Mechanoluminescent hybrid crystal material

Abstract

The invention provides a mechanoluminescent hybrid crystal material, the mechanoluminescent hybrid crystal material is an organic-inorganic hybrid crystal formed by manganese halide and alkyl triphenyl phosphine halide, and the hybrid crystal material contains a chlorine element and a bromine element at the same time; wherein the hybrid crystal material can generate visible light emission under the action of mechanical external force. According to the invention, a hybrid crystal material formed by manganese halide and specific organic molecules is prepared, so that the obtained material can generate mechanoluminescence under the action of external force; meanwhile, by adjusting the halogen composition in the crystal and the proportion thereof, the luminous efficiency of nearly 100% can be realized, and higher stability of the material is ensured.

Description

Technical Field

[0001] This invention belongs to the field of mechanoluminescent materials technology, and particularly relates to a mechanoluminescent hybrid crystal material. Background Technology

[0002] Methocynical materials are a class of functional materials that can directly convert mechanical energy into visible light radiation when subjected to mechanical forces such as compression, friction, and impact. They have broad application prospects in passive visual sensing, smart wearable devices, structural health monitoring, information security, and dynamic anti-counterfeiting. Compared with traditional light-emitting systems that rely on external power sources or light sources, methocynical materials have advantages such as requiring no external energy, intuitive response, and relatively simple structure, and have attracted widespread attention in recent years.

[0003] Existing mechanoluminescent materials can be mainly classified into inorganic mechanoluminescent materials, organic mechanoluminescent materials, and organic-inorganic composite mechanoluminescent materials according to their composition. Among them, inorganic mechanoluminescent materials, such as sulfide systems, aluminate systems, and some oxide systems, generally have good environmental stability, but their preparation process often requires high-temperature sintering or complex doping processes, resulting in high energy consumption and significant difficulties in material processing and device integration. Near-infrared garnet-based inorganic materials, for example, can achieve a luminescence efficiency of approximately 25%. Organic mechanoluminescent materials typically rely on molecular conformational changes or aggregation-induced emission effects. Their preparation conditions are relatively mild, but they generally suffer from low luminescence efficiency and insufficient environmental stability, limiting their practical applications. Even the more efficient metal-organic complex systems typically only achieve about 10% luminescence. Meanwhile, the crystallization behavior and the influence of the crystallization process on the luminescence performance of existing organic-inorganic hybrid mechanoluminescent materials still lack systematic research, and the material compositions are mostly concentrated in a few known systems.

[0004] Therefore, there is an urgent need to provide a mechanoluminescent material with controllable composition, stable structure, and high luminous efficiency, whose composition differs from known systems. By introducing a rationally designed organic-inorganic hybrid crystal structure at the material level, the luminescent properties of manganese halides can be effectively controlled, thereby obtaining a material with excellent mechanoluminescence response and environmental stability under mechanical forces to meet practical application requirements. Summary of the Invention

[0005] The purpose of this invention is to provide a mechanoluminescent hybrid crystal material. By preparing a hybrid crystal material formed by manganese halides and specific organic molecules, the resulting material can generate mechanoluminescence under external force. At the same time, by adjusting the halogen composition and ratio in the crystal, a luminous efficiency of nearly 100% can be achieved, while ensuring that the material has high stability.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is: a mechanoluminescent hybrid crystal material, wherein the mechanoluminescent hybrid crystal material is an organic-inorganic hybrid crystal formed by manganese halide and alkyltriphenylphosphine halide, and the hybrid crystal material contains both chlorine and bromine elements; The hybrid crystal material can emit visible light when subjected to mechanical force.

[0007] Furthermore, the manganese halide includes one or both of manganese chloride and manganese bromide.

[0008] Furthermore, the alkyltriphenylphosphine halide includes one or more of methyltriphenylphosphine chloride, ethyltriphenylphosphine chloride, methyltriphenylphosphine bromide, or ethyltriphenylphosphine bromide.

[0009] Furthermore, the mechanical external force includes at least one of compression, friction, or impact.

[0010] Furthermore, the molar ratio of chlorine to bromine in the hybrid crystal material is (1-7):1.

[0011] Furthermore, the molar ratio of the manganese halide to the alkyltriphenyl phosphine halide is 1:(2-2.1).

[0012] Those skilled in the art can adjust the molar ratio of the manganese halide to the alkyltriphenylphosphine halide according to the selected crystallization method to meet the crystallization requirements under different process conditions. For example, when using solution crystallization, the molar ratio of the manganese halide to the alkyltriphenylphosphine halide is preferably 1:2; when using high-temperature melt-cooling crystallization, the molar ratio of the manganese halide to the alkyltriphenylphosphine halide is preferably 1:(2-2.1) to provide a relatively higher proportion of alkyltriphenylphosphine halide, which is not only beneficial for reducing the melting temperature but also for the formation of the target crystal.

[0013] Furthermore, the hybrid crystal material is a crystal material formed by supersaturation crystallization in a solution system. Its preparation methods include, but are not limited to, the following examples: A mechanoluminescent hybrid crystal material, comprising the following preparation steps: Manganese halides and alkyltriphenylphosphine halides are dissolved in a polar solvent to form a homogeneous solution; by controlling the supersaturation state of the solution, supersaturated crystallization is induced in the system to obtain a hybrid crystalline material. The hybrid crystal material can produce mechanoluminescence under the action of external force.

[0014] In other embodiments, the polar solvent includes one of N,N-dimethylformamide, acetonitrile, or ethanol.

[0015] In other embodiments, the dissolution method includes one of heating dissolution, magnetic stirring dissolution, heating and magnetic stirring dissolution, or ultrasonic dissolution. The temperature of the heating dissolution does not exceed 100°C.

[0016] Furthermore, the hybrid crystal material is a crystal material formed by cooling and crystallizing in a molten system. Its preparation methods include, but are not limited to, the following examples: A mechanoluminescent hybrid crystal material, comprising the following preparation steps: Manganese halide was mixed with alkyltriphenylphosphine halide to obtain a mixture; The mixture is subjected to high-temperature melting treatment to form a homogeneous molten system; The molten system was cooled to obtain an organic-inorganic hybrid manganese halide solid material with mechanoluminescence properties; The temperature of the high-temperature melting treatment is 220–270°C.

[0017] Furthermore, the supersaturated crystallization method includes at least one of the following: Introducing nonpolar solvents into the solution system to induce crystallization, or inducing crystallization through solvent evaporation.

[0018] The beneficial effects of this invention are mainly reflected in the following: This invention provides an organic-inorganic hybrid crystal material composed of manganese halides and a specific organic molecule, alkyltriphenylphosphine halide. In the mechanoluminescent hybrid crystal material of this invention, by introducing different halogens and controlling the halogen composition and ratio, the coordination environment and crystal structure characteristics of manganese ions can be effectively adjusted, thereby achieving precise control over the material's emission performance and luminescence efficiency. Under appropriate halogen composition conditions, the material can achieve a near 100% luminescence quantum yield, exhibiting excellent mechanoluminescence performance.

[0019] Furthermore, the hybrid crystal material described in this invention can produce a stable and repeatable mechanoluminescence response when subjected to mechanical forces such as compression, friction, or impact, exhibiting good mechanical response consistency and luminescence stability. After being placed in an air environment for a prolonged period, the fluorescence quantum yield of this material remains essentially unchanged, indicating its good environmental stability.

[0020] In summary, this invention achieves a harmonious balance between high luminous efficiency, high stability, and excellent mechanoluminescence response by rationally designing an organic-inorganic hybrid crystal material formed from manganese halides and alkyltriphenylphosphine halides. The material has promising applications in fields such as mechanoluminescence displays, stress sensing, anti-counterfeiting labels, and structural health monitoring. Attached Figure Description

[0021] Figure 1The image shows the actual mechanoluminescent material of the green crystal obtained in Example 1 of this invention. Figure 2 This is a photograph of the green crystal mechanoluminescent material obtained in Example 1 of the present invention emitting light when subjected to mechanical external force; Figure 3 The mechanoluminescence spectrum of the green crystal obtained in Example 2 of this invention; Figure 4 This is a comparison of the emission spectra of crystal materials with different chlorine-bromine ratios in this invention; Figure 5 This is a comparison chart of the fluorescence quantum yield of crystal materials with different chlorine-bromine ratios in this invention; Figure 6 The emission spectra of the organic-inorganic hybrid manganese halide solid material obtained in Example 9 of this invention at different excitation wavelengths; Figure 7 The emission spectra of the green crystal obtained in Comparative Example 1 of this invention at different excitation wavelengths are shown. Figure 8 This is the mechanoluminescence spectrum of the green crystal obtained in Comparative Example 2 of this invention. Detailed Implementation

[0022] To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0023] Example 1: 1 mmol of manganese chloride and 2 mmol of ethyltriphenylphosphine bromide were mixed and 2 mL of acetonitrile was added. The reaction system was magnetically stirred at 60 °C to ensure complete dissolution of the reactants. The reaction was stopped, and after the temperature of the reaction system cooled to room temperature, the solution was filtered, allowing the acetonitrile to evaporate naturally and gradually precipitate green crystals with mechanoluminescence properties. The emission peak of the green crystal was located at 523 nm, with a quantum yield of 92.4%, and the quantum yield was 92.3% after being exposed to air for one month.

[0024] Example 2: Mix 2 mmol of manganese bromide and 4 mmol of ethyltriphenylphosphine chloride, then add 4 mL of acetonitrile. Heat the reaction system at 60 °C to fully dissolve the reactants. Stop heating and allow the reaction system to cool to room temperature. Filter the solution, allowing the acetonitrile to evaporate naturally, gradually precipitating green crystals with mechanoluminescent properties. Figure 3 As shown, the mechanoluminescence peak of the green crystal is located at 523 nm.

[0025] Example 3: 1 mmol manganese chloride, 1 mmol manganese bromide, 2 mmol ethyltriphenylphosphine chloride, and 2 mmol ethyltriphenylphosphine bromide were mixed and 6 mL acetonitrile was added. The reaction system was sonicated to ensure complete dissolution of the reactants. After sonication, the bottle was opened to allow the ethanol to evaporate naturally, and green crystals with mechanoluminescence properties were gradually precipitated. The emission peak of the green crystals was located at 523 nm, and the quantum yield was 99.4%.

[0026] Example 4: Mix 2 mmol manganese chloride, 2 mmol methyltriphenylphosphine chloride and 2 mmol ethyltriphenylphosphine bromide, and add 6 mL N,N-dimethylformamide; stir the reaction system magnetically at 100 °C to fully dissolve the reactants; stop the reaction, and after the temperature of the reaction system drops to room temperature, filter the solution and accelerate the precipitation of green crystals with mechanoluminescence properties through diffusion in diethyl ether.

[0027] Example 5: 2 mmol of manganese chloride, 3 mmol of ethyltriphenylphosphine chloride, and 1 mmol of ethyltriphenylphosphine bromide were mixed and 4 mL of acetonitrile was added. The reaction system was heated at 60 °C to fully dissolve the reactants. Heating was stopped, and after the reaction system cooled to room temperature, the solution was filtered, allowing the acetonitrile to evaporate naturally and gradually precipitate green crystals with mechanoluminescence properties. The emission peak of the green crystals was located at 523 nm.

[0028] Example 6: 2 mmol of manganese chloride, 3 mmol of methyltriphenylphosphine chloride, and 1 mmol of methyltriphenylphosphine bromide were mixed and 6 mL of acetonitrile was added. The reaction system was magnetically stirred at 60 °C to ensure complete dissolution of the reactants. The reaction was stopped, and after the temperature of the reaction system cooled to room temperature, the solution was filtered, allowing the acetonitrile to evaporate naturally and gradually precipitate green crystals with mechanoluminescence properties. The emission peak of the green crystals was located at 512 nm.

[0029] Example 7: The difference from Example 3 is that the molar ratio of chlorine to bromine in the hybrid crystal material is changed by altering the amount of manganese chloride, manganese bromide, ethyltriphenylphosphine chloride, and ethyltriphenylphosphine bromide added.

[0030] like Figure 4 The image shows a comparison of the emission spectra of crystalline materials with different chlorobromine ratios, as shown below. Figure 5 The figure shows a comparison of the fluorescence quantum yield of crystal materials with different chlorobromine ratios.

[0031] Example 8: The difference from Examples 1-7 is that the hybrid crystalline material is obtained through a molten system.

[0032] 2 mmol of manganese chloride and 4 mmol of ethyltriphenylphosphine bromide were mixed and heated to 270 °C at a heating rate of 10 °C / min. After the reaction was complete, the heating was stopped and the mixture was rapidly cooled using a graphite mold to obtain an organic-inorganic hybrid manganese halide solid material with mechanoluminescence properties.

[0033] Example 9: 2 mmol of manganese bromide and 4.2 mmol of ethyltriphenylphosphine chloride were mixed and heated to 220 °C at a heating rate of 5 °C / min. After the reaction was complete, heating was stopped, and the mixture was allowed to cool naturally to obtain an opaque solid material of organic-inorganic hybrid manganese halide with mechanoluminescent properties. Figure 6 The figure shows the emission peaks of the solid material at different excitation wavelengths.

[0034] Examples 8-9 of this invention demonstrate the preparation of mechanoluminescent materials by directly melting manganese halide and alkyltriphenylphosphine halide within a specific temperature range and then cooling and solidifying them. Compared with the solvent crystallization process in Examples 1-7, this method avoids the use of organic solvents, significantly simplifies the process, reduces the requirements for environmental safety and solvent handling, and provides a feasible technical approach for the industrial-scale preparation of mechanoluminescent materials.

[0035] Comparative Example 1: Mix 1 mmol of manganese chloride and 2 mmol of methyltriphenylphosphine chloride, and add 4 mL of N,N-dimethylformamide; stir the reaction system magnetically at 100 °C to ensure complete dissolution of the reactants; stop the reaction, and after the reaction system cools to room temperature, filter the solution and accelerate the precipitation of green crystals with mechanoluminescence properties through diffusion in diethyl ether. Figure 7 As shown, the emission peak of the green crystal is located at 512 nm.

[0036] Comparative Example 2: Mix 1 mmol of manganese chloride and 2 mmol of ethyltriphenylphosphine chloride, and add 3 mL of ethanol; stir the reaction system magnetically at 50 °C to ensure complete dissolution of the reactants; stop the reaction, and after the reaction system cools to room temperature, filter the solution, allowing the ethanol to evaporate naturally, and gradually precipitate green crystals with mechanoluminescent properties. Figure 8 As shown, the mechanoluminescence peak of the green crystal is located at 523 nm.

[0037] It needs to be explained that: Figure 7 It is a emission spectrum, used to show the position of its emission peak.

[0038] Figure 3 , Figure 8The image shown is a mechanoluminescence spectrum. The mechanoluminescence spectrum presented in this application is the emission spectrum of the material acquired under the action of mechanical external force, used to characterize the luminescence behavior of the mechanoluminescent hybrid crystal material under external force stimulation.

[0039] In the specific testing process, the mechanoluminescent hybrid crystal material is placed on the test platform, and a mechanical external force is applied to the sample surface by a grinding rod in a scratching manner, so that the material generates mechanoluminescence during the force process; at the same time, an optical fiber probe is used to collect the emitted light generated by the sample at the moment of force, and the collected light signal is transmitted to the spectral acquisition system to obtain the corresponding mechanoluminescence emission spectrum.

[0040] It should be understood that the abrasive rod rubbing is merely one example of applying mechanical force, its function being to provide the sample with mechanical stimulation sufficient to induce mechanoluminescence; the fiber optic acquisition method is used to achieve rapid and stable acquisition of the emitted light signal. The spectrum obtained through the above method can accurately reflect the luminescence characteristics of the material under the action of mechanical force, including information such as the position and relative intensity of the emission peak.

[0041] The present invention has been illustrated with the above embodiments to explain the detailed preparation method of the present invention. However, the present invention is not limited to the above detailed preparation method, that is, it does not mean that the present invention must rely on the above product and detailed preparation method to be implemented. Those skilled in the art should understand that any improvement to the present invention, or the combination or equivalent substitution of the raw materials of the present invention, falls within the protection scope and disclosure scope of the present invention.

Claims

1. A mechanoluminescent hybrid crystal material, characterized in that, The mechanoluminescent hybrid crystal material is an organic-inorganic hybrid crystal formed by manganese halide and alkyltriphenylphosphine halide, and the hybrid crystal material contains both chlorine and bromine elements. The hybrid crystal material can emit visible light when subjected to mechanical force.

2. The mechanoluminescent hybrid crystal material according to claim 1, characterized in that, The manganese halide includes one or both of manganese chloride and manganese bromide.

3. The mechanoluminescent hybrid crystal material according to claim 1, characterized in that, The alkyltriphenylphosphine halide includes one or more of methyltriphenylphosphine chloride, ethyltriphenylphosphine chloride, methyltriphenylphosphine bromide, or ethyltriphenylphosphine bromide.

4. The mechanoluminescent hybrid crystal material according to claim 1, characterized in that, The mechanical external force includes at least one of compression, friction, or impact.

5. The mechanoluminescent hybrid crystal material according to claim 1, characterized in that, The molar ratio of chlorine to bromine in the hybrid crystal material is (1-7):

1.

6. The mechanoluminescent hybrid crystal material according to claim 1, characterized in that, The molar ratio of the manganese halide to the alkyltriphenyl phosphine halide is 1:(2-2.1).

7. A mechanoluminescent hybrid crystal material according to any one of claims 1 to 6, characterized in that, The hybrid crystal material is a crystal material formed by supersaturation crystallization in a solution system.

8. A mechanoluminescent hybrid crystal material according to any one of claims 1 to 6, characterized in that, The hybrid crystal material is a crystal material formed by cooling and crystallizing in a molten system.

9. A mechanoluminescent hybrid crystal material according to claim 7, characterized in that, The supersaturated crystallization method includes at least one of the following: Introducing nonpolar solvents into the solution system to induce crystallization, or inducing crystallization through solvent evaporation.

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