Preparation method and application of inorganic-organic hybrid adjustable luminous stimuli-responsive material

Abstract

The invention belongs to the technical field of adjustable luminous stimuli-responsive materials, and particularly relates to a preparation method and application of an inorganic-organic hybrid adjustable luminous stimuli-responsive material. The preparation method comprises the following steps: uniformly mixing 2, 4, 6-tri (4-pyridyl)-1, 3, 5-triazine, 2, 5-thiophenedicarboxylic acid, zinc perchlorate, europium nitrate, water, N, N '-dimethylacetamide and methanol by adopting a solvothermal method, and reacting at 90-140 DEG C for 24-48 hours to obtain a colorless crystal. The invention simultaneously explores the photochromic process, the electrochromic process and the adjustable photoluminescence process of the inorganic-organic hybrid material. The material has wide application prospects in the fields of inkless printing, electrochromic devices, photochromic decoration, optical memories, optical switches, photoelectric display, information encryption, anti-counterfeiting and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of adjustable luminescent stimulus-responsive materials, and in particular relates to a preparation method and application of an inorganic-organic hybrid adjustable luminescent stimulus-responsive material. Background Art

[0002] Photochromic compounds refer to compounds that change color under the action of light of a certain wavelength and intensity or a certain voltage, and this change is reversible.

[0003] Photoluminescent materials are considered one of the most promising anti-counterfeiting materials due to their outstanding features, including convenient visual readout, rapid identification, and high spatial resolution. In addition to spectral characteristics and emission color, excitation patterns and decay times can also serve as identification information, enabling multiple anti-counterfeiting measures and high security. Coordination polymers are a new type of inorganic-organic hybrid functional material formed by the coordination bond between metal ions and organic ligands. Metal-organic frameworks (MOFs) exhibit great potential for the synthesis of new stimuli-responsive photoluminescent materials due to their high chemical and structural tunability, well-defined pore structures, and diverse emission characteristics. In recent years, the construction of luminescent coordination polymers for applications in molecular recognition, anti-counterfeiting, sensing, and imaging has become a key research direction. The luminescent properties of coordination polymers can generally be derived from ligands, metal ions, guests, or host-guest interactions. Their diverse regulatory mechanisms enable the construction of coordination polymers with multiple fluorescent emissions.

[0004] However, due to the late development of this type of material, photoluminescent materials currently have problems such as slow response rate and poor reversibility, which hinders their further application in anti-counterfeiting and information encryption. Summary of the Invention

[0005] In order to solve the problems of slow response rate and poor reversibility of photoluminescent materials, the present invention provides a preparation method and application of an inorganic-organic hybrid tunable photoluminescent stimulus-responsive material. The present invention utilizes a porous photoresponsive coordination polymer containing electron-deficient ligands to introduce a rare earth ion Eu with characteristic emission into its pores. 3+ The guest molecules have realized the synthesis of multi-stimulus responsive coordination polymers with tunable photoluminescence and photoelectrochromism.

[0006] The present invention adopts the following technical solutions:

[0007] A method for preparing an inorganic-organic hybrid tunable luminescent stimulus-responsive material comprises the following steps: uniformly mixing 2,4,6-tris(4-pyridyl)-1,3,5-triazine, 2,5-thiophenedicarboxylic acid, zinc perchlorate, europium nitrate, water, N,N′-dimethylacetamide, and methanol to obtain a mixture; charging the mixture into a reaction vessel for reaction to obtain colorless needle-shaped crystals, which are the tunable luminescent stimulus-responsive material (denoted as compound 1-Eu).

[0008] Furthermore, the mass ratio of the 2,4,6-tris(4-pyridyl)-1,3,5-triazine, 2,5-thiophenedicarboxylic acid, zinc perchlorate, and europium nitrate is 1:(1-2):(2-5).

[0009] Furthermore, the mass ratio of the 2,4,6-tris(4-pyridyl)-1,3,5-triazine to europium nitrate is 7:(0.1-5).

[0010] Furthermore, the volume ratio of water, N,N′-dimethylacetamide and methanol is 4:1:(1-3).

[0011] Furthermore, the reaction temperature of the mixture is 90 to 140° C., and the reaction time is 24 to 48 hours.

[0012] Furthermore, a method for preparing an inorganic-organic hybrid tunable luminescent stimulus-responsive material includes the following steps: 7 mg of 2,4,6-tris(4-pyridyl)-1,3,5-triazine, 10 mg of 2,5-thiophenedicarboxylic acid, 30 mg of zinc perchlorate, 0.1-5 mg of europium nitrate, 4 mL of water, 1 mL of N,N′-dimethylacetamide, and 2 mL of methanol are sequentially added into a sealed reaction container, the reaction container is placed in an oven at 90-140°C and reacted for more than 24-48 hours, and then taken out after cooling to room temperature to obtain colorless needle-shaped crystals, which are the tunable luminescent stimulus-responsive material.

[0013] The present invention also provides a method for preparing an inorganic-organic hybrid tunable luminescent stimulus-responsive material, comprising the following steps: uniformly mixing 2,4,6-tris(4-pyridyl)-1,3,5-triazine, 2,5-thiophenedicarboxylic acid, zinc perchlorate, water, N,N′-dimethylacetamide, and methanol to obtain a mixture, charging the mixture into a reaction vessel for reaction to obtain needle-shaped colorless crystals, which are the tunable luminescent stimulus-responsive material (denoted as compound 1); the mass ratio of the 2,4,6-tris(4-pyridyl)-1,3,5-triazine, 2,5-thiophenedicarboxylic acid, and zinc perchlorate is 1:(1-2):(2-5); the volume ratio of the water, N,N′-dimethylacetamide, and methanol is 4:1:(1-3); the reaction temperature of the mixture is 90-140°C, and the reaction time is 24-48 hours.

[0014] Furthermore, the chemical formula of the hybrid tunable luminescent stimulus-responsive material (Compound 1) is C 30 H 16 N6O9S2Zn2, the inorganic part is Zn 2+ The organic part is 2,4,6-tris(4-pyridyl)-1,3,5-triazine and 2,5-thiophenedicarboxylic acid, monoclinic system, space group P21 / c, unit cell parameters α=90°, β=91.590(5)°, γ=90°.

[0015] The present invention also provides a method for preparing an inorganic-organic hybrid tunable luminescent stimulus-responsive material, and the tunable luminescent stimulus-responsive material prepared by the method is used in inkless printing, electrochromic devices, photochromic decoration, optical storage, optical switches and optoelectronic displays.

[0016] The present invention also provides an application of the adjustable luminescent stimulus-responsive material prepared by a method for preparing an inorganic-organic hybrid adjustable luminescent stimulus-responsive material in the fields of information encryption and anti-counterfeiting.

[0017] The two tunable luminescent stimulus-responsive materials prepared in the present invention are both photoelectrochromic materials, having photochromic and electrochromic properties, as follows:

[0018] The two compound crystals prepared by the present invention change color from colorless to light blue in 30 seconds under ultraviolet light irradiation, with a fast response rate. After 5 minutes of light irradiation, they can completely fade after being placed in the air for 6 hours, and there is no change after repeating five times.

[0019] The two compounds prepared by the present invention can be used to prepare electrochromic devices to observe the electrochromic properties by the following method: 10 mg of the sample is added to a mixed solution of 0.2 mL of PMMA solution and 0.2 mL of anhydrous ethanol, and ultrasonicated for 30 minutes until the crystals are evenly dispersed in the solution. The solution is encapsulated into an electrochromic device (the electrochromic device comprises two pieces of ITO conductive glass, the solution is coated between the two pieces of ITO conductive glass, and naturally dried). After the electrochromic device is energized at a certain voltage, an obvious color change occurs.

[0020] The hybrid photoelectrochromic material compound 1 prepared by the present invention is synthesized by adding europium nitrate during the in-situ synthesis process to obtain compound 1-Eu, which can make the crystal have obvious photoluminescence phenomenon, and as the amount of europium nitrate added increases, the fluorescence emission intensity of the compound gradually increases, reaching saturation when 1 mg of europium nitrate is added, and the fluorescence emission intensity no longer changes.

[0021] Compared with the prior art, the present invention has the following technical effects:

[0022] The present invention utilizes a solvothermal synthesis method to synthesize Compound 1, and then adds europium nitrate to the in situ synthesis process to obtain Compound 1-Eu. This method is simple to operate and safe. The in situ synthesized Compound 1-Eu exhibits rapid photochromism and significantly enhanced luminescence intensity. Based on the tunable photoluminescence and reversible light-regulated luminescence properties of the two compounds, they can be fabricated into anti-counterfeiting devices.

[0023] 2. Compound 1 and Compound 1-Eu, prepared according to the present invention, both exhibit photochromic and electrochromic properties. Both compounds achieve a visible blue color after 30 seconds of illumination, significantly improving the photochromic rate of Compound 1 and Compound 1-Eu compared to existing inorganic-organic hybrid photochromic materials. Furthermore, both compounds exhibit electrochromic properties and can be fabricated into electrochromic devices that change color upon application of a certain voltage.

[0024] 3. Compound 1 and Compound 1-Eu prepared by the present invention have broad application prospects in the fields of inkless printing, electrochromic devices, photochromic decoration, optical storage, optical switches, optoelectronic display and information encryption, and multiple anti-counterfeiting. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a structural stacking diagram of compound 1 obtained in Example 1 of the present invention;

[0026] Figure 2 This is a photochromic image of Compound 1 obtained in Example 1 of the present invention;

[0027] Figure 3 This is a photochromic image of compound 1-Eu obtained in Example 3 of the present invention;

[0028] Figure 4 The infrared spectra of compound 1 obtained in Example 1 of the present invention and compound 1-Eu obtained in Example 3 before and after irradiation;

[0029] Figure 5 1 is the powder diffraction pattern of compound 1 obtained in Example 1 of the present invention and compound 1-Eu obtained in Example 3 before and after irradiation;

[0030] Figure 6 This is a thermogravimetric analysis diagram of Compound 1 obtained in Example 1 of the present invention and Compound 1-Eu obtained in Example 3;

[0031] Figure 7 This is the EPR of compound 1 obtained in Example 1 of the present invention before and after light discoloration;

[0032] Figure 8 is the EPR of compound 1-Eu obtained in Example 3 of the present invention before and after light discoloration;

[0033] Figure 9 is the time-dependent solid-state diffuse reflectance spectrum of Compound 1 obtained in Example 1 of the present invention;

[0034] Figure 10 This is the time-dependent solid-state diffuse reflectance spectrum of compound 1-Eu obtained in Example 3 of the present invention;

[0035] Figure 11 The time-dependent fluorescence emission spectrum of compound 1 obtained in Example 1 of the present invention;

[0036] Figure 12 1 is the cyclic voltammetry curve and electrochromic image of compound 1 obtained in Example 1 of the present invention;

[0037] Figure 13 The cyclic voltammetry curve and electrochromic image of compound 1-Eu obtained in Example 3 of the present invention are shown;

[0038] Figure 14 This is a solid-state diffuse reflectance spectrum of Compound 1 obtained in Example 1 of the present invention as a function of voltage;

[0039] Figure 15 This is a solid-state diffuse reflectance spectrum of compound 1-Eu obtained in Example 3 of the present invention as a function of voltage;

[0040] Figure 16 is the fluorescence emission spectrum of compound 1-Eu obtained in Example 6 of the present invention;

[0041] Figure 17 This is a time-dependent solid-state emission spectrum of compound 1-Eu obtained in Example 3 of the present invention;

[0042] Figure 18 The photochromic image (a) and the photoluminescent image (b) of the compound 1 and compound 1-Eu of the present invention under fluorescent light are shown in FIG. DETAILED DESCRIPTION

[0043] The present invention will be further described below through examples and in conjunction with the accompanying drawings.

[0044] In the following examples, 2,4,6-tris(4-pyridyl)-1,3,5-triazine is referred to as TPT; N,N′-dimethylacetamide is referred to as DMA.

[0045] Example 1: Preparation of Compound 1

[0046] In this example, TPT (7 mg), 2,5-thiophenedicarboxylic acid (10 mg), zinc perchlorate (30 mg), H2O (4 mL), DMA (1 mL), and CH3OH (2 mL) were sequentially added into a 20 mL glass bottle and sealed. The mixture was reacted in an oven at 120°C for more than 36 hours. After the reaction was completed, the transparent glass bottle was gradually cooled to room temperature and taken out. The crystals generated in the glass bottle were removed to obtain colorless needle-shaped crystals, which were the target product, recorded as compound 1, with a yield of 43.7%.

[0047] The molecular formula of compound 1 is C 30 H 16 N6O9S2Zn2, the inorganic part is Zn 2+ The organic part is 2,4,6-tris(4-pyridyl)-1,3,5-triazine and 2,5-thiophenedicarboxylic acid, monoclinic system, space group P21 / c, unit cell parameters α=90°, β=91.590(5)°, γ=90°. Figure 1 This is a stacking diagram of the crystal structure of compound 1 obtained in this example.

[0048] Example 2: Comparison of reaction conditions for compound 1

[0049] A comparative test was conducted by changing the single reaction conditions of Example 1 as follows:

[0050] (1) Changing the amount of CH3OH added, the yield of compound 1 is shown in Table 1:

[0051] Table 1

[0052]

[0053] (2) Changing the reaction time, the yield of compound 1 is shown in Table 2:

[0054] Table 2

[0055]

[0056] (3) Changing the reaction temperature, the yield of compound 1 is shown in Table 3:

[0057] Table 3

[0058]

[0059] Example 3: Preparation of Compound 1-Eu

[0060] In this example, TPT (7 mg), 2,5-thiophenedicarboxylic acid (10 mg), zinc perchlorate (30 mg), europium nitrate (1 mg), H2O (4 mL), DMA (1 mL), and CH3OH (2 mL) were sequentially added into a 20 mL glass bottle and sealed. The mixture was reacted in an oven at 120°C for more than 36 hours. After the reaction was completed, the transparent glass bottle was gradually cooled to room temperature and taken out. The crystals generated in the glass bottle were removed to obtain colorless needle-shaped crystals, which were the target product and recorded as compound 1-Eu.

[0061] Example 4: Photochromic experiment

[0062] The light source used was a 365nm ultraviolet lamp. The bulk crystals of compound 1 prepared in Example 1 and compound 1-Eu prepared in Example 3 were placed under a microscope. At room temperature, after irradiation for 30 seconds, the color of the crystals changed from colorless to light blue. After irradiation for another 270 seconds, the color of the crystals changed to dark blue and continued to irradiate without changing color. That is, the light irradiation reached saturation after 5 minutes. For details, see Figure 2 and Figure 3 .

[0063] Figure 4 The infrared spectra of compound 1 and compound 1-Eu before and after irradiation are shown in Figure 1. The irradiation time is 3 minutes. Figure 4 It can be seen that the infrared spectra of compound 1 and compound 1-Eu after photochromism and before photochromism have similar peak positions, indicating that the structure of the crystal has not changed before and after illumination.

[0064] Figure 5 The simulated X-ray powder diffraction patterns of compound 1 and compound 1-Eu, the X-ray powder diffraction patterns of the sample before photochromism, and the X-ray powder diffraction patterns of the sample after photochromism (the sample after irradiation with UV light for 3 minutes) are shown in FIG. Figure 5 It can be seen that the X-ray powder diffraction patterns of compound 1 and compound 1-Eu before photochromism, the X-ray powder diffraction patterns of the samples after photochromism and the simulated X-ray powder diffraction patterns have similar peak positions, indicating that the structure of the crystal has not changed before and after irradiation.

[0065] Figure 6 is the thermogravimetric analysis diagram of compound 1 and compound 1-Eu, Figure 6 It can be seen that compound 1 and compound 1-Eu can be stable up to 360°C, and what is released before 360°C is physically adsorbed water, indicating that compound 1 and compound 1-Eu have good thermal stability.

[0066] Figure 7 and Figure 8 They are the EPR of compound 1 and compound 1-Eu before and after illumination, respectively. Figure 7 and Figure 8 It can be seen that after 10 minutes of UV light irradiation, the peak intensity of the sample at g = 2.0038 and g = 2.0039 increased, indicating that free radicals were generated after illumination.

[0067] Figure 9 and Figure 10 The illumination time-dependent solid-state diffuse reflectance spectra of compound 1 and compound 1-Eu were used to detect the photochromic process in the 365nm ultraviolet light wavelength region. As the illumination time increased, the color changed from white to blue, and the absorption intensity at 650nm in the ultraviolet-visible solid-state diffuse reflectance spectrum increased with the increase of illumination time. After continuous irradiation for 5 minutes, the ultraviolet absorption intensity no longer increased and the color no longer changed.

[0068] Figure 11 The illumination time-dependent solid-state emission spectrum of compound 1 is used to detect changes in fluorescence emission during the photochromic process in the 365nm ultraviolet light wavelength region. As the illumination time increases, the fluorescence emission intensity weakens. After continuous illumination for 5 minutes, the fluorescence emission intensity no longer changes. Therefore, the luminescence intensity can be regulated by the illumination time.

[0069] Example 5: Electrochromic Experiment

[0070] 10 mg of compound 1 prepared in Example 1 was added to a mixed solution of 0.2 mL of PMMA solution and 0.2 mL of anhydrous ethanol, and ultrasonicated for 30 min until compound 1 was evenly dispersed in the solution. The solution was packaged into an electrochromic device (the electrochromic device comprises two pieces of ITO conductive glass, the solution is coated between the two pieces of ITO conductive glass, and naturally dried). Compound 1-Eu was prepared using the same method. After the electrochromic device was energized at a certain voltage, an obvious color change occurred, and the cyclic voltammetry curves of compound 1 and compound 1-Eu showed redox peaks at -1.16 V and -1.38 V, and at -1.17 V and -1.38 V, respectively (see Figure 12 and Figure 13 ), and at the same time, the absorption intensity at 650nm in the UV-visible solid diffuse reflectance spectrum gradually increases with the increase of voltage (see Figure 14 and Figure 15 ).

[0071] Example 6: Luminescence Control of Compound 1-Eu

[0072] The amount of europium nitrate added in Example 3 was changed, and other conditions remained unchanged. That is, the amount of europium nitrate added in the in-situ synthesis of Example 3 was 0.10 mg, 0.50 mg, 1.00 mg, 3.00 mg and 5.00 mg respectively, and different emission intensities were obtained (see Figure 16) red light compound 1-Eu, and the X-ray powder diffraction pattern of 1-Eu has similar peak positions compared with the simulated X-ray powder diffraction pattern, indicating that the addition of Eu 3+ The structure of the crystal remains unchanged (see Figure 5 In addition, compared with the fluorescence intensity of 1@Eu obtained by simple physical mixing (compound 1 and europium nitrate in a mass ratio of 1:1), the fluorescence intensity of the in situ synthesized product was enhanced by 10 times, indicating that Eu 3+ It has a strong interaction with compound 1 and the compound can sensitize the luminescence of rare earth.

[0073] Figure 16 This is the solid-state emission spectrum of compound 1 and compound 1-Eu. In the figure, compound 1 has no emission peak at 550-700nm; while compound 1-Eu after adding europium nitrate has new absorption peaks at 590nm, 610nm and 700nm, and increases with the amount added. It reaches saturation when 1.00mg of europium nitrate is added, and the emission intensity no longer changes. Therefore, the luminescence intensity can be controlled by the amount of europium nitrate added.

[0074] Figure 17 This is a time-dependent solid-state fluorescence emission spectrum of compound 1-Eu after adding 1.00 mg of europium nitrate. As the illumination time increases, the fluorescence emission intensities at 460 nm, 590 nm, 610 nm, and 710 nm weaken. After illumination, the fluorescence emission intensity at 610 nm weakens by 94.4%. The quantum yield of compound 1-Eu before illumination is 16.5%, and the quantum yield after illumination is 1.51%. The quantum yield after illumination decreases by 90.85%. The luminescence intensity can be further regulated by adding illumination time.

[0075] Example 7

[0076] Figure 18 The butterfly pattern is composed of compound 1-Eu and compound 1. Compound 1 and compound 1-Eu have different luminescent colors. As the color of the two compounds deepens under fluorescent light during the photochromic process, their luminescence intensity gradually weakens (compound 1 emits weaker blue light, and compound 1-Eu emits very strong red light). However, after being placed in the dark for one hour, the luminescence intensity and color under fluorescent light gradually recover. Based on the different photoluminescence phenomena and similar photochromic phenomena of compound 1 and compound 1-Eu, they can be applied to information encryption and anti-counterfeiting.

[0077] The embodiments described above are only preferred embodiments of the present invention and are only used to explain the present invention, not to limit the scope of implementation of the present invention. For those skilled in the art, it is of course possible to easily make other implementation methods by replacing or changing the technical content disclosed in this specification. Therefore, all changes and improvements made to the principles and process conditions of the present invention should be included in the scope of the patent application of the present invention.

Claims

1. A method for preparing an inorganic-organic hybrid tunable luminescent stimulus-responsive material, characterized in that: The following steps are involved: 2,4,6-tris(4-pyridyl)-1,3,5-triazine, 2,5-thiophenedicarboxylic acid, zinc perchlorate, europium nitrate, water, N,N′-dimethylacetamide, and methanol are uniformly mixed to obtain a mixture, which is placed in a reaction vessel for reaction to obtain colorless needle-shaped crystals, which are tunable luminescent stimulus-responsive materials.

2. The method for preparing the inorganic-organic hybrid tunable luminescent stimulus-responsive material according to claim 1, characterized in that: The mass ratio of the 2,4,6-tris(4-pyridyl)-1,3,5-triazine, 2,5-thiophenedicarboxylic acid and zinc perchlorate is 1:(1-2):(2-5).

3. The method for preparing the inorganic-organic hybrid tunable luminescent stimulus-responsive material according to claim 1, characterized in that: The mass ratio of the 2,4,6-tris(4-pyridyl)-1,3,5-triazine to europium nitrate is 7:(0.1-5).

4. The method for preparing the inorganic-organic hybrid tunable luminescent stimulus-responsive material according to claim 1, wherein: The volume ratio of the water, N,N′-dimethylacetamide and methanol is 4:1:(1-3); the mass ratio of the 2,4,6-tris(4-pyridyl)-1,3,5-triazine and europium nitrate is 7:(0.1-1).

5. The method for preparing the inorganic-organic hybrid tunable luminescent stimulus-responsive material according to claim 1, wherein: The reaction temperature of the mixture is 90-140° C., and the reaction time is 24-48 hours.

6. The method for preparing the inorganic-organic hybrid tunable luminescent stimulus-responsive material according to claim 1, characterized in that: The method comprises the following steps: adding 7 mg of 2,4,6-tris(4-pyridyl)-1,3,5-triazine, 10 mg of 2,5-thiophenedicarboxylic acid, 30 mg of zinc perchlorate, 0.1-1 mg of europium nitrate, 4 mL of water, 1 mL of N,N′-dimethylacetamide, and 2 mL of methanol into a sealed reaction container in sequence, placing the reaction container in an oven at 90-140° C. for reaction for more than 24-48 hours, cooling to room temperature, and taking out to obtain colorless needle-shaped crystals, which are tunable luminescent stimulus-responsive materials.

7. A method for preparing an inorganic-organic hybrid tunable luminescent stimulus-responsive material, characterized in that: The following steps are involved: 2,4,6-tris(4-pyridyl)-1,3,5-triazine, 2,5-thiophenedicarboxylic acid, zinc perchlorate, water, N,N′-dimethylacetamide, and methanol are uniformly mixed to obtain a mixture, and the mixture is placed in a reaction vessel for reaction to obtain colorless needle-shaped crystals, which are tunable luminescent stimulus-responsive materials; The mass ratio of the 2,4,6-tris(4-pyridyl)-1,3,5-triazine, 2,5-thiophenedicarboxylic acid, and zinc perchlorate is 1:(1-2):(2-5); the volume ratio of the water, N,N′-dimethylacetamide, and methanol is 4:1:(1-3); the reaction temperature of the mixture is 90-140° C., and the reaction time is 24-48 hours.

8. The method for preparing an inorganic-organic hybrid tunable luminescent stimulus-responsive material according to claim 7, characterized in that: The chemical formula of the adjustable luminescent stimulus-responsive material is C 30 H 16 N6O9S2Zn2, the inorganic part is Zn 2+ , the organic part is 2,4,6-tris(4-pyridyl)-1,3,5-triazine and 2,5-thiophenedicarboxylic acid, monoclinic system, space group P 21 / c, unit cell parameters a=10.1802(5)Å, b=20.2120(10)Å, c=15.4794(8)Å, α=90°, β=91.590(5)°, γ=90°.

9. Application of the tunable luminescent stimulus-responsive material prepared by the preparation method of the inorganic-organic hybrid tunable luminescent stimulus-responsive material according to any one of claims 1 to 8 in inkless printing, electrochromic devices, photochromic decoration, optical storage, optical switch and optoelectronic display.

10. Use of the tunable luminescent stimulus-responsive material prepared by the method for preparing the inorganic-organic hybrid tunable luminescent stimulus-responsive material according to any one of claims 1 to 8 in the fields of information encryption and anti-counterfeiting.

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