Fluorescent material based on chiral binaphthol as well as preparation method and application of fluorescent material

Abstract

The invention discloses a chiral binaphthol-based fluorescent material as well as a preparation method and application thereof, and belongs to the technical field of organic photoelectric materials. The fluorescent material takes a chiral binaphthyl derivative as a skeleton, and a chiral binaphthyl group is introduced into a para-position position of tetrafluoroterephthalonitrile, so that a chiral space charge transfer luminescence system with a clear structure is formed. The preparation method comprises two steps of nucleophilic substitution reaction, the reaction condition is mild, the synthetic route is simple, and the yield is stable. The material has dual-state emission and aggregation enhanced luminescence characteristics, avoids aggregation quenching, has excellent circular polarization luminescence performance, has a luminescence asymmetry factor (Glum) of 3.6 * 10 <-3 >-5.9 * 10 <-3 >, and can still maintain stable chiral luminescence characteristics in a doped film. The material can be widely applied to the fields of commercial anti-counterfeiting, fluorescent ink, circular polarization luminescent devices, 3D display, information encryption, biological probes, LED light sources and the like, and has good industrial amplification potential and practical application value.

Description

Technical Field

[0001] This invention belongs to the field of organic optoelectronic materials technology, specifically relating to a fluorescent material based on chiral binaphthol, its preparation method, and its application. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] In recent years, chiral luminescent materials have attracted much attention due to their unique application prospects in fields such as circularly polarized light emission (CPL), 3D displays, information encryption, and biological probes. Compared with traditional luminescent materials, chiral organic luminescent materials can not only achieve efficient luminescence but also generate circularly polarized light, and their chiral optical properties can be tuned through molecular design. Various strategies exist for constructing chiral luminescent materials, including introducing spirocarbon central chirality, planar chirality, axial chirality, and helical chirality.

[0004] In the prior art, various chiral luminescent systems have been reported. The first category consists of space charge transfer (TSCT) materials with spirocarbon centers. The core of these materials lies in achieving a significant through-space charge transfer (TSCT) effect through the chiral construction of the spirocarbon center, thereby obtaining a luminescence spectroscopy (CPL). For example, materials based on spirofluorene, spirodiphenyl sulfone, and other spirocarbon chiral centers achieve CPL signals through TSCT by constructing donor-acceptor (DA) structures, with their luminescence asymmetry factor (g value) typically in the range of 10. -3 On a large scale, surface-chiral materials, such as chiral cage compounds or chiral macrocycles, also exhibit CPL properties. Axially chiral materials, especially derivatives based on binaphthol (BINOL), are also widely used to construct chiral luminescent materials due to their stable chiral configurations and ease of modification.

[0005] However, existing technologies still have the following shortcomings: chiral source construction is complex, often requiring cumbersome chiral separation steps, resulting in high costs and difficulty in controlling the configuration; the material molecular structure is complex, the synthesis route is long and the yield is low, which is not conducive to industrial production; the efficiency of chiral information transfer from the chiral center to the light-emitting unit is not high, resulting in generally low g values ​​of CPL and the stability needs to be improved; the range of light emission color control is limited, making it difficult to meet the application requirements of multicolor display and optical communication. Summary of the Invention

[0006] This invention addresses the shortcomings of existing technologies by providing a chiral binaphthol-based fluorescent material, its preparation method, and its applications. It aims to solve the problems commonly found in existing chiral luminescent materials, such as cumbersome synthesis steps, excessive extension of the conjugated system, large spatial distance between the chiral environment and the luminescent unit, and limited luminescence efficiency in the aggregated state.

[0007] To achieve the above objectives, the present invention adopts the following technical solution: This invention provides a fluorescent material based on chiral binaphthol, the structural formula of which is: Where X represents O, N, or S; and R represents halogen, hydrocarbon group, monocyclic aryl group, amino group, substituted amino group, alkoxy group, or fused cyclic substituent.

[0008] Furthermore, the halogen is preferably fluorine, chlorine, bromine, or iodine; the monocyclic aryl group is preferably phenyl, p-tolyl, or p-methoxyphenyl; the hydrocarbon group is preferably methyl, ethyl, propyl, isopropyl, benzyl, substituted alkenyl, substituted alkynyl, etc.; the alkoxy group is preferably methoxy or isopropoxy; the substituted amino group is preferably dimethylamino, diarylamino, etc.; and the cyclic substituent is preferably cyclic anolyte, heterocyclic anolyte, or saturated cyclic anolyte.

[0009] Furthermore, the structural formula of the chiral binaphthol-based fluorescent material can be specifically as follows: .

[0010] The present invention also provides a method for preparing the above-mentioned chiral binaphthol fluorescent material, the method comprising the following steps: chiral binaphthol I and tetrafluoroterephthalonitrile II are reacted under alkaline conditions to obtain key intermediate III; intermediate III and nucleophile IV are reacted under alkaline conditions to obtain the desired chiral space charge transfer fluorescent material V.

[0011] The specific reaction formula is as follows: ; Further, the molar ratio of the chiral binaphthol derivative, tetrafluoroterephthalonitrile, and base is 1:(1.8~4.0):(0.05~4.0); the chiral binaphthol derivative is (R) / (S)-ethylbinaphthol, and its structural formula is: .

[0012] Furthermore, the molar ratio of the intermediate, nucleophile, and base is 1:(2~4):(1~6).

[0013] Further, the base is an inorganic base or an organic base; the inorganic base is selected from carbonates, acetates or hydroxides; the organic base is selected from sodium alkoxides, potassium alkoxides, piperidine, morpholine, diethylamine or triethylamine.

[0014] Furthermore, the reaction is carried out in a solvent selected from tetrahydrofuran, dioxane, acetonitrile, toluene, N,N-dimethylformamide, or dimethyl sulfoxide.

[0015] Furthermore, the reaction temperature is room temperature to 140 °C, and the reaction time is 2 to 48 h.

[0016] The structure of the nucleophile is as follows: .

[0017] This invention also provides an application of the above-mentioned luminescent material in the fields of commercial anti-counterfeiting, fluorescent ink, circular polarization light emission conversion, 3D display, information encryption, chiral optoelectronic devices, biological probes and biological mirrors.

[0018] The beneficial effects of the technical solution provided by this invention are: (1) This invention constructs a donor-acceptor spatially adjacent non-conjugated charge transfer system by introducing a chiral binaphthyl unit at the para position of tetrafluoroterephthalonitrile. The luminescent unit is spatially close to the chiral center, resulting in high chiral information transfer efficiency and a high circular polarization luminescence asymmetry factor. g lum Up to 5.9 × 10 -3 And it remains stable in the thin film.

[0019] (2) The luminescent material prepared by the present invention has both efficient luminescence in solution state and aggregated state, exhibits obvious aggregation-enhanced luminescence characteristics, and significantly improves the aggregation fluorescence quenching problem of traditional conjugated materials; it is sensitive to solvent polarity, and can achieve precise control of luminescence color, and is suitable for multi-color display, fluorescence sensing and information encryption scenarios.

[0020] (3) This invention uses only two nucleophilic substitution reactions, with a simple synthetic route, mild reaction conditions, and high yield. At the same time, the structure is easy to modify and regulate by changing the nucleophile IV, which facilitates the regulation of the luminescence color and functional expansion, and has good potential for industrial scale-up. Attached Figure Description

[0021] Figure 1 These are fluorescence emission photographs of compounds (a) V-1, (b) V-2, and (c) V-3 in different solvents in the embodiments of the present invention; Figure 2 The following are the fluorescence emission spectra of compounds (a) V-1, (b) V-2 and (c) V-3 in different solvents in the embodiments of the present invention; Figure 3 The images show the fluorescence emission of compounds (a) V-1, (b) V-2 and (c) V-3 in the embodiments of the present invention at different THF-H2O volume fractions; Figure 4 These are fluorescence emission photographs of compounds (a) V-1, (b) V-2, and (c) V-3 in crystalline and powder states, respectively, as described in the embodiments of the present invention. Figure 5The following are fluorescence emission spectra of compounds (a,d,g) V-1, (b,e,h) V-2, and (c,f,i) V-3 in different aggregation states in the embodiments of the present invention. Figure 6 The circular dichroism and circular polarization emission spectra of compounds V-1 (a, d), V-2 (b, e), and V-3 (c, f) in toluene solution, and the corresponding emission asymmetry factor curves are shown in the embodiments of the present invention. Figure 7 The circularly polarized emission (CPL) spectra and corresponding emission asymmetry factor curves of compounds V-1 (a), V-2 (b) and V-3 (c) doped in PMMA thin films in the embodiments of the present invention are shown. Figure 8 The figures show the electroluminescence performance of coated LED devices doped with compounds V-1, V-2 and V-3 in the embodiments of the present invention, where (a–c) are EL spectra and (d) are brightness-current relationship curves. Figure 9 This is a CIE1931 color coordinate diagram of the light emitted by the coated LED devices doped with compounds V-1, V-2 and V-3 in the embodiments of the present invention. Detailed Implementation

[0022] The specific embodiments of the present invention are described in detail below. These embodiments are intended to more fully demonstrate the technical content of the present invention and help to understand the specific implementation process of the present invention, but their content should not be construed as limiting the scope of the claims of the present invention in any way. For those skilled in the art, various adjustments, modifications, and substitutions made to the embodiments without departing from the spirit and scope of the present invention are all within the scope of protection sought by the present invention.

[0023] Example 1 Synthesis of the intermediate: Tetrafluoroterephthalonitrile (640 mg, 3.2 mmol), (R) / (S)-ethylbinaphthol (2.00 g, 6.4 mmol), and potassium carbonate (K₂CO₃, 884 mg, 6.4 mmol) were added sequentially to a 100 mL three-necked flask. The flask was evacuated and purged three times with nitrogen. Then, anhydrous DMF (30 mL) was added via syringe under an inert atmosphere. The mixture was stirred overnight at room temperature, and thin-layer chromatography showed complete consumption of the starting materials. After the reaction was complete, saturated brine was added to precipitate the insoluble solid, which was then collected by vacuum filtration and dried. The crude product was separated by elution column chromatography (petroleum ether / ethyl acetate = 20:1) to give a pale yellow solid powder, which was the intermediate (2.41 g, 3.05 mmol), in 95.6% yield.

[0024] 1 H NMR (500 MHz, CDCl3) δ 7.96 (d, J = 8.9 Hz, 2H), 7.92 (d, J = 8.2Hz, 2H), 7.73 (d, J = 9.1 Hz, 2H), 7.52-7.47 (m, 2H), 7.44 (dd, J = 7.0, 6.9Hz, 2H), 7.33-7.24 (m, 4H), 7.24-7.15 (m, 8H), 6.95-6.88 (m, 2H), 4.08-3.92(m, 4H), 1.08 (t, J = 7.0 Hz, 6H) ppm.

[0025] According to the 1H NMR data, the signal in the δ 7.96–6.88 ppm range belongs to the aromatic hydrogens in the product skeleton; the signal in the δ 4.08–3.92 ppm range belongs to the methylene group (-OCH) bonded to oxygen. 2- The signal at δ 1.08 ppm is attributed to methyl (-CH3) hydrogen. The above data are consistent with the structure of the target product.

[0026] Example 2 Synthesis of target compound V-1: An intermediate (100 mg, 0.127 mmol), p-cresol (IV-1, 27.5 mg, 0.254 mmol), and K₂CO₃ (52.6 mg, 0.38 mmol) were added to a Schlenk tube. The system was evacuated and purged three times with nitrogen. Under nitrogen protection, anhydrous DMF (1.5 mL) was added via syringe. The reaction mixture was stirred overnight at 60 °C, and TLC monitoring showed complete consumption of the starting material. After cooling to room temperature, saturated brine was added, precipitating an insoluble solid. The solid was collected by vacuum filtration and dried. The crude product was purified by column chromatography (eluent: petroleum ether / CH₂Cl₂ = 2:1, v / v) to give the target product V-1, a pale yellow solid, in 83% yield.

[0027] V-1: yield 83%, light yellow solid, IR (KBr, cm -1 ): 2242, 1621, 1589,1440, 1205. 1 H NMR (500 MHz, CDCl3) δ 7.87 (d, J = 8.2 Hz, 2H), 7.84 (d,J = 9.1Hz, 2H), 7.77 (d, J = 9.0 Hz, 2H), 7.71 (d, J = 8.0 Hz, 2H), 7.41–7.35 (m, 2H), 7.28–7.19 (m, 6H), 7.16–7.08 (m, 6H), 6.92 (d, J = 8.0 Hz, 4H), 6.68 (d, J = 8.3Hz, 2H), 6.28 (d, J = 8.5 Hz, 4H), 3.89 (q, J = 6.9 Hz, 4H), 2.29 (s, 6H), 0.97(t, J = 7.0 Hz, 6H) ppm; 13 C NMR (125.8 MHz, CDCl3) δ 154.5, 154.3, 152.1, 145.5,133.9, 133.7, 132.8, 130.8, 129.9, 129.8, 128.9, 128.4, 127.9, 127.5, HRMS (ESI) m / z: found, 987.3412 [M+Na + ];calcd for C 66 H 48 N₂O₆ + Na + , 987.3405. The above-mentioned proton NMR spectrum, carbon NMR spectrum and high-resolution mass spectrometry data are consistent with the structure of the target compound V-1.

[0028] Example 3 An intermediate (100 mg, 0.127 mmol), o-methylphenol (IV-2, 27.5 mg, 0.254 mmol), and K₂CO₃ (52.6 mg, 0.38 mmol) were added to a Schlenk tube. The system was evacuated and purged three times with nitrogen. Under nitrogen protection, anhydrous DMF (1.5 mL) was added via syringe. The reaction mixture was stirred overnight at 60 °C, and TLC monitoring showed complete consumption of the starting material. After cooling to room temperature, saturated brine was added, precipitating an insoluble solid. The solid was collected by vacuum filtration and dried. The crude product was purified by column chromatography (eluent: petroleum ether / CH₂Cl₂ = 2:1, v / v) to give the target product V-2 as a pale yellow solid, in 86% yield.

[0029] IV-2 is o-methylphenol, and product V-2 is a pale yellow solid with a yield of 86%.

[0030] V-2: yield 86%, light yellow solid, IR (KBr, cm -1 ): 2239, 1628, 1594,1440, 1246. 1 H NMR (500 MHz, CDCl3) δ 7.87 (d, J = 8.1 Hz, 2H), 7.86 (d, J = 9.1Hz, 2H), 7.74 (d, J = 7.5 Hz, 2H), 7.69 (d, J = 9.0 Hz, 2H), 7.39 (dd, J = 7.8, 7.1Hz, 2H), 7.31–7.19 (m, 6H), 7.14–7.03 (m, 10H), 6.98 (dd, J = 7.4, 7.2 Hz, 2H),6.50 (br, 2H), 5.85 (d, J = 7.1 Hz, 2H), 3.91 (q, J = 7.5 Hz, 4H), 1.66 (s, 6H), 0.98 (t, J = 7.3 Hz, 6H) ppm; 13C NMR (125.8 MHz, CDCl3) δ 154.6, 154.5, 151.9,146.8, 133.7, 133.6, 131.1, 130.9, 130.2, 128.6 (2C), 128.34, 128.26, 127.8,127.49, 127.47, 126.8 (2C), 126.4, 126.3, 125.8, 125.3, 124.9, 123.7, 123.2,121.5, 117.7, 116.8, 113.9, 112.9, 64.3, 15.7, 14.7 ppm. HRMS (ESI) m / z:found, 987.3413 [M+Na + ]; calcd for C 66 H 48 N₂O₆ + Na + , 987.3405. Example 4 An intermediate (100 mg, 0.127 mmol), 2,6-dimethylphenol (IV-3, 31.0 mg, 0.254 mmol), and K₂CO₃ (52.6 mg, 0.38 mmol) were added to a Schlenk tube. The system was evacuated and purged three times with nitrogen. Under nitrogen protection, anhydrous DMF (1.5 mL) was added via syringe. The reaction mixture was stirred overnight at 60 °C, and TLC monitoring showed complete consumption of the starting material. After cooling to room temperature, saturated brine was added, precipitating an insoluble solid. The solid was collected by vacuum filtration and dried. The crude product was purified by column chromatography (eluent: petroleum ether / CH₂Cl₂ = 2:1, v / v) to give the target product V-3 as a pale yellow solid, in 78% yield.

[0031] IV-3 is 2,6-dimethylphenol, and product V-3 is a yellow solid with a yield of 78%.

[0032] V-3: yield 78%, yellow solid, IR (KBr, cm -1 ): 2237, 1624, 1595, 1433,1215. 1 H NMR (500 MHz, CDCl3) δ 7.98–7.86 (m, 6H), 7.79 (d, J= 7.5 Hz, 2H),7.46–7.30 (m, 4H), 7.30–7.20 (m, 3H), 7.20–7.09 (m, 4H), 7.08–6.87 (m, 7H),6.85-6.50 (m, 4H), 4.20-3.60 (m, 4H), 1.78 (s, 6H), 1.30 (br, 6H), 0.87 (br,6H) ppm; 13 C NMR (125.8 MHz, CDCl3) δ 154.8, 152.6, 151.4, 145.8, 134.2, 133.8,130.4, 130.0, 129.6, 129.0, 128.81, 128.75, 128.68, 127.9, 127.4, 126.6,126.2, 125.9 (2C), 125.8, 125.3, 124.6, 123.4, 121.0, 118.0, 116.3, 114.9,108.7, 64.8, 16.4, 16.1, 14.6 ppm HRMS (ESI) m / z: found, 1015.3721 [M+Na + ];calcd for C 68 H 52 N₂O₆ + Na + , 1015.3718. Example 5 IV-4 is p-bromophenol, and product V-4 is a yellow solid with a yield of 71%.

[0033] An intermediate (100 mg, 0.127 mmol), p-bromophenol (IV-4, 43.9 mg, 0.254 mmol), and K₂CO₃ (52.6 mg, 0.38 mmol) were added to a Schlenk tube. The system was evacuated and purged three times with nitrogen. Under nitrogen protection, anhydrous DMF (1.5 mL) was added via syringe. The reaction mixture was stirred overnight at 60 °C, and TLC monitoring showed complete consumption of the starting material. After cooling to room temperature, saturated brine was added, precipitating an insoluble solid. The solid was collected by vacuum filtration and dried. The crude product was purified by column chromatography (eluent: petroleum ether / CH₂Cl₂ = 2:1, v / v) to give the target product V-4 as a pale yellow solid, in 71% yield. V-4: yield 71%, yellow solid. 1 H NMR (500 MHz, CDCl3) δ 7.88 (d,J = 8.2 Hz, 2H), 7.85 (d, J = 9.1 Hz, 2H), 7.79 (d, J = 9.0 Hz, 2H), 7.76 (d, J = 8.3Hz, 2H), 7.40 (dd, J = 7.1, 7.1 Hz, 2H), 7.29 (dd, J = 7.7, 7.2 Hz, 2H), 7.27–7.24 (m, 2H), 7.24-7.20 (m, 6H), 7.14 (dd, J = 7.8, 7.5 Hz, 2H), 7.10 (d, J = 8.5Hz, 2H), 7.05 (d, J = 8.5 Hz, 2H), 6.67 (d, J = 8.4 Hz, 2H), 6.20 (d, J = 8.9 Hz,4H), 3.90 (q, J = 7.0 Hz, 4H), 0.99 (t, J = 6.9 Hz, 6H) ppm; 13 C NMR (125.8 MHz, CDCl3) δ 155.1, 154.5, 151.7, 143.6, 133.8, 133.5, 132.3, 130.9, 130.0, 129.1, 128.4, 128.0, 127.6, 126.8, 126.7, 125.9, 125.2, 125.1, 124.9, 123.7, 121.3, 117.7, 117.1, 116.7, 116.1, 114.0, 109.5, 107.8, 64.3, 14.7 ppm. HRMS(ESI) m / z: found, 1115.1308 [M+Na + ; calcd for C 64 H 42 N2O6Br2+Na + , 1115.1302. Example 6 An intermediate (100 mg, 0.127 mmol), o-bromophenol (IV-5, 43.9 mg, 0.254 mmol), and K₂CO₃ (52.6 mg, 0.38 mmol) were added to a Schlenk tube. The system was evacuated and purged three times with nitrogen. Under nitrogen protection, anhydrous DMF (1.5 mL) was added via syringe. The reaction mixture was stirred overnight at 60 °C, and TLC monitoring showed complete consumption of the starting material. After cooling to room temperature, saturated brine was added, precipitating an insoluble solid. The solid was collected by vacuum filtration and dried. The crude product was purified by column chromatography (eluent: petroleum ether / CH₂Cl₂ = 2:1, v / v) to give the target product V-5 as a pale yellow solid, in 68% yield.

[0034] IV-5 is o-bromophenol, and product V-5 is a yellow solid with a yield of 68%.

[0035] V-5:yield 68%, yellow solid, 1 H NMR (500 MHz, CDCl3) δ 7.89 (d, J = 8.2Hz, 2H), 7.85 (d, J = 9.1 Hz, 2H), 7.75 (d, J = 9.0 Hz, 4H), 7.46 (dd, J = 7.5, 1.5Hz, 2H), 7.39 (dd, J = 7.5, 7.5 Hz, 2H), 7.33–7.13 (m, 12H), 7.08 (d, J = 8.5 Hz, 2H), 6.95 (dd, J = 7.8, 7.5 Hz, 2H), 6.47 (br, 2H), 5.98 (br, 2H), 3.96-3.82(m, 4H), 1.00-0.88 (m, 6H) ppm; 13C NMR (125.8 MHz, CDCl3) δ 154.6, 152.6,150.2, 148.1, 133.85, 133.77, 131.6, 131.4, 131.2, 130.0, 129.2, 128.3,128.0, 127.9, 127.4, 126.9, 126.5, 126.1, 125.8, 125.7, 124.9, 124.6, 123.7,119.5, 118.7, 116.8, 114.2, 112.5, 110.3, 109.2, 64.4, 14.7 ppm HRMS (ESI)m / z: found, 1115.1311 [M+Na + ]; calcd for C 64 H 42 N₂O₆Br₂ + Na + , 1115.1302. Example 7 An intermediate (100 mg, 0.127 mmol), o-methoxyphenol (IV-6, 31.5 mg, 0.254 mmol), and K₂CO₃ (52.6 mg, 0.38 mmol) were added to a Schlenk tube. The system was evacuated and purged three times with nitrogen. Under nitrogen protection, anhydrous DMF (1.5 mL) was added via syringe. The reaction mixture was stirred overnight at 60 °C, and TLC monitoring showed complete consumption of the starting material. After cooling to room temperature, saturated brine was added, precipitating an insoluble solid. The solid was collected by vacuum filtration and dried. The crude product was purified by column chromatography (eluent: petroleum ether / CH₂Cl₂ = 2:1, v / v) to give the target product V-6 as a pale yellow solid in 84% yield.

[0036] IV-6 is o-methoxyphenol, and product V-6 is a yellow solid with a yield of 84%.

[0037] V-6:yield 84%, yellow solid, 1 H NMR (500 MHz, CDCl3) δ 7.84 (d, J = 9.0Hz, 2H), 7.83 (d, J = 10.0 Hz, 2H), 7.74 (d, J = 9.0 Hz, 2H), 7.67 (d, J = 7.5 Hz, 2H), 7.37 (dd, J= 7.7, 7.2 Hz, 2H), 7.28–7.18 (m, 8H), 7.15–7.07 (m, 4H), 7.00(dd, J = 7.8, 7.7 Hz, 2H), 6.74 (d, J = 7.5 Hz, 4H), 6.66 (d, J = 7.5 Hz, 2H), 6.25(d, J = 7.5 Hz, 2H), 3.88 (q, J = 6.5 Hz, 4H), 3.43 (s, 6H), 0.94 (t, J = 6.5 Hz, 6H) ppm; 13 C NMR (125.8 MHz, CDCl3) δ 154.6, 152.0, 149.6, 145.3, 138.3, 134.0,133.7, 132.4, 130.7, 129.8, 128.7, 128.5, 127.8, 127.4, 126.6, 126.4, 125.9,125.8, 124.6, 124.5, 123.6, 121.0, 120.3, 117.5, 116.7, 114.6, 112.7, 111.7,109.9, 106.3, 64.5, 55.6, 14.7 ppm. HRMS (ESI) m / z: found, 1019.3310 [M+Na + ];calcd for C 66 H 48 N₂O₈ + Na + , 1019.3303. Example 8 An intermediate (100 mg, 0.127 mmol), 1-naphthol (IV-7, 36.6 mg, 0.254 mmol), and K₂CO₃ (52.6 mg, 0.38 mmol) were added to a Schlenk tube. The system was evacuated and purged three times with nitrogen. Under nitrogen protection, anhydrous DMF (1.5 mL) was added via syringe. The reaction mixture was stirred overnight at 60 °C, and TLC monitoring showed complete consumption of the starting material. After cooling to room temperature, saturated brine was added, precipitating an insoluble solid. The solid was collected by vacuum filtration and dried. The crude product was purified by column chromatography (eluent: petroleum ether / CH₂Cl₂ = 2:1, v / v) to give the target product V-7 as a pale yellow solid, in 78% yield.

[0038] IV-7 is 1-naphthol, and product V-7 is a pale yellow solid with a yield of 78%.

[0039] V-6:yield 84%, yellow solid, 1 H NMR (500 MHz, CDCl3) δ 7.84 (d, J = 9.0Hz, 2H), 7.83 (d, J = 10.0 Hz, 2H), 7.74 (d, J = 9.0 Hz, 2H), 7.67 (d, J = 7.5 Hz, 2H), 7.37 (dd, J = 7.7, 7.2 Hz, 2H), 7.28–7.18 (m, 8H), 7.15–7.07 (m, 4H), 7.00(dd, J = 7.8, 7.7 Hz, 2H), 6.74 (d, J = 7.5 Hz, 4H), 6.66 (d, J = 7.5 Hz, 2H), 6.25(d, J = 7.5 Hz, 2H), 3.88 (q, J = 6.5 Hz, 4H), 3.43 (s, 6H), 0.94 (t, J = 6.5 Hz, 6H) ppm; 13 C NMR (125.8 MHz, CDCl3) δ 154.6, 152.0, 149.6, 145.3, 138.3, 134.0,133.7, 132.4, 130.7, 129.8, 128.7, 128.5, 127.8, 127.4, 126.6, 126.4, 125.9,125.8, 124.6, 124.5, 123.6, 121.0, 120.3, 117.5, 116.7, 114.6, 112.7, 111.7,109.9, 106.3, 64.5, 55.6, 14.7 ppm. HRMS (ESI) m / z: found, 1019.3310 [M+Na + ];calcd for C 66 H 48 N₂O₈ + Na + , 1019.3303. Example 9 An intermediate (100 mg, 0.127 mmol), 2,6-dimethylthiophenol (IV-8, 35.1 mg, 0.254 mmol), and K₂CO₃ (52.6 mg, 0.38 mmol) were added to a Schlenk tube. The system was evacuated and purged three times with nitrogen. Under nitrogen protection, anhydrous DMF (1.5 mL) was added via syringe. The reaction mixture was stirred overnight at 60 °C, and TLC monitoring showed complete consumption of the starting material. After cooling to room temperature, saturated brine was added, precipitating an insoluble solid. The solid was collected by vacuum filtration and dried. The crude product was purified by column chromatography (eluent: petroleum ether / CH₂Cl₂ = 2:1, v / v) to give the target product V-8 as a pale yellow solid, in 76% yield.

[0040] IV-8 is 2,6-dimethylbenzylthiophenol, and product V-8 is a yellow solid with a yield of 76%.

[0041] V-8: yield 76%, yellow solid, 1 H NMR (500 MHz, CDCl3) δ 7.95–7.76 (m,6H), 7.37 (t, J = 7.0 Hz, 2H), 7.32 (d, J = 9.0 Hz, 2H), 7.28–7.17 (m, 8H), 7.13–7.04 (m, 4H), 7.01 (d, J = 7.5 Hz, 2H), 6.99–6.91 (m, 4H), 6.87 (s, 2H), 4.04–3.86 (m, 4H), 2.20–1.81 (m, 12H), 1.00–0.90 (m, 6H) ppm; 13C NMR (125.8 MHz, CDCl3) δ 154.8, 153.8, 152.7, 142.0, 141.1, 134.7, 134.3, 133.7, 133.5, 130.4, 129.9, 129.3, 129.2, 129.0, 128.5, 128.0, 127.6, 126.7, 126.6, 125.9,124.7, 123.5, 120.8, 117.4, 117.2, 116.3, 114.1, 110.6, 64.19, 64.15, 31.6,22.6, 21.9, 14.7, 14.1 ppm. HRMS (ESI) m / z: found, 1047.3268 [M+Na + ]; calcdfor C 68 H 52 N₂O₄S₂ + Na + , 1047.3261. The target compounds V-1 to V-8 synthesized in Examples 2-9 above have infrared spectra in the range of ~2240 cm⁻¹. -1 The presence of characteristic absorption peaks of nitrile groups (-CN) in the vicinity confirms the successful introduction of the tetrafluoroterephthalonitrile unit. In the 1H NMR spectrum, methylene groups (-OCH) bonded to oxygen atoms appear in the vicinity of δ 4.0–3.8 ppm. 2- The presence of a quartet signal and a triplet signal of methyl groups in the δ range of 1.0–0.8 ppm confirms the existence of a chiral binaphthol unit. Furthermore, the signal differences between different compounds in the aromatic and aliphatic regions are consistent with the structures of the different introduced nucleophiles IV. The errors between the high-resolution mass spectrometry measurements and theoretical calculations are within acceptable limits. Based on the above analysis, the successful synthesis of target compounds V-1 to V-8 can be confirmed.

[0042] Example 10 The optical properties of compounds V-1, V-2, and V-3 were studied.

[0043] (1) Solvation effect: The three compounds were dissolved in solvents of different polarities (such as toluene, dichloromethane, tetrahydrofuran, acetonitrile, etc.), and their fluorescence emission spectra were measured. The results showed that ( Figure 1 , Figure 2 All three compounds exhibited significant solvochromic effects, with the emission spectrum red-shifting as solvent polarity increased, indicating their sensitivity to environmental polarity.

[0044] (2) Aggregation-induced emission enhancement (AIEE) properties: Fluorescence emission of the three compounds in THF / H2O mixed solvents with different water contents was tested. The results showed that ( Figure 3 When the water content is low, the fluorescence is weak; as the water content increases (>70%), the fluorescence intensity is significantly enhanced due to molecular aggregation, exhibiting typical AIEE characteristics.

[0045] (3) Solid-state luminescence: Fluorescence emission of the three compounds in crystalline and powder states was tested. Figure 4 , Figure 5 The results show that it maintains good luminescence performance in the solid state.

[0046] (4) Quantum yield: In toluene solution, the fluorescence quantum yields of V-1, V-2 and V-3 reached 21.3%, 24.4% and 21.4% respectively, showing good luminescence efficiency.

[0047] Example 11 The chiral optical properties of compounds V-1, V-2, and V-3 were studied.

[0048] (1) Circular dichroism (CD) spectroscopy: The CD spectra of three compounds and their enantiomers were tested in toluene solution. The results showed that ( Figure 6 Each enantiomer exhibits a clear mirror Cotton effect, indicating that the material has good ground-state chirality and that the information from the chiral center is successfully transferred to the entire molecule.

[0049] (2) Circularly polarized emission (CPL) spectroscopy: The CPL performance of the three compounds in toluene solution and doped PMMA films was tested. The results showed that ( Figure 6 , Figure 7 All compounds exhibited a clear CPL signal, and the enantiomer signals were mirror images. In toluene solution, the luminescence asymmetry factors |go of V-1, V-2, and V-3 were... lum | 5.9 × 10 -3 3.6×10 -3 and 3.7×10 -3 In PMMA films, its |g lum The values ​​are 3.2 × 10 -3 3.6×10 -3 3.5×10 -3 This indicates that it can still maintain stable chiral luminescence properties in a solid matrix.

[0050] Example 12 Luminescent materials V-1, V-2, and V-3 were mixed with epoxy resin (doping concentration 1.2 wt%) and uniformly coated onto a commercial 365 nm LED chip to fabricate a simple coated LED device. Its electroluminescence (EL) performance was tested. The results showed ( Figure 8 , Figure 9 The resulting devices exhibited emission peaks at 480 nm, 496 nm, and 548 nm, displaying bright cyan to blue-green light. The brightness of the devices steadily increased with increasing driving current, with the highest brightness exceeding 1.0 × 10⁻⁶. 4 cd·m -2 Among them, the V-2-based device achieved a luminance of 32,680 cd·m² at a current of 50 mA. -2 The results show that this type of material has good application prospects in the field of optoelectronic devices.

[0051] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A fluorescent material based on chiral binaphthol, characterized in that, The general structural formula of the fluorescent material is as follows: ; Where X is O, N or S; R is hydrogen, halogen, C1-C6 hydrocarbon group, monocyclic aryl group, amino group, substituted amino group, C1-C6 alkoxy group or fused cyclic substituent.

2. A method for preparing a fluorescent material based on chiral binaphthol as described in claim 1, characterized in that, The preparation method comprises the following steps: (1) The chiral binaphthol derivative was reacted with tetrafluoroterephthalonitrile under alkaline conditions to obtain an intermediate; (2) The intermediate obtained in step (1) is reacted with a nucleophilic reagent under alkaline conditions to obtain the fluorescent material based on chiral binaphthol.

3. The method for preparing fluorescent materials based on chiral binaphthol according to claim 2, characterized in that, The chiral binaphthol derivative mentioned in step (1) is (R) / (S)-ethylbinaphthol, and its structural formula is: .

4. The method for preparing fluorescent materials based on chiral binaphthol according to claim 2, characterized in that, Nucleophile IV is an aromatic or heteroaromatic substituted alcohol, thiol, or amine compound with the following structural formula: .

5. The method for preparing fluorescent materials based on chiral binaphthol according to claim 3, characterized in that, The nucleophile IV is one of p-cresol, o-cresol, 2,6-dimethylphenol, p-bromophenol, o-bromophenol, o-methoxyphenol, 1-naphthol, and 2,6-dimethylthiophenol.

6. The method for preparing fluorescent materials based on chiral binaphthol according to claim 2, characterized in that, In step (1), the molar ratio of the chiral naphthol derivative, tetrafluoroterephthalonitrile and base is 1:(1.8~4.0):(0.05~4.0); in step (2), the molar ratio of intermediate III, nucleophile IV and base is 1:(2~4):(1~6).

7. The method for preparing fluorescent materials based on chiral binaphthol according to claim 2, characterized in that, The base is an inorganic base or an organic base; the inorganic base is selected from carbonates, acetates or hydroxides; the organic base is selected from sodium alkoxide, potassium alkoxide, piperidine, morpholine, diethylamine or triethylamine.

8. The method for preparing a fluorescent material based on chiral binaphthol according to claim 2, characterized in that, The reaction is carried out in a solvent selected from at least one of tetrahydrofuran, dioxane, acetonitrile, toluene, N,N-dimethylformamide, and dimethyl sulfoxide.

9. The method for preparing a fluorescent material based on chiral binaphthol according to claim 2, characterized in that, The reaction temperature is between room temperature and 140 °C, and the reaction time is between 2 and 48 h.

10. The application of a chiral binatol-based fluorescent material according to claim 1 or a chiral binatol-based fluorescent material prepared by the preparation method according to any one of claims 2 to 7, characterized in that, The applications are in the preparation of optoelectronic devices, anti-counterfeiting materials, fluorescent inks, circularly polarized light-emitting materials, 3D display materials, information encryption materials, biological probes, or biological imaging reagents.

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