A high-stability zero-dimensional organic-inorganic hybrid manganese metal halide and a preparation method thereof

Abstract

The application discloses a kind of high stability zero-dimensional organic-inorganic hybrid manganese metal halide and preparation method thereof, it is related to photoelectric material technical field. Including the following steps: synthesis of polyaromatic ring triazine derivative;The polyaromatic ring triazine derivative is six (diphenyl amino) triazine, recorded as TNZ-3;Polyaromatic ring triazine derivative is dissolved in aqueous hydrobromic acid, add organic solvent and manganese source, slowly evaporate solvent method growth single crystal, obtain (TNZ-3) 2MnBr4, the structural formula of product is shown in specification.The zero-dimensional organic-inorganic hybrid manganese metal halide of the application has excellent stability, high luminous performance, optimized crystal structure and excellent practical performance.

Description

Technical Field

[0001] This invention relates to the field of optoelectronic materials technology, and more specifically, to a highly stable zero-dimensional organic-inorganic hybrid manganese metal halide and its preparation method. Background Technology

[0002] Organic-inorganic metal halides (OIMHs) have shown great potential in fields such as light-emitting diodes (LEDs), X-ray imaging, anti-counterfeiting, and solar cells due to their excellent photoelectric properties. However, lead-based perovskites suffer from heavy metal toxicity and poor hygrothermal stability, which limits their commercialization.

[0003] To address the toxicity issue, researchers have attempted to replace lead with low-toxicity or non-toxic metal ions such as Mn(II), Cu(I), and Bi(II), but most metal halides are still prone to decomposition in humid environments, and the stability problem has not been fundamentally solved.

[0004] Zero-dimensional organic-inorganic metal halides (OIMHs) have attracted much attention due to their strong quantum confinement effect and high exciton binding energy. Among them, manganese-based materials are characterized by low toxicity and rich coordination chemistry, and their luminescence color can be regulated by the coordination environment. However, existing manganese-based OIMHs generally suffer from high hygroscopicity and poor thermal stability. They are extremely prone to deliquescence or hydrolysis in water and oxygen environments, leading to a rapid decay of luminescence performance and seriously hindering their practical applications.

[0005] In existing technologies, although long-chain alkyl or aromatic groups are introduced to enhance hydrophobicity, it is often difficult to achieve both high luminous efficiency and long-term stability.

[0006] Therefore, developing organic-inorganic hybrid manganese metal halides that combine high humidity stability, high thermal stability, and high luminescence performance is a technical challenge that urgently needs to be solved. Summary of the Invention

[0007] The present invention aims to overcome the defects of poor stability, easy hydrolysis and low quantum yield of organic-inorganic hybrid manganese metal halides in the prior art, and to provide a zero-dimensional manganese-based metal halide material with high humidity stability, high thermal stability and efficient green luminescence and its preparation method.

[0008] In view of this, the present invention provides a highly stable zero-dimensional organic-inorganic hybrid manganese metal halide and its preparation method.

[0009] A method for preparing highly stable zero-dimensional organic-inorganic hybrid manganese metal halides includes the following steps: (1) Synthesize a polyaromatic cyclic triazine derivative; the polyaromatic cyclic triazine derivative is hexa(diphenylamino)triazine, denoted as TNZ-3; (2) Dissolve the polyaromatic triazine derivative in an aqueous solution of hydrobromic acid, add an organic solvent and a manganese source, and grow a single crystal by slow solvent evaporation to obtain the zero-dimensional organic-inorganic hybrid manganese metal halide. The zero-dimensional organic-inorganic hybrid manganese metal halide is (TNZ-3)2MnBr4; The synthesis method of TNZ-3 includes the following steps: mixing diphenylamine and melamine chloride and heating, stirring continuously while maintaining the temperature, then cooling, adding deionized water, cooling the mixture to room temperature for crystallization, washing repeatedly with ethanol 3 times, and finally drying to obtain TNZ-3.

[0010] Further, in step (1), the synthesis method of TNZ-3 includes the following steps: 43.3 mmol diphenylamine and 5.4 mmol melamine chloride are mixed and heated to 185°C, kept at the temperature and stirred continuously for 2 hours, then cooled to 140°C, deionized water is added, the mixture is cooled to room temperature for crystallization, washed repeatedly with ethanol 3 times, and finally dried in a vacuum oven at 60°C for 1 hour to obtain TNZ-3.

[0011] Further, the specific steps of step (2) are as follows: 0.077 mmol TNZ-3 and 0.7 mmol manganese bromide tetrahydrate are dissolved in 9 mL of 48wt% hydrobromic acid aqueous solution and 28 mL of methanol. The solution is stirred at 100°C until a clear solution is formed. The solution is filtered through a polyethersulfone filter with a pore size of 0.45 μm. The filtrate is heated at 50°C to evaporate the solvent. After three days, a crystal precipitate forms at the bottom of the solution. Finally, it is collected by vacuum filtration to obtain (TNZ-3)2MnBr4.

[0012] The present invention also provides a highly stable zero-dimensional organic-inorganic hybrid manganese metal halide prepared by the preparation method described above.

[0013] Furthermore, the (TNZ-3)2MnBr4 belongs to the tetragonal crystal system with space group I-42d.

[0014] Compared with the prior art, the present invention has the following beneficial effects: 1. Excellent stability: By introducing a sterically hindered, rigid polyaromatic triazine derivative cation (TNZ-3), in inorganic [MnBr4]... 2- An effective hydrophobic protective layer was constructed around the luminescent center. Among them, the (TNZ-3)2MnBr4 powder maintained stable crystal structure and fluorescence performance after being exposed to 70% relative humidity for 30 days, and its thermal decomposition temperature reached as high as 280℃, which is far superior to traditional organic-inorganic hybrid manganese metal halides.

[0015] 2. High luminescence performance: The strong quantum confinement effect generated by the zero-dimensional structure enables the material to have efficient intrinsic luminescence. The photoluminescence quantum yield (PLQY) of (TNZ-3)2MnBr4 reaches 33.11%, with the emission peak located at 516 nm, exhibiting bright green light.

[0016] 3. Optimized crystal structure: The large-volume rigid cation effectively weakens the hydrogen bonding interactions between organic and inorganic components, reducing the [MnBr4] content. 2- The tetrahedral structural distortion suppresses nonradiative recombination and improves luminescence efficiency. Attached Figure Description

[0017] Figure 1 This is the structural formula of the organic ligand TNZ-3 synthesized in this invention.

[0018] Figure 2 The structure of the organic ligand (TNZ-3)2MnBr4 synthesized in this invention is shown.

[0019] Figure 3 This is a schematic diagram illustrating the synthesis of the organic ligand TNZ-3 of this invention.

[0020] Figure 4 This is a schematic diagram of the synthesis of the (TNZ-3)2MnBr4 crystal of the present invention.

[0021] Figure 5 This is a structural diagram of the (TNZ-3)2MnBr4 crystal of the present invention.

[0022] Figure 6 These are the experimental powder XRD and crystal XRD patterns of (TNZ-3)2MnBr4 of this invention.

[0023] Figure 7 This is the fluorescence spectrum (emission / excitation) of the (TNZ-3)2MnBr4 powder of the present invention.

[0024] Figure 8 This is a quantum yield test chart of the (TNZ-3)2MnBr4 powder of the present invention, with an absolute quantum yield of 33.11%.

[0025] Figure 9 Figure a) shows a comparison of the (TNZ-3)2MnBr4 powder of this invention after being kept at 70% humidity for 30 days, and the fluorescence emission spectra before and after the test. The fluorescence emission peak positions did not change, indicating that the material properties are stable. Figure b) shows the comparison of the (TNZ-3)2MnBr4 powder of this invention after being kept at 70% humidity for 30 days.

[0026] Figure 10 The XRD patterns of the (TNZ-3)2MnBr4 powder of this invention were tested at multiple time points over 30 days at 70% humidity. The XRD patterns showed almost no change, indicating that the material is stable under high humidity conditions.

[0027] Figure 11 The XRD patterns of the (TNZ-3)2MnBr4 powder of this invention were tested at multiple time points over 30 days at 100℃. The XRD patterns showed almost no change, indicating that the material is stable under high temperature conditions.

[0028] Figure 12 This is a thermogravimetric analysis result of the (TNZ-3)2MnBr4 powder of the present invention. The decomposition temperature is 280℃, indicating that it has high temperature resistance. Detailed Implementation

[0029] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Example

[0030] A method for preparing zero-dimensional organic-inorganic hybrid manganese metal halides includes the following steps: (1) The synthesis method of TNZ-3 includes the following steps: 43.3 mmol of diphenylamine and 5.4 mmol of cyanuric chloride are mixed and heated to 185°C, and stirred continuously for 2 hours. Then, the mixture is cooled to 140°C, deionized water is added, and the mixture is cooled to room temperature for crystallization. The mixture is washed three times with ethanol, and finally dried in a vacuum oven at 60°C for 1 hour to obtain TNZ-3. The structure of TNZ-3 is as follows: Its crystal structure was confirmed to be in space group R-3c by single-crystal X-ray diffraction. The molecule has a rigid, gear-like structure and exhibits remarkable room-temperature phosphorescence properties (afterglow of about 1 second).

[0031] (2) 0.077 mmol TNZ-3 and 0.7 mmol manganese bromide tetrahydrate were dissolved in 9 mL of 48 wt% hydrobromic acid aqueous solution and 28 mL of methanol. The solution was stirred at 100 °C until a clear solution was formed. The solution was filtered through a 0.45 μm polyethersulfone filter. The solvent in the filtrate was evaporated by heating at 50 °C. After three days, a crystal precipitate formed at the bottom of the solution. The precipitate was collected by vacuum filtration to obtain (TNZ-3)2MnBr4 single crystals. The structural formula of (TNZ-3)2MnBr4 is shown in [reference needed]. Figure 2 (TNZ-3)₂MnBr₄ belongs to the tetragonal crystal system, space group I-42d. It contains isolated [MnBr₄] crystals. 2- Tetrahedral with Mn-Mn spacing of 10.5916 Å.

[0032] Performance testing: 1. The (TNZ-3)2MnBr4 single crystal obtained in Example 1 was ground into a fine powder. Humidity stability testing was performed: the (TNZ-3)2MnBr4 powder was placed in an environment with 70% relative humidity for 30 days, and its XRD pattern was basically consistent with the initial state. Figure 10 The fluorescence intensity retention rate exceeds 90%. Figure 10 ).

[0033] 2. The (TNZ-3)2MnBr4 single crystal obtained in Example 1 was ground into fine powder. Thermal stability testing was performed: the (TNZ-3)2MnBr4 powder was placed in a high-temperature environment of 100℃ for 30 days, and its XRD pattern was basically consistent with the initial state. Figure 11 ).

[0034] 3. The (TNZ-3)2MnBr4 single crystal obtained in Example 1 was ground into a fine powder. Thermogravimetric analysis showed that its material decomposition temperature was 280℃, indicating high-temperature resistance. Figure 12 ).

[0035] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing highly stable zero-dimensional organic-inorganic hybrid manganese metal halides, characterized in that, Includes the following steps: (1) Synthesize a polyaromatic cyclic triazine derivative; the polyaromatic cyclic triazine derivative is hexa(diphenylamino)triazine, denoted as TNZ-3; (2) Dissolve the polyaromatic triazine derivative in an aqueous solution of hydrobromic acid, add an organic solvent and a manganese source, and grow a single crystal by slow solvent evaporation to obtain the zero-dimensional organic-inorganic hybrid manganese metal halide. The zero-dimensional organic-inorganic hybrid manganese metal halide is (TNZ-3)2MnBr4; The synthesis method of TNZ-3 includes the following steps: mixing diphenylamine and melamine chloride and heating, stirring continuously while maintaining the temperature, then cooling, adding deionized water, cooling the mixture to room temperature for crystallization, washing repeatedly with ethanol three times, and finally drying to obtain TNZ-3.

2. The method for preparing a highly stable zero-dimensional organic-inorganic hybrid manganese metal halide according to claim 1, characterized in that, In step (1), the synthesis method of TNZ-3 includes the following steps: 43.3 mmol diphenylamine and 5.4 mmol melamine chloride are mixed and heated to 185°C, kept at the temperature and stirred continuously for 2 hours, then cooled to 140°C, deionized water is added, the mixture is cooled to room temperature for crystallization, washed repeatedly with ethanol 3 times, and finally dried in a vacuum oven at 60°C for 1 hour to obtain TNZ-3.

3. The method for preparing a highly stable zero-dimensional organic-inorganic hybrid manganese metal halide according to claim 1, characterized in that, The specific steps of step (2) are as follows: 0.077 mmol TNZ-3 and 0.7 mmol manganese bromide tetrahydrate were dissolved in 9 mL of 48wt% hydrobromic acid aqueous solution and 28 mL of methanol. The solution was stirred at 100℃ until a clear solution was formed. The solution was filtered through a polyethersulfone filter with a pore size of 0.45 μm. The solvent was evaporated by heating the filtrate at 50℃. After three days, a crystal precipitate was formed at the bottom of the solution. The precipitate was finally collected by vacuum filtration to obtain (TNZ-3)2MnBr4.

4. A highly stable zero-dimensional organic-inorganic hybrid manganese metal halide prepared by the preparation method according to any one of claims 1-3.

5. The highly stable zero-dimensional organic-inorganic hybrid manganese metal halide according to claim 4, characterized in that, The (TNZ-3)2MnBr4 belongs to the tetragonal crystal system and has a space group of I-42d.

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