Optical switch molecule and preparation method and application thereof

Abstract

The invention relates to the technical field of molecular switches, and discloses an optical switch molecule and a preparation method and application thereof. The structural general formula of the optical switch molecule is as follows: R1 is a hydrogen bond acceptor group, R2 is an electron donating group or an electron withdrawing group, and R3 and R4 are spatial substituent groups. According to the invention, sp3 hybrid carbon atoms are used as bridging units, and a series of space folding type ESIPT optical switch molecules are constructed for the first time and are applied to the aspects of chemical sensing, information encryption, data storage and the like. According to the method, light is used as an external stimulation condition to induce the photoswitch molecules to generate a rapid six-level photophysical-chemical process and generate a cis-trans isomerization process in an excited state, so that the photoswitch molecules are macroscopically represented as high-contrast color change before and after photostimulation.

Description

Technical Field

[0001] This invention relates to the field of molecular switch technology, and in particular to an optical switch molecule, its preparation method, and its application. Background Technology

[0002] Rapid economic and technological development has also brought increasing challenges to information security, making the design and development of smart materials for high-level information encryption and data storage crucial. Photostimulation-responsive materials, due to their intelligent response to light, are widely used in sensing, military, medical, and information security fields. However, traditional photo-switching molecules such as azobenzene, spiropyran, diarylethylene, benzoic anhydride, and their derivatives severely limit their application in information encryption and data storage due to insufficient photostimulation response behavior and the problem of single signal in the solid state. Furthermore, the presence of isomers in the ground state of traditional photo-switching molecules often leads to frequent spurious signal outputs and low contrast of the true signal output, which is detrimental to high-level information security.

[0003] Therefore, existing technologies still need to be improved and developed. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the purpose of this invention is to provide an optical switch molecule, its preparation method and application, which aims to solve the problems of slow optical response rate, low signal output contrast and poor fatigue resistance of traditional optical switch molecules in the solid state.

[0005] The technical solution of the present invention is as follows:

[0006] In a first aspect, the present invention provides a light-switching molecule, the general structural formula of which is as follows:

[0007] In this group, R1 is a hydrogen bond acceptor group, R2 is an electron-donating or electron-withdrawing group, and R3 and R4 are both steric substituent groups.

[0008] Preferably, R1 is selected from one of the following groups: benzothiazole group, benzoxazole group, benzimidazole group, diphenylimidazolium group, pyridine group, quinoline group, aldehyde group, carbonyl group, carbonyl sulfide group, imine group, secondary amine group, hydrazone group, and selenium group, but is not limited thereto.

[0009] Preferably, R2 is selected from one of the following groups: methyl group, tert-butyl group, methoxy group, ethoxy group, N,N-dimethyl group, triphenylamine group, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, carboxylic acid ester group, trifluoromethyl group, nitro group, pyridine group, pyridine salt group, benzothiazole group, benzoxazole group, benzimidazole group, diphenylimidazolium group, quinoline group, quinoline salt group, aldehyde group, and pyranonitrile group, but is not limited thereto.

[0010] Preferably, R3 is selected from one of the following groups: methyl group, benzene ring group, methoxy group, carboxylic acid group, carboxylic acid ester group, peptide bond-derived group, and hydrogen atom, but is not limited thereto.

[0011] Preferably, R4 is selected from one of the following groups: methyl group, benzene ring group, methoxy group, carboxylic acid group, carboxylic acid ester group, peptide bond-derived group, and hydrogen atom, but is not limited thereto.

[0012] Preferably, the optical switch molecule has one of the following structures:

[0013]

[0014] Preferably, the wavelength range of the light stimulation of the light-switching molecule is 200nm-800nm.

[0015] In a second aspect, the present invention provides a method for preparing the above-mentioned optical switch molecule, wherein the optical switch molecule is prepared by a mixed solvent rotary evaporation method, a crystallization method, or a mechanical stirring method.

[0016] A third aspect of the present invention provides the application of the above-described optical switching molecule in the fields of chemical sensing, information encryption, or data storage.

[0017] The present invention has the following beneficial effects:

[0018] This invention proposes an optical switch molecule, its preparation method, and its applications. The ESIPT (Excited-State Intramolecular Proton Transfer) solid-state optical switch molecule provided by this invention undergoes photoactivated cis-trans isomerization under light stimulation, enabling high-level information encryption and data storage. The optical switch molecule developed in this invention exhibits high signal output contrast under light stimulation, changing from pure white to yellow. Compared to traditional optical switch molecules, the optical switch molecule developed in this invention has a faster optical response rate in the solid state, rapidly undergoing photochromism under light stimulation and reaching saturation within seconds. After stimulation with white light, its recovery rate is faster than that of traditional optical switch molecules (such as the contrasting molecule BS-SP1). The isomerization process in the solid state of the optical switch molecule developed in this invention is rapid and exhibits strong fatigue resistance, exceeding 50 cycles, far superior to traditional optical switch molecules. Attached Figure Description

[0019] Figure 1 The photon nuclear magnetic resonance (NMR) spectrum of the compound TPOH-CHO prepared in Example 1 of this invention in deuterated dimethyl sulfoxide (DMSO-d6).

[0020] Figure 2 The UV-Vis absorption spectrum and fluorescence spectrum of the compound TPOH-CHO prepared in Example 1 of this invention are shown in the solid state.

[0021] Figure 3 The hydrogen nuclear magnetic resonance spectrum of the compound TPOH-2CHO prepared in Example 4 of this invention in DMSO-d6.

[0022] Figure 4 The UV-Vis absorption spectrum and fluorescence spectrum of the compound TPOH-2CHO prepared in Example 4 of this invention are shown in the solid state.

[0023] Figure 5 The hydrogen nuclear magnetic resonance spectrum of the compound TPOH-Nph prepared in Example 7 of this invention in DMSO-d6.

[0024] Figure 6 The UV-Vis absorption spectrum and fluorescence spectrum of the compound TPOH-Nph prepared in Example 7 of this invention are shown in the solid state.

[0025] Figure 7 The hydrogen nuclear magnetic resonance spectrum of the compound TPOH-Nnap prepared in deuterated chloroform (CDCl3) in Example 10 of this invention.

[0026] Figure 8 The UV-Vis absorption spectrum and fluorescence spectrum of the compound TPOH-Nnap prepared in Example 10 of this invention are shown in the solid state.

[0027] Figure 9 The photon nuclear magnetic resonance (NMR) spectrum of the compound TPOH-Nph-CF3 prepared in Example 13 of this invention in DMSO-d6 is shown.

[0028] Figure 10 The UV-Vis absorption spectrum and fluorescence spectrum of the compound TPOH-Nph-CF3 prepared in Example 13 of this invention are shown in the solid state.

[0029] Figure 11 The photon nuclear magnetic resonance (NMR) spectrum of the compound BPOH-CHO prepared in Example 16 of this invention in DMSO-d6 is shown.

[0030] Figure 12 Absorption and fluorescence images of the compound BPOH-CHO prepared in Example 16 of this invention, taken in an oily liquid state.

[0031] Figure 13 The hydrogen nuclear magnetic resonance spectrum of the compound BPOH-2CHO prepared in Example 19 of this invention in DMSO-d6.

[0032] Figure 14 The UV-Vis absorption spectrum and fluorescence spectrum of the compound BPOH-2CHO prepared in Example 19 of this invention are shown in the solid state.

[0033] Figure 15 The photon nuclear magnetic resonance (NMR) spectrum of the compound TPOH-Nph-OMe prepared in Example 22 of this invention in DMSO-d6 is shown.

[0034] Figure 16 The UV-Vis absorption spectrum and fluorescence spectrum of the compound TPOH-Nph-OMe prepared in Example 22 of this invention are shown in the solid state.

[0035] Figure 17 The hydrogen nuclear magnetic resonance spectrum of the compound TPOH-Nph-CN prepared in Example 25 of this invention in DMSO-d6.

[0036] Figure 18 The UV-Vis absorption spectrum and fluorescence spectrum of the compound TPOH-Nph-CN prepared in Example 25 of this invention are shown in the solid state.

[0037] Figure 19 The photon nuclear magnetic resonance (NMR) spectrum of the compound CPOH-CHO prepared in Example 28 of this invention in DMSO-d6 is shown.

[0038] Figure 20 Absorption and fluorescence images of the compound CPOH-CHO prepared in Example 28 of this invention, taken in an oily liquid state.

[0039] Figure 21 The photon nuclear magnetic resonance (NMR) spectrum of the compound CPOH-2CHO prepared in Example 31 of this invention in DMSO-d6 is shown.

[0040] Figure 22 Absorption and fluorescence images of the compound CPOH-2CHO prepared in Example 31 of this invention, taken in an oily liquid state.

[0041] Figure 23 The hydrogen nuclear magnetic resonance spectrum of the compound TPOH-Nph-N(Me)2 prepared in Example 34 of this invention in DMSO-d6 is shown.

[0042] Figure 24 The UV-Vis absorption spectrum and fluorescence spectrum of the compound TPOH-Nph-N(Me)2 prepared in Example 34 of this invention are shown in the solid state.

[0043] Figure 25 The hydrogen nuclear magnetic resonance spectrum of the compound TPOH-Nph-F prepared in Example 37 of this invention in DMSO-d6.

[0044] Figure 26The UV-Vis absorption spectrum and fluorescence spectrum of the compound TPOH-Nph-F prepared in Example 37 of this invention are shown in the solid state.

[0045] Figure 27 The UV-Vis absorption spectrum and fatigue resistance performance of the conventional optical switching molecule spiropyran derivative BS-SP1 in Comparative Example 1 of this invention were tested.

[0046] Figure 28 The fatigue resistance of the compound TPOH-CHO prepared in Example 1 of this invention was tested in the solid state. Detailed Implementation

[0047] This invention provides an optically switching molecule, its preparation method, and its application. 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 only for explaining the invention and are not intended to limit the invention.

[0048] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0049] This invention provides an optical switch molecule, the general structural formula of which is as follows: In this group, R1 is a hydrogen bond acceptor group, R2 is an electron-donating or electron-withdrawing group, and R3 and R4 are both steric substituent groups.

[0050] Research has revealed that the ESIPT-effect-enabled optical switch molecule provided in this invention can undergo cis-trans isomerization in the excited state, avoiding the drawback of low signal output contrast caused by photophysical and chemical changes in the ground state in traditional optical switch molecules. Introducing folded bridging methylene groups and bulky triphenylmethyl groups into the ESIPT-effect-enabled optical switch molecule structure effectively expands intermolecular stacking, increases molecular motion space, provides ample space for free movement between molecules, and promotes the excited-state photochromic behavior of the ESIPT-effect-enabled optical switch molecule in the solid state, thus improving the optical response rate of the optical switch molecule in the solid state. Since the basicity of the O atom in the ESIPT-effect-enabled optical switch molecule is weaker than that of the N atom, the ESIPT-effect-enabled optical switch molecule with O-proton acceptor characteristics can greatly restrict intramolecular proton transfer (GSIPT) behavior in the ground state. Inhibition of GSIPT causes the ESIPT-effect light-switching molecule with O-proton acceptor to initially appear white and exhibit ultra-low background signal. Under light stimulation, it changes from white to yellow, promoting the improvement of photochromic contrast. Furthermore, the isomerization transformation process before and after light stimulation is rapid and has strong anti-fatigue properties, enabling high-level encrypted copying of information and high-density data storage.

[0051] In some embodiments, R1 is preferably an aldehyde group, an imine group or a derivative thereof, R2 is preferably an aldehyde group or a hydrogen atom, and R3 and R4 are preferably methyl groups, benzene ring groups or hydrogen atoms.

[0052] The prerequisites for the photo-switching molecules involved in this invention to generate a photoresponse are: 1. Under light stimulation, the molecules first undergo the ESIPT process; 2. Sufficient spatial volume is required for molecular motion. The preferred groups R1 and R2, as effective proton acceptors, are more conducive to the ESIPT process, leading to cis-trans isomerization and thus photochromism. The preferred groups R3 and R4, as folded bridging structures and large-volume groups, provide the spatial volume required for the photo-switching molecules to move under light stimulation.

[0053] The following detailed description uses specific examples.

[0054] Example 1

[0055] The preparation of compound TPOH-CHO includes the following steps:

[0056] 1.0 equivalent of 4-triphenylmethylphenol, 3.0 equivalent of hexamethylenetetramine, and 10 equivalent of trifluoroacetic acid were mixed in a 500 mL round-bottom flask with stirring. The mixture was refluxed at 70 °C for 3 h until the reaction was complete. 360 mL of a 4 mol / L hydrochloric acid aqueous solution was added to the reaction solution, and the mixture was stirred for 1 h to hydrolyze and form a large amount of precipitate. The precipitate was filtered under reduced pressure and dried to obtain a yellow solid TPOH-CHO. The crude product was purified by column chromatography using dichloromethane / petroleum ether as the eluent to obtain a white powder, pure TPOH-CHO. The reaction route is as follows:

[0057]

[0058] Example 2

[0059] Characterization of the compound TPOH-CHO obtained in Example 1:

[0060] A small amount (20 mg) of TPOH-CHO powder was dissolved in DMSO-d6, and the sample was subjected to nuclear magnetic resonance spectroscopy. The spectrum is shown in the figure. Figure 1 .

[0061] Example 3

[0062] The UV-Vis absorption and fluorescence spectra of the compound TPOH-CHO prepared in Example 1 in the solid state.

[0063] A small amount of TPOH-CHO powder was placed in the sample cell, and the sample was irradiated with ultraviolet light for different times. The absorption and fluorescence spectra at different irradiation times were measured. The spectra are shown in the figure. Figure 2 .

[0064] Example 4

[0065] The preparation of compound TPOH-2CHO includes the following steps:

[0066] 1.0 equivalent of 4-triphenylmethylphenol, 12.0 equivalents of hexamethylenetetramine, and 10 equivalents of trifluoroacetic acid were mixed in a 500 mL round-bottom flask with stirring. The mixture was refluxed at 120 °C for 72 h until the reaction was complete. 360 mL of a 4 mol / L hydrochloric acid aqueous solution was added to the reaction mixture, and the mixture was stirred for 1 h to hydrolyze and form a large amount of precipitate. The precipitate in the reaction mixture was filtered under reduced pressure and dried to obtain a yellow solid.

[0067] TPOH-2CHO. The crude product was purified by column chromatography using dichloromethane / petroleum ether as eluent to obtain pure white powder TPOH-2CHO. The reaction route is as follows:

[0068]

[0069] Example 5

[0070] Characterization of the compound TPOH-2CHO obtained in Example 4:

[0071] A small amount (20 mg) of TPOH-2CHO powder was dissolved in DMSO-d6, and the sample was subjected to nuclear magnetic resonance spectroscopy. The spectrum is shown in the figure. Figure 3 .

[0072] Example 6

[0073] The UV-Vis absorption and fluorescence spectra of the compound TPOH-2CHO prepared in Example 4 in the solid state.

[0074] A small amount of TPOH-2CHO powder was placed in the sample cell, and the sample was irradiated with ultraviolet light for different times. The absorption and fluorescence spectra at different irradiation times were measured. The spectra are shown in the figure. Figure 4 .

[0075] Example 7

[0076] The preparation of compound TPOH-Nph includes the following steps:

[0077] 1.0 equivalent of TPOH-CHO, 1.02 equivalent of 1-aniline, and 10 equivalent of methanol were mixed in a 250 mL round-bottom flask with stirring. The mixture was refluxed at 65 °C for 2 h to complete the reaction. The reaction solution was cooled to room temperature, and the precipitate in the reaction solution was filtered under reduced pressure and dried to obtain a yellow solid TPOH-Nph. The crude product was recrystallized from the crude product with a mixed solvent of ethyl acetate / n-hexane to obtain a pure yellow powder TPOH-Nph. The reaction route is as follows:

[0078]

[0079] Example 8

[0080] Characterization of the compound TPOH-Nph obtained in Example 7:

[0081] A small amount (20 mg) of TPOH-Nph powder was dissolved in DMSO-d6, and the sample was subjected to nuclear magnetic resonance spectroscopy. The spectrum is shown in the figure. Figure 5 .

[0082] Example 9

[0083] A small amount of TPOH-Nph powder was placed in the sample cell, and the sample was irradiated with ultraviolet light for different times. The absorption and fluorescence spectra at different irradiation times were measured. The spectra are shown in the figure. Figure 6 .

[0084] Example 10

[0085] The preparation of compound TPOH-Nnap includes the following steps:

[0086] 1.0 equivalent of TPOH-CHO, 1.02 equivalent of 1-naphthylamine, and 10 equivalent of methanol were mixed in a 250 mL round-bottom flask with stirring. The mixture was refluxed at 65 °C for 4 h to complete the reaction. The reaction solution was cooled to room temperature, and the precipitate in the reaction solution was filtered under reduced pressure and dried to obtain a yellow solid TPOH-Nnap. The crude product was recrystallized from the crude product with a mixed solvent of ethyl acetate / n-hexane to obtain a pure yellow powder TPOH-Nnap. The reaction route is as follows:

[0087]

[0088] Example 11

[0089] Characterization of the compound TPOH-Nnap obtained in Example 10:

[0090] A small amount (20 mg) of TPOH-Nph powder was dissolved in CDCl3, and the sample was subjected to nuclear magnetic resonance spectroscopy. The spectrum is shown in the figure. Figure 7 .

[0091] Example 12

[0092] The UV-Vis absorption and fluorescence spectra of the compound TPOH-Nph prepared in Example 10 in the solid state.

[0093] A small amount of TPOH-Nnap powder was placed in the sample cell, and the sample was irradiated with ultraviolet light for different times. The absorption and fluorescence spectra at different irradiation times were measured. The spectra are shown in the figure. Figure 8 .

[0094] Example 13

[0095] The preparation of compound TPOH-Nph-CF3 includes the following steps:

[0096] 1.0 equivalent of TPOH-CHO, 1.02 equivalent of 4-trifluoromethylaniline, and 10 equivalent of methanol were mixed in a 250 mL round-bottom flask with stirring. The mixture was refluxed at 65 °C for 2 h to complete the reaction. The reaction solution was cooled to room temperature, and the precipitate in the reaction solution was filtered under reduced pressure and dried to obtain a yellow solid TPOH-Nph-CF3. The crude product was recrystallized from the crude product with a mixed solvent of ethyl acetate / n-hexane to obtain a yellow powder.

[0097] The reaction route for pure TPOH-Nph-CF3 is as follows:

[0098]

[0099] Example 14

[0100] Characterization of TPOH-Nph-CF3 prepared in Example 13:

[0101] A small amount (20 mg) of TPOH-Nph-CF3 powder was dissolved in CDCl3, and the sample was subjected to nuclear magnetic resonance spectroscopy. The spectrum is shown in the figure. Figure 9 .

[0102] Example 15

[0103] The UV-Vis absorption and fluorescence spectra of the compound TPOH-Nph-CF3 prepared in Example 13 in the solid state.

[0104] A small amount of TPOH-Nph-CF3 powder was placed in the sample cell, and the sample was irradiated with ultraviolet light for different times. The absorption and fluorescence spectra at different irradiation times were measured. The spectra are shown in the figure. Figure 10 .

[0105] Example 16

[0106] The preparation of compound BPOH-CHO includes the following steps:

[0107] 1.0 equivalent of 4-benzylphenol, 3.0 equivalent of hexamethylenetetramine, and 10 equivalent of trifluoroacetic acid were mixed in a 500 mL round-bottom flask with stirring. The mixture was refluxed at 70 °C for 3 h until the reaction was complete. 360 mL of a 4 mol / L hydrochloric acid aqueous solution was added to the reaction solution, and the mixture was stirred for 1 h to hydrolyze and form a large amount of precipitate. The precipitate was filtered under reduced pressure and dried to obtain a yellow solid BPOH-CHO. The crude product was purified by column chromatography using dichloromethane / petroleum ether as the eluent to obtain pure oily BPOH-CHO. The reaction route is as follows:

[0108]

[0109] Example 17

[0110] Characterization of the compound BPOH-CHO obtained in Example 16:

[0111] A small amount (20 mg) of BPOH-CHO oily liquid was dissolved in DMSO-d6, and the sample was subjected to nuclear magnetic resonance spectroscopy. The spectrum is shown in the figure. Figure 11 .

[0112] Example 18

[0113] Images of UV-Vis absorption and fluorescence of the compound BPOH-CHO prepared in Example 16 in an oily liquid state.

[0114] A small amount of BPOH-CHO oily liquid was used to irradiate the sample with a UV lamp for different durations. Absorption and fluorescence images were captured at different UV irradiation times. (See attached image.) Figure 12 .

[0115] Example 19

[0116] The preparation of compound BPOH-2CHO includes the following steps:

[0117] 1.0 equivalent of 4-benzylphenol, 12.0 equivalents of hexamethylenetetramine, and 10 equivalents of trifluoroacetic acid were mixed in a 500 mL round-bottom flask with stirring. The mixture was refluxed at 120 °C for 72 h until the reaction was complete. 360 mL of a 4 mol / L hydrochloric acid aqueous solution was added to the reaction solution, and the mixture was stirred for 1 h until a large amount of precipitate formed. The precipitate in the reaction solution was filtered under reduced pressure and dried to obtain a yellow solid BPOH-2CHO. The crude product was purified by column chromatography using dichloromethane / petroleum ether as the eluent to obtain pure oily BPOH-2CHO. The reaction route is as follows:

[0118]

[0119] Example 20

[0120] Characterization of the compound BPOH-2CHO obtained in Example 19:

[0121] A small amount (20 mg) of BPOH-2CHO solid was dissolved in DMSO-d6, and the sample was subjected to nuclear magnetic resonance spectroscopy. The spectrum is shown in the figure. Figure 13 .

[0122] Example 21

[0123] The UV-Vis absorption and fluorescence spectra of the compound BPOH-2CHO prepared in Example 19 in the solid state.

[0124] A small amount of BPOH-2CHO solid was placed in the sample cell, and the sample was irradiated with ultraviolet light for different times. The absorption and fluorescence spectra at different irradiation times were measured. The spectra are shown in the figure. Figure 14 .

[0125] Example 22

[0126] The preparation of compound TPOH-Nph-OMe includes the following steps:

[0127] 1.0 equivalent of TPOH-CHO, 1.02 equivalent of 4-methoxyaniline, and 10 equivalent of methanol were mixed in a 250 mL round-bottom flask with stirring. The mixture was refluxed at 65 °C for 2 h to complete the reaction. The reaction solution was cooled to room temperature, and the precipitate in the reaction solution was filtered under reduced pressure and dried to obtain a yellow solid TPOH-Nph-OMe. The crude product was recrystallized from the crude product with a mixed solvent of ethyl acetate / n-hexane to obtain a yellow powder.

[0128] The reaction route for pure TPOH-Nph-OMe is as follows:

[0129]

[0130] Example 23

[0131] Characterization of the compound TPOH-Nph-OMe obtained in Example 22:

[0132] A small amount (20 mg) of TPOH-Nph-OMe powder was dissolved in DMSO-d6, and the sample was subjected to nuclear magnetic resonance spectroscopy. The spectrum is shown in the figure. Figure 15 .

[0133] Example 24

[0134] The UV-Vis absorption and fluorescence spectra of the compound TPOH-Nph-OMe prepared in Example 22 in the solid state.

[0135] A small amount of TPOH-Nph-OMe powder was placed in the sample cell, and the sample was irradiated with ultraviolet light for different times. The absorption and fluorescence spectra at different irradiation times were measured. The spectra are shown in the figure. Figure 16 .

[0136] Example 25

[0137] The preparation of compound TPOH-Nph-CN includes the following steps:

[0138] 1.0 equivalent of TPOH-CHO, 1.02 equivalent of 4-aminobenzonitrile, and 10 equivalent of methanol were mixed in a 250 mL round-bottom flask with stirring. The mixture was refluxed at 65 °C for 48 h to complete the reaction. The reaction solution was cooled to room temperature, and the precipitate in the reaction solution was filtered under reduced pressure and dried to obtain a yellow solid TPOH-Nph-CN. The crude product was then subjected to hot filtration with ethyl acetate to obtain a pure yellow powder TPOH-Nph-CN. The reaction route is as follows:

[0139]

[0140] Example 26

[0141] Characterization of the compound TPOH-Nph-CN obtained in Example 25:

[0142] A small amount (5 mg) of TPOH-Nph-CN powder was dissolved in Acetone-d6, and the sample was subjected to nuclear magnetic resonance spectroscopy. The spectrum is shown in the figure. Figure 17 .

[0143] Example 27

[0144] The UV-Vis absorption and fluorescence spectra of the compound TPOH-Nph-CN prepared in Example 25 in the solid state.

[0145] A small amount of TPOH-Nph-CN powder was placed in the sample cell, and the sample was irradiated with ultraviolet light for different times. The absorption and fluorescence spectra at different irradiation times were measured. The spectra are shown in the figure. Figure 18 .

[0146] Example 28

[0147] The preparation of compound CPOH-CHO includes the following steps:

[0148] 1.0 equivalent of 4-cinnamylphenol, 3.0 equivalent of hexamethylenetetramine, and 10 equivalent of trifluoroacetic acid were mixed in a 500 mL round-bottom flask with stirring. The mixture was refluxed at 70 °C for 3 h until the reaction was complete. 360 mL of a 4 mol / L hydrochloric acid aqueous solution was added to the reaction solution, and the mixture was stirred for 1 h to hydrolyze and form a large amount of precipitate. The precipitate was filtered under reduced pressure and dried to obtain a yellow solid CPOH-CHO. The crude product was purified by column chromatography using dichloromethane / petroleum ether as the eluent to obtain pure oily CPOH-CHO. The reaction route is as follows:

[0149]

[0150] Example 29

[0151] Characterization of the compound CPOH-CHO obtained in Example 28:

[0152] A small amount (20 mg) of CPOH-CHO oily liquid was dissolved in DMSO-d6, and the sample was subjected to nuclear magnetic resonance spectroscopy. The spectrum is shown in the figure. Figure 19 .

[0153] Example 30

[0154] Images of UV-Vis absorption and fluorescence of the compound CPOH-CHO prepared in Example 28 in an oily liquid state.

[0155] A small amount of CPOH-CHO oily liquid was used to irradiate the sample with ultraviolet light for different durations. Absorption and fluorescence images were taken at different irradiation times. (See attached image). Figure 20 .

[0156] Example 31

[0157] The preparation of compound CPOH-2CHO includes the following steps:

[0158] 1.0 equivalent of 4-cinnamylphenol, 12.0 equivalents of hexamethylenetetramine, and 10 equivalents of trifluoroacetic acid were mixed in a 500 mL round-bottom flask with stirring. The mixture was refluxed at 120 °C for 72 h until the reaction was complete. 360 mL of a 4 mol / L hydrochloric acid aqueous solution was added to the reaction solution, and the mixture was stirred for 1 h until a large amount of precipitate formed. The precipitate in the reaction solution was filtered under reduced pressure and dried to obtain a yellow solid CPOH-2CHO. The crude product was purified by column chromatography using dichloromethane / petroleum ether as the eluent to obtain pure oily CPOH-2CHO. The reaction route is as follows:

[0159]

[0160] Example 32

[0161] Characterization of the compound CPOH-2CHO obtained in Example 31:

[0162] A small amount (5 mg) of CPOH-2CHO oily liquid was dissolved in DMSO-d6, and the sample was subjected to nuclear magnetic resonance spectroscopy. The spectrum is shown in the figure. Figure 21 .

[0163] Example 33

[0164] Images of UV-Vis absorption and fluorescence of the compound CPOH-2CHO prepared in Example 31 in an oily liquid state.

[0165] A small amount of CPOH-2CHO oily liquid was used to irradiate the sample with ultraviolet light for different durations. Absorption and fluorescence images were taken at different irradiation times. (See attached image). Figure 22 .

[0166] Example 34

[0167] The preparation of compound TPOH-Nph-N(Me)2 includes the following steps:

[0168] 1.0 equivalent of TPOH-CHO, 1.02 equivalent of 4-amino-N,N-dimethylaniline, and 10 equivalent of methanol were mixed in a 250 mL round-bottom flask with stirring. The mixture was refluxed at 65 °C for 2 h to complete the reaction. The reaction solution was cooled to room temperature, and the precipitate in the reaction solution was filtered under reduced pressure and dried to obtain a yellow solid TPOH-Nph-N(Me)2. The crude product was recrystallized from tetrahydrofuran / n-hexane mixed solvent to obtain a pure yellow powder TPOH-Nph-N(Me)2. The reaction route is as follows:

[0169]

[0170] Example 35

[0171] Characterization of the compound TPOH-Nph-N(Me)2 obtained in Example 34:

[0172] A small amount (10 mg) of TPOH-Nph-N(Me)2 solid was dissolved in DMSO-d6, and the sample was subjected to nuclear magnetic resonance spectroscopy. The spectrum is shown in the figure. Figure 23 .

[0173] Example 36

[0174] The UV-Vis absorption and fluorescence spectra of the compound TPOH-Nph-N(Me)2 prepared in Example 34 in the solid state.

[0175] A small amount of TPOH-Nph-N(Me)2 powder was placed in the sample cell, and the sample was irradiated with ultraviolet light for different times. The absorption and fluorescence spectra at different irradiation times were measured. The spectra are shown in the figure. Figure 24 .

[0176] Example 37

[0177] The preparation of compound TPOH-Nph-F includes the following steps:

[0178] 1.0 equivalent of TPOH-CHO, 1.02 equivalent of 4-fluoroaniline, and 10 equivalent of methanol were mixed in a 250 mL round-bottom flask with stirring. The mixture was refluxed at 65 °C for 2 h to complete the reaction. The reaction solution was cooled to room temperature, and the precipitate in the reaction solution was filtered under reduced pressure and dried to obtain a yellow solid TPOH-Nph-F. The crude product was recrystallized from the crude product with a mixed solvent of ethyl acetate / n-hexane to obtain a pure yellow powder TPOH-Nph-F. The reaction route is as follows:

[0179]

[0180] Example 38

[0181] Characterization of the compound TPOH-Nph-F obtained in Example 37:

[0182] A small amount (20 mg) of TPOH-Nph-F solid was dissolved in DMSO-d6, and the sample was subjected to nuclear magnetic resonance spectroscopy. The spectrum is shown in the figure. Figure 25 .

[0183] Example 39

[0184] The UV-Vis absorption and fluorescence spectra of the compound TPOH-Nph-F obtained in Example 37 in the solid state.

[0185] A small amount of TPOH-Nph-F powder was placed in the sample cell, and the sample was irradiated with ultraviolet light for different times. The absorption and fluorescence spectra at different irradiation times were measured. The spectra are shown in the figure. Figure 26 .

[0186] Comparative Example 1

[0187] Preparation of Comparative Compound BS-SP1

[0188] 1.0 equivalent of 2-hydroxy-5-methylbenzaldehyde, 1.1 equivalent of 2-aminothiophenol, 1 equivalent of sodium metabisulfite, and 6 equivalents of N,N-dimethylformamide were stirred and mixed in a 500 mL round-bottom flask. The mixture was refluxed at 120 °C for 2 h until the reaction was complete. After adding 400 mL of deionized water to the reaction solution, a large amount of precipitate formed. The mixture was stirred until room temperature. The precipitate was filtered under reduced pressure and dried to obtain a yellow solid HBT. The crude product was purified by column chromatography using dichloromethane / petroleum ether as the eluent to obtain a white powder of pure HBT.

[0189] 1.0 equivalent of pure HBT, 3.0 equivalents of hexamethylenetetramine, and 10 equivalents of trifluoroacetic acid were mixed in a 500 mL round-bottom flask with stirring. The mixture was refluxed at 100 °C for 12 h until the reaction was complete. 360 mL of a 4 mol / L hydrochloric acid aqueous solution was added to the reaction solution, and the mixture was stirred for 1 h to hydrolyze and form a large amount of precipitate. The precipitate in the reaction solution was filtered under reduced pressure and dried to obtain a yellow solid HBT-MA. The crude product was purified by column chromatography using dichloromethane / petroleum ether as the eluent to obtain a yellow powder, pure HBT-MA.

[0190] 1.0 equivalent of 4-hydrazinobenzenesulfonic acid, 2.0 equivalent of 3-methyl-2-butanone, and 3 equivalents of glacial acetic acid were stirred and mixed in a 500 mL round-bottom flask. The mixture was refluxed at 110 °C for 3 h until the reaction was complete. After stirring and cooling to room temperature, a large amount of precipitate was formed. The precipitate in the reaction solution was filtered under reduced pressure and dried to obtain a red solid. After drying overnight, the reddish-brown precipitate was completely dissolved in methanol, and a saturated sodium hydroxide isopropanol solution was slowly added to the mixture. A large amount of brownish-yellow precipitate was observed to precipitate. The precipitate was filtered and the brownish-yellow solid powder W1 was collected.

[0191] 1.0 equivalent of W1, 3.0 equivalents of 1,3-propanesulfonyl lactone, and 10 equivalents of 1,2-dichlorobenzene were stirred and mixed in a 500 mL round-bottom flask. The mixture was refluxed at 120 °C for 36 h until the reaction was complete. After stirring and cooling to room temperature, a large amount of reddish-brown precipitate was formed. The precipitate in the reaction solution was filtered under reduced pressure and washed three times with anhydrous ethanol. After drying overnight, a light pink solid powder W1' was collected.

[0192] 1.0 equivalent of HBT-MA, 1.2 equivalent of W1', 1.2 equivalent of triethylamine, and 10 equivalent of ethanol were mixed in a 250 mL round-bottom flask with stirring. The mixture was refluxed at 80 °C for 12 h until the reaction was complete. After stirring and cooling to room temperature, the solvent was removed by rotary evaporation under reduced pressure. Using dichloromethane / methanol as the eluent, the crude product was purified by column chromatography to obtain a deep yellow powder, BS-SP1, as pure. The reaction route is as follows:

[0193]

[0194] Comparative Example 2

[0195] A small amount of BS-SP1 powder was dissolved in deionized water to prepare a test solution (20 μM). The sample was subjected to one UV lamp irradiation and repeated UV lamp irradiation. The absorption spectrum and fatigue resistance absorption spectrum were measured. The spectra are shown in the figure. Figure 27 .

[0196] like Figure 27As shown, the BS-SP1 molecule prepared in Comparative Example 1 exhibits an absorption peak at 600 nm in its initial state, indicating that the molecule contains both open and closed ring components in its initial state. This non-uniformity of components will lead to signal distortion in information encryption applications. In contrast, the TPOH-CHO photoswitch molecule prepared in Example 1 shows no absorption in its initial state, exhibiting an ultra-low white powder background signal. Furthermore, BS-SP1 cannot achieve photochromism in the solid state and exhibits poor fatigue resistance in solution; the absorption peak of this molecule gradually decreases with increasing cycle count. In contrast, the TPOH-CHO photoswitch molecule not only displays ultra-high photochromic contrast in the solid state but also exhibits fatigue resistance exceeding 50 cycles. These results demonstrate that the photoswitch molecule provided by this invention can achieve high-contrast signal output in the solid state.

[0197] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. An optical switch molecule, characterized in that, The structure general formula of the optical switch molecule is as follows: Wherein, R1 is a hydrogen bond acceptor group, R2 is an electron donor group or an electron withdrawing group, R3 and R4 are both space type substituent groups.

2. The optical switch molecule of claim 1, wherein, The R1 is selected from one of benzothiazole group, benzoxazole group, benzimidazole group, diphenyl imidazole group, pyridine group, quinoline group, aldehyde group, carbonyl group, carbonyl sulfur group, imine group, secondary amine group, hydrazone group, selenol group.

3. The optical switch molecule of claim 1, wherein, The R2 is selected from one of methyl group, tert-butyl group, methoxy group, ethoxy group, N,N-dimethyl group, triphenylamine group, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, carboxylate group, trifluoromethyl group, nitro group, pyridine group, pyridine salt group, benzothiazole group, benzoxazole group, benzimidazole group, diphenyl imidazole group, quinoline group, quinoline salt group, aldehyde group, pyryl nitrile group.

4. The optical switch molecule of claim 1, wherein, The R3 is selected from one of methyl group, benzene ring group, methoxy group, carboxylic acid group, carboxylate group, peptide bond derived group, hydrogen atom.

5. The optical switch molecule of claim 1, wherein, The R4 is selected from one of methyl group, benzene ring group, methoxy group, carboxylic acid group, carboxylate group, peptide bond derived group, hydrogen atom.

6. The optical switch molecule of claim 1, wherein, The optical switch molecule is one of the following structures:

7. The optical switch molecule of claim 1, wherein, The light irradiation stimulation wavelength range of the optical switch molecule is 200nm-800nm.

8. A method of preparing the photoswitching molecule of claim 1, wherein, The optical switch molecule is prepared by mixed solvent rotary evaporation method, crystallization method or mechanical stirring method.

9. The application of the optical switch molecule of claim 1 in the field of chemical sensing, information encryption or data storage.

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