreoretin complexes as described in claim 1, characterized in that, Includes the following steps: (1) CdCl 2· 2H2O and viologen organic ligands are added to deionized water and stirred to form a clear solution; (2) the clear solution is filtered and slowly evaporated to obtain blocky yellow crystals; the blocky yellow crystals are washed with deionized water and air-dried at room temperature to obtain the target product based on viologen cadmium complex crystalline material.
3. The preparation method of crystalline materials based on cadmium vitreoretin complexes as described in claim 2, characterized in that: In step (1), a clear solution is formed by stirring at 80°C for 40 minutes.
4. An application of the crystalline material based on cadmium vizimon complex as described in claim 1 in the visualization of mercury ion sensing materials.