A photochromic molecule, a visible light-regulated solid-state composite film and a preparation method and application thereof

Abstract

The application belongs to the field of intelligent photoluminescent materials, and relates to a photochromic molecule, a visible light-regulated solid-state composite film and a preparation method and application thereof. The photochromic molecule is formed by connecting a fluorescent molecule on a diarylethene skeleton, and a structural formula of the photochromic molecule is: a preparation method thereof comprises the following steps: taking diarylethene aldehyde as raw material, and sequentially performing alkenyl aldehyde modification, benzimidazole modification and benzimidazole salt modification to prepare the photochromic molecule. The solid-state composite film comprises the solid-state composite film and the photochromic molecule loaded on the solid-state composite film, the solid-state composite film is made of PP and PMMA, and the solid-state composite film can be reversibly regulated under visible light. The preparation method is simple, the raw material consumption is small, the prepared solid-state composite film has high photoluminescent intensity, and reversible regulation of the fluorescent molecule under visible light is realized. The solid-state composite film has very important significance for developing high-safety anti-counterfeiting, and has wide application prospect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of intelligent photoluminescence materials, and relates to a photochromic molecule, a visible light-regulated solid-state composite film and a preparation method and application thereof. BACKGROUND

[0002] Molecular photoswitches are a common class of photoactive molecules that can reversibly switch between two isomers under different light irradiation, and are widely used in anti-counterfeiting, optical recording and biological imaging, etc. See: (1) Da-Hui Qu, Qiao-Chun Wang, Qi-Wei Zhang, Xiang Ma, and He Tian, Chem. Rev. 2015, 115, 15, 7543-7588. (2) H.-B. Cheng, S. Zhang, E. Bai, X. Cao, J. Wang, J. Qi, J. Liu, J. Zhao, L. Zhang, J. Yoon, Adv. Mater. 2022, 34, 2108289. (3) G. Liu, X. Xu, X. Dai, C. Jiang, Y. Zhou, L. Lu, Y. Liu, Mater. Horiz. 2021, 8, 2494-2502. Generally, most molecular photoswitches switch between different molecular configurations under ultraviolet light, but strict protection against ultraviolet irradiation is required in biological applications. Therefore, it is of great significance to develop visible light-induced molecular bidirectional switches.

[0003] Diarylethene (DAE) derivatives are one of the most promising photochromic molecules due to their excellent thermal stability, fast photoresponse and good reversibility. In previous work, visible or near-infrared photochromism was achieved by strategies such as energy transfer, multi-photon absorption, electron transfer or intramolecular proton transfer, see: (1) Z. Zhang, W. Wang, P. Jin, J. Xue, L. Sun, J. Huang, J. Zhang, H. Tian, Nat. Commun. 2019, 10, 4232. (2) Mori, K.; Ishibashi, Y.; Matsuda, H.; Ito, S.; Nagasawa, Y.; Nakagawa, H.; Uchida, K.; Yokojima, S.; Nakamura, S.; Irie, M.; Miyasaka, H. J. Am. Chem. Soc. 2011, 133, 2621-2625. (3a) M. Herder, M. Utecht, N. Manicke, L. Grubert, M. Ptzel, P. Saalfrank, S. Hecht, Chem. Sci. 2013, 4, 1028-1040. (3b) S. Lee, Y. You, K. Ohkubo, S. Fukuzumi, W. Nam, Chem. Sci. 2014, 5, 1463-1474. (4) H. Xi, Z. Zhang, W. Zhang, M. Li, C. Lian, Q. Luo, H. Tian, W.-H. Zhu, J. Am. Chem. Soc. 2019, 141, 18467-18474. (5) T. Fukaminato, T. Hirose, T. Doi, M. Hazama, K. Matsuda, M. Irie, J. Am. Chem. Soc. 2014, 136, 17145-17154. The simplest one is to modify the aromatic groups on the central hexatriene skeleton to expand the pi-conjugated system, thereby changing the absorption band of the open-ring diarylethene in the visible or near-infrared region. However, for most diarylethene derivatives with aromatic dyes at the side, the ability of the excited singlet state of the central hexatriene part is not effectively enhanced due to the expansion of the pi-conjugated system, and their visible light reactivity is obviously inhibited.

[0004] Therefore, it is an innovative research topic to construct a solid-state composite film that can be reversibly adjusted under visible light, which has very important practical application value for the development of high-safety anti-counterfeiting materials. SUMMARY

[0005] In order to solve the technical problems that the above-mentioned molecular optical switch cannot be reversibly adjusted under visible light and the visible light reactivity is inhibited, the application provides a photochromic molecule, a visible light-adjusted solid composite film and a preparation method and application thereof.The visible light-adjusted solid composite film system is a solid film formed by mixing two high molecular polymers of PP (polypropylene) and PMMA (polymethyl methacrylate), and contains many nanometer cavities capable of accommodating fluorescent molecules.The fluorescent molecules are accommodated while their free rotation is limited, mechanical energy dissipation is reduced, and photoluminescence intensity is enhanced, which makes it possible to realize reversible adjustment of fluorescent molecules under visible light.

[0006] In order to achieve the above-mentioned purpose, the technical scheme of the application is implemented as follows:

[0007] A photochromic molecule is formed by connecting a fluorescent molecule to a diarylethene skeleton, and the structural formula of the photochromic molecule is as follows:

[0008]

[0009] Further, the preparation method of the photochromic molecule is as follows:

[0010] (1) Preparation of aldehyde-modified diarylethene: diarylethene aldehyde and tributyl (1,3-dioxalate-2-methyl) phosphonium bromide are dissolved in tetrahydrofuran, sodium hydride is added under nitrogen protection, and stirring reaction is carried out at room temperature.After the reaction is completed, ice water is used for quenching, extraction, drying and column chromatography to obtain aldehyde-modified diarylethene.

[0011] (2) Preparation of benzimidazole-modified diarylethene: 2-aminothiophenol and the aldehyde-modified diarylethene obtained in step (1) are dissolved in acetic acid, and heating reflux reaction is carried out.After the reaction is completed, ice water is poured in, the pH is adjusted to neutral, and extraction, drying and column chromatography are carried out to obtain benzimidazole-modified diarylethene.

[0012] (3) Preparation of photochromic molecule: CH3I solution and the benzimidazole-modified diarylethene obtained in step (2) are mixed and heated for reaction, and after the reaction is completed, cooling to room temperature and suction filtration are carried out, and the obtained solid is stirred with ammonium hexafluorophosphate at room temperature to obtain the photochromic molecule.

[0013] Further, in step (1), the mass ratio of diarylethene and tributyl (1,3-dioxalate-2-methyl) phosphonium bromide is 0.58:(0.81-0.91), the mass ratio of sodium hydride and diarylethene is 1:(2-4), and the stirring reaction time at room temperature is 12-15 h.

[0014] Further, in step (1), the eluent for column chromatography is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate is (2-5):1.

[0015] Further, the mass ratio of the enal-modified diarylethene and 2-aminothiophenol in step (2) is 0.31:(0.15-0.25), the heating reflux reaction time is 12-15 h, and the heating reflux reaction temperature is 120-125 DEG C.

[0016] Further, the eluent for column chromatography in step (2) is a mixed solvent of petroleum ether and dichloromethane, and the volume ratio of petroleum ether to dichloromethane is (1-2):3.

[0017] Further, the mass-volume ratio of the benzimidazole-modified diarylethene and CH3I in step (3) is 0.39 g:(3-4.5) mL, the heating reaction time is 24-26 h, the heating reaction temperature is 110-120 DEG C, and the mass ratio of ammonium hexafluorophosphate to the benzimidazole-modified diarylethene is (5-10):1.

[0018] A visible light-regulated solid-state composite film, comprising a solid-state composite film and the above-mentioned photochromic molecules loaded on the solid-state composite film, wherein the solid-state composite film is made of a mixture of PP and PMMA; and the visible light-regulated solid-state composite film is reversibly regulated under visible light.

[0019] Further, the preparation method of the visible light-regulated solid-state composite film is as follows: dissolving the photochromic molecules and PMMA in acetonitrile and chloroform respectively to obtain solution I and solution II, then mixing solution I and solution II uniformly to obtain solution III, and then immersing PP in solution III, and taking out and air-drying after the immersion to obtain the visible light-regulated solid-state composite film.

[0020] Further, the concentration of solution I is 4.8 g / L, and the concentration of solution II is 60 g / L.

[0021] Further, the visible light-regulated solid-state composite film is applied to the construction of intelligent photoluminescent materials.

[0022] The present application has the following advantages:

[0023] 1. The preparation method provided by the present application is simple and requires less raw materials.

[0024] 2, The prepared visible light reversible regulating solid-state composite film has high photoluminescence intensity. Under 420nm light irradiation, the visible light reversible regulating solid-state composite film gradually changes from the initial strong yellow fluorescent state to the fluorescent quenching state; under greater than 550nm light irradiation, the initial strong yellow fluorescence is completely restored within 20s, realizing the reversible regulation of the fluorescent molecules under visible light, and also indicating that the visible light reversible regulating solid-state composite film has little loss to the structural change of the fluorescent molecules.

[0025] 3, The fluorescence intensity of the visible light reversible regulating solid-state composite film can be reciprocated at least four times without obvious reduction under the alternating irradiation of 420nm and 550nm light, showing excellent fatigue resistance.

[0026] 4, The prepared visible light reversible regulating solid-state composite film has great significance for developing high-safety anti-counterfeiting materials and has great application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0027] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the drawings needed to be used in the embodiment or prior art description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0028] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the alkenal modified diarylethene prepared in the embodiment 1 of the present application.

[0029] Figure 2 The nuclear magnetic resonance hydrogen spectrum of the benzimidazole modified diarylethene prepared in the embodiment 1 of the present application.

[0030] Figure 3 The nuclear magnetic resonance hydrogen spectrum of the benzimidazole salt modified diarylethene (photochromic molecule) prepared in the embodiment 1 of the present application.

[0031] Figure 4 The change diagram of the ultraviolet-visible absorption spectrum of the (4a) solid-state DAE-FMR / PMMA film prepared in the application example under the alternating irradiation of 420nm and greater than 550nm visible light, and the change diagram of the ultraviolet-visible absorption spectrum of the acetonitrile solution of the benzimidazole salt modified diarylethene under 420nm visible light irradiation.

[0032] Figure 5Solid state fluorescence spectra of DAE-FMR / PMMA-PP prepared in the application example, DAE-FMR / PMMA prepared in the application example comparative example 1 and DAE-FMR / PP prepared in the application example comparative example 2.

[0033] Figure 6 Solid state fluorescence spectra of (6a) DAE-FMR / PMMA-PP prepared in the application example under 420 nm visible light irradiation (insert: fluorescence photo change of DAE-FMR / PMMA-PP under 365 nm ultraviolet light irradiation); (6b) solid state fluorescence spectra of DAE-FMR / PMMA-PP under greater than 550 nm visible light irradiation (insert: fluorescence photo change of DAE-FMR / PMMA-PP under 365 nm ultraviolet light irradiation).

[0034] Figure 7 Solid state fluorescence spectra of DAE-FMR / PMMA-PP prepared in the application under 420 nm and 550 nm alternating irradiation. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative effort belong to the scope of protection of the present application.

[0036] In the following examples, compound 1 refers to diarylethene aldehyde, compound 2 refers to aldehyde-modified diarylethene, compound 3 refers to benzimidazole-modified diarylethene, DAE-FMR refers to a photochromic molecule, DAE-FMR / PMMA-PP refers to a reversible solid-state composite film under visible light. PP refers to polypropylene, PMMA refers to polymethyl methacrylate, and all reagents used in the present application are commercially available.

[0037] Example 1

[0038] This embodiment is a preparation method of a photochromic molecule, and the steps are as follows:

[0039] The reaction equation of the photochromic molecule (DAE-FMR) is as follows:

[0040]

[0041] The specific preparation steps are as follows:

[0042] (1) Preparation of compound 2 (aldehyde-modified diarylethene)

[0043] Compound 1 (0.58 g) and tributyl(1,3-dioxalan-2-ylmethyl)phosphonium bromide (0.81 g) were dissolved in tetrahydrofuran, and sodium hydride (0.145 g) was added under nitrogen protection, and stirred at room temperature for 12 h. Then quenched with ice water. Extraction, drying, column, eluent petroleum ether / ethyl acetate = 2:1, to obtain compound 2 (enal-modified diarylethene).

[0044] Figure 1 The H NMR spectrum of compound 2 of Example 1 is shown in the following table. Compound 2 (yield: 78%) 1 H NMR (400 MHz, CDCl3) δ (ppm) = 9.72 (d, J = 7.6 Hz, 2H), 7.63-7.58 (m, 8H), 7.48 (d, J = 15.9 Hz, 2H), 7.38 (s, 2H), 6.74 (dd, J = 15.9, 7.7 Hz, 2H), 2.00 (s, 6H).

[0045] (2) Preparation of compound 3 (benzimidazole-modified diarylethene)

[0046] Compound 2 (0.31 g) and 2-aminobenzenethiol (0.15 g) were dissolved in acetic acid, and heated to reflux at 120°C for 12 h. Then pour into ice water, adjust pH to neutral, extraction, drying, column, eluent petroleum ether / dichloromethane = 1:3, to obtain compound 3 (benzimidazole-modified diarylethene).

[0047] Figure 2 The H NMR spectrum of compound 3 of this example is shown in the following table. Compound 3 (yield: 85%) 1 H NMR (400 MHz, CDCl3) δ (ppm) = 8.01 (d, J = 8.1 Hz, 2H), 7.88 (d, J = 7.8 Hz, 2H), 7.61 (br, 8H), 7.55-7.51 (m, 3H), 7.49-7.45 (m, 3H), 7.40 (d, J = 7.9 Hz, 2H), 7.36 (s, 2H), 2.00 (s, 6H).

[0048] (3) Preparation of DAE-FMR

[0049] Compound 3 (0.39 g) and CH3I (3 mL) were placed in a 10 mL pressure tube, heated at 110°C for 24 h, cooled to room temperature, suction filtration, and the obtained solid was ion exchanged with 5 times solid ammonium hexafluorophosphate under stirring at room temperature to obtain the final product DAE-FMR.

[0050] Figure 3 The H NMR spectrum of DAE-FMR of this example is shown in the following table. DAE-FMR (yield: 90%)1 H NMR (400 MHz, DMSO) δ (ppm) = 8.46 (d, J = 8.0 Hz, 2H), 8.28 (d, J = 4.0 Hz, 2H), 8.25 (d, J = 11.6 Hz, 2H), 8.13 (d, J = 8.8 Hz, 4H), 8.10 (s, J = 16.4 Hz, 2H), 7.91 (d, J = 7.2 Hz, 2H), 7.88 (d, J = 8.0 Hz, 4H), 7.83 (d, J = 7.2 Hz, 2H), 7.80 (s, 2H), 4.39 (s, 6H), 2.04 (s, 6H).

[0051] Example 2

[0052] This example is a preparation method of a photochromic molecule, and the steps are as follows:

[0053] (1) Preparation of compound 2 (enal-modified diarylethene)

[0054] Compound 1 (0.58 g) and tributyl (1,3-dioxalate-2-methyl) phosphonium bromide (0.86 g) were dissolved in tetrahydrofuran, and sodium hydride (0.193 g) was added under nitrogen protection, and stirred at room temperature for 13 h. Then quench with ice water. Extract, dry, pass through a column, and eluent is petroleum ether / ethyl acetate = 3:1 to obtain compound 2 (enal-modified diarylethene).

[0055] (2) Preparation of compound 3 (benzimidazole-modified diarylethene)

[0056] Compound 2 (0.31 g) and 2-aminothiophenol (0.25 g) were dissolved in acetic acid, and heated to reflux at 125°C for 14 h. Then pour into ice water, adjust pH to neutral, extract, dry, pass through a column, and eluent is petroleum ether / dichloromethane = 2:3 to obtain compound 3 (benzimidazole-modified diarylethene).

[0057] (3) Preparation of DAE-FMR

[0058] Compound 3 (0.39 g) and CH3I (5 mL) were placed in a 10 mL pressure tube, heated at 115°C for 25 h, cooled to room temperature, and suction filtered. The obtained solid was ion exchanged with 7 times solid ammonium hexafluorophosphate under stirring at room temperature to obtain the final product DAE-FMR.

[0059] Example 3

[0060] This example is a preparation method of a photochromic molecule, and the steps are as follows:

[0061] (1) Preparation of compound 2 (enal-modified diarylethene)

[0062] Compound 1 (0.58 g) and tributyl(1,3-dioxalan-2-ylmethyl)phosphonium bromide (0.91 g) were dissolved in tetrahydrofuran, and sodium hydride (0.29 g) was added under nitrogen protection. The mixture was stirred at room temperature for 15 h. Then it was quenched with ice water. Extraction, drying, column chromatography, and eluent of petroleum ether / ethyl acetate = 5:1, gave compound 2 (enal-modified diarylethene).

[0063] (2) Preparation of compound 3 (benzimidazole-modified diarylethene)

[0064] Compound 2 (0.31 g) and 2-aminobenzenethiol (0.20 g) were dissolved in acetic acid, and the mixture was heated to reflux at 123 °C for 15 h. Then it was poured into ice water, and the pH was adjusted to neutral. Extraction, drying, column chromatography, and eluent of petroleum ether / dichloromethane = 1:3, gave compound 3 (benzimidazole-modified diarylethene).

[0065] (3) Preparation of DAE-FMR

[0066] Compound 3 (0.39 g) and CH3I (4 mL) were placed in a 10 mL pressure tube, and the mixture was heated at 120 °C for 26 h. After cooling to room temperature, the mixture was suction filtered. The obtained solid was ion exchanged with 10 times solid ammonium hexafluorophosphate under stirring at room temperature, to give the final product DAE-FMR.

[0067] Application Example

[0068] This application example is a preparation method of a solid-state composite film (DAE-FMR / PMMA-PP) reversibly adjusted under visible light, and the steps are as follows:

[0069] DAE-FMR (2.4 mg) and PMMA (0.12 g) were respectively dissolved in acetonitrile (0.5 mL) and chloroform (2 mL), and the mixture was mixed uniformly. Then PP was soaked in the above solution, and after 2 h, it was taken out and air dried, to give the solid-state composite film DAE-FMR / PMMA-PP.

[0070] Figure 4Fig. (4a) is a diagram showing the change of UV-Vis absorption spectrum of the solid-state DAE-FMR / PMMA-PP film prepared in this application example under the irradiation of 420 nm and greater than 550 nm visible light alternately, and Fig. (4b) is a diagram showing the change of UV-Vis absorption spectrum of the acetonitrile solution of the benzimidazole salt modified diaryarylethene under the irradiation of 420 nm visible light. Fig. (4a) shows that under the irradiation of 420 nm visible light, the absorbance maximum of DAE-FMR / PMMA-PP decreases; a new absorbance appears at 666 nm and increases, indicating that the photo-cyclization of DAE occurs from the open form to the closed form, which is probably the constraint of the conformation, and the irradiation of light greater than 550 nm can restore it. Fig. (4b) shows that the solution-state benzimidazole salt modified diaryarylethene cannot effectively undergo photo-cyclization under the irradiation of 420 nm visible light.

[0071] Figure 6 Fig. (6a) and Fig. (6b) show the change of solid-state fluorescence spectrum of DAE-FMR / PMMA-PP film under the irradiation of 420 nm and greater than 550 nm visible light alternately. Fig. (6a) and Fig. (6b) show that under the irradiation of 420 nm light, the fluorescence of DAE-FMR / PMMA-PP film is quenched, while under the irradiation of 365 nm light, the strong yellow fluorescence photo darkens, which is due to the photo-cyclization of diaryarylethene to form the closed form. Subsequently, the irradiation of light greater than 550 nm to DAE-FMR / PMMA-PP film can completely restore the initial fluorescence intensity.

[0072] Figure 7 Fig. (7) shows the change of solid-state fluorescence spectrum of DAE-FMR / PMMA-PP film prepared in Example 1 under the irradiation of 420 nm and 550 nm alternately. Figure 7 It is shown that the fluorescence of the composite film can be reciprocated at least four times without obvious decrease, which shows its excellent anti-fatigue performance.

[0073] Application Example Comparative Example 1

[0074] The preparation method of DAE-FMR / PMMA in this application example is as follows:

[0075] The preparation method of DAE-FMR is the same as that in Example 1.

[0076] DAE-FMR (2.4 mg) and PMMA (0.12 g) were dissolved in acetonitrile (0.5 mL) and chloroform (2 mL) respectively, and mixed uniformly. The mixture was uniformly spread on a quartz sheet and air-dried to obtain DAE-FMR / PMMA.

[0077] Application Example Comparative Example 2

[0078] The application example comparative example is a preparation method of DAE-FMR / PP, and the steps are as follows:

[0079] The preparation method of DAE-FMR is the same as that in Example 1.

[0080] DAE-FMR (2.4 mg) was dissolved in acetonitrile (0.5 mL), and then PP was soaked in the above solution. After 2 h, the PP was taken out and air-dried to obtain DAE-FMR / PP.

[0081] Figure 5 Solid-state fluorescence spectra of DAE-FMR / PMMA-PP prepared in the application example, DAE-FMR / PMMA prepared in the application example comparative example 1, and DAE-FMR / PP prepared in the application example comparative example 2. Figure 5 It is illustrated that, compared with other films, the DAE-FMR / PMMA-PP composite film forms small-size micropores with cross-networks, and thus has the strongest fluorescence intensity.

[0082] The prepared DAE-FMR / PMMA-PP solid-state composite film doped with PMMA and PP illustrates that the solid-state composite film can greatly enhance the fluorescence intensity, by comparison with the fluorescence intensity of PMMA alone and PP alone. It is illustrated that the solid-state composite film has very small loss to the structural change of fluorescent molecules, by alternating irradiation of it with 420 nm and visible light greater than 550 nm. It is illustrated that the solid-state composite film has excellent fatigue resistance, by four times of fluorescence reciprocation of the solid-state composite film under visible light. The research has very important significance and application value in high-safety anti-counterfeiting materials.

[0083] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A visible light modulated solid state composite film, characterized by: The application relates to a visible light adjustable solid composite film comprising a solid composite film and a photochromic molecule loaded on the solid composite film, wherein the solid composite film is made of PP and PMMA; and the photochromic molecule is formed by connecting a fluorescent molecule on a diarylethene skeleton. The photochromic molecule is formed by connecting a fluorescent molecule on a diarylethene skeleton. 。 2. The visible light modulated solid state composite film of claim 1, wherein, The preparation steps of the photochromic molecule are as follows. (1) Preparation of alkenal-modified diarylethene: diarylethene alkenal and dissolved in tetrahydrofuran, sodium hydride was added under nitrogen protection, the reaction was stirred at room temperature, after the reaction was completed, ice water was quenched, extracted, dried, and columned to obtain alkenal-modified diarylethene; The structure of the diarylethene aldehyde is shown in formula 1. ； The structure of the aldehyde-modified diarylethene is shown in formula 2. ； The preparation of the benzimidazole-modified diarylethene is as follows: 2-aminothiophenol and the aldehyde-modified diarylethene obtained in step (1) are dissolved in acetic acid, heated to reflux, poured into ice water after the reaction is completed, the pH is adjusted to neutral, and then extracted, dried and columned to obtain the benzimidazole-modified diarylethene. The structure of the benzimidazole-modified diarylethene is shown in formula 3. ； The preparation of the photochromic molecule is as follows: CH3I and the benzimidazole-modified diarylethene obtained in step (2) are mixed and heated to react, cooled to room temperature after the reaction is completed, and then extracted and filtered to obtain the photochromic molecule.

3. The visible light modulated solid state composite film according to claim 2, wherein: In step (1), diarylethylene and The mass ratio of sodium hydride to diarylethylene is 0.58:(0.81~0.91), the mass ratio of sodium hydride to diarylethylene is 1:(2~4), and the reaction time at room temperature is 12~15h. The eluent for column chromatography is a mixed solvent of petroleum ether and ethyl acetate, with a volume ratio of petroleum ether to ethyl acetate of (2~5):

1.

4. The visible light modulated solid-state composite film according to claim 2 or 3, characterized in that: In step (2), the mass ratio of the aldehyde-modified diarylethene to 2-aminothiophenol is 0.31: (0.15-0.25), the heating reflux reaction time is 12-15 h, and the heating reflux reaction temperature is 120-125 DEG C.

5. The visible light modulated solid state composite film according to claim 4, wherein: In step (2), the eluent for column chromatography is a mixed solvent of petroleum ether and dichloromethane, and the volume ratio of petroleum ether to dichloromethane is (1-2):

3.

6. The visible light modulated solid state composite film according to any one of claims 2, 3 or 5, wherein: In step (3), the mass-volume ratio of the benzimidazole-modified diarylethene to CH3I is 0.39 g: (3-4.5) mL, the heating reaction time is 24-26 h, the heating reaction temperature is 110-120 DEG C, and the mass ratio of ammonium hexafluorophosphate to the benzimidazole-modified diarylethene is (5-10):

1.

7. The method of making a visible light modulated solid state composite film of claim 1, characterized by: The photochromic molecule and PMMA are respectively dissolved in acetonitrile and chloroform to obtain solution I and solution II, then solution I and solution II are uniformly mixed to obtain solution III, and then PP is soaked in solution III, taken out and air-dried to obtain the visible light adjustable solid composite film.

8. The method of claim 7, wherein the method further comprises: The concentration of solution I is 4.8 g / L, and the concentration of solution II is 60 g / L.

9. The application of the visible light adjustable solid composite film in claim 7 in the construction of intelligent photoluminescent materials.

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