Solvent response optical crystal and preparation method and application thereof

Abstract

The invention belongs to the technical field, and particularly discloses a solvent response optical crystal as well as a preparation method and application thereof. The crystal is of a novel structure with a molecular formula of C30H48Cl9N3Sb2 and belongs to a monoclinic system, the space group is P21 / c, the cell parameters are as follows: a = 9.2515 (6), b = 25.738 (2), c = 17.5757 (14), alpha = 90 degrees, beta = 92.463 (2) degrees and gamma = 90 degrees, and when the crystal is in contact with solvent molecules with different polarities, different luminous color changes are shown. The relationship between the emission peak tuning of the crystal material and the solvent polarity can be divided into three types: the luminescence color is almost unchanged in a weak polar solvent; carrying out luminescence red shift in a moderate polar solvent; the strong polar solvent quenches luminescence. Meanwhile, the material also shows excellent cyclicity, and is expected to be applied to anti-counterfeiting, information security, information encryption and solvent detection directions.

Description

Technical Field

[0001] This invention belongs to the field of intelligent luminescent materials technology, specifically relating to a solvent-responsive optical crystal, its preparation method, and its application. Background Technology

[0002] Intelligent responsive luminescent materials exhibit controllable tunability in their luminescence properties, such as intensity, position, or photoluminescence lifetime, under external stimuli (light, heat, solvent molecules, pressure, pH, X-ray radiation, etc.), attracting widespread attention in fields such as optical thermometry, solvent detection, information security, and information storage. Among these, solvogenetic luminescent materials have garnered significant interest due to their advantages in visualization, specific response, and low cost. Solvent molecules can induce phase transformations, changes in coordination number at luminescent centers, and variations in local lattice volume in luminescent materials, thereby significantly altering the luminescence position and intensity.

[0003] Organic-inorganic hybrid metal halides possess advantages such as simple synthesis methods and high structural tunability. These materials can be classified into three main categories at the molecular level: two-dimensional, one-dimensional, and zero-dimensional (OD) structures. The highly localized excited states of OD organic-inorganic hybrid metal halides lead to strong electron-phonon coupling interactions, resulting in highly efficient emission. In particular, those with 5s... 2 Lone-pair configurations of 0D hybrid antimony halides are strong candidates due to their stereochemical reactivity, soft structure, and the stereochemical influence of the metal coordination environment. Furthermore, 0D hybrid antimony halides possess a variety of coordination configurations (e.g., [SbX5]). 2- [SbX6] 3- and dimer [Sb2X8] 2- With its unique advantages such as diverse structures and susceptibility to soft lattice structures, its luminescence can be significantly modulated from green light to near-infrared light.

[0004] Although solvent-responsive phenomena are frequently reported in hybrid metal halides, research in this field is still in its early stages of development and exploration. Most reported solvent-responsive materials rarely exhibit multimode photoluminescence in response to external changes. Furthermore, the intrinsic solvochromic mechanisms underlying solvent selection, structure, and luminescence changes remain unclear. Therefore, developing hybrid smart responsive luminescent materials with multiple response modes and good cycling performance is of great significance. Summary of the Invention

[0005] The purpose of this invention is to address the above-mentioned shortcomings of the prior art by providing a solvent-responsive optical crystal, its preparation method, and its applications. By changing the polarity of the solvent, the luminescence performance of the solvent-responsive optical crystal changes accordingly, and it can be applied to fields such as anti-counterfeiting, information security encryption, and solvent monitoring.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: The first objective of this invention is to provide a solvent-responsive optical crystal, wherein the molecular formula of the solvent-responsive optical crystal is C0. 30 H 48 Cl9N3Sb2 has the following cell parameters: a = 9.2515(6) Å, b = 25.738(2) Å, c = 17.5757(14) Å, α = 90°, β = 92.463(2)°, γ = 90°. The crystal structure of the solvent-responsive optical crystal belongs to the monoclinic system, and the space group is [missing information]. P2 1 / c .

[0007] Furthermore, the inorganic framework portion of the solvent-responsive optical crystal consists of isolated [Sb₂Cl₉] particles. 3- Composed of dimers, with Sb 3+ Centered on a [SbCl5] 2- A square pyramid and a [SbCl6] 3- Octahedrons are connected by edge sharing, and organic cations interact through hydrogen bonds and Coulomb forces around the inorganic framework.

[0008] Furthermore, the organic cation is a benzyltrimethylammonium cation with the structure of Formula 1: Formula 1.

[0009] According to the present invention, the solvent-responsive optical crystal has excellent luminescence properties and solvent-responsive properties.

[0010] Furthermore, the solvent-responsive optical crystal exhibits a redshift in emission under neutral polarity, and the Et(30) polarity parameter of the neutral polarity solvent ranges from 45.6 to 51.9.

[0011] A second objective of this invention is to provide a method for preparing the above-mentioned solvent-responsive optical crystal, comprising the following steps: S1. Antimony trichloride and benzyltrimethylammonium chloride are dissolved in methanol, heated and stirred to obtain a colorless, transparent, and clear solution, which is then cooled to room temperature and evaporated to obtain rod-shaped single crystals; the mass molar ratio of antimony trichloride and benzyltrimethylammonium chloride is 1:(1.5~3). S2. The single crystal sample is washed multiple times with a specific solvent and dried to remove solvent molecules, finally obtaining an organic-inorganic hybrid antimony halide single crystal, which is the solvent-responsive optical crystal.

[0012] Furthermore, the heating and stirring temperature is 50~60℃, and the stirring time is 20~30 min.

[0013] Furthermore, in step S2, the washing solvent is n-hexane or cyclohexane.

[0014] Furthermore, in step S2, the drying temperature is 60~70℃ and the drying time is 3~7 days.

[0015] A third objective of this invention is to provide another method for preparing the solvent-responsive optical crystal described above, wherein antimony trichloride and benzyltrimethylammonium chloride are mixed in a mass molar ratio of 1:(1.5~3) and ground to obtain the solvent-responsive optical crystal.

[0016] Furthermore, the grinding time is 20-30 minutes.

[0017] A fourth objective of this invention is to provide an application of the solvent-responsive optical crystal described above, characterized in that the solvent-responsive optical crystal is used to prepare anti-counterfeiting devices, information security encryption devices, and solvent detection devices.

[0018] Compared with the prior art, the beneficial effects of the present invention are: (1) This invention provides a molecular formula C 30 H 48 A novel solvent-responsive optical crystal with the structure Cl9N3Sb2, belonging to the monoclinic crystal system and space group [missing information]. P twenty one / c The crystal has unit cell parameters a = 9.2515(6) Å, b = 25.738(2) Å, c = 17.5757(14) Å, α = 90°, β = 92.463(2)°, γ = 90°. Under 344 nm UV excitation, this crystal exhibits bright broadband yellow-green emission (560 nm), a full width at half maximum (FWHM) of 132 nm, and a fluorescence quantum efficiency of 81%. It also exhibits different solvent responses with solvents of different polarities. The empirical parameter E for solvent polarity is used. T (30) Classification by solvent polarity: This material is classified with weakly polar solvents (E... T (30) < 38.9) The luminescent color hardly changed after the response; with a neutral polar solvent (45.6) <E T (30) < 51.9) emission redshift; with strongly polar small molecule solvents (E T (30)>51.9) The luminescence quenches upon contact.

[0019] (2) This invention unexpectedly discovered that upon response to moderately polar solvents (such as ethanol, n-propanol, isopropanol, etc.), the emission color immediately changes from yellow-green to orange-red (670 nm). Subsequently, heating causes solvent desorption, and the emission color changes from orange-red to yellow (600 nm). After being placed in air, the emission color of the sample gradually changes from yellow to yellow-green. These four solvent-induced emission modulation modes are rarely reported in existing studies. However, upon response to strongly polar small molecule solvents (such as water, methanol, etc.), the yellow-green emission immediately quenches, and after heating causes solvent desorption, yellow light emission occurs. After being placed in air, the emission color of the sample changes from yellow to yellow-green, ultimately achieving a three-mode emission switch. All exhibit rapid dynamic response characteristics and cyclicity.

[0020] (3) The raw materials required by the present invention are low cost and the process is simple. Powder crystals can be synthesized in large quantities through mechanical grinding. The material is non-toxic and can replace traditional lead-based halides. Moreover, the material has promising application prospects in solvent monitoring and information security.

[0021] (4) This invention achieves a comprehensive breakthrough in the sensitivity, speed, stability and applicability of solvent-responsive luminescent materials through molecular design innovation, providing efficient, low-cost and visualized solutions for information security, environmental monitoring and anti-counterfeiting. Attached Figure Description

[0022] Figure 1 The crystal structure diagram of the single crystal of organic-inorganic hybrid antimony(III) halide prepared in Example 1 is shown. Figure 2 The XRD patterns of the organic-inorganic hybrid antimony (III) single crystal powder prepared in Example 1 and the powder crystal and single crystal prepared in Example 4 are shown. Figure 3 The XRD patterns of the organic-inorganic hybrid antimony(III) halide powder and single-crystal simulated powder prepared according to the present invention are shown. Figure 4 The photoluminescence excitation and emission spectra of the organic-inorganic hybrid antimony(III) halides prepared in Example 1 are shown. Figure 5 The images show the luminescence of the powder prepared in Example 4 during the dynamic response processes with ethanol and water, with a scale bar of 1 cm. Figure 6 The image shows the excitation spectrum of the powder prepared in Example 4 during its response to ethanol. Figure 7 The emission spectrum of the powder prepared in Example 4 during its response to ethanol; Figure 8 The image shows the excitation spectrum of the powder prepared in Example 4 during its response to water. Figure 9 The emission spectrum of the powder prepared in Example 4 during its response to water is shown.

[0023] Figure 10 This is a diagram of the single-crystal structure of Example 1 after its response to methanol; Figure 11 The images show the powder XRD patterns of Example 4 after responding to water and methanol, respectively, and the single-crystal simulation diagram of Example 1 after responding to methanol. Figure 12 The emission spectra of the powder prepared in Example 4 are shown under different humidity levels. As the humidity increases, the luminescence intensity gradually decreases. Figure 13 The image shows the optical performance monitoring of the powder prepared in Example 4 during 100 cycles of water response. During the 100 cycles, the luminescence intensity, full width at half maximum (FWHM), and peak position of the material did not change significantly. Figure 14 This is a cycle diagram of Example 4 during 100 dynamic cycles in response to ethanol; Figure 15 The powder prepared in Example 4 is used to create a pattern plate by using a groove filling method. This plate can display different information during the response with ethanol, thereby achieving the purpose of encrypted information storage. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of this invention clearer, the specific embodiments and accompanying drawings are described in further detail below. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0025] The present invention provides a method for preparing a solvent-responsive optical crystal, comprising the following steps: S1. Dissolve antimony trichloride and benzyltrimethylammonium chloride in methanol, heat and stir until completely dissolved to obtain a colorless, transparent, and clear solution, then slowly cool to room temperature and allow it to evaporate slowly to obtain rod-shaped single crystals. S2. The single crystal sample is washed multiple times with a specific solvent and dried to remove solvent molecules, finally obtaining an organic-inorganic hybrid antimony halide single crystal, which is the solvent-responsive optical crystal.

[0026] In the specific implementation, the mass molar ratio of antimony trichloride and benzyltrimethylammonium chloride is 1:(1.5~3); the heating and stirring temperature is 50~60℃, the stirring time is 20~30 min, the washing solvent is n-hexane or cyclohexane, the drying temperature is 60~70℃, and the drying time is 3~7 days.

[0027] Another method for preparing solvent-responsive optical crystals provided by the present invention involves grinding and mixing high-purity antimony trichloride and benzyltrimethylammonium chloride thoroughly in an air environment using a mortar and pestle to obtain organic-inorganic hybrid antimony halide powder crystals. The mass molar ratio of antimony trichloride to benzyltrimethylammonium chloride is 1:3, the grinding time is 20~30 min, and no inert gas protection is required.

[0028] The solvent-responsive optical crystal prepared by the above method has the molecular formula C0 30 H 48 Cl9N3Sb2 has the following cell parameters: a = 9.2515(6) Å, b = 25.738(2) Å, c = 17.5757(14) Å, α = 90°, β = 92.463(2)°, γ = 90°. The crystal structure of the solvent-responsive optical crystal belongs to the monoclinic system, and the space group is [missing information]. P2 1 / c The inorganic framework of this solvent-responsive optical crystal consists of isolated [Sb₂Cl₉] particles. 3- Composed of dimers, with Sb 3+ Centered on a [SbCl5] 2- A square pyramid and a [SbCl6] 3- Octahedrons are connected by edge sharing, and organic cations interact through hydrogen bonds and Coulomb forces around the inorganic framework.

[0029] The embodiments of the present invention have achieved some positive results during the research and development or use process, and have indeed great advantages compared with the prior art. The following content describes them in conjunction with the data, charts and other information of the experimental process.

[0030] Example 1 This example provides a method for preparing a solvent-responsive optical crystal (inorganic hybrid antimony (III) halide (Me3BzN)3Sb2Cl9 single crystal): (1) Dissolve 0.5 mmol of antimony trichloride and 1.5 mmol of benzyltrimethylammonium chloride in 5 mL of methanol, then heat and stir to 60 °C, react for 30 min, let stand and slowly cool to room temperature, and wait 7 to 14 days to obtain colorless transparent rod-shaped single crystals.

[0031] (2) Take out the colorless and transparent rod-shaped single crystal obtained in step 1, wash it three times with n-hexane, and dry it in an oven at 60 °C for 3 to 7 days.

[0032] Example 2 The method is basically the same as in Example 1, except that 1 mmol of antimony trichloride and 1.5 mmol of benzyltrimethylammonium chloride are dissolved in 5 mL of methanol.

[0033] Example 3 The method is basically the same as in Example 1, except that 0.75 mmol of antimony trichloride and 1.5 mmol of benzyltrimethylammonium chloride are dissolved in 5 mL of methanol.

[0034] The solvent-responsive optical crystals prepared in Examples 1-3 all have similar crystal structures. The single-crystal diffraction data of the prepared crystals were collected using a Bruker D8 Venture single-crystal diffractometer. The cell parameters of (Me3BzN)3Sb2Cl9 were obtained by analysis: a = 9.2515(6) Å, b = 25.738(2) Å, c = 17.5757(14) Å, α = 90°, β = 92.463(2)°, γ = 90°. P twenty one / c Space group. Taking Example 1 as an example, the crystal structure is described in detail, refer to... Figure 1 As shown in the figure, the inorganic framework of this crystal consists of isolated [Sb₂Cl₉] particles. 3- Composed of dimers, with Sb 3+ Centered on a [SbCl5] 2- A square pyramid and a [SbCl6] 3- The octahedrons are connected by edge sharing, and the benzyltrimethylammonium cations surround the inorganic framework through hydrogen bonding and coulombic interactions.

[0035] Example 4 This example provides a method for preparing organic-inorganic hybrid antimony(III) halide (Me3BzN)3Sb2Cl9 powder: High-purity antimony trichloride and benzyltrimethylammonium chloride (molar ratio 1:3) are thoroughly ground and mixed in an air environment using a mortar for about 30 minutes to obtain organic-inorganic hybrid antimony halide powder crystals.

[0036] Example 5 It is basically the same as Example 4, except that the molar ratio of antimony trichloride and benzyltrimethylammonium chloride is 1:1.5.

[0037] Example 6 It is basically the same as Example 4, except that the molar ratio of antimony trichloride and benzyltrimethylammonium chloride is 1:2.

[0038] The solvent-responsive optical crystals prepared in Examples 4-6 all have similar crystal structures. The single-crystal diffraction data of the prepared crystals were collected using a Bruker D8 Venture single-crystal diffractometer. The cell parameters of (Me3BzN)3Sb2Cl9 were obtained by analysis: a = 9.2515(6) Å, b = 25.738(2) Å, c = 17.5757(14) Å, α = 90°, β = 92.463(2)°, γ = 90°. P twenty one / c Space group. Taking Example 4 as an example, the crystal structure is described in detail, refer to... Figure 1 As shown in the figure, the inorganic framework of this crystal consists of isolated [Sb₂Cl₉] particles. 3- Composed of dimers, with Sb 3+ Centered on a [SbCl5] 2- A square pyramid and a [SbCl6] 3- The octahedrons are connected by edge sharing, and the benzyltrimethylammonium cations surround the inorganic framework through hydrogen bonding and coulombic interactions.

[0039] like Figure 2 The image shows a comparison of the powder XRD of the single-crystal powder sample prepared in Example 1, the powder XRD of the sample prepared in Example 4, and the SCXRD of the simulated single-crystal data prepared in Example 1. Figure 2 It can be seen that the results obtained by testing actual powder samples are consistent with the simulated XRD cards, indicating that the phases of powder crystals and single crystals obtained by different methods are consistent and can be identified as the same phase.

[0040] like Figure 3 The image shows a comparison of the SCXRD patterns of the powder XRD obtained in Example 4 and the single-crystal simulation data obtained in Example 1. Figure 3 It can be seen that the results obtained from the actual powder sample test are consistent with the simulated XRD card, indicating that the powder has high phase purity.

[0041] To better illustrate the performance of the solvent-responsive optical crystal prepared in this invention, the applicant conducted the following research: refer to Figure 4 Figure 1 shows the excitation and emission spectra obtained in Example 4. The figure indicates that the material has an optimal excitation position at 344 nm, an optimal emission position at 560 nm, and a full width at half maximum (FWHM) of 132 nm.

[0042] Solvent response tests were conducted using ethanol as a representative of moderately polar solvents.

[0043] refer to Figure 5The image shows the luminescence (λ) during the dynamic processes of responding to ethanol and water, respectively, in Example 4. ex = 365nm), demonstrating the material's rapid response color change phenomenon and good recoverability.

[0044] refer to Figure 6 and Figure 7 The excitation and emission spectra of Example 4 during the ethanol response process were acquired using an FLS 1000 steady-state and transient fluorescence spectrometer in Edinburgh, UK. Under initial conditions, the material exhibited a broad yellow-green emission at 560 nm. After responding to ethanol, the emission position red-shifted to 670 nm, with a full width at half maximum (FWHM) of 178 nm. Heating caused ethanol desorption, resulting in a change in emission color from orange-red to yellow, and the emission peak shifted to 600 nm. Upon exposure to air, the emission color changed again, returning to yellow-green emission at 560 nm, indicating that the material exhibits an adjustable four-mode dynamic luminescence solvent response during the ethanol response.

[0045] refer to Figure 8 and Figure 9 The figure shows the excitation and emission spectra of Example 4 during its response to water. Data were acquired using an Edinburgh FLS 1000 steady-state and transient fluorescence spectrometer. Example 4 also exhibited a dynamic solvent response with strongly polar small molecules. The material initially emitted a yellow-green light at 560 nm. Upon response to water, the emission was immediately quenched. Heating to desorb water restored the fluorescence to a yellow light emission of 600 nm. After being exposed to air, the emission color changed again, returning to the yellow-green emission at 560 nm, indicating that the material exhibits an adjustable three-mode dynamic emission solvent response during the ethanol response.

[0046] refer to Figure 10 This is a schematic diagram of the crystal structure after the phase transformation following the reaction with methanol in Example 1. The crystal structure of the crystalline material undergoes a phase transformation upon reaction with methanol, with methanol molecules inserting into the material's spatial structure. The newly generated crystal has the molecular formula (Me3BzN)3Sb2Cl9·MeOH, and its unit cell parameters are: a = 9.4840(16) Å, b = 16.217(2) Å, c = 28.484(4) Å, α = 90°, β = 90°, γ = 90°, belonging to the orthorhombic crystal system. P Space group 212121. As shown in the figure, the inorganic framework of this crystal consists of isolated [Sb₂Cl₉] particles. 3- Composed of dimers, with Sb 3+ Centered on a [SbCl5] 2- A square pyramid and a [SbCl6] 3-The octahedrons are connected by edge sharing, and the benzyltrimethylammonium cation and methanol molecules surround the inorganic framework through hydrogen bonding and coulombic interactions.

[0047] refer to Figure 11 The figures show a comparison between the powder XRD patterns of Example 4 after reacting with water and methanol, and the simulated single-crystal XRD pattern of Example 1 after reacting with methanol. The characteristic peaks of the XRD patterns are observed to be largely consistent, suggesting that the phase transformation that occurred after reacting with water and methanol in Example 4 is to the same phase.

[0048] refer to Figure 12 The humidity within the sealed space was controlled by adjusting the vapor pressure above the solution using a saturated salt solution method, thus obtaining the emission spectra of Example 4 under different humidity conditions. As can be observed from the graph, the luminescence intensity of the material gradually decreases with increasing humidity until it is completely quenched.

[0049] refer to Figure 13 The figure shows the cycle diagram of Example 4 during 100 dynamic cycles in response to water. The figure compares the luminescence intensity, half-width at half-maximum (WHM), and emission peak position during the 100 cycles. It can be seen that there are no significant changes in luminescence intensity, WHM, and emission peak position during the 100 cycles, indicating that the material has good cycle performance, which is significantly better than most organic-inorganic hybrid metal halide luminescent materials.

[0050] Figure 14 This is a cycle diagram of Example 4 during 100 cycles of dynamic response with ethanol. The figure compares the luminescence intensity, half-width at half-maximum (HWHM), and emission peak position during 100 cycles. It can be seen that there are no significant changes in luminescence intensity, HWHM, and emission peak position during 100 cycles, indicating that the material has good cycle performance, which is significantly better than most organic-inorganic hybrid metal halide luminescent materials.

[0051] Example 7 This embodiment provides the application of solvent-responsive optical crystals.

[0052] The powder prepared in Example 4 was filled into a non-fluorescent grooved silicone pattern template using a groove filling method. During the response with ethanol, it could present different information to achieve the purpose of encrypted information storage.

[0053] refer to Figure 15This is the pattern template designed for ethanol response in Example 4. Based on the four-mode emission color characteristics of Example 4, an information encryption anti-counterfeiting pattern was constructed. The yellow emission signal was considered the correct encrypted information, while signals of other colors were considered interference. Under sunlight, the pattern is white, and then under 365 nm ultraviolet light, the white pattern turns into a bright yellow-green light. After treatment with a small amount of ethanol, the pattern rapidly turns into orange-red emission within 1 second. Furthermore, with continuous treatment with ethanol, the orange-red pattern gradually becomes invisible under ultraviolet light. Moreover, when the sample is heated, yellow light gradually appears, indicating the correct information. Finally, the emission color returns to the invalid mode of yellow-green emission, covering the encrypted information and making the decoding process trackless. It should be noted that the solvent-responsive optical crystal provided by this invention possesses excellent luminescence performance and solvent-responsive properties, and can be used to fabricate multifunctional devices, specifically including anti-counterfeiting devices, information security encryption devices, and solvent detection devices. In the field of anti-counterfeiting, the crystal can trigger multi-level color development or pattern display through solvents, and combined with micro-nano processing or time-dependent response to achieve high-security anti-counterfeiting labels; in the field of information encryption, the solvent-erasable and rewritable properties of the crystal or its synergy with light response can be used to develop dynamic encryption and rewritable systems; in terms of solvent detection, high-throughput solvent identification or environmental pollutant monitoring can be achieved by constructing crystal sensor arrays or microfluidic integrated devices. In addition, crystal composites (such as composites with polymers to improve flexibility), patterned fabrication processes (such as inkjet printing and photolithography), and performance optimization methods (such as nanoporous structures to accelerate response and surface hydrophobic modifications to improve stability) can be implemented, ultimately forming a complete technical solution covering material composition, device design, and application scenarios, with advantages of high sensitivity, multi-mode response, and scalable production.

[0054] For any points not covered above, existing technologies shall apply.

[0055] This application is not limited to the specific methods or compositions described herein, and therefore may vary. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting, as the scope of this application will be limited only by the appended claims and their equivalents.

Claims

1. A solvent-responsive optical crystal, characterized in that, The molecular formula of the solvent-responsive optical crystal is C 30 H 48 Cl9N3Sb2, with cell parameters a = 9.2515(6) Å, b = 25.738(2) Å, c = 17.5757(14) Å, α = 90°, β = 92.463(2)°, γ = 90°, the solvent-responsive optical crystal has a monoclinic crystal system and a space group of . P2 1 / c .

2. The solvent-responsive optical crystal according to claim 1, characterized in that, The inorganic framework of the solvent-responsive optical crystal consists of isolated [Sb₂Cl₉]₂. 3- Composed of dimers, with Sb 3+ Centered on a [SbCl5] 2- A square pyramid and a [SbCl6] 3- Octahedrons are connected by edge sharing, and organic cations interact through hydrogen bonds and Coulomb forces around the inorganic framework.

3. The solvent-responsive optical crystal according to claim 2, characterized in that, The organic cation is a benzyltrimethylammonium cation, with the structure of Formula 1: Formula 1.

4. The solvent-responsive optical crystal according to claim 3, characterized in that, The solvent-responsive optical crystal exhibits a redshift in emission under neutral polar solvent conditions, and the Et(30) polarity parameter of the neutral polar solvent ranges from 45.6 to 51.

9.

5. The method for preparing the solvent-responsive optical crystal as described in claim 3, characterized in that, Includes the following steps: S1. Antimony trichloride and benzyltrimethylammonium chloride are dissolved in methanol, heated and stirred to obtain a colorless, transparent, and clear solution, which is then cooled to room temperature and evaporated to obtain rod-shaped single crystals; the mass molar ratio of antimony trichloride and benzyltrimethylammonium chloride is 1:(1.5~3). S2. The single crystal sample is washed multiple times with a specific solvent and dried to remove solvent molecules, finally obtaining an organic-inorganic hybrid antimony halide single crystal, which is the solvent-responsive optical crystal.

6. The preparation method according to claim 5, characterized in that, The heating and stirring temperature is 50~60℃, and the stirring time is 20~30 min.

7. The preparation method according to claim 6, characterized in that, In step S2, the washing solvent is n-hexane or cyclohexane; the drying temperature is 60~70℃, and the drying time is 3~7 days.

8. The method for preparing the solvent-responsive optical crystal as described in claim 3, characterized in that, Antimony trichloride and benzyltrimethylammonium chloride were mixed in a mass molar ratio of 1:(1.5~3) and ground to obtain the solvent-responsive optical crystal.

9. The preparation method according to claim 8, characterized in that, The grinding time is 20~30 min.

10. Use of a solvent-responsive optical crystal as described in any one of claims 1-3, characterized in that, The solvent-responsive optical crystal is used to prepare anti-counterfeiting devices, information security encryption devices, and solvent detection devices.

Images