Photochromic diarylethene compound as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of photochromic compounds, and particularly discloses a photochromic diarylethene compound as well as a preparation method and application thereof. The preparation method comprises the following steps: carrying out coupling reaction on 2, 3-dibromo-1, 1-dimethyl-1H-indene and a borate compound to obtain a diarylethene compound; the boric acid ester compound comprises one or more of 2-methyl-5-phenyl-thiophene boric acid ester, 5-methyl-2-phenyl-thiazole boric acid ester and 2-methylnaphthalene boric acid ester. The present invention provides a diarylethene photochromic compound using indene as an alkene bridge, which can reversibly change between open-loop isomers and closed-loop isomers under the condition of illumination with a specific wavelength, and can reversibly change properties such as color and absorption spectrum of the compound. The invention further provides a preparation method of the compound. The preparation method has the advantages that the preparation method is simple, the product safety is high, the raw material cost is low, the product is easy to separate, and industrial synthesis is easy to realize.

Description

Technical Field

[0001] The invention relates to the technical field of photochromic compounds, and in particular to a photochromic diarylethene compound and a preparation method and application thereof. Background Art

[0002] In recent years, with the continuous development of modern industrial chemistry, more and more high-performance scientific and technological products have entered people's daily lives. Among them, optical switch materials have been explored and mined by people due to their excellent chemical properties and broad application prospects.

[0003] Due to the unique reversible photocyclization reaction and the excellent thermal stability of the open and closed ring isomers, diarylethenes photochromic compounds can show excellent data transmission capabilities and super fatigue resistance in different media and states. These characteristics make them stand out among many photochromic materials. At present, the most classic diarylethenes photochromic compound uses perfluorocyclopentene as the olefin bridge, but its high price and strong toxicity have inhibited its application in photochemistry.

[0004] Therefore, how to provide a photochromic diarylethene compound and a preparation method and application thereof, improve the safety of the photochromic compound, and reduce the preparation cost is a difficult problem to be solved urgently in the art. Summary of the invention

[0005] In view of this, the present invention provides a photochromic diarylethene compound and a preparation method and application thereof, so as to solve the problem that the existing photochromic compounds are expensive and highly toxic, which inhibits their application in the field of photochemistry.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

[0007] A photochromic diarylethene compound, the structure of the diarylethene compound is as follows:

[0008]

[0009] Wherein, Ar1 and Ar2 groups are independently one or more of 2-methyl-5-phenyl-thiophene, 5-methyl-2-phenyl-thiazole and 2-methylnaphthalene.

[0010] Another object of the present invention is to provide a method for preparing a photochromic diarylethene compound, the method comprising the following steps:

[0011] The 2,3-dibromo-1,1-dimethyl-1H-indene is subjected to a coupling reaction with a boric acid lipid compound to obtain a diarylethene compound;

[0012] The boric acid lipid compound comprises one or more of 2-methyl-5-phenyl-thiophene borate, 5-methyl-2-phenyl-thiazole borate and 2-methylnaphthalene borate.

[0013] Preferably, the molar ratio of the 2,3-dibromo-1,1-dimethyl-1H-indene to the boric acid lipid compound is 1-3:2-7.

[0014] Preferably, the coupling reaction temperature is 70 to 110° C., and the coupling reaction time is 12 to 48 hours.

[0015] Preferably, the coupling reaction is carried out under catalyst conditions;

[0016] The catalyst includes tetrakis(triphenylphosphine)palladium, palladium acetate and bis(diphenylphosphino)ferrocenepalladium dichloride.

[0017] Preferably, the preparation method of the diarylethene compound is as follows:

[0018] 2,3-dibromo-1,1-dimethyl-1H-indene, a boric acid lipid compound, a catalyst, an alkaline substance, water and an organic solvent are mixed to carry out a coupling reaction to obtain a diarylethene compound.

[0019] Preferably, the molar volume ratio of the 2,3-dibromo-1,1-dimethyl-1H-indene, the boric acid lipid compound, the catalyst, the alkaline substance, water and the organic solvent is 1-3 mol: 2-7 mol: 0.1-1 mol: 40-70 mol: 20-40 L: 20-40 L.

[0020] Preferably, the boric acid lipid compound is One or more of the .

[0021] Preferably, the alkaline substance includes one or more of sodium carbonate, tripotassium nitrate and potassium phosphate;

[0022] The organic solvent includes tetrahydrofuran and / or 1,4-dioxane.

[0023] Another object of the present invention is to provide a diarylethene compound prepared by the preparation method for use in the fields of medicine, information storage, anti-counterfeiting components and photosensitive liquid crystal materials.

[0024] It can be seen from the above technical solutions that, compared with the prior art, the present invention has the following beneficial effects:

[0025] The present invention provides a photoresponsive diarylethene compound. The present invention provides a diarylethene photochromic compound with indene as an olefin bridge, which can undergo light-induced molecular structure changes under the irradiation of visible light and ultraviolet light. In this process, the diarylethene compound has a significant color change and has significant absorption in the visible light region.

[0026] The present invention also provides a method for preparing a diarylethene compound with light responsiveness. Based on the diarylethene structure, a novel photochromic diarylethene compound with photoisomerization reaction is obtained through Suzuki-Miyaura coupling reaction. The synthesis steps are relatively few, the synthesis method is simple, the raw material cost is low, the product is easy to separate and purify, and industrial synthesis is easy to realize.

[0027] The photochromic diarylethene compound based on indene prepared by the present invention has the characteristics of simple structure, small space occupation and short synthesis cycle, and is easier to achieve chemical modification than the diarylethene compound based on perfluorocyclopentane as the olefin bridge. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0029] Figure 1 is a UV-visible absorption spectrum of the diarylethene compound at different concentrations in chromatographic methanol in Example 1;

[0030] Figure 2 The UV-visible absorption spectra of the diarylethene compound in Example 1 under different irradiation times in chromatographic methanol;

[0031] Figure 3 The UV-visible absorption spectra of the diarylethene compound in Example 1 at different concentrations in chromatographic acetonitrile are shown;

[0032] Figure 4 The UV-visible absorption spectra of the diarylethene compound in Example 1 under different irradiation times in chromatographic acetonitrile;

[0033] Figure 5 The UV-visible absorption spectra of the diarylethene compound in Example 1 at different concentrations in chromatographic n-hexane;

[0034] Figure 6The UV-visible absorption spectra of the diarylethene compound in Example 1 under different irradiation times in chromatographic n-hexane.

[0035] Figure 7 is a UV-visible absorption spectrum of the diarylethene compound at different concentrations in chromatographic methanol in Example 2;

[0036] Figure 8 The UV-visible absorption spectra of the diarylethene compound in Example 2 under different irradiation times in chromatographic methanol;

[0037] Fig. 9 The UV-visible absorption spectra of the diarylethene compound in Example 2 at different concentrations in chromatographic acetonitrile are shown;

[0038] Fig.10 The UV-visible absorption spectra of the diarylethene compound in Example 2 under different irradiation times in chromatographic acetonitrile;

[0039] Fig.11 The UV-visible absorption spectra of the diarylethene compound in Example 2 at different concentrations in chromatographic n-hexane;

[0040] Fig.12 The UV-visible absorption spectra of the diarylethene compound in Example 2 under different irradiation times in chromatographic n-hexane.

[0041] Fig.13 is a UV-visible absorption spectrum of the diarylethene compound at different concentrations in chromatographic methanol in Example 3;

[0042] Fig.14 The UV-visible absorption spectra of the diarylethene compound in Example 3 at different irradiation times in chromatographic methanol;

[0043] Fig.15 The UV-visible absorption spectra of the diarylethene compound in Example 3 at different concentrations in chromatographic acetonitrile are shown;

[0044] Fig.16 The UV-visible absorption spectra of the diarylethene compound in Example 3 at different irradiation times in chromatographic acetonitrile;

[0045] Fig.17 The UV-visible absorption spectra of the diarylethene compound in Example 3 at different concentrations in chromatographic n-hexane;

[0046] Fig.18 The UV-visible absorption spectra of the diarylethene compound in Example 3 under different irradiation times in chromatographic n-hexane;

[0047] in, Figures 1 to 18 In the equation, Absorbance refers to absorbance, and Wavelength refers to wavelength. DETAILED DESCRIPTION

[0048] The present invention provides a photochromic diarylethene compound, the structure of which is as follows:

[0049]

[0050] Wherein, Ar1 and Ar2 groups are independently one or more of 2-methyl-5-phenyl-thiophene, 5-methyl-2-phenyl-thiazole and 2-methylnaphthalene.

[0051] The present invention also provides a method for preparing a photochromic diarylethene compound, the preparation method comprising the following steps:

[0052] The 2,3-dibromo-1,1-dimethyl-1H-indene is subjected to a coupling reaction with a boric acid lipid compound to obtain a diarylethene compound;

[0053] The boric acid lipid compound comprises one or more of 2-methyl-5-phenyl-thiophene borate, 5-methyl-2-phenyl-thiazole borate and 2-methylnaphthalene borate.

[0054] In the present invention, the molar ratio of the 2,3-dibromo-1,1-dimethyl-1H-indene to the boric acid lipid compound is 1-3:2-7, preferably 1.5-2.5:4-6, and more preferably 2:5.

[0055] In the present invention, the temperature of the coupling reaction is 70-110°C, specifically 75°C, 80°C, 85°C, 90°C, 95°C, 100°C; the time of the coupling reaction is 12-48h, specifically 15h, 18h, 20h, 24h, 30h, 35h, 36h, 40h, 45h.

[0056] In the present invention, the coupling reaction is carried out under catalyst conditions.

[0057] In the present invention, the catalyst comprises tetrakis(triphenylphosphine)palladium, palladium acetate and bis(diphenylphosphino)ferrocenepalladium dichloride.

[0058] In the present invention, the preparation method of the diarylethene compound is as follows:

[0059] 2,3-dibromo-1,1-dimethyl-1H-indene, a boric acid lipid compound, a catalyst, an alkaline substance, water and an organic solvent are mixed to carry out a coupling reaction to obtain a diarylethene compound.

[0060] In the present invention, the molar volume ratio of the 2,3-dibromo-1,1-dimethyl-1H-indene, boric acid lipid compound, catalyst, alkaline substance, water and organic solvent is 1-3 mol: 2-7 mol: 0.1-1 mol: 40-70 mol: 20-40 L: 20-40 L, preferably 1.5-2.5 mol: 4-6 mol: 0.2-0.8 mol: 50-60 mol: 25-35 L: 25-35 L, and further preferably 2 mol: 5 mol: 0.5 mol: 55 mol: 30 L: 30 L.

[0061] In the present invention, the boric acid lipid compound is One or more of the .

[0062] In the present invention, the alkaline substance includes one or more of sodium carbonate, tripotassium nitrate and potassium phosphate.

[0063] In the present invention, the organic solvent includes tetrahydrofuran and / or 1,4-dioxane.

[0064] In the present invention, the coupling reaction is preferably carried out under an inert atmosphere, specifically one or more of a rare gas atmosphere and a nitrogen atmosphere.

[0065] In the present invention, the coupling reaction also includes a post-treatment step, wherein the post-treatment is washing, extraction, concentration, drying and purification performed in sequence.

[0066] In the present invention, the detergent is preferably water, the extractant is preferably ethyl acetate, the number of extractions is preferably greater than or equal to 2 times, more preferably greater than or equal to 3 times, and more preferably 4 times; the instrument used for concentration is preferably a rotary evaporator.

[0067] In the present invention, the purification is preferably performed by chromatography column purification, the mesh size of the silica gel in the chromatography column is preferably 200-300 mesh, or 300-400 mesh; the developing agent in the chromatography column purification process is preferably petroleum ether.

[0068] The present invention also provides an application of the diarylethene compound prepared by the preparation method in the field of physics and medicine, information storage, anti-counterfeiting components and photosensitive liquid crystal materials.

[0069] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0070] The preparation methods of compounds 1 to 4 in Examples 1 to 3 of the present invention do not limit the scheme of the present invention.

[0071] Example 1

[0072]

[0073] Compound 1: (E)-3,4-dibromo-2-methyl-4-phenylbut-3-ene-2-ol (50 mg, 0.156 mmol), dichloromethane (2.00 mL), trifluoroborane ethyl ether (0.060 mL, 0.469 mmol) were added to the reaction flask, and the reaction flask was placed at room temperature for 15 minutes. After the reaction was completed (TLC was used to detect the reaction progress), an appropriate amount of methanol was added to the reaction system, and the mixture was extracted twice with dichloromethane. The organic phases were combined and concentrated with a rotary evaporator to obtain a crude yellow oily liquid product (2,3-dibromo-1,1-dimethyl-1H-indene). A white solid was obtained by column chromatography (silica gel: 200-300 mesh, developing solvent: petroleum ether) with a yield of 68%.

[0074] 1 H NMR (400MHz, CDCl3) δ: 1.32 (s, 6H), 7.2-7.4 (m, 4H).

[0075]

[0076] Compound 2: Under the protection of argon, 3-bromo-2-methyl-5-phenylthiophene (0.20 g, 0.781 mmol) and anhydrous tetrahydrofuran (10 mL) were added to the reaction bottle, and the reaction bottle was placed in a constant temperature low temperature reaction bath and cooled to -78 ° C. n-BuLi (0.50 mL, 0.80 mmol, 1.6 mol / L inhexane) was slowly added dropwise to the reaction bottle. After one hour of reaction, isopropanol pinacol borate (0.20 mL, 0.862 mmol) was added. After 15 minutes of reaction, the reaction bottle was taken out of the constant temperature low temperature reaction bath and reacted overnight under stirring at room temperature. After the reaction was completed (TLC was used to detect the progress of the reaction), an appropriate amount of saturated salt water was added to the reaction system, and the reaction was performed twice with ethyl acetate. The organic phases were combined and concentrated using a rotary evaporator to obtain a crude yellow oily liquid product. The crude product was separated and purified by column chromatography (silica gel: 200-300 mesh, developing solvent: petroleum ether: ethyl acetate = 20:1) to obtain 0.27 g of a light yellow solid with a yield of 96%.

[0077] 1H NMR (500MHz, CDCl3) δ: 7.56-7.58 (2H, m), 7.43 (1H, s), 7.32-7.36 (2H, t, J = 8.0MHz), 7.21-7.24 (1H, t, J = 7.5MHz), 2.70 (3H, s), 1.34 (12H, s).

[0078]

[0079] DAE-1 (diarylethene compound): Under argon conditions, reactant 1 (2,3-dibromo-1,1-dimethyl-1H-indene) (50.0 mg, 0.166 mmol), reactant 2 (0.12g, 0.414mmol), tetrakis(triphenylphosphine)palladium (48.0mg, 0.041mmol), sodium carbonate (0.66g, 6.62mmol), 1,4-epoxyhexadecane (3.0mL, 3.31mmol), distilled water (3.5mL) were mixed and reacted in an oil bath at 100°C for 48 hours. After the reaction was completed (TLC was used to detect the progress of the reaction), water was added to the reaction system for washing, and ethyl acetate was used for extraction twice. The organic phases were combined and concentrated by rotary evaporator to obtain a brown solid crude product. The above crude product was separated and purified by column chromatography (silica gel: 200-300 mesh, developing solvent: petroleum ether) to obtain 50mg of purple solid with a yield of 71%. The obtained compound was recorded as DAE-1.

[0080] 1 H NMR (400MHz, CDCl3) δ: 1.96 (s, 6H), 2.08 (s, 6H), 7.45 (m, 2H), 7.52 (d, 4H, J = 8Hz), 7.58 (d, 4H, J = 8Hz).

[0081] 13 C NMR (400MHz, CDCl3) δ153.39,149.41,142.72,140.21,140.07,136.88,136.28,134.76,134.60,134.58,133.92,133.02,128.96 ,128.92,127.19,127.12,126.77,125.64,125.48,125.43,124.53,123.68,121.57,120.93,51.79,24.89,21.12,14.77,14.29.

[0082] HR-MS m / z:calcd for[M] + C 33 H29 S2 + :cald for 489.1704; found:489.1711.

[0083] The structural formula of DAE-1 is:

[0084] Example 2

[0085]

[0086] Compound 3: Under the protection of argon, 4-bromo-5-methyl-2-phenylthiazole (1.00 g, 3.93 mmol) and anhydrous tetrahydrofuran (20 mL) were added to the reaction bottle, and the reaction bottle was placed in a constant temperature low temperature reaction bath and cooled to -78 ° C. n-Butyl lithium (5.0 mL, 8.00 mmol, 1.6 mol / L in hexane) was slowly added dropwise to the reaction bottle. After one hour of reaction, isopropanol pinacol borate (1.70 mL, 7.86 mmol) was added. After 60 minutes of reaction, the reaction bottle was taken out of the constant temperature low temperature reaction bath and reacted overnight under stirring at room temperature. After the reaction was completed (TLC was used to detect the progress of the reaction), an appropriate amount of saturated salt water was added to the reaction system, and the reaction was performed twice with ethyl acetate. The organic phases were combined and concentrated using a rotary evaporator to obtain a crude yellow oily liquid product. The crude product was separated and purified by column chromatography (silica gel: 200-300 mesh, developing solvent: petroleum ether: ethyl acetate = 20:1) to obtain 0.87 g of a light yellow solid with a yield of 73.37%.

[0087] 1 H NMR(500MHz, CDCl3)δ:1.38(s,12H),2.74(s,3H),7.37-7.42(m,3H),7.94-7.97(s,1H).

[0088]

[0089] DAE-2 (diarylethene compound): Under argon protection, 2,3-dibromo-1,1-dimethyl-1H-indene (50.0 mg, 0.166 mmol) and reactant 3 (124.7mg, 0.414mmol), tetrakis(triphenylphosphine)palladium (48.0mg, 0.041mmol), potassium phosphate (1.4g, 6.62mmol), 1.4-epoxyhexadecane (3.5mL, 3.86mmol), and distilled water (3.5mL) were mixed and reacted in an oil bath at 100°C for 24 hours. After the reaction was completed (TLC was used to detect the progress of the reaction), water was added to the reaction system for washing, and ethyl acetate was used for extraction twice. The organic phases were combined and concentrated by rotary evaporator to obtain a yellow solid crude product. The above crude product was separated and purified by column chromatography technology (silica gel: 200-300 mesh, developing solvent: petroleum ether) to obtain 48mg of pink oily solid with a yield of 59%. The obtained compound was recorded as DAE-2.

[0090] 1 H NMR (400MHz, CDCl3) δ=δ8.27–8.25(m,1H),8.03(dd,J=9.52,1.68Hz,2H),7.97(dd,J=7.64,1.4 Hz,2H),7.51–7.45(m,6H),7.36–7.32(m,3H),1.95(d,J=5.6Hz,6H),1.76(s,3H),1.59(s,3H).

[0091] 13 C NMR (400MHz, CDCl3) δ164.51,163.79,163.39,154.13,148.79,148.49,147.71, 146.73,142.21,134.24,134.07,134.05,133.49,132.53,132.07,131.95,129.7 6,129.71,129.67,129.14,129.00,128.97,128.30,126.79,126.49,126.45,12 6.34,126.31,126.07,122.28,121.36,52.38,25.11,13.22,12.44,12.36.HR-MS m / z:calcd for[M] + C 31 H 26 N2S2 + :cald for491.1624; found:491.1616.

[0092] Example 3

[0093]

[0094] Compound 4: Under argon protection, add 1-bromo-2-methylnaphthalene (2.21mL, 1.49mL, 10.0mmol) and anhydrous tetrahydrofuran (120mL) to the reaction bottle, and place the reaction bottle in a low-temperature reactor at -78°C. Add n-BuLi (6.9mL, 11mmol, 1.6mol / L in hexane) dropwise with a syringe. After one hour of reaction, add isopropanol pinacol borate (2.23g, 2.45mL, 12mmol) to the system, take the reaction bottle out of the low-temperature reactor and place it at room temperature to react overnight. Add an appropriate amount of saturated salt water to the reaction system, extract twice with ethyl acetate, combine the organic phases, and concentrate with a rotary evaporator to obtain a yellow oily liquid crude product. The crude product was separated and purified by column chromatography (silica gel: 200-300 mesh, developing solvent: petroleum ether: ethyl acetate = 20:1) to obtain 2.40 g of a light yellow solid with a yield of 89.55%.

[0095] 1 H NMR (500MHz, CDCl3): δ = 8.10 (1H, d, J = 8.5Hz), 7.76 (2H, t, J = 6.5Hz), 7.45 (1H, dt, J = 1.0Hz ,8.0Hz),7.38(1H,dt,J=1.0Hz,8.0Hz),7.27(1H,t,J=8.5Hz),2.62(3H,s),1.49(12H,s).

[0096]

[0097] DAE-3 (diarylethene compound): Under argon protection, 2,3-dibromo-1,1-dimethyl-1H-indene (100.0 mg, 0.331 mmol) and compound 4 (221.5mg, 0.826mmol), tetrakis(triphenylphosphine)palladium (96.0mg, 0.082mmol), potassium phosphate (2.8g, 13.2mmol), 1.4-epoxyhexadecane (7.0mL, 7.72mmol), and distilled water (7.0mL) were mixed and reacted in an oil bath at 100°C for 24 hours. After the reaction was completed (TLC was used to detect the progress of the reaction), water was added to the reaction system for washing, and ethyl acetate was used for extraction twice. The organic phases were combined and concentrated by rotary evaporator to obtain a yellow solid crude product. The above crude product was separated and purified by column chromatography technology (silica gel: 200-300 mesh, developing solvent: petroleum ether) to obtain 84mg of a light yellow solid with a yield of 60%. The obtained compound was recorded as DAE-3.

[0098] 1H NMR (400MHz, CDCl3) δ = 8.05 (d, J = 8.5Hz, 1H), 7.91 (d, J = 8.5Hz, 1H), 7.60–7.51 (m, 5H), 7.31 (t, J = 7.4Hz, 1H), 7 .21-7.16(m,5H),7.13-7.05(m,2H),6.82(d,J=7.5Hz,1H),2.43(s,3H),2.35(s,3H),1.53(s,3H),1.47(s,3H).

[0099] 13 C NMR (400MHz, CDCl3) δ153.27,153.21,144.08,140.19,135.62,135.12,1 32.93,132.32,132.13,132.07,131.07,130.55,129.24,128.99,128.87 ,127.98,127.92,127.39,127.35,127.32,126.94,125.58,124.95,124. 65,124.63,124.19,121.44,121.28,55.74,27.27,26.91,22.98,22.44.

[0100] HR-MS m / z:calcd for[M] + C 33 H 28 + :cald for425.2269; found:425.2267.

[0101] Experimental Example 1

[0102] Weigh 0.25 mg, 0.125 mg, 0.0625 mg, 0.0312 mg and 0.0156 mg of DAE-1 respectively into a 10 mL volumetric flask and dilute to volume with chromatographic methanol solution to obtain five bottles of sample solutions with different concentrations. The concentrations of the sample solutions are 5.09 × 10 -5 mol / L,2.55×10 -5 mol / L,1.27×10 -5 mol / L,6.37×10 -6 mol / L,3.18×10 -6 mol / L, UV-visible absorption spectra of the five different concentrations of DAE-1 samples were measured using a UV-visible spectrophotometer. The results are as follows Figure 1As shown, it can be concluded that DAE-1 is an open-ring isomer at this time, and the maximum absorption wavelength λ is 288 nm; regression analysis of the maximum absorption wavelength shows that the absorbance of compound DAE-1 at the same wavelength is positively correlated with its corresponding concentration, which conforms to the Lambert-Beer law (Abs=εbc).

[0103] DAE-1 was irradiated under 254nm ultraviolet light in a chromatographic methanol solution. The UV-visible absorption spectra at different irradiation times are shown in the figure below. Figure 2 As shown. Figure 2 It can be seen that with the increase of illumination time, the absorption intensity at the maximum absorption wavelength of DAE-1 gradually weakened, while the absorption intensity at 361nm, 377nm and 556nm gradually increased, and its isosbestic point was at 321nm, which confirmed the existence of two isomers in the system, namely open-ring isomers and closed-ring isomers.

[0104] Weigh 0.2 mg, 0.16 mg, 0.12 mg, 0.08 mg and 0.04 mg of DAE-1 in a 10 mL volumetric flask, and dilute to volume with chromatographic acetonitrile solution to obtain five bottles of sample solutions with different concentrations. The concentrations of the sample solutions are 4.07 × 10 -5 mol / L,3.26×10 -5 mol / L,2.45×10 -5 mol / L,1.63×10 -5 mol / L,8.15×10 -6 mol / L. The UV-visible absorption spectra of the five different concentrations of DAE-1 samples were measured using a UV-visible spectrophotometer. The results are as follows: Figure 3 As shown, it can be concluded that DAE-1 is an open-ring isomer at this time, and the maximum absorption wavelength λ=293nm; regression analysis of the maximum absorption wavelength shows that the absorbance of compound DAE-1 at the same wavelength is positively correlated with its corresponding concentration, which conforms to the Lambert-Beer law (Abs=εbc).

[0105] DAE-1 was irradiated under 254nm ultraviolet light in chromatographic acetonitrile solution. The UV-visible absorption spectra at different irradiation times are shown in the figure below. Figure 4 As shown, from Figure 4 It can be seen that with the increase of illumination time, the absorption intensity at the maximum absorption wavelength of DAE-1 gradually weakened, while the absorption intensity at 361nm, 377nm and 556nm gradually increased, and its isosbestic point was at 321nm, which confirmed the existence of two isomers in the system, namely open-ring isomers and closed-ring isomers.

[0106] Weigh 0.20 mg, 0.10 mg, 0.05 mg, 0.025 mg, and 0.013 mg of DAE-1 in a 10 mL volumetric flask, and dilute to volume with chromatographic n-hexane solution to obtain five bottles of sample solutions with different concentrations. The concentrations of the sample solutions are 1.10 × 10 - 4 mol / L,5.09×10 -5 mol / L,2.55×10 -5 mol / L,1.27×10 -5 mol / L,6.37×10 -6 mol / L. The UV-visible absorption spectra of the five different concentrations of DAE-1 samples were measured using a UV-visible spectrophotometer. The results are as follows: Figure 5 As shown, it can be concluded that DAE-1 is an open-ring isomer at this time, and the maximum absorption wavelength λ is 288 nm; regression analysis of the maximum absorption wavelength shows that the absorbance of compound DAE-1 at the same wavelength is positively correlated with its corresponding concentration, which conforms to the Lambert-Beer law (Abs=εbc).

[0107] DAE-1 was irradiated in chromatographic n-hexane solution under 254nm ultraviolet light. The UV-visible absorption spectra at different irradiation times are shown in the figure below. Figure 6 As shown, from Figure 6 It can be seen that with the increase of illumination time, the absorption intensity at the maximum absorption wavelength of DAE-1 gradually weakened, while the absorption intensity at 361nm, 377nm and 556nm gradually increased, and its isosbestic point was at 321nm, which confirmed the existence of two isomers in the system, namely open-ring isomers and closed-ring isomers.

[0108] The above experiments show that before irradiation, the maximum absorption wavelength of DAE-1 open-ring isomer in different chromatographically pure solutions is approximately at 288nm, and there is no significant absorption in the visible light region, and the solution color is colorless at this time. The reason for the significant change in the UV-visible absorption spectrum of DAE-1 may be that its open-ring isomer undergoes a photoisomerization reaction under 254nm light conditions, and the closed-ring isomer is generated from the open-ring isomer. After irradiation with visible light >480nm, the absorption spectrum of the compound changes back to its original state, that is, the compound is generated from the closed-ring isomer to the open-ring isomer.

[0109] Similarly, DAE-2 and DAE-3 also underwent the same photoisomerization reaction as DAE-1 under light conditions ( Figure 7 is a UV-visible absorption spectrum of the diarylethene compound at different concentrations in chromatographic methanol in Example 2; Figure 8The UV-visible absorption spectra of the diarylethene compound in Example 2 under different irradiation times in chromatographic methanol; Fig. 9 The UV-visible absorption spectra of the diarylethene compound in Example 2 at different concentrations in chromatographic acetonitrile are shown; Fig.10 The UV-visible absorption spectra of the diarylethene compound in Example 2 under different irradiation times in chromatographic acetonitrile;

[0110] Fig.11 The UV-visible absorption spectra of the diarylethene compound in Example 2 at different concentrations in chromatographic n-hexane; Fig.12 The UV-visible absorption spectra of the diarylethene compound in Example 2 under different irradiation times in chromatographic n-hexane; Fig.13 is a UV-visible absorption spectrum of the diarylethene compound at different concentrations in chromatographic methanol in Example 3; Fig.14 The UV-visible absorption spectra of the diarylethene compound in Example 3 at different irradiation times in chromatographic methanol; Fig.15 The UV-visible absorption spectra of the diarylethene compound in Example 3 at different concentrations in chromatographic acetonitrile are shown;

[0111] Fig.16 The UV-visible absorption spectra of the diarylethene compound in Example 3 at different irradiation times in chromatographic acetonitrile; Fig.17 The UV-visible absorption spectra of the diarylethene compound in Example 3 at different concentrations in chromatographic n-hexane; Fig.18 3 is a UV-visible absorption spectrum of the diarylethene compound in Example 3 under different irradiation times in chromatographic n-hexane).

[0112] It can be seen from the above embodiments that the present invention provides a photochromic diarylethene compound with light responsiveness. The photochromic compound prepared according to the method of the present invention has the following advantages: a short synthesis route, a simple synthesis method, cheap raw materials required, and strong operability; it has the photochromic properties, strong fatigue resistance and stability of traditional diarylethene compounds; it has light-responsive structural characteristics, which can broaden the scope of photochemical applications of diarylethene photochromic compounds. The diarylethene compound provided by the present invention is different from the traditional diarylethene photochromic compound. Under the condition of ultraviolet light irradiation, the maximum absorption wavelength of the closed-ring isomer of DAE-1 is about 550nm, the maximum absorption wavelength of the closed-ring isomer of DAE-2 is about 510nm, and the maximum absorption wavelength of the closed-ring isomer of DAE-3 is about 460nm. The change in the maximum absorption wavelength of the closed-ring isomer mainly depends on the length of the π-conjugated system of the closed-ring isomer after the photoisomerization reaction. This characteristic makes its application in molecular switches, optical devices and anti-counterfeiting labels have important research significance.

[0113] The various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referenced to each other.

[0114] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A photochromic diarylethene compound, characterized in that: The structure of the diarylethene compound is as follows: Wherein, Ar1 and Ar2 groups are independently one or more of 2-methyl-5-phenyl-thiophene, 5-methyl-2-phenyl-thiazole and 2-methylnaphthalene.

2. The method for preparing a photochromic diarylethene compound according to claim 1, characterized in that: The preparation method comprises the following steps: The 2,3-dibromo-1,1-dimethyl-1H-indene is subjected to a coupling reaction with a boric acid lipid compound to obtain a diarylethene compound; The boric acid lipid compound comprises one or more of 2-methyl-5-phenyl-thiophene borate, 5-methyl-2-phenyl-thiazole borate and 2-methylnaphthalene borate.

3. The method for preparing a photochromic diarylethene compound according to claim 2, characterized in that: The molar ratio of the 2,3-dibromo-1,1-dimethyl-1H-indene to the boric acid lipid compound is 1-3:2-7.

4. The method for preparing a photochromic diarylethene compound according to claim 3, characterized in that: The coupling reaction temperature is 70-110° C., and the coupling reaction time is 12-48 hours.

5. The method for preparing a photochromic diarylethene compound according to any one of claims 2 to 4, characterized in that: The coupling reaction is carried out under catalyst conditions; The catalyst includes tetrakis(triphenylphosphine)palladium, palladium acetate and bis(diphenylphosphino)ferrocenepalladium dichloride.

6. The method for preparing a photochromic diarylethene compound according to claim 5, characterized in that: The preparation method of the diarylethene compound is as follows: 2,3-dibromo-1,1-dimethyl-1H-indene, a boric acid lipid compound, a catalyst, an alkaline substance, water and an organic solvent are mixed to carry out a coupling reaction to obtain a diarylethene compound.

7. The method for preparing a photochromic diarylethene compound according to claim 6, characterized in that: The molar volume ratio of the 2,3-dibromo-1,1-dimethyl-1H-indene, the boric acid lipid compound, the catalyst, the alkaline substance, water and the organic solvent is 1-3 mol: 2-7 mol: 0.1-1 mol: 40-70 mol: 20-40 L: 20-40 L.

8. The method for preparing a photochromic diarylethene compound according to claim 7, characterized in that: The boric acid lipid compound is One or more of the .

9. The method for preparing a photochromic diarylethene compound according to claim 7 or 8, characterized in that: The alkaline substance includes one or more of sodium carbonate, tripotassium nitrate and potassium phosphate; The organic solvent includes tetrahydrofuran and / or 1,4-dioxane.

10. Use of the diarylethene compound prepared by the preparation method according to any one of claims 2 to 9 in optical information recording, anti-counterfeiting components and photosensitive liquid crystal materials.

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