Compounds, photochromic materials and uses

Abstract

The application belongs to the technical field of photochromic, and proposes a compound, a photochromic material and purposes thereof. The compound is a compound shown in formula (1) or a stereoisomer or a tautomer of the compound shown in formula (1): formula (1) wherein R1 is -CH2-, -CH(CH2) n1 CH3- or -C(CH2) n1 CH3(CH2) n2 CH3-; R2 is H, -(CH2) n3 CH3, a phenyl group or a fused ring aromatic hydrocarbon group; n1, n2 and n3 are independently selected from integers between 0 and 6, the phenyl group or the fused ring aromatic hydrocarbon group is optionally substituted by one or more R n , and R n is a C1-C6 alkyl group. The compound has an electrochromic property, and has a relatively fast color changing and restoring speed, and can be used for three-dimensional imaging.

Description

Technical Field

[0001] This invention relates to the field of photochromic technology, specifically to a compound, a photochromic material, and its uses. Background Technology

[0002] Breakthroughs in computer and optical technologies have enabled a variety of display products for reconstructing the visual world, which is changing our daily lives. Currently, commercially available display products mainly rely on panel display technology, providing only two-dimensional (2D) images. Due to the significant advantages of stereoscopic imaging in understanding and interpreting visual information—such as providing greater information, wider viewing angles, and more three-dimensional image information—the demand for developing 3D display technology is constantly increasing, especially in fields such as military command and control, industrial design, flight simulators, medical imaging, advertising, film, and exhibitions. 3D display technology can currently be divided into four main categories: automatic beam-splitting stereoscopic displays, beam-splitting stereoscopic glasses, holographic displays, and volumetric 3D displays. The first two categories, automatic beam-splitting stereoscopic displays and beam-splitting stereoscopic glasses, use parallax to create the feeling of 3D display. The 3D scenes constructed by this artificially created parallax are unnatural and increase the mental burden on the observer. Holography, on the other hand, utilizes the interference and diffraction phenomena of light waves. Based on this mechanism, holography can generally only generate static three-dimensional optical scenes and can only be viewed from specific angles. Volumetric 3D display technology displays 3D objects using volumetric pixels in 3D space. This technology presents a realistic stereoscopic image that can provide full depth information and meet the needs of all-around observation.

[0003] In volumetric 3D display technology, the properties of the display medium material are crucial to the imaging effect under current computer technology. Taking static volumetric display systems as an example, commonly used materials include dual-frequency upconversion materials (TSTF-UC), rare-earth-doped single crystals, dye-based composite materials, and gas materials. Upconversion materials have fast response speeds but low luminous efficiency, requiring high-energy lasers as light sources; gas display technology is difficult to apply practically due to differences in the type and refractive index of the medium; single-crystal medium materials are costly to manufacture and difficult to scale up. Dye-based medium materials are diverse, but some dyes and solvents are harmful and difficult to control. Furthermore, organic dyes generally have small emission shifts, and the excitation and emission wavelengths are similar, resulting in poor image clarity.

[0004] In organic materials, photochromic compounds can reversibly switch between colorless and colored states under the influence of light stimulation. Their photoinduction and reversibility can be used to modulate fluorescence in molecular and supramolecular structures. Specifically, fluorescent and photochromic components can be covalently or non-covalently paired, and the interconversion of the latter can adjust the emission intensity of the formed body according to the transfer of electrons or energy between the components; therefore, they are also called light-switching materials. Organic photochromic materials have advantages such as low cost, flexible performance, large formation area, sensitive absorption, and controllable physical parameters such as refractive index and dielectric constant. Their inherent light-switching characteristics have significant potential in the field of spatial point addressing. Reports on the use of organic photochromic materials for volumetric 3D displays are increasing year by year, but most reports demonstrate static 2D image effects. Because the switching speed of the materials involved in these reports is slow and cannot update images at the human eye's refresh rate, it is difficult to achieve dynamic changes in graphics.

[0005] Schiff bases are a class of materials with rapid photochromic rates. They mainly refer to organic compounds containing imine or methylimine characteristic groups (-RC=N-). Schiff bases are typically formed by the condensation of an amine and an active carbonyl group. Schiff bases derived from salicylaldehyde derivatives with 2-hydroxyl groups are primarily due to the presence of OH···N and O···HN type hydrogen bonds. These hydrogen bonds undergo excited-state tautomerization between enol imines and ketene enamines via excited-state intramolecular proton transfer (ESIPT). Currently, most research on Schiff bases focuses on photochromism and catalysis, with few reports on their application in volumetric 3D displays. This is mainly because the materials are opaque in powder form, making spatial display impossible; in solution, the Schiff base environment changes, making it difficult to observe significant photochromic phenomena; and current Schiff bases still suffer from poor luminosity, slow color change and recovery times, leading to difficulties in designing optical paths for 3D displays. Summary of the Invention

[0006] The present invention aims to at least partially solve one of the technical problems in the related art.

[0007] In one aspect, the present invention provides a compound, said compound being a compound of formula (1) or a stereoisomer or tautomer of the compound of formula (1): Equation (1) Where R1 is -CH2- or -CH(CH2). n1 CH3- or -C(CH2) n1 CH3(CH2) n2 CH3-; R2 is H, -(CH2) n3CH3, phenyl or fused-ring aromatic hydrocarbon group; n1, n2, n3 are each independently selected from integers between 0 and 6, wherein the phenyl or fused-ring aromatic hydrocarbon group is optionally surrounded by one or more R n Replaced by, R n It is a C1~C6 alkyl group.

[0008] The compound of this invention exhibits photochromic properties. In its closed-ring state, it is colorless and highly transparent; visible light can directly penetrate the material without fluorescence when not irradiated by short-wave ultraviolet light. Upon ultraviolet irradiation, it forms an open-ring isomer, resulting in photochromism. Fluorescent spots are generated at the intersection of visible and ultraviolet light irradiation, immediately forming spatial fluorescence spots (intersection luminescence characteristics). The significant color difference between the fluorescent spots and the ultraviolet light results in good contrast. The compound exhibits rapid photochromic changes and recovery, with the recovery process being a thermal recovery reaction, allowing for rapid recovery at room temperature. The compound is chemically stable and can be reused multiple times.

[0009] According to embodiments of the present invention, R1 is -CH2-, -CHCH2CH3-, or -CH(CH2). 14 CH3-, -CCH2CH3CH2CH3-, -CHCH3- or -C(CH3)2-.

[0010] According to an embodiment of the present invention, R2 is H or -(CH2). n3 CH3, phenyl or naphthyl, wherein the phenyl or naphthyl group is optionally surrounded by one or more R groups. n Replaced by, R n It is a C1~C6 alkyl group.

[0011] According to an embodiment of the present invention, the R n It is methyl.

[0012] According to embodiments of the present invention, the compound has one of the following structures: , , , , , , .

[0013] According to embodiments of the present invention, the compound has one of the following structures: , , .

[0014] In another aspect of the invention, a photochromic material is provided, comprising the aforementioned compound. This photochromic material exhibits good luminescence and rapid photochromic change and recovery, enabling its application in the field of volumetric three-dimensional imaging. Furthermore, the raw materials for this photochromic material are inexpensive and readily available.

[0015] In another aspect of the invention, an application of a photochromic material in three-dimensional imaging is proposed. In this invention, by utilizing the photochromic characteristics of the photochromic material, the photochromic material can be used in the field of three-dimensional imaging, and the three-dimensional imaging process using the photochromic material of this invention is simple.

[0016] According to an embodiment of the present invention, the three-dimensional imaging includes the following steps: subjecting the photochromic material to a first irradiation treatment using ultraviolet light; subjecting the photochromic material to a second irradiation treatment using visible light, thereby forming a three-dimensional image at the intersection of the ultraviolet light and the visible light sources.

[0017] According to an embodiment of the present invention, the direction in which the visible light source irradiates the photochromic material is perpendicular to the direction in which the ultraviolet light source irradiates the photochromic material. Attached Figure Description

[0018] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which: Figure 1 Here are some examples of compound synthesis flowcharts; Figure 2 This is a schematic diagram of the photochromic process of the compounds in some embodiments; Figure 3 A schematic diagram illustrating the optical path design principle for achieving three-dimensional imaging with photochromic materials in some embodiments; Figure 4 This demonstrates the spatial point luminescence effect of the photochromic material in Example 1. Figure 5 This is a spatial three-dimensional image display of the photochromic material in Example 1; Figure 6 The 1H NMR spectrum of compound S-1 from Example 1; Figure 7 The 1H NMR spectrum of compound S-2 in Example 2; Figure 8 The 1H NMR spectrum of compound S-3 in Example 3; Figure 9 The 1H NMR spectrum of compound S-4 in Example 4; Figure 10 The image shows the 1H NMR spectrum of compound S-5 from Example 5.

[0019] Figure label: 1: Screen; 2: Ultraviolet light; 3: Spatial three-dimensional voxel. Detailed Implementation

[0020] Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0021] In one aspect of the invention, a compound is provided, said compound being a compound of formula (1) or a stereoisomer or tautomer of the compound of formula (1): Equation (1) Where R1 is -CH2- or -CH(CH2). n1 CH3- or -C(CH2) n1 CH3(CH2) n2 CH3-; R2 is H, -(CH2) n3 CH3, phenyl or fused-ring aromatic hydrocarbon group; n1, n2, n3 are each independently selected from integers between 0 and 6, wherein the phenyl or fused-ring aromatic hydrocarbon group is optionally surrounded by one or more R n Replaced by, R n It is a C1~C6 alkyl group.

[0022] The compounds of this invention exhibit photochromic properties. In their closed-ring state, they are colorless and highly transparent; visible light can directly penetrate the material without fluorescence when not irradiated by short-wave ultraviolet light. Upon ultraviolet irradiation, they form an open-ring isomer, resulting in photochromism. Fluorescent spots are generated at the intersection of visible and ultraviolet light irradiation, immediately forming spatial fluorescence spots (intersection luminescence). The significant color difference between the fluorescent spots and the ultraviolet light results in good contrast. The compounds exhibit rapid photochromic changes and recovery, with the recovery process being a thermal recovery reaction, allowing for rapid recovery at room temperature. The compounds are chemically stable and can be reused multiple times. Furthermore, in the compounds of this invention, R1 is -CH2- or -CH(CH2). n1 CH3- or -C(CH2) n1 CH3(CH2) n2 CH3-; R2 is H, -(CH2) n3 CH3, phenyl or fused-ring aromatic hydrocarbon group; n1, n2, n3 are each independently selected from integers between 0 and 6, wherein the phenyl or fused-ring aromatic hydrocarbon group is optionally surrounded by one or more R n Replaced by, R n It is a C1~C6 alkyl group.

[0023] Specifically, the color-changing mechanism of the compounds in this invention is as follows: The closed-ring compound, under external stimulation (such as ultraviolet light), undergoes O2 oxidation within the adsorption chamber. H···N to →O···H In the proton transfer process of N-type hydrogen bonding, the H atom in the hydroxyl group initially connected to the N atom in the amino group via a virtual bond transfers to the N atom. The O···H group of the hydroxyl group... The dummy N-type hydrogen bond opens, and the Schiff base amine moiety shifts to form an open-ring isomer. This process is shown below: .

[0024] It is understood that, as described in this invention, the compounds of this invention may optionally be substituted with one or more substituents, such as the general formula compounds above, or the specific examples, subclasses, and classes of compounds included in this invention, as described in the embodiments. It should be understood that the term "optionally substituted" is used interchangeably with the term "substituted or unsubstituted." The terms "optionally," "optionally," or "optionally" mean that the event or condition described below may or may not occur, and the description includes both cases where the event or condition occurs and cases where it does not occur. Generally, the term "optionally," whether preceding the term "substituted," indicates that one or more hydrogen atoms in the given structure are substituted by a specific substituent. Unless otherwise indicated, an optional substituent group may be substituted at each substituted position of the group. When more than one position in the given structural formula can be substituted by one or more substituents selected from a specific group, the substituents may be substituted at the same or different positions. The substituents may be C1-C6 alkyl groups.

[0025] The term fused-ring aromatic hydrocarbon group refers to a group consisting of several benzene rings fused together, wherein the fused-ring aromatic hydrocarbon group is optionally surrounded by one or more R n What it replaced.

[0026] The term alkyl refers to a monovalent hydrocarbon group containing 1 to 6 carbon atoms, either a saturated straight-chain or branched chain.

[0027] In some embodiments, R1 is -CH2-, -CHCH2CH3-, or -CH(CH2). 14 CH3-, -CCH2CH3CH2CH3, -CHCH3- or -C(CH3)2-.

[0028] In some embodiments, R2 is H, -CH3, phenyl, or naphthyl, wherein the phenyl or naphthyl group is optionally surrounded by one or more R groups. n Replaced by, R n It is a C1~C6 alkyl group.

[0029] In some embodiments, examples of alkyl groups include, but are not limited to, methyl (-CH3), ethyl (-CH2CH3), n-propyl (-CH2CH2CH3), isopropyl (-CH(CH3)2), n-butyl (-CH2CH2CH2CH3), isobutyl (-CH2CH(CH3)2), sec-butyl (-CH(CH3)CH2CH3), tert-butyl (-C(CH3)3), n-pentyl (-CH2CH2CH2CH2CH3), etc.

[0030] As some examples, the compound is a Schiff base derivative having the following structure: , , , , , , .

[0031] As other examples, the Schiff base derivative has one of the following structures: , , In these compounds, R1 contains a chiral C atom, which gives them good electrochromic properties and allows them to recover their color quickly after the color change.

[0032] In another aspect of the present invention, the present invention proposes a method for preparing the above-mentioned compound, comprising the following steps: (1) subjecting a compound with the structure shown in formula (II) and a first amine compound to a protonation reaction to obtain compound 1 (as shown in formula (III)); (2) subjecting compound 1 to a substitution reaction with sodium methoxide to obtain compound 2 (as shown in formula (IV)); (3) subjecting compound 2 to an alcoholysis reaction to obtain compound 3 (as shown in formula (V)); (4) subjecting compound 3 to a bonding reaction with hexamethylenetetramine to obtain compound 4 (as shown in formula (VI)); (5) subjecting compound 4 to a condensation reaction with a second amine compound to obtain the compound. Formula (II), where X is selected from bromine or chlorine. Formula (Ⅲ), Formula (Ⅳ). Formula (V), Formula (VI).

[0033] The method of the present invention is simple in process. Through a series of protonation, substitution, alcoholysis, bonding and condensation reactions, a compound with photochromic properties can be obtained.

[0034] Specifically, the protonation reaction involves a dehydration condensation reaction between the first amine compound and 4-X-1,8-naphthalenedicarboxylic anhydride in formula (2), allowing the first amine compound to replace the oxygen in the anhydride, forming the desired compound 1. The first amine compound has electron-withdrawing ability, which can reduce the energy required for the Schiff base derivative ESIPT process. Furthermore, the small molecular group of the first amine compound facilitates the conversion between isomers formed through bond rotation. The substitution reaction involves the substitution of X in compound 1 by the methoxy group in sodium methoxide, resulting in sodium bromide (or sodium chloride) and reactant 2. Sodium methoxide is a strong base, resulting in a good substitution reaction effect. The alcoholysis reaction involves the substitution reaction between hydroiodic acid and the methoxy group in reactant 2 to generate reactant 3 and iodoalkane. The bonding reaction involves adding an aldehyde group to the ortho position of the hydroxyl group of reactant 3, and then reacting the reactant with hexamethylenetetramine to generate formaldehyde under acidic conditions. Subsequently, formaldehyde bonds with reactant 3 to generate reactant 4. The condensation reaction is the condensation of aldehyde compound 4 with the second amine compound to obtain the compound. The second amine compound is selected for the reaction because it contains electron-donating groups, which can promote the ESIPT process. Moreover, the second amine compound is a small molecule group, making the reaction simple and controllable. The final product containing this small molecule group has a small conjugation energy, making it easy to achieve isomerization through bond rotation.

[0035] According to the present invention, in step (1), the compound with the structure shown in formula (2) and the first amine compound are subjected to a protonation reaction to obtain compound 1.

[0036] Generally, first amine compounds, being organic compounds with an amino group, can undergo protonation reactions.

[0037] In some embodiments, the first amine compound includes n-butylamine, tert-butylamine, 3-pentylamine, etc.

[0038] In some embodiments, the conditions for the protonation reaction include reflux at 110-125°C in a protective atmosphere for 4-8 hours.

[0039] In some embodiments, step (1) further includes washing, filtering and recrystallization to obtain compound 1.

[0040] According to the present invention, in step (2), compound 1 and sodium methoxide are subjected to a substitution reaction to obtain compound 2.

[0041] Generally, sodium methoxide has the properties of strong alkalinity and good substitution effect with halogen molecules. Sodium methoxide is used to substitute halogen molecules in compounds to generate alkyl bromides and reaction products 2 with methoxy groups.

[0042] In some embodiments, step (2) is performed in the presence of the first catalyst.

[0043] Optionally, the first catalyst includes copper sulfate, ferric chloride, zinc sulfate, etc.

[0044] Understandably, there are no particular restrictions on the form in which sodium methoxide is added; for example, sodium methoxide can be added directly to the reaction system.

[0045] In some embodiments, the conditions for the substitution reaction include reflux at 70-80°C in a protective atmosphere for 6-10 hours.

[0046] In some embodiments, step (2) further includes filtration and washing to obtain compound 2.

[0047] According to the present invention, in step (3), the compound 2 is subjected to an alcoholysis reaction to obtain compound 3.

[0048] Generally, alcoholysis reactions are carried out in the presence of acid.

[0049] In some embodiments, the acid includes hydroiodic acid and hydrobromic acid.

[0050] Optionally, the mass fraction of the hydroiodic acid and hydrobromic acid is 40-60%.

[0051] In some embodiments, the conditions for the alcoholization reaction include reflux at 100-120°C under a protective atmosphere for 8-12 hours.

[0052] In some embodiments, step (3) further includes filtration, washing and purification to obtain compound 3.

[0053] Optionally, the purification process is performed using silica column chromatography.

[0054] According to the present invention, in step (4), compound 3 and hexamethylenetetramine undergo a bonding reaction to obtain compound 4; Generally, hexamethylenetetramine undergoes a bonding reaction with compound 3, which can bond the formaldehyde generated by hexamethylenetetramine under acidic conditions to compound 3, and the second catalyst can promote the bonding reaction.

[0055] In some embodiments, step (4) is performed in the presence of a second catalyst.

[0056] Optionally, the second catalyst includes trifluoroacetic acid and acetic acid.

[0057] In some embodiments, the bonding reaction conditions include reflux at 65-70°C under a protective atmosphere for 8-12 hours.

[0058] In some embodiments, step (4) further includes filtration, washing and purification to obtain compound 4.

[0059] Optionally, the purification process can be performed using a short silicon plug.

[0060] In some embodiments, the molar ratio of compound 3, hexamethylenetetramine, and the second catalyst is (1): (1-3): (5-20).

[0061] According to the present invention, in step (5), the compound 4 and the second amine compound are subjected to a condensation reaction to obtain the compound.

[0062] Generally, the second amine compound and compound 4 undergo a condensation reaction in the presence of a solvent to obtain the compound.

[0063] In some embodiments, the structural formula of the second amine compound is shown in formula (VII). Equation (VII), where R1 is -CH2- or -CH(CH2). n1 CH3- or -C(CH2) n1 CH3(CH2) n2 CH3-; R2 is H, -(CH2) n3 CH3, phenyl or fused-ring aromatic hydrocarbon group; n1, n2, n3 are each independently selected from integers between 0 and 6, wherein the phenyl or fused-ring aromatic hydrocarbon group is optionally surrounded by one or more R n Replaced by, R n It is a C1~C6 alkyl group.

[0064] Furthermore, the second amine compound includes at least one of chiral methylbenzylamine, achiral methylbenzylamine, chiral 1-(p-tolyl)ethylamine, achiral 1-(p-tolyl)ethylamine, chiral (1-naphthyl)-2-ethylamine, achiral (1-naphthyl)-2-ethylamine, isophenylpropylamine, and alkylamine.

[0065] In some embodiments, the conditions for the condensation reaction include reflux at 75-85°C in a protective atmosphere for 2-6 hours.

[0066] In some embodiments, step (5) further includes filtration and washing to obtain the compound.

[0067] In some embodiments, the molar ratio of compound 4, the second amine compound, and ethanol is (1):(0.9-2):(20-100).

[0068] In some embodiments, the molar ratio of the compound with the structure shown in formula (2), the amine compound, the sodium methoxide, the first catalyst, the hexamethylenetetramine, and the second amine compound is 1:(2-4):(7-8):(0.1-0.3):(1-3):(0.8-1.5). Thus, the compound can be obtained.

[0069] As an example, the compound with the structure shown in formula (2) is 4-bromo-1,8-naphthalenedicarboxylic anhydride, the amine compound is n-butylamine, the first catalyst is copper sulfate, the second amine compound is S-α-methylbenzylamine, and the second catalyst is HFT (trifluoroacetic acid) or hexamethylenetetramine (HMTA). The process for synthesizing the above compound using the method of the present invention is as follows: Figure 1 As shown.

[0070] In another aspect of the invention, a photochromic material is provided, comprising the aforementioned compound. This photochromic material exhibits good luminescence and rapid photochromic change and recovery, enabling its application in the field of volumetric three-dimensional imaging. Furthermore, the raw materials for this photochromic material are inexpensive and readily available.

[0071] In some embodiments, the photochromic material further includes a nonpolar solution. Using a nonpolar solution as the medium makes it easier to scale up production in urban and rural areas compared to solid materials.

[0072] Optionally, the nonpolar solution includes a cyclohexane solution with a concentration of 0.001-0.01 mg / ml.

[0073] In some embodiments, the molar ratio of the compound to the nonpolar solution is 1:(3000-30000).

[0074] In another aspect of the invention, an application of a photochromic material in three-dimensional imaging is proposed. In this invention, by utilizing the photochromic characteristics of the photochromic material, the photochromic material can be used in the field of three-dimensional imaging, and the three-dimensional imaging process using the photochromic material of this invention is simple.

[0075] In some embodiments, such as Figure 2-5 As shown, by utilizing the photochromic properties of the compound under single irradiation with ultraviolet and visible light sources, photochromic materials can be applied in the fields of erasable organic photonic information storage devices, light-controlled switches, and volumetric 3D display devices.

[0076] As an example, the working process of a light-controlled switch is as follows: the compound of a photochromic material, after changing color, can absorb visible light. Linking it with fluorescent molecules allows for the switching control of the fluorescent molecules' luminescence. Specifically, if the material linked to the fluorescent molecules is irradiated with ultraviolet light, the compound changes color and absorbs the light from the fluorescent molecules, leaving the fluorescent molecules in a non-luminescent state. Irradiating with visible light causes the compound to return to its initial state, the fluorescent molecules no longer absorb visible light, and the fluorescent molecules become luminescent, thus achieving the function of a light-controlled switch.

[0077] In some embodiments, the three-dimensional imaging includes the following steps: S1 applying ultraviolet light to the photochromic material for a first irradiation treatment; S2 applying visible light to the photochromic material for a second irradiation treatment, forming a spatial three-dimensional image at the intersection of the ultraviolet light and the visible light source.

[0078] In step S1, the photochromic material is irradiated with ultraviolet light, causing the compound to change color. Specifically, by selecting an appropriate wavelength of ultraviolet light, the compound undergoes ring-opening isomerization at the irradiated portion of the photochromic material, resulting in the photochromic phenomenon.

[0079] As a specific example, when ultraviolet light is used to irradiate a photochromic material, the size of the light spot can be adjusted to a suitable size using an optical lens or aperture. After the light source is adjusted by a galvanometer and a reflector, it shines into the interior of the photochromic material perpendicular to the side of the transparent container containing the photochromic material, forming a spatial light switch opening and closing area in the closed photochromic material.

[0080] In step S2, the photochromic material is subjected to a second irradiation treatment using visible light at the intersection of the ultraviolet and visible light sources, forming a spatial three-dimensional image. In this step, fluorescence emission occurs at the intersection of the ultraviolet and visible light, forming a spatial three-dimensional image, thus achieving spatial three-dimensional imaging. Specifically, the photochromic material is first irradiated with ultraviolet light to induce photochromism, and then sunlight is used to irradiate it. Combined with the optical path design, fluorescent points are generated at the intersection of the two beams, forming a three-dimensional image. No spatial fluorescent points are generated in areas not irradiated by visible light. The significant color difference between these fluorescent points and the ultraviolet light results in good contrast of the three-dimensional image. Furthermore, compared to other photochromic materials, the photochromic area of ​​this invention does not diffuse in organic solvents, and the image clarity does not become blurred due to the movement of the light source (ultraviolet or visible light). In addition, according to the optical path design, controlling the movement of the intersection of ultraviolet and visible light within the photochromic material allows the spatial three-dimensional image at the intersection to move accordingly.

[0081] In some embodiments, the visible light is incident on the photochromic material in a direction perpendicular to the ultraviolet light source. This helps improve image quality and reduce image distortion or deformation caused by the angle between the color-changing plane and the direction of ultraviolet light irradiation.

[0082] Optionally, the wavelength of the ultraviolet light source is 365-450nm.

[0083] Optionally, the wavelength of the visible light source is 470-500nm.

[0084] The present invention will now be described with reference to specific embodiments. It should be noted that these embodiments are merely descriptive and do not limit the present invention in any way.

[0085] Example 1: Synthesized compound S-1: 2-Butyl-6-hydroxy-5-{[( E )-[(1 S [1-Phenylacetyl]azine]methyl}-2,3-dihydro-1 H -benzo[ de Isoquinoline-1,3-dione, with the following structural formula:

[0086] The specific synthetic steps of compound S-1 are as follows: (1) According to Figure 1 As shown in the flowchart, 4-bromo-1,8-naphthalenedicarboxylic anhydride (27.71 g, 100 mmol) and n-butylamine (21.94 g, 300 mmol) were mixed in acetic acid and refluxed at 120 °C under a protective atmosphere for 5 h. After cooling, the mixture was poured into water, and a precipitate was formed. The precipitate was filtered and recrystallized to obtain compound 1.

[0087] (2) Compound 1 (26.58 g, 80 mmol), sodium methoxide (34.03 g, 630 mmol) and copper sulfate (1.44 g, 9 mmol) were mixed in dry methanol and refluxed at 75 °C under a protective atmosphere for 10 h. After cooling, the mixture was filtered and washed to obtain compound 2.

[0088] (3) The mixture of compound 2 (14.15 g, 50 mmol) and 57% hydroiodic acid (700 mL) was refluxed at 125 °C under a protective atmosphere for 12 h. The product was filtered and washed to obtain the crude product. The crude product was purified by silica column chromatography to obtain compound 3.

[0089] (4) Compound 3 (6.73 g, 25 mmol), hexamethylenetetramine (7.01 g, 50 mmol), and trifluoroacetic acid (22.8 g, 200 mmol) were refluxed at 70 °C for 12 h. The reaction mixture was diluted with distilled water, filtered, and the precipitate was washed. The crude product was purified with a short silica stopper to obtain compound 4.

[0090] (5) Compound 4 (2.93 g, 10 mmol), S-α-methylbenzylamine (1.21 g, 10 mmol), and ethanol (36 g, 500 mmol) were refluxed at 80 °C for 4 h, and then filtered and washed to obtain the target compound S-1.

[0091] like Figure 4 As shown in Figure a, the compound is a pale yellow powder; Figure 6 According to nuclear magnetic resonance data, the method of this invention can synthesize the compound 2-butyl-6-hydroxy-5-{[( E )-[(1 S [1-Phenylacetyl]azine]methyl}-2,3-dihydro-1 H -benzo[ de Isoquinoline-1,3-dione, as can be seen in the figure. 1 H NMR (400 MHz, DMSO- d6 ) δ13.32 (s, 1H), 8.88 (d, J = 13.5 Hz, 1H), 8.55 – 8.49 (m, 1H), 8.45 – 8.37 (m,2H), 7.63 (t, J = 7.7 Hz, 1H), 7.38 (d, J = 7.9 Hz, 2H), 7.25 (d, J = 7.9 Hz, 2H), 5.09 (p, J = 6.6 Hz, 1H), 4.00 (t, J = 7.4 Hz, 2H), 2.31 (s, 3H), 1.73 (d, J = 6.8Hz, 3H), 1.57 (tt, J = 8.0, 6.4 Hz, 2H), 1.33 (h, J = 7.4 Hz, 2H), 0.92 (t, J = 7.3Hz, 3H). 13 C NMR (101 MHz, DMSO- d6) δ 13.72, 19.80, 20.65, 21.18, 29.77, 58.64,106.29, 109.49, 121.85, 125.14, 126.40, 128.48, 129.49, 130.99, 132.15,132.33, 137.53, 137.85, 162.66, 163.65.

[0092] Example 2 Synthesized compound S-1: 2-Butyl-6-hydroxy-5-{[( E )-[(1 S 1-(4-methylphenyl)ethyl]aza-2,3-dihydro-1 H -benzo[ de Isoquinoline-1,3-dione, with the following structural formula:

[0093] (1) According to Figure 1 As shown in the flowchart, 4-bromo-1,8-naphthalenedicarboxylic anhydride (27.71 g, 100 mmol) and n-butylamine (21.94 g, 300 mmol) were mixed in acetic acid and refluxed at 120 °C under a protective atmosphere for 5 h. After cooling, the mixture was poured into water, and a precipitate was formed. The precipitate was filtered and recrystallized to obtain compound 1.

[0094] (2) Compound 1 (26.58 g, 80 mmol), sodium methoxide (34.03 g, 630 mmol) and copper sulfate (1.44 g, 9 mmol) were mixed in dry methanol and refluxed at 75 °C under a protective atmosphere for 10 h. After cooling, the mixture was filtered and washed to obtain compound 2.

[0095] (3) The mixture of compound 2 (14.15 g, 50 mmol) and 57% hydroiodic acid (700 mL) was refluxed at 125 °C under a protective atmosphere for 12 h. The product was filtered and washed to obtain the crude product. The crude product was purified by silica column chromatography to obtain compound 3.

[0096] (4) Compound 3 (6.73 g, 25 mmol), hexamethylenetetramine (7.01 g, 50 mmol), and trifluoroacetic acid (22.8 g, 200 mmol) were refluxed at 70 °C for 12 h. The reaction mixture was diluted with distilled water, filtered, and the precipitate was washed. The crude product was purified with a short silica stopper to obtain compound 4.

[0097] (5) Compound 4 (2.93 g, 10 mmol), (1 SThe target compound S-2 was obtained by refluxing 1-(4-methylphenyl)ethyl-1-amine (1.35 g, 10 mmol) and ethanol (36 g, 500 mmol) at 80 °C for 4 h, followed by filtration and washing.

[0098] Combination Figure 7 According to nuclear magnetic resonance data, the method of this invention can synthesize the compound 2-butyl-6-hydroxy-5-{[( E )-[(1 S 1-(4-methylphenyl)ethyl]aza-2,3-dihydro-1 H -benzo[ de Isoquinoline-1,3-dione Figure 7 It can be seen 1 H NMR (400 MHz, DMSO- d6 ) δ 13.32 (s, 1H), 8.88 (d, J =13.5 Hz, 1H), 8.55 – 8.49 (m, 1H), 8.45 – 8.37 (m, 2H), 7.63 (t, J = 7.7 Hz, 1H), 7.38 (d, J = 7.9 Hz, 2H), 7.25 (d, J = 7.9 Hz, 2H), 5.09 (p, J = 6.6 Hz, 1H), 4.00 (t, J = 7.4 Hz, 2H), 2.31 (s, 3H), 1.73 (d, J = 6.8 Hz, 3H), 1.57 (tt, J =8.0, 6.4 Hz, 2H), 1.33 (h, J = 7.4 Hz, 2H), 0.92 (t, J = 7.3 Hz, 3H). 13 C NMR (101MHz, DMSO-) d6 )δ 13.72, 19.80, 20.65, 21.18, 29.77, 58.64, 106.29, 109.49,121.85, 125.14, 126.40, 128.48, 129.49, 130.99, 132.15, 132.33, 137.53,137.85, 162.66, 163.65.

[0099] Example 3 Synthesized compound S-3: 2-Butyl-6-hydroxy-5-{[( E )-[(1 S 1-(naphthyl-2-yl)ethyl]azine]methyl}-2,3-dihydro-1 H -benzo[ de Isoquinoline-1,3-dione, with the following structural formula:

[0100] (1) According to Figure 1 As shown in the flowchart, 4-bromo-1,8-naphthalenedicarboxylic anhydride (27.71 g, 100 mmol) and n-butylamine (21.94 g, 300 mmol) were mixed in acetic acid and refluxed at 120 °C under a protective atmosphere for 5 h. After cooling, the mixture was poured into water, and a precipitate was formed. The precipitate was filtered and recrystallized to obtain compound 1.

[0101] (2) Compound 1 (26.58 g, 80 mmol), sodium methoxide (34.03 g, 630 mmol) and copper sulfate (1.44 g, 9 mmol) were mixed in dry methanol and refluxed at 75 °C under a protective atmosphere for 10 h. After cooling, the mixture was filtered and washed to obtain compound 2.

[0102] (3) The mixture of compound 2 (14.15 g, 50 mmol) and 57% hydroiodic acid (700 mL) was refluxed at 125 °C under a protective atmosphere for 12 h. The product was filtered and washed to obtain the crude product. The crude product was purified by silica column chromatography to obtain compound 3.

[0103] (4) Compound 3 (6.73 g, 25 mmol), hexamethylenetetramine (7.01 g, 50 mmol), and trifluoroacetic acid (22.8 g, 200 mmol) were refluxed at 70 °C for 12 h. The reaction mixture was diluted with distilled water, filtered, and the precipitate was washed. The crude product was purified with a short silica stopper to obtain compound 4.

[0104] (5) Compound 4 (2.93 g, 10 mmol), (1 S The target compound S-2 was obtained by refluxing 1-(4-methylphenyl)ethyl-1-amine (1.35 g, 10 mmol) and ethanol (36 g, 500 mmol) at 80 °C for 4 h, followed by filtration and washing.

[0105] Combination Figure 8 According to nuclear magnetic resonance data, the method of this invention can synthesize the compound 2-butyl-6-hydroxy-5-{[( E )-[(1 S 1-(naphthyl-2-yl)ethyl]azine]methyl}-2,3-dihydro-1H -benzo[ de Isoquinoline-1,3-dione. As can be seen from the figure... 1 H NMR (400 MHz, DMSO- d6 ) δ 8.95 (s, 1H), 8.56 – 8.38 (m,3H), 8.02 – 7.92 (m, 4H), 7.69 – 7.59 (m, 2H), 7.57 – 7.52 (m, 2H), 5.29 (s,1H), 4.00 (t, J = 7.4 Hz, 2H), 1.85 (d, J = 6.8 Hz, 3H), 1.57 (p, J = 7.3 Hz, 2H), 1.33 (q, J = 7.4 Hz, 2H), 0.91 (t, J = 7.3 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ13.87, 20.41, 22.69, 30.29, 40.02, 60.27, 109.10, 109.68, 122.67, 123.67,125.57, 125.80, 126.92, 127.01, 127.85, 128.05, 128.72, 129.70, 131.33,132.72, 133.28, 133.34, 136.84, 138.94, 162.25, 163.74, 164.55.

[0106] Example 4 Synthesized compound S-4: 2-Butyl-6-hydroxy-5-{[( E )-[(1 S 1-(naphthyl-2-yl)ethyl]azine]methyl}-2,3-dihydro-1 H -Benzisoquinoline-1,3-dione, with the following structural formula:

[0107] (1) According to Figure 1 As shown in the flowchart, 4-bromo-1,8-naphthalenedicarboxylic anhydride (27.71 g, 100 mmol) and n-butylamine (21.94 g, 300 mmol) were mixed in acetic acid and refluxed at 120 °C under a protective atmosphere for 5 h. After cooling, the mixture was poured into water, and a precipitate was formed. The precipitate was filtered and recrystallized to obtain compound 1.

[0108] (2) Compound 1 (26.58 g, 80 mmol), sodium methoxide (34.03 g, 630 mmol) and copper sulfate (1.44 g, 9 mmol) were mixed in dry methanol and refluxed at 75 °C under a protective atmosphere for 10 h. After cooling, the mixture was filtered and washed to obtain compound 2.

[0109] (3) The mixture of compound 2 (14.15 g, 50 mmol) and 57% hydroiodic acid (700 mL) was refluxed at 125 °C under a protective atmosphere for 12 h. The product was filtered and washed to obtain the crude product. The crude product was purified by silica column chromatography to obtain compound 3.

[0110] (4) Compound 3 (6.73 g, 25 mmol), hexamethylenetetramine (7.01 g, 50 mmol), and trifluoroacetic acid (22.8 g, 200 mmol) were refluxed at 70 °C for 12 h. The reaction mixture was diluted with distilled water, filtered, and the precipitate was washed. The crude product was purified with a short silica stopper to obtain compound 4.

[0111] (5) Compound 4 (2.93 g, 10 mmol), (1 S The target compound S-2 was obtained by refluxing 1-(naphth-2-yl)ethyl-1-amine (1.71 g, 10 mmol) and ethanol (36 g, 500 mmol) at 80 °C for 4 h, followed by filtration and washing.

[0112] Combination Figure 9 According to nuclear magnetic resonance data, the method of this invention can synthesize the compound 2-butyl-6-hydroxy-5-{[( E )-[(1 S 1-(naphthyl-2-yl)ethyl]azine]methyl}-2,3-dihydro-1 H -Benzoisoquinoline-1,3-dione. As can be seen in the figure, 1 H NMR (400 MHz, CDCl3) δ 8.66 (d, J = 8.0 Hz, 1H), 8.58 (d, J =7.5 Hz, 1H), 8.28 (s, 1H), 8.08 (d, J = 13.1 Hz, 1H), 7.61 (t, J = 7.7 Hz, 1H), 4.15 (dd, J = 8.6, 6.5 Hz, 2H), 1.70 (dd, J = 10.2, 4.9 Hz, 2H), 1.55 (s, 9H), 1.44 (q, J= 7.6 Hz, 2H), 0.97 (t, J = 7.3 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ13.89,20.44, 29.49, 30.32, 40.02, 55.80, 108.54, 109.32, 122.64, 125.41, 128.88,131.26, 132.72, 133.24, 139.19, 159.55, 163.86, 164.64.

[0113] Example 5 Synthesized compound S-5: 2-Butyl-6-hydroxy-5-{[( E [-hexadecylazine-1-methyl]-2,3-dihydro-1 H -Benzisoquinoline-1,3-dione, with the following structural formula:

[0114] (1) According to Figure 1 As shown in the flowchart, 4-bromo-1,8-naphthalenedicarboxylic anhydride (27.71 g, 100 mmol) and n-butylamine (21.94 g, 300 mmol) were mixed in acetic acid and refluxed at 120 °C under a protective atmosphere for 5 h. After cooling, the mixture was poured into water, and a precipitate was formed. The precipitate was filtered and recrystallized to obtain compound 1.

[0115] (2) Compound 1 (26.58 g, 80 mmol), sodium methoxide (34.03 g, 630 mmol) and copper sulfate (1.44 g, 9 mmol) were mixed in dry methanol and refluxed at 75 °C under a protective atmosphere for 10 h. After cooling, the mixture was filtered and washed to obtain compound 2.

[0116] (3) The mixture of compound 2 (14.15 g, 50 mmol) and 57% hydroiodic acid (700 mL) was refluxed at 125 °C under a protective atmosphere for 12 h. The product was filtered and washed to obtain the crude product. The crude product was purified by silica column chromatography to obtain compound 3.

[0117] (4) Compound 3 (6.73 g, 25 mmol), hexamethylenetetramine (7.01 g, 50 mmol), and trifluoroacetic acid (22.8 g, 200 mmol) were refluxed at 70 °C for 12 h. The reaction mixture was diluted with distilled water, filtered, and the precipitate was washed. The crude product was purified with a short silica stopper to obtain compound 4.

[0118] (5) Compound 4 (2.93 g, 10 mmol), pentadecane-1-amine (2.28 g, 10 mmol), and ethanol (36 g, 500 mmol) were refluxed at 80 °C for 4 h, and then filtered and washed to obtain the target compound S-2.

[0119] Combination Figure 10 According to nuclear magnetic resonance data, the method of this invention can synthesize the compound 2-butyl-6-hydroxy-5-{[( E [-hexadecylazine-1-methyl]-2,3-dihydro-1 H -Benzoisoquinoline-1,3-dione. As can be seen in the figure, 1 H NMR (400 MHz, CDCl3) δ 8.67 (d, J = 8.1 Hz, 1H), 8.58 (d, J = 7.4 Hz, 1H),8.27 (s, 1H), 7.98 (d, J = 10.7 Hz, 1H), 7.61 (t, J = 7.5 Hz, 1H), 4.17 – 4.12(m, 2H), 3.65 (s, 2H), 1.80 (q, J = 7.3 Hz, 2H), 1.70 (t, J = 7.6 Hz, 2H), 1.45(p, J = 7.4 Hz, 8H), 1.25 (s, 20H), 0.97 (t, J = 7.3 Hz, 3H), 0.88 (t, J = 6.8 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ13.88, 14.11, 20.44, 22.69, 26.53, 29.07, 29.37,29.52, 29.59, 29.65, 29.68, 30.07, 30.32, 31.93, 40.04, 51.33, 108.72,109.49, 122.64, 125.45, 128.84, 131.37, 132.76, 133.29, 138.94, 163.71,163.87, 164.60.

[0120] Test case The three-dimensional image display test method for compound S-1 is as follows: (1) Using compound S-1 and cyclohexane as photochromic materials, the cyclohexane solution concentration was 0.005 mg / ml, and cyclohexane was used as the imaging medium. The photochromic materials were placed in a transparent container with dimensions of 6*6*6 cm. According to Figure 3 The optical path diagram shown illustrates that the photochromic material is irradiated with 200 mW 405 nm ultraviolet light 2 to form a photochromic region 3 (a three-dimensional voxel). This photochromic region can be projected onto screen 1. The principle of the color-changing reaction is as follows: Figure 2 As shown; (2) Along the direction perpendicular to the direction of ultraviolet light irradiation, a 100mW 488nm blue light source is controlled by a scanning galvanometer to project the cut surface. (3) By using a scanning galvanometer to control the emission pattern of 405nm ultraviolet light, a specific, clear spatial luminous point can be generated at the intersection with the 488nm blue light path.

[0121] Figure 4 This image shows the spatial point luminescence effect of a photochromic material composed of compound S-1 and a nonpolar reagent solution. a) is an image of compound S-1; b) is a photochromic material solution containing compound S-1 and cyclohexane, the solution being pale yellow and transparent with a concentration of 0.005 mg / ml; c) shows the yellow-green point luminescence produced at the intersection of 405 nm violet light and 488 nm sky blue light when irradiated together.

[0122] Figure 5 This is a spatial static three-dimensional image representation of a photochromic material composed of a compound (compound S-1) and a nonpolar reagent solution. Image a shows a three-dimensional cubic fluorescence image of the material under simultaneous irradiation with 405nm ultraviolet light and 488nm sky blue light; image b shows a three-dimensional image after filtering the 405nm ultraviolet light with a 510nm long-pass filter; image c shows a three-dimensional pentagram-shaped fluorescence image under simultaneous irradiation with 405nm ultraviolet light and 488nm sky blue light. Figure 5 a and Figure 5 As shown in Figure b, a three-dimensional cube pattern with yellow-green light can be generated at the intersection of the two light paths; changing the scanning trajectory of the light paths can form other spatial patterns, such as... Figure 5 The three-dimensional pentagram pattern shown in C is a spatial representation of a star.

[0123] In summary, since the photochromic reaction of the compound is a reversible reaction that recovers thermally, in this design, when the intersection position of the two beams of light is changed, the spatial luminous point also moves accordingly; by adjusting the intersection position of the violet laser source and the blue light source in the solution at a certain speed, a moving spatial three-dimensional image can be generated, thereby realizing the dynamic refresh of the spatial three-dimensional image.

[0124] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0125] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A compound, characterized in that, The structure of the compound is as follows: 。 2. A photochromic material, characterized in that, Includes the compound described in claim 1.

3. The use of the photochromic material according to claim 2 in three-dimensional imaging.

4. The use according to claim 3, characterized in that, The three-dimensional imaging includes the following steps: The photochromic material is subjected to a first irradiation treatment using ultraviolet light; The photochromic material is subjected to a second irradiation treatment using visible light, forming a three-dimensional image at the intersection of the ultraviolet light and the visible light source.

5. The use according to claim 4, characterized in that, The direction in which the visible light source irradiates the photochromic material is perpendicular to the direction in which the ultraviolet light source irradiates the photochromic material.

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