A two-dimensional Cu(I) coordination polymer green fluorescent material and preparation method thereof
Through the preparation of two-dimensional Cu(I) coordination polymer, 4-amino-1,2,4-triazole reacts with CuI, the problems of high cost of existing fluorescent materials and waste of resources are solved, and high efficiency is achieved. Low-cost green fluorescent material preparation with wide range of LED photoluminescence applications.
Patent Information
- Application Number
- CN202410652166.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-05-24
- Publication Date
- 2024-12-20
- Estimated Expiration
- 2044-05-24
AI Technical Summary
Existing fluorescent materials rely mostly on precious metals and rare earth metal complexes, which are costly and wasteful, making it difficult to efficiently, low-cost and high-quality green fluorescent materials with high quantum yields.
Using a two-dimensional Cu(I) coordination polymer, 4-amino-1,2,4-triazole as an organic ligand reacts with CuI to prepare a two-dimensional Cu(I) coordination with green fluorescence emission characteristics. Polymer, obtain efficient LED photoluminescent materials through simple synthesis methods.
It has achieved high-efficiency, low-cost and green-prepared fluorescent materials, with high fluorescence quantum yield and broad application prospects, especially in the field of LED photoluminescence.
Smart Images
Figure CN118388788B_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the field of fluorescent materials, and in particular to a two-dimensional Cu(I) coordination polymer green fluorescent material and a preparation method thereof. Background Art
[0002] Fluorescent materials are a class of materials that can emit visible light after absorbing energy and have a wide range of applications. Fluorescent materials can be used to manufacture lighting equipment such as fluorescent tubes and phosphors, and are often used to manufacture backlight sources for liquid crystal displays to provide brightness and color enhancement effects. In addition, fluorescent materials are also used in devices such as fluorescent screens, televisions, and electronic displays. The high brightness and long-lasting luminescence characteristics of fluorescent materials make them widely used in safety signs and markings. For example, fluorescent protective clothing, safety signs, escape signs, etc. can provide visible warnings and guidance in dark environments. Fluorescent dyes and fluorescent markers are widely used in biomedical research and clinical diagnosis. Fluorescent dyes can be used for imaging, cell tracking, labeling proteins and nucleic acids, etc. Fluorescent materials have important applications in material research, such as in optical sensing, optical storage, photocatalysis, and fluorescent probes. Fluorescent materials are widely used in stage lighting, fireworks, and visual arts, and can create unique light and shadow effects and visual feasts.
[0003] Compared with traditional luminescent materials, inorganic-organic hybrid luminescent materials have incomparable advantages, which are mainly reflected in their composition, synthesis and structure. For example, the composition combines the properties of both organic and inorganic materials, thereby increasing the diversity of luminescent forms; the reaction conditions are mild in synthesis, and they can also be synthesized by ultrasound, microwave, mechanical grinding and other methods, which can significantly shorten the reaction time and control the particle size of the reaction product; the structural controllability can indirectly control the fluorescence properties of the material. Metal halide luminescent materials have great application prospects in photoluminescence, electroluminescence and photovoltaic devices due to their rich crystal structure and excellent optoelectronic properties. Among them, copper (I)-based organic-inorganic hybrid metal halides have attracted unprecedented interest due to their wide wavelength tunability, high PLQY, large Stokes shift, simple preparation method and other advantages. Among the many luminescent inorganic-organic hybrid materials, the coordination polymer materials constructed by cuprous iodide have attracted extensive attention from scientific researchers in recent years due to their practical advantages such as high fluorescence yield, low price and energy saving and environmental protection. The earliest research on the luminescence properties of cuprous iodide materials can be traced back to 1985 when Elizabeth's team studied the fluorescence properties of Cu4I4 and Cu2I2 molecular complexes.
[0004] Currently, most of the luminescent materials on the market are based on complexes of precious metals and rare earth metals. Such materials are not only expensive, but also waste precious rare earth resources. Therefore, people are in urgent need of a luminescent material with high quantum yield and cheap and easy access. Although lead halide perovskite nanocrystals and copper (I)-based organic-inorganic hybrid metal halides with diverse crystal structures and excellent luminescent properties have been discovered, there are still many challenges in how to prepare them efficiently, at low cost, with high quality and in a green way and expand their applications. Summary of the invention
[0005] The purpose of the present invention is to overcome the problems existing in the prior art and provide a two-dimensional Cu(I) coordination polymer green fluorescent material and a preparation method thereof. Cuprous iodide complexes have become a research hotspot due to their high fluorescence quantum yield and low price. Cuprous iodide complexes have the following advantages:
[0006] (1) Variable coordination geometry. The coordination number of Cu(I) can be 2, 3, or 4. The clusters formed by copper and iodine can vary from terminal two-bridged to eight-bridged. Moreover, the cuprous iodide clusters in the same compound can also be different, thus forming a rich and varied coordination system.
[0007] (2) Multiple luminescence mechanisms. Common luminescence mechanisms of cuprous iodide complexes include ligand-centered luminescence, electron transfer luminescence, and metal-centered luminescence. Generally speaking, terminal ligands or bridging ligands with variable substituents play an important role in cuprous iodide complexes. They not only control the size and configuration of cuprous iodide clusters and complexes, but also affect the fluorescence properties of the complexes.
[0008] (3) Most cuprous iodide complexes have remarkably high photoluminescence quantum yields in the solid state.
[0009] (4) The reagents are cheap and the final product is relatively easy to obtain. In previous studies on cuprous iodide complexes, the ligands were mostly pyridines, alkyl phosphines and triethylenediamine, but there have been no reports on cuprous iodide complexes with 4-amino-1,2,4-triazole as a ligand. The present invention uses 4-amino-1,2,4-triazole as an organic ligand to react with CuI to obtain a two-dimensional Cu(I) coordination polymer with green fluorescence emission characteristics. The preparation method is simple and has good potential application prospects in fluorescent materials.
[0010] In order to achieve the above object, the technical solution adopted by the present invention is:
[0011] The first aspect of the present invention provides a two-dimensional Cu(I) coordination polymer, the chemical formula of the two-dimensional Cu(I) coordination polymer is:
[0012] [Cu4I4(NH2-trz)2], wherein NH2-trz is 4-amino-1,2,4-triazole.
[0013] Preferably, the two-dimensional Cu(I) coordination polymer is monoclinic and has a space group of P21 / n.
[0014] Preferably, the single crystal diffraction parameters of the two-dimensional Cu(I) coordination polymer are: α=90°, β=104.686(4)°, γ=90°,
[0015] Preferably, the two-dimensional Cu(I) coordination polymer does not lose weight in the range of room temperature to 230°C, and loses weight by less than 20% in the range of 230-350°C.
[0016] Preferably, the two-dimensional Cu(I) coordination polymer has a solid fluorescence emission peak of 520 nm at an excitation wavelength of 340 nm.
[0017] The second aspect of the present invention provides a method for preparing the two-dimensional Cu(I) coordination polymer, comprising the following steps:
[0018] (1) CuI is dissolved in acetonitrile to obtain solution A; 4-amino-1,2,4-triazole is dissolved in ethanol to obtain solution B;
[0019] (2) Solution A and solution B are mixed, stirred at room temperature to obtain a precipitate, and the precipitate is filtered, washed, and dried to obtain the two-dimensional Cu(I) coordination polymer.
[0020] Preferably, the concentration of solution A is (0.03-0.05) mol / L; further preferably, the concentration of solution A is (0.035-0.045) mol / L.
[0021] Preferably, the concentration of solution B is (0.01-0.03) mol / L; further preferably, the concentration of solution B is (0.015-0.025) mol / L.
[0022] Preferably, in step (2), the stirring time at room temperature is 1.5-2.5 h; further preferably, the stirring time at room temperature is 1.8-2.2 h.
[0023] Compared with the prior art, the present invention has the following beneficial effects:
[0024] Compared with other existing fluorescent materials, the novel Cu(I) complex fluorescent material of the invention has easy-to-obtain raw materials for synthesis, a simple synthesis method, high yield, emits green fluorescence, is a high-efficiency LED photoluminescent material, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] Figure 1 Schematic diagram of the synthesis of Cu(I) complex;
[0026] Figure 2 It is an asymmetric structural unit of the Cu(I) complex;
[0027] Figure 3 is a schematic diagram of the two-dimensional structure of the Cu(I) complex;
[0028] Figure 4 is the X-ray diffraction pattern of Cu(I) complex crystal powder;
[0029] Figure 5 Thermogravimetric diagram of Cu(I) complex crystal;
[0030] Figure 6 The powder luminescence images of Cu(I) complex under natural light and ultraviolet light;
[0031] Figure 7 The fluorescence spectrum of the new Cu(I) complex measured by F-7000 fluorescence spectrophotometer. DETAILED DESCRIPTION
[0032] The specific embodiments of the present invention are further described below. It should be noted that the description of these embodiments is used to help understand the present invention, but does not constitute a limitation of the present invention. In addition, the technical features involved in each embodiment of the present invention described below can be combined with each other as long as they do not conflict with each other.
[0033] The experimental methods in the following examples are conventional methods unless otherwise specified, and the experimental materials used in the following examples are commercially available unless otherwise specified.
[0034] Example 1
[0035] This embodiment provides a novel Cu(I) complex fluorescent material, and the reaction steps are as follows:
[0036] As attached Figure 1As shown, 0.2 mmol of CuI (0.0380 g) was weighed and placed in a beaker, 5 mL of acetonitrile solution was added, and the solid was dissolved using an ultrasonic machine to obtain solution A. 0.1 mmol of 4-amino-1,2,4-triazole (0.0084 g) was weighed and placed in a beaker, 5 mL of ethanol solution was added, and the solid was dissolved using an ultrasonic machine to obtain solution B. Solution A and solution B were mixed and stirred at room temperature for 2 hours to produce a white precipitate. Filtered and washed with water to obtain a white powder sample. The yield was 54.5%.
[0037] The chemical structure of the product prepared in the above embodiment was determined by X-ray single crystal diffraction, X-ray powder diffraction, thermogravimetric analysis and fluorescence characterization to be [Cu4I4(NH2-trz)2], (NH2-trz = 4-amino-1,2,4-triazole).
[0038] (1) Crystal structure determination of Cu(I) coordination polymer
[0039] The results of single crystal diffraction are as follows: molecular weight is 929.94, monoclinic system, P21 / n space group, α=90°, β=104.686(4)°, γ=90°, The spatial structure was solved by SHELXT and drawn by Diamond. The final spatial structure diagram is shown in the attached figure. Figure 2 The crystal data show that the asymmetric unit structure of the complex is composed of four crystallographically dependent Cu(I) ions and four I- plus two organic ligands 4-amino-1,2,4-triazole ( Figure 2 The central ion Cu(I) adopts a four-coordinated mode, forming a slightly distorted tetrahedral configuration. The complex is connected in the bc plane through the Cu(I)-I coordination bond to form a two-dimensional structure ( Figure 3 ).
[0040] (2) Characterization of the purity of Cu(I) coordination polymer single crystals
[0041] Specifically, Figure 4 The XRD pattern of the prepared Cu(I) coordination polymer powder and the XRD pattern of the simulated Cu(I) coordination polymer are clearly shown; it can be seen that the measured spectrum perfectly matches the simulated spectrum, indicating that the prepared Cu(I) coordination polymer has a high purity.
[0042] (3) Characterization of thermal stability of Cu(I) coordination polymers
[0043] Specifically, Figure 5The thermogravimetric curve of the prepared Cu(I) coordination polymer is shown, which shows that it does not lose weight in the range of room temperature to 230°C, indicating its thermal stability. The weight loss is 18% in the range of 230-350°C (corresponding to the loss of two NH2-trz ligands in the coordination polymer); after 500°C, the structure of the coordination polymer is completely decomposed.
[0044] (4) Fluorescence characterization of Cu(I) coordination polymers
[0045] Attached Figure 6 This is a picture of the new Cu(I) complex under fluorescent light and ultraviolet light. It can be seen from the picture that the complex can emit green fluorescence under ultraviolet light. The test was carried out at room temperature using a Japanese Hitachi F-7000 fluorescence spectrophotometer. Figure 7 It can be seen that the solid fluorescence emission peak of the complex is 520nm under an excitation wavelength of 340nm, and it has very good green fluorescence emission performance.
[0046] The embodiments of the present invention are described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions and variations of these embodiments are made without departing from the principles and spirit of the present invention, and still fall within the protection scope of the present invention.
Claims
1. A two-dimensional Cu(I) coordination polymer, characterized in that: The chemical formula of the two-dimensional Cu(I) coordination polymer is: [Cu4I4(NH2-trz)2], wherein NH2-trz is 4-amino-1,2,4-triazole; The two-dimensional Cu(I) coordination polymer is a monoclinic crystal with a space group of P21 / n. The two-dimensional Cu(I) coordination polymer does not lose weight in the range of room temperature to 230°C, and loses weight by less than 20% in the range of 230-350°C. The two-dimensional Cu(I) coordination polymer has a solid fluorescence emission peak of 520nm at an excitation wavelength of 340nm. The preparation method of the two-dimensional Cu(I) coordination polymer comprises the following steps: (1) CuI is dissolved in acetonitrile to obtain solution A; 4-amino-1,2,4-triazole is dissolved in ethanol to obtain solution B; (2) Solution A and solution B are mixed, stirred at room temperature to obtain a precipitate, and the precipitate is filtered, washed, and dried to obtain the two-dimensional Cu(I) coordination polymer.
2. The two-dimensional Cu(I) coordination polymer according to claim 1, characterized in that The single crystal diffraction parameters of the two-dimensional Cu(I) coordination polymer are: α=90°, β=104.686(4)°, γ=90°, 3. The two-dimensional Cu(I) coordination polymer according to claim 1, characterized in that The concentration of the solution A is (0.03-0.05) mol / L.
4. The two-dimensional Cu(I) coordination polymer according to claim 1, characterized in that The concentration of the solution B is (0.01-0.03) mol / L.
5. The two-dimensional Cu(I) coordination polymer according to claim 1, characterized in that In step (2), the stirring time at room temperature is 1.5-2.5h.