Vinyl ether compound capable of enhancing photoinduced fluorescence as well as preparation method and application of vinyl ether compound

Abstract

The invention discloses a photoinduced fluorescence enhanced vinyl ether compound as well as a preparation method and application thereof. The vinyl ether compound comprises a sulfuryl vinyl ether compound, a carbon-based vinyl ether compound and an ester-based vinyl ether compound, the vinyl ether compound is subjected to photochemical rearrangement under the irradiation of 254 nm ultraviolet light to generate a planar fused ring structure, and the fluorescence intensity is greatly improved. Through substituent group regulation and control, accurate adjustment of emission wavelength can be realized. The synthesis method is based on click reaction of phenolic monomers and activated alkyne, and the process is simple and efficient. The molecules still keep photoresponsiveness in a solid film (such as a PMMA substrate), are successfully applied to a mask-assisted information input and erasing system, and provide a new technical scheme for the fields of anti-counterfeiting and information storage.

Description

Technical Field

[0001] This invention relates to the field of organic optical functional materials, specifically to a sulfone-based alkenyl ether compound with photofluorescence enhancement properties, its efficient synthesis method, and the application of the photofluorescence-enhanced alkenyl ether compound in optical information encryption storage. Background Technology

[0002] Photoresponsive fluorescent molecules have significant value in information storage, anti-counterfeiting, and encryption fields due to their tunable luminescence behavior. Traditional photochromic materials (such as diarylethene and spiropyran) typically require complex synthetic steps and exhibit low solid-state fluorescence efficiency. Activated alkynes, due to their strong electron-withdrawing properties, show high reactivity in click reactions (Macromolecules 2019, 52, 4526), ​​but the photoresponsive behavior of the resulting alkenyl ether compounds has not yet been developed.

[0003] The alkenyl ether compounds shown in this invention can undergo a highly efficient photorearrangement reaction under 254 nm ultraviolet light irradiation to generate a planarized fused ring structure, with fluorescence intensity increasing by up to 1325 times. Furthermore, the emission wavelength can be precisely controlled through substituents. This characteristic provides an innovative solution for developing novel integrated optical writing / erasing optical information storage materials. Summary of the Invention

[0004] The purpose of this invention is to provide a sulfone-based alkenyl ether compound with photofluorescence enhancement, its preparation method, and its application. Specifically, it provides:

[0005] 1. A sulfone-based alkenyl ether small molecule having the structure of formula (I);

[0006] 2. A simplified synthetic method based on click chemistry;

[0007] 3. Innovative applications of the photoluminescence-enhancing properties of the sulfone-based alkenyl ether compounds in information writing and erasing. The applications described in this invention also include carbonyl alkenyl ether compounds. and ester-based alkenyl ether compounds

[0008] The objective of this invention is achieved through the following technical solution:

[0009] In a first aspect, the present invention provides a sulfone-based alkenyl ether compound with photofluorescence enhancement, having the structure of formula (I):

[0010]

[0011] Formula (I) can be either E or Z, and R1 and R2 are the same or different organic groups.

[0012] R1 and R2 can be any of the following structural formulas, but R1 and R2 cannot both be structural formulas 1 to 3:

[0013]

[0014] Where n is an integer from 0 to 20; * indicates the replacement position.

[0015] Secondly, the present invention provides a method for preparing the above-mentioned sulfone-based alkenyl ether compounds, comprising the following steps: under the protection of an inert gas and under the condition of an organic base catalyst, reacting an alkyne compound and a hydroxyl compound in an organic solvent, and purifying the mixture after the reaction is complete to obtain the alkenyl ether compounds.

[0016] The general structural formula of the alkyne compound is:

[0017]

[0018] The general structural formula of the hydroxyl compound is:

[0019]

[0020] R1 and R2 are the same as the organic groups selected for R1 and R2 mentioned above.

[0021] The molar ratio of the alkynyl compound to the hydroxyl compound is 0.5 to 2.

[0022] The preparation method can be carried out in a variety of solvents. Preferably, the organic solvent is one or more of tetrahydrofuran, chloroform, dichloromethane, toluene, dimethyl sulfoxide, 1,4-dioxane, and N,N-dimethylformamide; more preferably, the organic solvent is tetrahydrofuran.

[0023] Preferably, the organic base catalyst is one or more of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N-methylmorpholine, and triethylenediamine; more preferably, the organic base catalyst is N-methylmorpholine.

[0024] Preferably, the reaction temperature is 20–100°C and the reaction time is 2–12 h. More preferably, the temperature is 20–30°C.

[0025] Thirdly, the present invention provides the application of photofluorescence-enhancing alkenyl ether compounds as fluorescence-enhancing materials in the fabrication of optical devices, wherein the photofluorescence-enhancing alkenyl ether compounds include sulfone-based alkenyl ether compounds. and carbonyl alkenyl ether compounds and ester-based alkenyl ether compounds R1 and R2 are the same organic groups selected as R1 and R2 mentioned above, and R1 and R2 can be structural formulas 1 to 3 at the same time.

[0026] The applications include optical information storage applications, optical writing of information, and optical erasure of information. Specifically,

[0027] Photofluorescence-enhancing alkenyl ether compounds and commercial polymers were co-dissolved in dichloroethane and spin-coated into a film:

[0028] Writing: UV irradiation (254nm) is performed through a mask, and fluorescent products are generated in the unmasked area;

[0029] Reading: Under 365nm illumination, the unmasked area fluoresces, and information can be read from it;

[0030] Erasure: Full-area 254nm irradiation homogenizes fluorescence, achieving information self-destruction.

[0031] Preferably, the commercially available polymer is polymethyl methacrylate (PMMA).

[0032] Preferably, the alkenyl ether compound is a sulfone alkenyl ether compound.

[0033] More preferably, the sulfone-based alkenyl ether compound is (E)-2-M4.

[0034]

[0035] The sulfone-based alkenyl ether compounds of this invention undergo photochemical rearrangement under 254 nm ultraviolet light irradiation, generating planarized fused-ring structures with significantly enhanced fluorescence intensity. Precise tuning of the emission wavelength can be achieved through substituent modulation. The synthetic method is based on the click reaction of phenolic monomers with activated alkynes, a simple and efficient process. These molecules retain photoresponsiveness in solid films (such as PMMA matrices) and have been successfully applied to mask-assisted information input and erasure systems, providing a new technical solution for anti-counterfeiting and information storage.

[0036] Compared with the prior art, the beneficial effects of this invention are as follows:

[0037] (1) The sulfone-based alkenyl ether compounds prepared by this invention can achieve >1000 times fluorescence enhancement after irradiation with 254nm ultraviolet light, with high photoresponse efficiency and extremely high contrast.

[0038] (2) The present invention uses a simple synthetic method based on click chemistry to synthesize sulfone-based alkenyl ether compounds, and the photo-enhanced emission peak of alkenyl ether compounds can be precisely controlled by controlling the type and position of substituents.

[0039] (3) The synthesis method of the sulfone-based alkenyl ether compounds described in this invention is simple and can efficiently obtain the products at room temperature.

[0040] (4) The optical information storage application of the photofluorescently enhanced alkenyl ether compounds described in this invention demonstrates information input with high contrast. Attached Figure Description

[0041] Figure 1 The UV-Vis absorption spectrum (A) and fluorescence spectrum (B) of compound (E)-2-M4 in Example 4 in DMSO as a function of 254 nm UV light irradiation time, with an excitation wavelength of 330 nm; and the curve (C) showing the change of relative fluorescence intensity I / I0 at 514 nm as a function of irradiation time, where I0 is the fluorescence intensity before irradiation and I is the fluorescence intensity at different irradiation times.

[0042] Figure 2 The UV-Vis absorption spectrum (A) and fluorescence spectrum (B) of compound (Z)-2-M4 in Example 4 in DMSO as a function of 254 nm UV light irradiation time, with an excitation wavelength of 330 nm; the curve (C) showing the change of relative fluorescence intensity I / I0 at 514 nm as a function of irradiation time, where I0 is the fluorescence intensity before irradiation and I is the fluorescence intensity at different irradiation times.

[0043] Figure 3 The molecular and crystal structures of compound (Z)-2-M4(A) and photo-irradiated product 2-24(B) in Example 5 are shown.

[0044] Figure 4 The frontier molecular orbital electron cloud distribution of compound (Z)-2-M4(A) and photo-irradiated product 2-24(B) in Example 6.

[0045] Figure 5 The molecular structures of compounds (E)-2-M1 to (E)-2-M7 in Example 7 and the new carbon-carbon double bond linkage sites after light irradiation are shown (indicated by arrows).

[0046] Figure 6 The normalized fluorescence spectra of DMSO solutions of compounds (E)-2-M1 to (E)-2-M7 in Example 7 after irradiation with 254 nm ultraviolet light for 30 min are compared.

[0047] Figure 7 This is a schematic diagram and a physical image of the application of compound (E)-2-M4 for information entry and erasure in Example 8. Detailed Implementation

[0048] The following examples will further illustrate how the invention is implemented, but the implementation and protection of the invention are not limited thereto. It should be noted that if the following steps are not specifically described, these steps will be implemented or understood by those skilled in the art by referring to existing technology. The reagents and instruments used, unless otherwise specified, are conventional commodities that can be purchased commercially.

[0049] Example 1: Synthesis of compounds (E)-2-M1 and (Z)-2-M1

[0050]

[0051] Take a 25 mL reaction tube and add a magnetic magnet, ethynyl-p-tolyl sulfone (180 mg, 1 mmol), p-tert-butylphenol (150 mg, 1 mmol), and THF (4.9 mL) sequentially. After the reaction system is thoroughly mixed, add dropwise a pre-diluted 4-methylmorpholine (NMM) (11 μL, 0.1 mmol) solution in THF (0.1 mL). After reacting at room temperature for 3 h, extract the reaction solution three times with DCM and deionized water and collect the organic phase. After drying with anhydrous MgSO4, collect the filtrate by vacuum filtration and then remove the solvent by vacuum distillation using a rotary evaporator. Finally, using a mixed solvent of PE and DCM (1 / 1, v / v) as the eluent, separate and purify the trans isomer (E)-2-M1 and the cis isomer (Z)-2-M1 by silica gel column chromatography to obtain them.

[0052] (E)-1-(Tert-butyl)-4-((2-tosylvinyl)oxy)benzene(E)-2-M1): White solid (238 mg), yield 72%. 13C NMR (125MHz, CDCl3), δ (TMS, ppm): 158.27 (=CO), 153.22, 148.90, 144.07, 139.27, 129.98, 127.26, 127. 09,117.97,111.77(C=CO),34.64,31.52,21.73.1HNMR(400MHz,CDCl3),δ(TMS,ppm):7.80(d,J=11.9Hz, 1H,C=CH-O),7.77(d,J=8.4Hz,2H,Ar-H),7.38(d,J=8.9Hz,2H,Ar-H),7.32(d,J=8.0Hz,2H,Ar-H),6.98( d,J=8.8Hz,2H,Ar-H),5.96(d,J=11.9Hz,1H,CH=CO),2.43(s,3H,CH3),1.31(s,9H,C(CH3)3).FT-IR(KBr disk),υ(cm-1):3062,2960,1628(C=C),1596,1509,1317,1293,1246,1203,1146,1079,1013,949,889,784,678,654,572,540.

[0053] (Z)-1-(Tert-butyl)-4-((2-tosylvinyl)oxy)benzene((Z)-2-M1): White solid (40 mg), yield 12%. ¹H NMR (400 MHz, CDCl₃), δ (TMS, ppm): 7.94 (d, J = 8.3 Hz, 2H, Ar-H), 7.36–7.28 (m, 4H, Ar-H), 6.86 (d, J = 8.9 Hz, 2H, Ar-H), 6.84 (d, J = 6.4 Hz, 1H, C = CH₃-O), 5.83 (d, J = 6.4 Hz, 1H, CH = CO), 2.42 (s, 3H, CH₃), 1.28 (s, 9H, C(CH₃)₃).

[0054] Example 2: Synthesis of compounds 2-M2 to 2-M7

[0055]

[0056] Sulfonyl alkenyl ethers 2-M2 to 2-M7 with different substituents and substitution sites were synthesized using the same method as 2-M1. During the synthesis, only the reaction substrate p-tert-butylphenol needed to be replaced with the corresponding phenolic compound.

[0057] (E)-1-Methyl-4-((2-phenoxyvinyl)sulfonyl)benzene((E)-2-M2): White solid, yield 70%. 13 C NMR (100MHz, CDCl3), δ (TMS, ppm): 157.73, 155.52, 144.15, 139.15, 130.28, 130.01, 127.28, 125.79, 118.43, 112.30, 21.73. 1 H NMR (500MHz, CDCl3), δ (TMS, ppm): 7.81 (d, J = 11.8Hz, 1H, C = CH-O), 7.77 (d, J = 8.2Hz, 2H, Ar-H), 7.39 (t, J = 8.0Hz, 2H, Ar-H), 7.33 (d,J=8.2Hz,2H,Ar-H),7.22(t,J=7.4Hz,1H,Ar-H),7.06(d,J=8.6Hz,2H,Ar-H),6.00(d,J=11.9Hz,1H,CH=CO),2.44(s,3H,CH3).

[0058] (Z)-1-Methyl-4-((2-phenoxyvinyl)sulfonyl)benzene((Z)-2-M2): White solid, yield 12%. 13 C NMR (100MHz, CDCl3), δ (TMS, ppm): 156.41, 151.22, 144.24, 139.65, 130.14, 129.60, 127.93, 125.46, 117.60, 112.56, 21.78. 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.95 (d, J=8.3Hz, 2H, Ar-H), 7.36-7.30 (m, 4H, Ar-H), 7.18 (t, J=7.4Hz, 1H, Ar-H ).6.95(dd,J=8.6,0.9Hz,2H,Ar-H),6.85(d,J=6.4Hz,1H,C=CH-O),5.87(d,J=6.4Hz,1H,CH=CO),2.43(s,3H,CH3).

[0059] (E)-1-Methoxy-4-((2-tosylvinyl)oxy)benzene((E)-2-M3): White solid, yield 71%. 13CNMR (100MHz, CDCl3), δ (TMS, ppm): 158.90, 157.41, 149.08, 144.06, 139.27, 129.97, 127.23, 119.81, 115.16, 111.41, 55.82, 21.72. 1 H NMR (500MHz, CDCl3), δ (TMS, ppm): 7.75 (dd, J=10.1, 4.9Hz, 3H, Ar-H, C=CH-O), 7.32 (d, J=8.1Hz, 2H, Ar-H), 6.98 (d, J=9.1Hz,2H,Ar-H),6.87(d,J=9.1Hz,2H,Ar-H),5.89(d,J=11.9Hz,1H,CH=CO),3.79(s,3H,OCH3),2.43(s,3H,CH3).

[0060] (Z)-1-Methoxy-4-((2-tosylvinyl)oxy)benzene((Z)-2-M3): pale yellow solid, yield 14%. 13 C NMR (100MHz, CDCl3), δ (TMS, ppm): 157.16, 152.35, 150.53, 144.15, 139.75, 129.57, 127.88, 118.84, 114.99, 111.67, 55.81, 21.77. 1 H NMR (500MHz, CDCl3), δ (TMS, ppm): 7.94 (d, J = 8.2Hz, 2H, Ar-H), 7.32 (d, J = 8.0Hz, 2H, Ar-H), 6.85 (q, J = 9.2Hz ,4H,Ar-H),6.76(d,J=6.4Hz,1H,C=CH-O),5.81(d,J=6.4Hz,1H,CH=CO),3.78(s,3H,OCH3),2.44(s,3H,CH3).

[0061] (E)-2-((2-Tosylvinyl)oxy)benzonitrile ((E)-2-M4): white solid, yield 80%. 13 C NMR (100MHz, CDCl3), δ (TMS, ppm): 156.59, 154.95, 144.69, 138.23, 134.98 ,134.32,130.16,127.51,125.86,117.80,115.55,114.77,104.66,21.77. 1H NMR (500MHz, CDCl3), δ (TMS, ppm): 7.82-7.77 (m, 3H, Ar-H, C=CH-O), 7.69-7.64 (m, 2H, Ar-H), 7.35 (d, J=8.0Hz, 2H, Ar -H),7.32(td,J=7.7,0.9Hz,1H,Ar-H),7.23(d,J=8.1Hz,1H,Ar-H),6.23(d,J=11.8Hz,1H,CH=CO),2.45(s,3H,CH3).

[0062] (Z)-2-((2-Tosylvinyl)oxy)benzonitrile((Z)-2-M4): white solid, yield 15%. 13 C NMR (100MHz, CDCl3), δ (TMS, ppm): 157.19, 148.48, 144.79, 138.72, 134.86 ,134.32,130.05,128.07,125.49,117.09,116.41,114.99,104.04,21.79. 1 H NMR (500MHz, CDCl3), δ (TMS, ppm): 8.05 (d, J = 8.3Hz, 2H, Ar-H), 7.68 (dd, J = 7.7, 1.6Hz, 1H, Ar-H), 7.62 (ddd, J = 8.4, 7.7, 1.7Hz, 1H, Ar-H), 7.38 (d, J = 8.0H z,2H,Ar-H),7.29(td,J=7.7,0.8Hz,1H,Ar-H),7.10(d,J=8.4Hz,1H,Ar-H),6 .79(d,J=6.4Hz,1H,C=CH-O),6.07(d,J=6.4Hz,1H,CH=CO),2.44(s,3H,CH3).

[0063] (E)-4-((2-Tosylvinyl)oxy)benzonitrile ((E)-2-M5): white solid, yield 78%. 13 C NMR (100MHz, CDCl3), δ (TMS, ppm): 158.38, 154.73, 144.66, 138.43, 134.65, 130.16, 127.44, 118.65, 118.03, 115.25, 109.43, 21.77. 1H NMR (500MHz, CDCl3), δ (TMS, ppm): 7.82-7.77 (m, 3H, Ar-H, C=CH-O), 7.71 (d, J=8.8Hz, 2H, Ar-H), 7.35 (d,J=8.0Hz,2H,Ar-H),7.18(d,J=8.8Hz,2H,Ar-H),6.20(d,J=11.8Hz,1H,CH=CO),2.45(s,3H,CH3).

[0064] (Z)-4-((2-Tosylvinyl)oxy)benzonitrile ((Z)-2-M5): white solid, yield 15%. 13 C NMR (100MHz, CDCl3), δ (TMS, ppm): 156.41, 151.22, 144.24, 139.65, 130.14, 129.60, 127.93, 125.46, 117.60, 112.56, 21.78. 1 H NMR (500MHz, CDCl3), δ (TMS, ppm): 7.91 (d, J=8.3Hz, 2H, Ar-H), 7.68-7.63 (m, 2H, Ar-H), 7.33 (d, J=8.0Hz, 2H, Ar -H),7.06(d,J=8.8Hz,2H,Ar-H),6.85(d,J=6.4Hz,1H,C=CH-O),6.02(d,J=6.4Hz,1H,CH=CO),2.43(s,3H,CH3).

[0065] (E)-3-((2-Tosylvinyl)oxy)benzonitrile ((E)-2-M6): white solid, yield 75%. 13 C NMR (100MHz, CDCl3), δ (TMS, ppm): 156.59, 154.95, 144.69, 138.23, 134.98, 134.32,130.16,127.51,125.86,117.80,115.55,114.77,104.66,21.77.1H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.80-7.73 (m, 3H, Ar-H, C=CH-O), 7.53 (d, J=5.1Hz, 2H,Ar-H),7.37-7.32(m,4H,127.51,125.86,117.80,115.55,114.77,104.66,21.77. 1H NMR (500MHz, CDCl3), δ (TMS, ppm): 7.82-7.77 (m, 3H, Ar-H, C=CH-O), 7.69-7.64 (m, 2H, Ar-H), 7.35 (d, J=8.0Hz, 2H, Ar -H),7.32(td,J=7.7,0.9Hz,1H,Ar-H),7.23(d,J=8.1Hz,1H,Ar-H),6.23(d,J=11.8Hz,1H,CH=CO),2.45(s,3H,CH3).

[0066] (Z)-3-((2-Tosylvinyl)oxy)benzonitrile((Z)-2-M6): white solid, yield 12%. 13 C NMR (100MHz, CDCl3), δ (TMS, ppm): 156.05, 149.14, 144.71, 139.15, 131.27 ,129.78,129.03,127.91,122.23,120.92,117.58,115.11,114.20,21.80. 1 H NMR (500MHz, CDCl3), δ (TMS, ppm): 7.92 (d, J = 8.2Hz, 2H, Ar-H), 7.48 (d, J = 5.0Hz, 2H, Ar-H), 7.34 (d, J = 8.1Hz, 2H ,Ar-H),7.26-7.19(m,2H,Ar-H),6.80(d,J=6.4Hz,1H,C=CH-O),6.00(d,J=6.4Hz,1H,CH=CO),2.45(s,3H,CH3).

[0067] (E)-1-Methyl-4-((2-(4-(trifluoromethyl)phenoxy)vinyl)sulfonyl)benzene((E)-2-M7): White solid, yield 80%. 13 C NMR (100MHz, CDCl3), δ (TMS, ppm): 156.59, 154.95, 144.69, 138.23, 134.98 ,134.32,130.16,127.51,125.86,117.80,115.55,114.77,104.66,21.77. 1H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.85-7.75 (m, 3H, Ar-H, C=CH-O), 7.67 (d, J=8.6Hz, 2H, Ar-H), 7.35 (d,J=8.1Hz,2H,Ar-H),7.18(d,J=8.6Hz,2H,Ar-H),6.13(d,J=11.8Hz,1H,CH=CO),2.45(s,3H,CH3).

[0068] (Z)-1-Methyl-4-((2-(4-(trifluoromethyl)phenoxy)vinyl)sulfonyl)benzene((Z)-2-M7): White solid, yield 13%. 13 C NMR (100MHz, CDCl3), δ (TMS, ppm): 158.25, 149.37, 144.58, 139.28, 129.72, 127.95, 127.66, 127.63, 117.62, 114.61, 21.78. 1 H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.93 (d, J = 8.3Hz, 2H, Ar-H), 7.62 (d, J = 8.6Hz, 2H, Ar-H), 7.33 (d, J = 8.0Hz, 2H, Ar-H), 7.06 (d, J = 8.5Hz, 2H, Ar-H), 6.85 (d, J = 6.4Hz, 1H, C = CH-O), 5.98 (d, J = 6.4Hz, 1H, CH = CO), 2.44 (s, 3H, CH3).

[0069] Example 3: Photochemical rearrangement of (E)-2-M4 under 254 nm UV irradiation

[0070]

[0071] The specific steps for the light irradiation experiment and the separation of the light-irradiated product (E)-2-hydroxy-3-(2-tosylvinyl)benzonitrile (2-24) are as follows:

[0072] A 25 mL quartz reaction tube was used to sequentially add a magnetic flux, (E)-2-M4 (89.7 mg, 0.3 mmol), HPLC-grade THF (3 mL), and HPLC-grade MeOH (2 mL). After the (E)-2-M4 was completely dissolved, the quartz reaction tube was placed in a photoreactor and reacted under 254 nm ultraviolet light. The reaction progress was monitored by thin-layer chromatography (TLC). After 24 h of reaction, TLC showed that the reactant (E)-2-M4 was almost completely consumed, and a distinct green fluorescent spot was formed. After the reaction was complete, the solvent was removed by vacuum distillation using a rotary evaporator. A mixed solvent of PE and THF (2 / 1, v / v) was used as the eluent, and the crude product was separated and purified by silica gel preparative grade thin-layer chromatography (PTLC) to obtain the crude product. The crude product was further cultured in a mixture of THF and n-hexane (3 / 1, v / v) by solvent diffusion evaporation. The final yellow crystals (9.0 mg) were 2-24, with a yield of 10%. 1 H NMR (500MHz, CDCl3), δ (TMS, ppm): 7.83 (d, J = 8.2Hz, 2H, Ar-H), 7.78 (d, J = 15.5Hz, 1H, C = CH-Ar), 7.63 (d, J = 7.8Hz, 1H, Ar-H), 7.53 (d, J = 7.8 Hz,1H,Ar-H),7.35(d,J=8.1Hz,2H,Ar-H),7.15(d,J=15.5Hz,1H,SO2-CH=C),7.05(t,J=7.8Hz,1H,Ar-H),6.35(s,1H,OH),2.44(s,3H,CH3). 13 C NMR (125MHz, CDCl3), δ (TMS, ppm): 144.80, 137.50, 135.56, 135.30, 134.46, 13 4.40,131.59,130.20,128.00,121.74,121.65,100.13,99.24,21.80.Crystal Data for C 16 H 13 NO3S (M=299.33g / mol) (CCDC 2334758): monoclinic, space group P21 / n (no.14), β=92.885(3)°, Z=4, T=170.00K, μ(GaKα)=1.413mm-1, Dcalc=1.432g / cm3, 2420reflections measured(9.274°≤2Θ≤107.78°), 2420unique(Rint=0.0928, Rsigma=0.0724) which were used in all calculations.The final R1 was 0.1414(I>2σ(I))and wR2 was 0.3493(all data).

[0073] Example 4: Photoinduced absorption and fluorescence changes of (E)-2-M4 and (Z)-2-M4

[0074] (E)-2-M4 or (Z)-2-M4 dissolved in DMSO. After irradiation with 254nm ultraviolet light, as... Figure 1 As shown, the main absorption peak of (E)-2-M4 at 256 nm weakens, the secondary absorption peak at 290 nm slightly strengthens, and a new absorption peak appears at 327 nm. Furthermore, the fluorescence intensity of the emission peak at 514 nm after 30 min of illumination is 1103 times that of the initial state. (Z)-2-M4 exhibits almost identical spectral changes to (E)-2-M4, such as... Figure 2 The main absorption peak at 258 nm weakened, the secondary absorption peak at 289 nm slightly strengthened, and a new absorption peak appeared at 327 nm. In addition, a significant emission also appeared at 514 nm in the fluorescence spectrum. After 30 min of irradiation with 254 nm ultraviolet light, the fluorescence intensity of this emission peak was 1325 times that before irradiation.

[0075] Example 5: Crystal structures of model compound (Z)-2-M4 and photoproduct 2-24

[0076] The crystal structures of the model compound (Z)-2-M4 and the photo-exposed product 2-24 are as follows: Figure 3 As shown, the twist angle within the molecule decreased from 20.3° to 1.2° after rearrangement, indicating that the molecular structure became more planar and the degree of conjugation increased after rearrangement, which is conducive to the enhancement of fluorescence emission. This result is consistent with the change in the spectrum.

[0077] Example 6: Frontier molecular orbital electron cloud distribution of compound (Z)-2-M4 and photo-irradiated product 2-24

[0078] We performed density functional theory (DFT) calculations on the electron cloud distribution of the molecular orbitals before and after the rearrangement at the B3LYP / 6-31G(d,p) level using Gaussian 16 software. Figure 4It is known that the lowest unoccupied molecular orbital (LUMO) level of the model compound (Z)-2-M4 is mainly distributed on the carbon-carbon double bond and the cyano-substituted benzene ring, while its highest occupied molecular orbital (HOMO) level is mainly distributed on the methyl-substituted benzene ring and the sulfone oxygen atom. After rearrangement, the molecular structure becomes more planar, and the distribution of orbital electron clouds also changes significantly. The LUMO level of product 2-24 shows a small distribution on the methyl-substituted benzene ring, and the HOMO level also shows a significant distribution on the cyano-substituted benzene ring, with a significantly larger overlap region of electron clouds. At the same time, the LUMO level of the rearranged molecule decreases from -1.80 eV to -2.21 eV, and the HOMO level increases from -6.71 eV to -6.69 eV, with a corresponding decrease in the band gap of 0.43 eV, resulting in a redshift in the absorption of the rearranged product, and a corresponding redshift and enhancement in the emission.

[0079] Example 7: Comparison of photofluorescence spectra of (E)-2-M1 to (E)-2-M7

[0080] (E)-2-M1~(E)-2-M7( Figure 5 The fluorescence spectra of DMSO solutions were compared after irradiation with 254 nm UV light for 30 min. The comparison is shown in the normalized fluorescence spectrum diagram. Figure 6 It can be seen that the introduction of different substituents can adjust the position of the fluorescence emission peak between 429 and 548 nm, and the introduction of electron-withdrawing groups causes a significant red shift in the emission wavelength. Further comparison of the emission wavelengths of model compounds containing cyano groups after illumination with different substitution positions reveals that the meta-substituted (E)-2-M6 exhibits the longest emission wavelength after illumination. This is because, after photochemical reaction, the meta-substituted cyano group rearranges to the para position of the carbon-carbon double bond, thus exhibiting the strongest electron-withdrawing effect, resulting in a significant red shift in emission.

[0081] Example 8: Optical Information Storage Application

[0082] like Figure 7 As shown, using polymethyl methacrylate (PMMA) as a matrix, a photoresponsive alkenyl ether compound (the sulfone-based alkenyl ether compound, carbonyl alkenyl ether compound, or ester-based alkenyl ether compound of this invention) is dissolved in DCE and a thin film is formed on a 3×3 cm quartz sheet by spin coating. Subsequently, the film is irradiated with 254 nm ultraviolet light for 5 minutes using a handheld ultraviolet lamp, and the information "528" is recorded using a mask. After removing the mask and reading the information, continued illumination (approximately 10 minutes) allows the remaining areas not covered by the mask to undergo a photochemical reaction, thereby achieving complete erasure of the information.

[0083] The above examples are merely preferred embodiments of the present invention. These examples are only illustrative and not intended to limit the invention. Any changes, substitutions, modifications, etc., made by those skilled in the art without departing from the spirit and scope of the invention should be protected by the present invention.

Claims

1. A sulfone-based alkenyl ether compound with photofluorescence enhancement, characterized in that, It has the structure of formula (I): Formula (I) can be either E or Z, and R1 and R2 are the same or different organic groups.

2. The sulfone-based alkenyl ether compound with photofluorescence enhancement according to claim 1, characterized in that, In the formula (I), R1 and R2 are any of the following structural formulas, but R1 and R2 are not simultaneously structural formulas 1 to 3; Where n is an integer from 0 to 20; * indicates the replacement position.

3. The method for preparing the photofluorescence-enhanced sulfone-based alkenyl ether compound according to claim 1 or 2, characterized in that, Includes the following steps: Under inert gas protection and with an organic base catalyst, alkynyl compounds and hydroxyl compounds are reacted in an organic solvent. After the reaction is complete, the mixture is purified to obtain sulfone-based alkenyl ether compounds.

4. The preparation method according to claim 3, characterized in that, The general structural formula of the alkyne compound is: The general structural formula of the hydroxyl compound is: R1 and R2 are the same as the organic groups selected for R1 and R2 in claim 2.

5. The preparation method according to claim 3, characterized in that, The molar ratio of the alkynyl compound to the hydroxyl compound is 0.5 to 2.

6. The preparation method according to claim 3, characterized in that, The organic base catalyst is one or more of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, 4-dimethylaminopyridine, triethylenediamine, and N-methylmorpholine.

7. The preparation method according to claim 3, characterized in that, The organic solvent is one or more of tetrahydrofuran, chloroform, dichloromethane, toluene, dimethyl sulfoxide, 1,4-dioxane, and N,N-dimethylformamide.

8. The preparation method according to claim 3, characterized in that, The reaction temperature is 20–100℃, and the reaction time is 2–12 h.

9. The application of a photofluorescence-enhancing alkenyl ether compound as a fluorescence-enhancing material in the fabrication of optical devices, characterized in that, The photofluorescence-enhancing alkenyl ether compounds include the sulfone-based alkenyl ether compounds of claim 1. and carbonyl alkenyl ether compounds and ester-based alkenyl ether compounds Wherein R1 and R2 are the same organic groups selected in claim 2, and R1 and R2 can be structural formulas 1 to 3 at the same time.

10. The application according to claim 9, characterized in that, The applications include optical information storage applications, optical writing of information, and optical erasure of information.

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