Photochromic molecule generated based on reversible C-N bond and preparation method and application thereof

Abstract

The invention relates to a photochromic molecule generated based on a reversible C-N bond and a preparation method and application thereof, and belongs to the technical field of photoresponse functional materials. The photochromic molecule comprises any one or more of structural formulae shown as a formula IA and a formula IB, the photochromic molecule provided by the invention has the characteristics of high light conversion efficiency, excellent light fatigue stability, good water compatibility, T type / P type adjustability and the like. Various solid-phase materials, such as filter paper, silica gel plates, thermoplastic plastics and the like, are easy to adhere; the method has a wide application prospect in the fields of biomarkers, intelligent materials, information storage, visual sensing and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of light-responsive functional materials, in particular to a photochromic molecule based on reversible C-N bond generation and a preparation method and application thereof. BACKGROUND

[0002] Photochromic molecules are a class of compounds that can undergo transformation between two different structural states or isomers under the action of light.

[0003] The photochromic molecules widely studied at present include azobenzene, spiropyran and diarylethene compounds, which have defects such as short wavelength regulation, poor reversibility and the like in practical application. Development of new photochromic molecule systems is expected to realize longer wavelength photochromic regulation, higher photoconversion rate and better fatigue resistance, so as to obtain more abundant photochromic materials. SUMMARY

[0004] The purpose of the present application is to provide a photochromic molecule based on reversible C-N bond generation and a preparation method and application thereof. The photochromic molecule has the characteristics of high photoconversion efficiency, excellent light fatigue stability, good water compatibility and T / P type adjustable, etc. And it is easy to adhere to various solid materials, such as filter paper, silica gel plate, thermoplastic plastic, etc.; has broad application prospects in the fields of biological markers, intelligent materials, information storage and visual sensing, etc.

[0005] The first aspect of the present application is to provide a photochromic molecule based on reversible C-N bond generation, comprising

[0006] Any one or more of the following formula IA, formula IB schematic structural formula;

[0007]

[0008] wherein Ar1 and Ar2 are each independently selected from any one of C6-C30 aryl and C6-C30 heteroaryl;

[0009] R1, R2 and R3 are each independently selected from any one of hydrogen, halogen, nitro, amino, hydroxyl, sulfonic acid group, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylamino, substituted or unsubstituted C1-C20 alkenyl, and substituted or unsubstituted C1-C20 alkynyl;

[0010] The substituted substituent group includes any one or more of hydrogen, halogen, nitro, amino, sulfonic acid group, C1-C20 alkyl, C1-C20 alkylamino, C1-C20 alkoxy, C6-C12 aryl and C6-C12 heteroaryl.

[0011] In some embodiments, Ar1 is selected from C6-C30 aryl, and Ar2 is selected from heteroaryl;

[0012] R2 is selected from any one or more of substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy;

[0013] R3 is selected from hydrogen, halogen, nitro, amino, hydroxyl, sulfonic acid group, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkylamino;

[0014] The substituted substituent includes any one or more of hydrogen, halogen, nitro, amino, sulfonic acid group, C1-C20 alkyl, C1-C20 alkylamino, C1-C20 alkoxy, C6-C12 aryl, C6-C12 heteroaryl.

[0015] In some embodiments, the photochromic molecule includes any one or more of the following specific structural formulas:

[0016]

[0017] R1 is selected from any one of hydrogen, halogen, nitro, amino, hydroxyl, sulfonic acid group;

[0018] R2 is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl;

[0019] R3 is selected from any one or more of hydrogen, substituted or unsubstituted C1-C20 alkylamino, C6-C12 aryl, C6-C12 heteroaryl;

[0020] The substituted substituent includes any one or more of hydrogen, halogen, nitro, amino, sulfonic acid group.

[0021] In some embodiments, the photochromic molecule includes any one or more of the following specific structural formulas:

[0022]

[0023]

[0024] A second aspect of the present application is to provide a preparation method of a photochromic molecule generated based on a reversible C-N bond, including the following preparation process:

[0025] The following compounds of Formula III and Formula IV are condensed in an organic solvent to obtain a photochromic molecule including any one or more of the following Formula IA, Formula IB structural formulas:

[0026]

[0027] wherein Ar1and Ar2are each independently selected from any one of C6-C30 aryl group, C6-C30 heteroaryl group;

[0028] R1, R2and R3are each independently selected from any one of hydrogen, halogen, nitro group, amino group, hydroxyl group, sulfonic acid group, substituted or unsubstituted C1-C20 alkyl group, substituted or unsubstituted C1-C20 alkoxy group, substituted or unsubstituted C1-C20 alkylamino group, substituted or unsubstituted C1-C20 alkenyl group, substituted or unsubstituted C1-C20 alkynyl group;

[0029] The substituted substituent includes any one or more of hydrogen, halogen, nitro group, amino group, sulfonic acid group, C1-C20 alkyl group, C1-C20 alkylamino group, C1-C20 alkoxy group, C6-C12 aryl group, C6-C12 heteroaryl group.

[0030] In some embodiments, the organic solvent includes any one or more of acetic anhydride, ethanol and toluene;

[0031] and / or;

[0032] The reaction temperature is 20℃-65℃, and the reaction time is 1h-5h.

[0033] A third aspect of the present application is to provide a solution with photochromic properties, including the photochromic molecule of the first aspect or the photochromic molecule prepared by the preparation method of the second aspect, and further including a solvent, which includes any one or more of water, methanol, acetonitrile, dichloromethane.

[0034] A fourth aspect of the present application is to provide a filter paper or silica gel plate with photochromic properties, including a filter paper substrate or a silica gel plate substrate, and a photochromic layer located on at least one side surface of the filter paper substrate or the silica gel plate substrate, wherein the photochromic layer includes the photochromic molecule of the first aspect or the photochromic molecule prepared by the preparation method of the second aspect.

[0035] A fifth aspect of the present application is to provide a thin film with photochromic properties, including a polymer film, wherein the polymer film includes a thermoplastic polymer and the photochromic molecule of the first aspect or the photochromic molecule prepared by the preparation method of the second aspect;

[0036] The mass ratio between the photochromic molecule and the thermoplastic polymer is 1:500-2000;

[0037] The thermoplastic polymer includes any one or more of polymethyl methacrylate, polyethyl methacrylate.

[0038] The sixth aspect of the present application provides a photoresponsive smart material, comprising the photochromic molecule of the first aspect or the photochromic molecule prepared by the preparation method of the second aspect or the solution of the third aspect or the filter paper or the silica gel plate of the fourth aspect or the film of the fifth aspect.

[0039] The beneficial technical effects of the present application are:

[0040] 1. The photochromic molecule provided by the present application is a nitrogen-containing heterocyclic substituted merocyanine compound (PMCs). The pyridine-substituted merocyanine of the compound is T-shaped, and has good water compatibility. The quinoline-substituted merocyanine is P-shaped. The reversible C-N bond formation mechanism induced by visible light can realize controllable adjustment of the molecular configuration, and has the characteristics of high photoconversion efficiency, excellent light fatigue stability, good water compatibility, and adjustable T / P shape. It shows broad application prospects in the fields of biological markers, smart materials, information storage and visual sensing.

[0041] 2. The photochromic molecule provided by the present application is suitable for attaching various solid-phase materials, such as filter paper, silica gel plate, and thermoplastic plastic. The preparation method is simple and can be mass-produced.

[0042] The above description is only a summary of the technical solutions of the present application. In order to more clearly understand the technical means of the present application, the specific embodiments of the present application can be implemented in accordance with the content of the description, and in order to make the above and other purposes, characteristics and advantages of the present application more obvious and easy to understand, the following specific embodiments of the present application are described. BRIEF DESCRIPTION OF DRAWINGS

[0043] Figure 1 The above description is only a summary of the technical solutions of the present application. In order to more clearly understand the technical means of the present application, the specific embodiments of the present application can be implemented in accordance with the content of the description, and in order to make the above and other purposes, characteristics and advantages of the present application more obvious and easy to understand, the following specific embodiments of the present application are described.

[0044] Figure 2 The above description is only a summary of the technical solutions of the present application. In order to more clearly understand the technical means of the present application, the specific embodiments of the present application can be implemented in accordance with the content of the description, and in order to make the above and other purposes, characteristics and advantages of the present application more obvious and easy to understand, the following specific embodiments of the present application are described.

[0045] Figure 3 The above description is only a summary of the technical solutions of the present application. In order to more clearly understand the technical means of the present application, the specific embodiments of the present application can be implemented in accordance with the content of the description, and in order to make the above and other purposes, characteristics and advantages of the present application more obvious and easy to understand, the following specific embodiments of the present application are described.

[0046] Figure 4 The above description is only a summary of the technical solutions of the present application. In order to more clearly understand the technical means of the present application, the specific embodiments of the present application can be implemented in accordance with the content of the description, and in order to make the above and other purposes, characteristics and advantages of the present application more obvious and easy to understand, the following specific embodiments of the present application are described.

[0047] Figure 5 The above description is only a summary of the technical solutions of the present application. In order to more clearly understand the technical means of the present application, the specific embodiments of the present application can be implemented in accordance with the content of the description, and in order to make the above and other purposes, characteristics and advantages of the present application more obvious and easy to understand, the following specific embodiments of the present application are described.

[0048] Figure 6 Absorption spectra of the photochromic molecule in different solvents for Example 4 of the present application; before light (solid line), after light (dashed line);

[0049] Figure 7 Absorption spectra of the photochromic molecule in different solvents for Example 5 of the present application; before light (solid line), after light (dashed line);

[0050] Figure 8 Absorption spectra of the photochromic molecule in different solvents for Example 6 of the present application; before light (solid line), after light (dashed line);

[0051] Figure 9 Absorption spectra of the photochromic molecule for Example 6 of the present application; illustration of the change in absorbance after recovery in the dark after light;

[0052] Figure 10 Absorption spectra of the photochromic molecule for Example 6 of the present application; illustration of the change in absorbance after 10 cycles of bleaching with 660 nm light and coloration with 500 nm light;

[0053] Figure 11 Absorption spectra of the photochromic molecule in different solvents for Example 7 of the present application; before light (solid line), after light (dashed line);

[0054] Figure 12 Absorption spectra of the photochromic material for Test Example 1 of the present application; illustration of the bleaching with 500 nm light and the thermal coloration process;

[0055] Figure 13 Absorption spectra of the photochromic material for Test Example 2 of the present application; illustration of the change in absorbance after 16 cycles of bleaching with 500 nm light and thermal coloration;

[0056] Figure 14 Absorption spectra of the photochromic material for Test Example 2 of the present application; illustration of the change in absorbance after 16 cycles of bleaching with 500 nm light and thermal coloration;

[0057] Figure 15 Test diagram of the photochromic molecule for the comparative example of the present application, wherein, Figure 15 A is the absorption spectrum, Figure 15 B is the illustration of the change in absorbance after multiple cycles. DETAILED DESCRIPTION

[0058] Hereinafter, specific embodiments of the modified carbon nanotube material of the present application, its preparation method and use thereof will be explained in detail with appropriate reference to the accompanying drawings. However, there will be cases where unnecessary detailed explanation will be omitted. For example, there will be cases where detailed explanation of matters known well, repeated explanation of substantially identical structures will be omitted. This is to avoid the following explanation from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. In addition, the accompanying drawings and the following explanation are provided in order for those skilled in the art to fully understand the present application and are not intended to limit the subject matter recited in the claims.

[0059] Hereinafter, specific embodiments of the modified carbon nanotube material of the present application, its preparation method and use thereof will be explained in detail with appropriate reference to the accompanying drawings. However, there will be cases where unnecessary detailed explanation will be omitted. For example, there will be cases where detailed explanation of matters known well, repeated explanation of substantially identical structures will be omitted. This is to avoid the following explanation from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. In addition, the accompanying drawings and the following explanation are provided in order for those skilled in the art to fully understand the present application and are not intended to limit the subject matter recited in the claims.

[0060] The compounds and derivatives provided in the present application can be named according to the IUPAC (International Union of Pure and Applied Chemistry) or CAS (Chemical Abstract Service, Columbus, OH) nomenclature system.

[0061] Definitions of terms used in the present application: Unless otherwise indicated, the initial definition of a group or term provided herein applies to that group or term throughout the specification; for terms not specifically defined herein, those terms should be given their art-recognized meaning and definition as set forth in the disclosure and context.

[0062] "Substitution" means replacement of a hydrogen atom in a molecule by another different atom or molecule.

[0063] The minimum and maximum number of carbon atoms in a hydrocarbon group is indicated by a prefix, e.g., the prefix C a～b Alkyl indicates any alkyl group having "a" to "b" carbon atoms. Thus, for example, "C 1～4 Alkyl" means an alkyl group containing 1 to 4 carbon atoms.

[0064] "Alkyl" means a saturated hydrocarbon chain having the specified number of member atoms. For example, C 1～8 Alkyl means an alkyl group having 1 to 8 (i.e., 1, 2, 3, 4, 5, 6, 7, or 8) member atoms, C 1～6 Alkyl means an alkyl group having 1 to 6 (i.e., 1, 2, 3, 4, 5, or 6) member atoms, e.g., 1 to 4 (i.e., 1, 2, 3, or 4) member atoms. The alkyl group can be straight-chained or branched. Representative branched alkyl groups have one, two, or three branches. The alkyl group can be optionally substituted with one or more substituents as defined herein. Alkyl includes methyl, ethyl, propyl (n-propyl and isopropyl), butyl (n-butyl, isobutyl, and t-butyl), pentyl (n-pentyl, isopentyl, and neopentyl), and hexyl. The alkyl group can also be part of other groups, e.g., C1-C6alkoxy.

[0065] "Alkenyl" refers to a straight or branched chain hydrocarbyl group having from 2 to 10 (i.e., 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbon atoms and in some embodiments from 2 to 6 (i.e., 2, 3, 4, 5, or 6) carbon atoms or 2 to 4 (i.e., 2, 3, or 4) carbon atoms and having at least one site of ethylenic unsaturation (>C=C<). For example, (C2-C6)alkenyl is intended to encompass ethylenic unsaturation in, for example, ethenyl, 1-propenyl, 2-propenyl, 1,3- butadienyl, and the like. a -C b )alkenyl refers to an alkenyl group having a to b carbon atoms and is intended to include, for example, vinyl, propenyl, isopropenyl, 1,3-butadienyl, and the like.

[0066] "Alkynyl" refers to a straight chain monovalent hydrocarbon radical or branched chain monovalent hydrocarbon radical containing at least one triple bond. The term "alkynyl" is also intended to include those hydrocarbyl radicals having one triple bond and one double bond. For example, (C2-C6)alkynyl is intended to include ethynyl, propynyl, and the like.

[0067] "Aryl" refers to any functional group or substituent derived from a simple aromatic ring, such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene, and the like.

[0068] "Heteroaryl" refers to an aryl group in which a carbon atom is replaced by another heteroatom, such as nitrogen, oxygen, sulfur, selenium, and the like, such as quinoline, pyridine, imidazole, tetrazine, thiazole, and the like.

[0069] "Alkoxy" refers to an alkyl group linked via an oxygen atom, such as methoxy, ethoxy, and the like,

[0070] "Alkylamino" refers to an alkyl group linked via a nitrogen atom, such as methylamino, and the like.

[0071] "Halogen" is fluorine, chlorine, bromine, or iodine.

[0072] Photochromic molecules are a class of compounds that can undergo transformation between two different structural states or isomers under the action of light.

[0073] According to the mechanism of conformation recovery of the molecules after being irradiated by light, photochromic molecules can be divided into two types: thermal recovery (T type) and light recovery (P type). Among them, T type molecules realize photochromic transformation through light induction, and the reverse recovery depends on the environmental thermal activation; while P type molecules can be regulated by two different wavelengths of light to make the structure in two different states.

[0074] The isomers of spiropyran molecules are two: colorless closed ring spiropyran structure (SP) and colored open ring merocyanine structure (MC). In a non-polar solvent environment, when UV irradiation is used, spiropyran will convert from colorless SP state to colored MC state; the thermodynamic instability of MC isomer can also spontaneously recover to colorless SP state (isomerization rate is closely related to molecular structure), and the whole process is cyclic and reversible.

[0075] The currently widely studied photochromic molecules include azobenzene, spiropyran and diarylethene compounds, which have defects such as short wavelength regulation, poor reversibility and the like in practical applications. Development of new photochromic molecule systems is expected to realize longer wavelength photochromic regulation, higher photoconversion rate and better fatigue resistance, thereby obtaining more abundant photochromic materials.

[0076] To solve the above technical problems, the application discloses a photochromic molecule based on reversible C-N bond generation, and a preparation method and application thereof. The photochromic molecule has the characteristics of high photoconversion efficiency, excellent light fatigue stability, good water compatibility and T / P type adjustment. And it is easy to adhere to various solid materials, such as filter paper, silica gel plate, thermoplastic plastic and the like; has a wide application prospect in the fields of biological markers, intelligent materials, information storage and visual sensing.

[0077] The first aspect of the application is to provide a photochromic molecule based on reversible C-N bond generation, which comprises any one or more of the following formula IA and formula IB schematic structural formulae;

[0078] Table 1 structure list of formula I

[0079]

[0080] Wherein, Ar1 and Ar2 are each independently selected from any one of C6-C30 aryl and C6-C30 heteroaryl;

[0081] R1, R2 and R3 are each independently selected from any one of hydrogen, halogen, nitro, amino, hydroxyl, sulfonic acid group, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylamino, substituted or unsubstituted C1-C20 alkenyl, and substituted or unsubstituted C1-C20 alkynyl;

[0082] The above-mentioned substituted substituent groups include any one or more of hydrogen, halogen, nitro, amino, sulfonic acid group, C1-C20 alkyl, C1-C20 alkylamino, C1-C20 alkoxy, C6-C12 aryl and C6-C12 heteroaryl.

[0083] In some embodiments, Ar1 is selected from C6-C30 aryl, and Ar2 is selected from heteroaryl;

[0084] R2 is selected from any one of substituted or unsubstituted C1-C20 alkyl and substituted or unsubstituted C1-C20 alkoxy;

[0085] R3 is selected from hydrogen, halogen, nitro, amino, hydroxyl, sulfonic acid group, substituted or unsubstituted C1-C20 alkyl, and substituted or unsubstituted C1-C20 alkylamino;

[0086] The above-mentioned substituents include any one or more of hydrogen, halogen, nitro, amino, sulfonic acid group, C1-C20 alkyl, C1-C20 alkylamino, C1-C20 alkoxy, C6-C12 aryl, C6-C12 heteroaryl.

[0087] In some embodiments, the photochromic molecules include any one or more of the following formula II A, formula II B:

[0088]

[0089] R1is selected from any one of hydrogen, halogen, nitro, amino, hydroxyl, sulfonic acid group;

[0090] R2is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl;

[0091] R3is selected from any one or more of hydrogen, substituted or unsubstituted C1-C20 alkylamino, C6-C12 aryl, C6-C12 heteroaryl;

[0092] The above-mentioned substituents include any one or more of hydrogen, halogen, nitro, amino, sulfonic acid group.

[0093] In some embodiments, the above-mentioned photochromic molecules include any one or more of the following specific structural formulas:

[0094]

[0095]

[0096] A second aspect of the present application is to provide a preparation method of photochromic molecules generated based on reversible C-N bond, including the following preparation process:

[0097] The following formula III and formula IV compounds are condensed in an organic solvent to obtain photochromic molecules including any one or more of the following formula IA, formula IB:

[0098] Table 2: Formula III and formula IV structure list

[0099]

[0100] The molecular structure of formula IA, formula IB is as shown in Table 1 above.

[0101] Wherein, Ar1and Ar2are each independently selected from any one of C6-C30 aryl, C6-C30 heteroaryl;

[0102] R1, R2and R3are each independently selected from any one of hydrogen, halogen, nitro, amino, hydroxyl, sulfonic acid group, substituted or unsubstituted C1-C20alkyl, substituted or unsubstituted C1-C20alkoxy, substituted or unsubstituted C1-C20alkylamino, substituted or unsubstituted C1-C20alkenyl, substituted or unsubstituted C1-C20alkynyl;

[0103] The above-mentioned substituted substituent includes any one or more of hydrogen, halogen, nitro, amino, sulfonic acid group, C1-C20alkyl, C1-C20alkylamino, C1-C20alkoxy, C6-C12aryl, C6-C12heteroaryl.

[0104] In some embodiments, the above-mentioned organic solvent includes any one or more of acetic anhydride, ethanol and toluene;

[0105] and / or;

[0106] The above-mentioned reaction temperature is 20℃-65℃, and the reaction time is 1h-5h.

[0107] The present application discloses in these embodiments that the reaction temperature is any one of 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, or any one of the above-mentioned any two range values.

[0108] The present application discloses in these embodiments that the reaction time is any one of 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, or any one of the above-mentioned any two range values.

[0109] The third aspect of the present application is to provide a solution with photochromic properties, including the photochromic molecules of the first aspect or the photochromic molecules prepared by the preparation method of the second aspect, and further including a solvent, which includes any one or more of water, methanol, acetonitrile, dichloromethane.

[0110] The fourth aspect of the present application is to provide a filter paper or silica gel plate with photochromic properties, including a filter paper substrate or a silica gel plate substrate, and a photochromic layer on at least one side surface of the filter paper substrate or the silica gel plate substrate, wherein the photochromic layer includes the photochromic molecules of the first aspect or the photochromic molecules prepared by the preparation method of the second aspect.

[0111] The present application discloses in some embodiments a preparation method of a filter paper or silica gel plate with photochromic properties, which specifically includes: immersing the filter paper or silica gel plate in the solution of the third aspect with a concentration of 100μM, and the soaking time is 10 minutes. Then the material is taken out and naturally dried to obtain a functionalized filter paper or silica gel plate with photochromic molecules loaded on the surface.

[0112] A fifth aspect of the present application provides a thin film with photochromic properties, comprising a polymer film, the polymer film comprising a thermoplastic polymer and the photochromic molecule of the first aspect or the photochromic molecule prepared by the method of the second aspect;

[0113] The mass ratio between the photochromic molecule and the thermoplastic polymer is 1:500-2000;

[0114] The thermoplastic polymer comprises any one or more of polymethyl methacrylate, polyethyl methacrylate.

[0115] In these embodiments, the present application discloses that the mass ratio between the photochromic molecule and the thermoplastic polymer is any one of 1:500, 1:600, 1:700, 1:800, 1:900, 1:1000, 1:1500, 1:2000 or any one of the ranges of any two of the above.

[0116] In some embodiments, the present application discloses a method for preparing a thin film with photochromic properties, taking polymethyl methacrylate as an example, comprising: dissolving 500 mg of polymethyl methacrylate (PMMA) in 5 mL of chloroform, and magnetically stirring at 50°C for 30 minutes until it is completely dissolved. Add the solution of the third aspect to the PMMA solution dropwise, so that the mass ratio of the photochromic molecule to PMMA is 1:1000 (w / w). The system is ultrasonically treated for 30 minutes to promote uniform dispersion. Pour the resulting uniform solution into a clean glass beaker and place it in an oven at 50°C for 48 hours to form a polymer film. The resulting solid thin film is then vacuum annealed at 40°C for 24 hours to remove residual solvents.

[0117] A sixth aspect of the present application provides a light-responsive smart material comprising the photochromic molecule of the first aspect or the photochromic molecule prepared by the method of the second aspect.

[0118] The present application is further illustrated by the following examples, but is not limited thereto.

[0119] Example 1

[0120] A method for preparing a photochromic molecule ((E)-2-[2-(5-amino-2-pyridyl) vinyl]-1-ethyl-3,3-dimethyl-3H-indolium salt (PMC1)) is provided, as shown in formula IIA-1.

[0121] The specific structural formula is as follows:

[0122]

[0123] The specific synthesis process comprises:

[0124] In a 50 mL vial, 1-ethyl-2,3,3-trimethyl-3H-indolium salt (316 mg) and 5- amino pyridine-2-carboxaldehyde (122 mg) were added into 10 mL of ethanol and the reaction was carried out at room temperature for 3 hours. After the reaction was completed, the compound was purified by column chromatography, and 155 mg of the product was collected in dichloromethane and methanol (10 / 1) with a yield of 37%.

[0125] The characterization of the photochromic molecule PMC1 represented by IIA-1 is as follows:

[0126] 1 H NMR (400 MHz, 298 K, CD3OD) δ (ppm): 8.31 (d, J = 15.5 Hz, 1H), 8.23 (d, J = 1.9 Hz, 1H), 7.82 (d, J = 8.6 Hz, 1H), 7.79-7.72 (m, 2H), 7.69 (d, J = 15.5 Hz, 1H), 7.60 (m, J = 7.1 Hz, 2H), 7.05 (dd, J = 8.6, 2.1 Hz, 1H), 4.60 (q, J = 7.2 Hz, 2H), 1.83 (s, 6H), 1.57 (t, J = 7.2 Hz, 3H).13C NMR (100 MHz, 298 K, CD3OD) δ (ppm): 180.93, 153.02, 149.43, 143.44, 140.61, 138.74, 138.66, 131.89, 129.10, 128.87, 122.69, 117.99, 113.89, 107.49, 51.95, 41.59, 25.49, 12.31.

[0127] HR-ESI-MS: m / z calcd for PMC1 (C 19 H 22 N3, [M] + ), 292.1808; found, 292.1808.

[0128] The photochromic properties of the synthesized compounds were measured in different solvents (concentration 10 μΜ) at 25 °C in the wavelength range of 300 nm-700 nm. After irradiation by white LED light, the color of the solution changed from yellow to colorless. Figure 1 The results of the measurement of the absorption spectrum are shown in FIG. 1. In FIG. 1, Figure 1 The results of the measurement of the absorption spectrum before and after irradiation are shown in FIG. 2, where the solid line is before irradiation and the dotted line is after irradiation. As shown in FIG. 2, Figure 1 It can be seen that the maximum absorption peak of the compound after irradiation is blue-shifted, and the maximum absorption peak is blue-shifted from 462 nm to 366 nm in aqueous solution.

[0129] Example 2

[0130] A method for preparing a photochromic molecule (E)-2-[2-(5-dimethylamino-2-pyridyl)vinyl]-1-ethyl-3,3-dimethyl-3H-indolium salt (PMC2) of Formula IIA-2 is provided;

[0131] The specific structural formula is as follows:

[0132]

[0133] The specific synthesis process includes:

[0134] Into a 50 mL tomato bottle, 1-ethyl-2,3,3-trimethyl-3H-indolium salt (316 mg) and 5-(dimethylamino)pyridine-2-carboxaldehyde (150 mg) were added, and 10 mL of ethanol was added at room temperature for 3 hours. After the reaction was completed, the compound was refined by column chromatography, and the component of dichloromethane and methanol (20 / 1) was collected, 201 mg, the yield was 45%.

[0135] And the photochromic molecule PMC2 of Formula IIA-2 is characterized as follows:

[0136] 1 H NMR (400 MHz, 298 K, CD2Cl2) δ (ppm): 8.27 (d, J = 3.1 Hz, 1H), 8.20 (d, J = 15.3 Hz, 1H), 8.04 (d, J = 8.3 Hz, 1H), 7.64 (d, J = 15.3 Hz, 1H), 7.54-7.45 (m, 4H), 6.96 (dd, J = 9.0, 3.1 Hz, 1H), 4.51 (q, J = 7.3 Hz, 2H), 3.14 (s, 6H), 1.77 (s, 6H), 1.52 (t, 3H). 13 C NMR (175 MHz, 298 K, CD2Cl2) δ (ppm): 1 13 C NMR (176 MHz, CDCl3) δ

[0137] 180.67, 154.47, 148.71, 143.59, 141.00, 138.96, 137.22, 132.64, 129.97, 129.55, 123.46, 116.85, 114.18, 107.76, 52.51, 42.85, 40.51, 27.63, 14.01.

[0138] HR-ESI-MS: m / z calcd for PMC2 (C 21 H 26 N3, [M] +) Found, 320.2124.

[0139] The photochromic properties of the synthesized compound were measured at 25 degrees Celsius in different solvents (concentration 10 μΜ) at wavelength 300-700 nm. The color of the solution showed a change from red to colorless after irradiation by 500 nm light. Figure 2 The results of the measurement of the absorption spectrum are shown. Among them, Figure 2 The results of the measurement of the absorption spectrum before and after irradiation are shown, the solid line is before irradiation, and the dotted line represents after irradiation. In combination with the above Figure 2 It can be seen that the maximum absorption peak of the compound after irradiation is blue-shifted, and the maximum absorption peak is blue-shifted from 517 nm to 412 nm in aqueous solution.

[0140] The recovery effect of the compound in aqueous solution after irradiation by 500 nm light is shown. It can slowly recover to the initial state in the dark for ten hours, and heating can accelerate this process. Figure 3 The change of 517 nm absorbance in the dark at two temperatures is shown. The recovery effect of the compound in aqueous solution after irradiation by 500 nm light is shown. It can slowly recover to the initial state in the dark for ten hours, and heating can accelerate this process. In combination with Figure 4 It can be seen that in aqueous solution, after 500 nm light decolorization and color recovery in the dark, this process is repeated ten times without obvious attenuation.

[0141] Example 3

[0142] A preparation method of a photochromic molecule (E)-2-[2-(5-pyrrolidinyl-2-pyridyl) vinyl]-1-ethyl-3,3-dimethyl-3H-indolium salt PMC3 shown in formula IIA-3 is provided;

[0143] The specific structural formula is as follows:

[0144]

[0145] The specific synthesis process includes:

[0146] Into a 50 mL tomato bottle, 1-ethyl-2,3,3-trimethyl-3H-indolium salt (316 mg) and 5-(pyrrolidinyl)pyridine-2-carboxaldehyde (176 mg) were added, and 10 mL of ethanol was added at room temperature. The reaction was carried out for 3 hours. After the reaction was completed, the compound was refined by column chromatography, and 99 mg of the component of dichloromethane and methanol (20 / 1) was collected, and the yield was 21%.

[0147] And the characterization of the photochromic molecule PMC3 shown in IIA-3 is as follows:

[0148] 1H NMR (400 MHz, 298 K, CDC13) δ (ppm): 8.61 (s, 1 H), 8.39 (d, J = 15.4 Hz, 1 H), 8.15 (s, 1 H), 7.71 (d, J = 15.4 Hz, 1 H), 7.63 - 7.42 (m, 4 H), 6.97 (d, J = 8.9 Hz, 1 H), 4.74 (d, J = 7.4 Hz, 2 H), 3.54 (s, 4 H), 2.13 (s, 4 H), 1.88 (s, 6 H), 1.64 (d, J = 7.4 Hz, 3 H). 13 C NMR (100 MHz, 298 K, CDC13) δ (ppm): 179.89, 154.54, 145.80, 143.03, 140.47, 138.74, 136.61, 132.92, 129.46, 128.76, 122.78, 117.29, 113.72, 106.97, 51.85, 47.99, 42.69, 27.43, 25.30, 13.86.

[0149] HR-ESI-MS: m / z calcd for PMC3 (C 23 H 28 N3, [M] + ), 346.2278; found, 346.2276.

[0150] The photochromic properties of the synthesized compounds were determined in different solvents (concentration 10 μΜ) at 25 degrees Celsius at a wavelength of 300-700 nm. After irradiation by white LED light, the color of the solution showed a change from red to colorless. Figure 5 The results of the determination of the absorption spectra before and after irradiation are shown in Figure 2. The solid line is before irradiation and the dashed line represents after irradiation. In combination with the Figure 5 It can be seen that the maximum absorption peak of the compound after irradiation is blue-shifted, and the maximum absorption in aqueous solution is blue-shifted from 530 nm to 419 nm.

[0151] Example 4

[0152] A method for preparing a photochromic molecule (E)-1-ethyl-3,3-dimethyl-2-[2-(2- pyridyl)vinyl]-3H-indolium salt (PMC4) is provided, as shown in formula IIA-4;

[0153] The specific structural formula is as follows:

[0154]

[0155] The specific synthesis process includes:

[0156] To a 50 mL vial was added 1-ethyl-2,3,3-trimethyl-3H-indolium salt (316 mg) and pyridine-2-carboxaldehyde (120 mg), ethanol 10 mL, at room temperature for 3 hours. After the reaction was completed, the compound was purified by column chromatography, collecting fractions of dichloromethane and methanol (30 / 1) 10 mg yield 5%. The PMC form spontaneously converts to the closed ring form (SIZ), a mixture of both.

[0157] The characterization of the photochromic molecule PMC4, as illustrated by IIA-4, is as follows:

[0158] 1 H NMR (300 MHz, CDCI3) δ (ppm): 8.80 (d, J = 8.0 Hz, 1 H), 8.69 (d, J = 8.0 Hz, 1 H), 8.66 (td, J = 8.1, 1.3 Hz, 1 H), 8.58 (d, J = 16.0 Hz, 1 H), 8.21 (d, J = 16.1 Hz, 1 H), 8.00 (t, J = 6.9 Hz, 2 H), 7.73 (t, J = 6.9 Hz, 1 H), 7.67-7.63 (m, 2 H), 5.01 (q, J = 7.4 Hz, 2 H), 1.96 (s, 6 H), 1.70 (t, J = 7.4 Hz, 3 H). SIZ4, 1 H NMR (300 MHz, CDCI3) δ (ppm): 8.74 (d, J = 4.7 Hz, 1 H), 7.94 (td, J = 8.1, 1.8 Hz, 1 H), 7.80-7.77 (m, 1 H), 7.67-7.63 (m, 1 H), 7.44 (dd, J = 7.7, 4.8 Hz, 1 H), 7.33 (td, J = 7.7, 1.3 Hz, 1 H), 7.25 (d, J = 6.7 Hz, 1 H), 7.19 (d, J = 7.4, 1 H), 6.99 (td, J = 7.4, J = 0.9, 1 H), 6.79 (d, J = 7.9 Hz, 1 H), 3.14 (b, 2 H), 1.26 (s, 6 H), 1.12 (t, J = 7.2 Hz, 3 H).

[0159] HR-ESI-MS: m / z calcd for PMC4 (C19H21N2, [M]+), 277.1699; found, 277.1702.

[0160] The photochromic properties of the synthesized compounds were determined in different solvents (concentration 10 μΜ) at 25 degrees Celsius, in the wavelength range 250-600 nm. After illumination by white LED light, the absorption peak of the solution around 380 nm decreased. Figure 6 The results of the determination of the absorption spectra before and after illumination are shown, the solid line is before illumination, the dashed line indicates after illumination. In combination with theFigure 6 It can be seen that the maximum absorption peak of the compound after illumination is blue-shifted, and the maximum absorption peak is blue-shifted from 370 nm to 280 nm in aqueous solution.

[0161] Example 5

[0162] A preparation method of a photochromic molecule (E)-2-[2-(5-nitro-2-pyridyl)vinyl]-1- ethyl-3,3-dimethyl-3H-indolium salt (PMC5) shown in formula IIA-5 is provided.

[0163] The specific structural formula is as follows:

[0164]

[0165] The specific synthesis process includes:

[0166] Into a 50 mL tomato bottle, 1-ethyl-2,3,3-trimethyl-3H-indolium salt (316 mg) and 5-nitropyridine-2-carboxaldehyde (152 mg) were added, and 10 mL of ethanol was added at room temperature for 3 hours. After the reaction was completed, the compound was refined by column chromatography, and 180 mg of components of dichloromethane and methanol (25 / 1) were collected, with a yield of 40%.

[0167] The photochromic molecule PMC5 shown in IIA-5 is characterized as follows:

[0168] 1 H NMR (400 MHz, 298 K, CD2Cl2) δ (ppm): 9.43 (d, J = 2.6 Hz, 1H), 8.89 (d, J = 8.6 Hz, 1H), 8.64 (d, J = 17.1 Hz, 1H), 8.62-8.57 (m, 1H), 8.27 (d, J = 16.0 Hz, 1H), 7.71-7.54 (m, 4H), 4.84 (q, J = 7.4 Hz, 2H), 1.89 (s, 6H), 1.63 (t, J = 7.4 Hz, 3H). 13 CNMR (100 MHz, 298 K, CDCl3) δ (ppm): 182.44, 156.15, 149.82, 145.24, 144.35, 140.10, 132.73, 131.42, 130.11, 128.86, 123.30, 118.17, 115.63, 53.81, 45.22, 26.25, 14.69.

[0169] HR-ESI-MS: m / z calcd for PMC5 (C 19 H 20 N3O2, [M] +Found: 322.1550; found, 322.1553.

[0170] The photochromic properties of the synthesized compound were measured at 25 degrees Celsius in different solvents (concentration 10 μΜ) at a wavelength of 250-600 nm. After irradiation by white LED light, the absorption peak of the solution at about 380 nm decreased, generating an absorption peak at about 310 nm. Figure 7 The results of the measurement of the absorption spectrum before and after irradiation are shown in the figure, the solid line is before irradiation, and the dashed line represents after irradiation. It can be seen that the maximum absorption peak of the compound after irradiation is blue-shifted, and the maximum absorption peak is blue-shifted from 384 nm to 306 nm in aqueous solution. Figure 7 The results of the measurement of the absorption spectrum before and after irradiation are shown in the figure, the solid line is before irradiation, and the dashed line represents after irradiation. It can be seen that the maximum absorption peak of the compound after irradiation is blue-shifted, and the maximum absorption peak is blue-shifted from 384 nm to 306 nm in aqueous solution.

[0171] Example 6

[0172] A method for preparing a photochromic molecule (E)-2-[2-(6-dimethylaminoquinolin-2-yl)vinyl]-1-ethyl-3,3-dimethyl-3H-indolium salt (PMC6) is provided.

[0173] The specific structural formula is as follows:

[0174]

[0175] The specific synthesis process includes:

[0176] Into a 50 mL tomato bottle, 1-ethyl-2,3,3-trimethyl-3H-indolium salt (316 mg) and 6-(dimethylamino)quinoline-2-carboxaldehyde (200 mg) were added, and 10 mL of ethanol was added at room temperature. The reaction was carried out for 3 hours. After the reaction was completed, the compound was refined by column chromatography, and 264 mg of components of dichloromethane and methanol (30 / 1) were collected, with a yield of 53%.

[0177] The photochromic molecule PMC6 represented by IIA-6 is characterized as follows:

[0178] 1 H NMR (400 MHz, 298 K, CD2Cl2) δ (ppm): 8.44 (d, J = 15.2 Hz, 1H), 8.08 (td, J = 22.6, 18.3, 12.7 Hz, 4H), 7.74-7.62 (m, 4H), 7.47 (dd, J = 9.4, 2.9 Hz, 1H), 6.84 (d, J = 2.9 Hz, 1H), 4.83 (d, J = 7.6 Hz, 2H), 3.20 (s, 6H), 1.91 (s, 6H), 1.69 (t, J = 7.3 Hz, 3H). 13C NMR (75 MHz, 298 K, CD2Cl2) δ (ppm): 181.24, 154.78, 150.45, 146.72, 143.74, 143.00, 140.40, 133.71, 131.75, 131.55, 129.93, 129.63, 124.83, 122.97, 120.20, 114.81, 112.45, 103.68, 52.66, 43.50, 40.26, 26.65, 14.04.

[0179] HR-ESI-MS: m / z calcd for PMC6 (C 25 H 28 N3, [M] + ), 370.2278; found, 370.2280.

[0180] The photochromic properties of the synthesized compounds were determined at 25 degrees Celsius in different solvents (concentration 10 μΜ) at a wavelength of 300-800 nm. After irradiation by 660 nm light, the solution changed from purple red or blue to colorless. Figure 8 The results of the determination of the absorption spectrum before and after light irradiation are shown, the solid line is before irradiation, and the dashed line represents after irradiation. It can be seen that the maximum absorption peak of the compound after irradiation is blue-shifted, and the maximum absorption peak is blue-shifted from 617 nm to 438 nm in aqueous solution. Figure 8

[0181] Figure 9 The change in absorbance of the compound at 617 nm under two conditions of darkness and 500 nm light stimulation is shown. It can be seen that the compound is difficult to recover to the initial state in the dark, and can only be recovered by shorter wavelength light, which is a P-type photochromic molecule. Figure 9 Figure 10 The change in absorbance of the compound in dichloromethane solution during the cycle process of 660 nm stimulation and 500 nm stimulation is shown. It can be seen that the compound in dichloromethane solution undergoes 660 nm discoloration and 500 nm color recovery. This process is repeated ten times without significant attenuation, and has good fatigue resistance. Figure 10

[0182] Example 7

[0183] A method for preparing a photochromic molecule (E)-3-[2-(2-(6-dimethylaminoquinolin-2-yl)vinyl)-1,1-dimethyl-1H-benzo[e]indol-3-ium-3-yl]propane-1-sulfonic acid inner salt (PMC7) is provided.

[0184] The specific structural formula is as follows:

[0185] The specific structural formula is as follows:​​

[0186] The specific synthesis procedure includes:

[0187] To a 50 mL vial was added 3-ethyl-1,1,2-trimethyl-1 H-benzo[e]indol-3-ium salt (360 mg) and 6-(dimethylamino)quinoline-2-carbaldehyde (200 mg), ethanol 10 mL, and the reaction was allowed to proceed at room temperature for 3 hours. After the reaction was complete, the compound was purified by column chromatography, and the fractions were collected in dichloromethane and methanol (30 / 1 ) to give 180 mg of product in 35% yield.

[0188] and the photochromic molecule PMC7, as illustrated in IIA-7, was characterized as follows:

[0189] 1 H NMR (400 MHz, 298 K, CD2CI2) δ (ppm): δ 8.47 (d, J = 9.8 Hz, 1 H), 8.41 (s, 1 H), 8.31 (d, J = 16.3 Hz, 1 H), 8.17 (d, J = 8.5 Hz, 1 H), 8.09 (d, J = 8.9 Hz, 1 H), 8.02 (d, J = 8.4 Hz, 2H), 7.89 (d, J = 9.4 Hz, 1 H), 7.81 (d, J = 8.9 Hz, 1 H), 7.70 (t, J = 7.6 Hz, 1 H), 7.62 (t, J = 7.6 Hz, 1 H), 7.34 (dd, J = 9.5, 2.8 Hz, 1 H), 6.74 (s, 1 H), 5.06 (t, J = 8.4 Hz, 2H), 3.10 (s, 6H), 2.95 (s, 2H), 2.43 (s, 2H), 2.03 (s, 6H). 13 C NMR (75 MHz, 298 K, CD2CI2) δ (ppm): 182.39, 150.51, 149.67, 138.17, 135.67, 133.87, 132.56, 131.93, 131.55, 131.05, 130.31, 130.19, 128.62, 127.62, 127.47, 125.07, 122.98, 122.34, 115.75, 115.17, 112.12, 111.06, 103.91, 46.80, 46.53, 40.26, 26.49, 25.45. HR-ESI-MS: m / z calcd for PMC7 (C 30 H 32 N3O3S, [M+H] + ), 514.2159; found, 514.2161.

[0190] The photochromic properties of the synthesized compounds were measured at 25 degrees Celsius in the wavelength range of 300-800 nm in different solvents (concentration of 10 μM). After irradiation by 660 nm light, the solution changed from purple red or blue to colorless. Figure 11 The results of the measurement of the absorption spectrum before and after light irradiation are shown, with the solid line representing before irradiation and the dashed line representing after irradiation. It can be seen that Figure 11 After light irradiation, the maximum absorption peak of the compound is blue-shifted, and in aqueous solution, the maximum absorption peak is blue-shifted from 607 nm to 434 nm.

[0191] Test Example 1

[0192] The filter paper or silica gel plate was immersed in a solution of PMC2 in acetonitrile with a concentration of 100 μM for 10 minutes. Then the material was taken out and naturally dried to obtain functionalized filter paper and silica gel plates loaded with photochromic molecules PMC2 on the surface.

[0193] 500 mg of polymethyl methacrylate (PMMA) was dissolved in 5 mL of chloroform under magnetic stirring at 50°C for 30 minutes until complete dissolution. To the above PMMA solution, PMC2 stock solution was added dropwise so that the mass ratio of PMC2 to PMMA was 1:1000 (w / w). The system was ultrasonically treated for 30 minutes to promote uniform dispersion. The resulting uniform solution was poured into a clean glass beaker and placed in a 50°C oven for 48 hours to form a polymer film. The obtained solid thin film was then vacuum annealed at 40°C for 24 hours to remove residual solvents. Functionalized polymer materials loaded with photochromic molecules were obtained.

[0194] These materials turned white or transparent when irradiated by white light LED and returned to red when placed in the dark or heated. Figure 12 The color change of the process was demonstrated.

[0195] Test Example 2

[0196] Polymethyl methacrylate (PMMA) 500 mg was weighed and added to 5 mL of chloroform (CHCl) and dissolved under continuous stirring at 50°C for 30 minutes. After the PMMA was completely dissolved, the stock solutions of PMC2 and PMC7 were slowly added dropwise to adjust the mass ratio of the three to PMC2:PMC7:PMMA=0.5:1:1000 (w / w).

[0197] The mixture was ultrasonically treated at room temperature for 30 minutes to ensure uniform dispersion of the dyes in the PMMA solution. Then, the solution was poured into a clean glass beaker and placed in a 50°C oven for 48 hours to naturally evaporate the solvent and obtain a preliminary dried polymer film.

[0198] The film can respond to 500 nm light and 660 nm light, and different results can be obtained according to the order of light irradiation. The initial state of the film is purple red, and the irradiation order is 500 nm first and then 660 nm, and a light yellow film is obtained; the irradiation order is 660 nm first and then 500 nm, and a dark blue film is obtained. Figure 13 The color change of the process is shown.

[0199] In summary, the photochromic molecule provided by the application has the characteristics of high photoconversion efficiency, excellent light fatigue stability, good water compatibility, and adjustable T type / P type. And it is easy to adhere to various solid phase materials such as filter paper, silica gel plate, thermoplastic plastic, etc.; has broad application prospects in the fields of biological markers, intelligent materials, information storage and visualization sensing.

[0200] The application of the application Figure 14 is a schematic diagram of the light timing regulation characteristics of PMC2 and PMC7 doped polymethyl acrylate, combined with Figure 14 It can be seen that the system will obtain different results when different light stimulation sequences are experienced. When 660 nm light irradiation is performed first and then 500 nm light irradiation is experienced, the film changes from red purple to dark blue; when 500 nm light irradiation is performed first and then 660 nm light irradiation is experienced, the film changes from red purple to yellow. That is, different input sequences will output different results, which is the characteristic of timing intelligent materials.

[0201] Comparative example

[0202] A kind of spiro pyran photochromic molecule of the following schematic is provided.

[0203]

[0204] The absorption spectrum of the above-mentioned spiro pyran photochromic molecule is as shown in Figure 15 A schematic, the absorbance change schematic diagram of multiple cycles is as shown in Figure 15 B.

[0205] Combined with the application of the application Figure 4 and Figure 15 B can be known, the photochromic molecule provided by the application has the advantages of high photoconversion efficiency, excellent light fatigue stability, good water compatibility, etc.

[0206] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than limit them. Although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that the technical solutions recorded in the foregoing embodiments can be modified, or some or all of the technical features can be replaced equivalently. Such modifications or replacements do not change the essence of the corresponding technical solutions, which should be covered in the scope of the claims and the specification of the present application. In particular, the technical features mentioned in each embodiment can be combined in any manner as long as there is no structural conflict. The present application is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims.

Claims

1. A photochromic molecule based on reversible C-N bond generation, characterized in that: Any one or more of the following Formula IA, Formula IB schematic structural formula; Wherein, Ar1 and Ar2 are each independently selected from any one of C6-C30 aryl, C6-C30 heteroaryl; R1, R2 and R3 are each independently selected from any one of hydrogen, halogen, nitro, amino, hydroxyl, sulfonic acid group, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylamino, substituted or unsubstituted C1-C20 alkenyl, substituted or unsubstituted C1-C20 alkynyl; the substituted substituent includes any one or more of hydrogen, halogen, nitro, amino, sulfonic acid group, C1-C20 alkyl, C1-C20 alkylamino, C1-C20 alkoxy, C6-C12 aryl, C6-C12 heteroaryl.

2. The photochromic molecule of claim 1, wherein: Ar1 is selected from C6-C30 aryl, and Ar2 is selected from heteroaryl; R2 is selected from any one of substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy; R3 is selected from any one of hydrogen, halogen, nitro, amino, hydroxyl, sulfonic acid group, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkylamino; The substituted substituent includes any one or more of hydrogen, halogen, nitro, amino, sulfonic acid group, C1-C20 alkyl, C1-C20 alkylamino, C1-C20 alkoxy, C6-C12 aryl, C6-C12 heteroaryl.

3. The photochromic molecule of claim 2, wherein: Any one or more of the following Formula II A, Formula IIB schematic structural formula; R1 is selected from any one of hydrogen, halogen, nitro, amino, hydroxyl, sulfonic acid group; R2 is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl; R3 is selected from any one or more of hydrogen, substituted or unsubstituted C1-C20 alkylamino, C6-C12 aryl, C6-C12 heteroaryl; The substituted substituent includes any one or more of hydrogen, halogen, nitro, amino, sulfonic acid group.

4. The photochromic molecule of claim 3, characterized in that: The photochromic molecule includes any one or more of the following specific structural formula:

5. A method for preparing a photochromic molecule based on a reversible C-N bond generation, characterized in that: Including the following preparation process: The following Formula III and Formula IV schematic compound is condensed in an organic solvent to obtain a photochromic molecule including any one or more of the following Formula IA, Formula IB schematic structural formula; Wherein, Ar1 and Ar2 are each independently selected from any one of C6-C30 aryl, C6-C30 heteroaryl; R1, R2 and R3 are each independently selected from any one of hydrogen, halogen, nitro, amino, hydroxyl, sulfonic acid group, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylamino, substituted or unsubstituted C1-C20 alkenyl, substituted or unsubstituted C1-C20 alkynyl; The substituted substituent includes any one or more of hydrogen, halogen, nitro, amino, sulfonic acid group, C1-C20 alkyl, C1-C20 alkylamino, C1-C20 alkoxy, C6-C12 aryl, C6-C12 heteroaryl. The substituent includes any one or more of hydrogen, halogen, nitro, amino, sulfonic acid group, C1-C20 alkyl, C1-C20 alkylamino, C1-C20 alkoxy, C6-C12 aryl, and C6-C12 heteroaryl.

6. The method of claim 5, wherein: The organic solvent includes any one or more of acetic anhydride, ethanol, and toluene. and / or; The reaction temperature is 20-65°C, and the reaction time is 1-5 hours.

7. A solution having photochromic properties, characterized in that: The photochromic molecule of any one of claims 1-4 or the photochromic molecule prepared by the method of any one of claims 5-6, further comprising a solvent, and the solvent includes any one or more of water, methanol, acetonitrile, and dichloromethane.

8. A filter paper or silica gel plate having photochromic properties, characterized by: The filter paper substrate or the silica gel plate substrate, and the photochromic layer on at least one side surface of the filter paper substrate or the silica gel plate substrate, and the photochromic layer includes the photochromic molecule of any one of claims 1-4 or the photochromic molecule prepared by the method of any one of claims 5-6.

9. A thin film having photochromic properties, characterized in that: The polymer film includes a thermoplastic polymer and the photochromic molecule of any one of claims 1-4 or the photochromic molecule prepared by the method of any one of claims 5-6. The mass ratio between the photochromic molecule and the thermoplastic polymer is 1:500-2000. The thermoplastic polymer includes any one or more of polymethyl methacrylate and polyethyl methacrylate.

10. A light-responsive smart material, characterized in that: The photochromic molecule of any one of claims 1-4 or the photochromic molecule prepared by the method of any one of claims 5-6, or the solution of claim 7, or the filter paper or the silica gel plate of claim 8, or the film of claim 9.

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