Circularly polarized luminescent material, preparation method and circularly polarized luminescence reversible switching method

Abstract

The invention belongs to the technical field of organic light-emitting materials, and particularly relates to a circularly polarized light-emitting material, a preparation method and a circularly polarized light-emitting reversible switching method. The preparation method comprises the following steps: dissolving reaction raw materials DTE and [6] helicene-2Br, a palladium catalyst, a ligand, a phase transfer catalyst and inorganic alkali in a solvent in a protective gas atmosphere, and carrying out SuzukiMiyaura coupling reaction to prepare the circularly polarized luminescent material. The material conformation can be reversibly switched between an open-loop state and a closed-loop state through 520 nm and 356 nm illumination cycle stimulation, so that the opening and closing of a circularly polarized light (CPL) signal are realized, and molecules in the open-loop state have a high asymmetric emission factor. The invention has the advantages of non-contact regulation, high sensitivity and excellent reversibility, and is suitable for the fields of optical devices, display technologies and information storage.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic luminescent materials, and in particular relates to a circularly polarized luminescent material, a preparation method and a method for reversibly switching circularly polarized luminescence. Background Art

[0002] Circularly polarized luminescence (CPL) materials, due to their unique optical properties, show great potential for applications in optical devices, display technology, information storage, and bioimaging. However, existing CPL materials generally suffer from insufficient responsiveness to external stimuli, making it difficult to dynamically control their luminescence properties, which severely restricts their further development and practical application.

[0003] Currently, several technologies attempt to manipulate CPL performance through changes in temperature, electric field, or chemical environment. However, these methods typically require direct contact with the material or rely on complex equipment, resulting in cumbersome operations and limited application scenarios. Therefore, developing a technology that can dynamically control CPL performance remotely and contactlessly has become a key challenge in this field.

[0004] Light, as a clean energy source, offers significant advantages, including non-contact operation, high spatiotemporal resolution, rapid response, reversibility, and environmental friendliness, making it an ideal stimulus for manipulating CPL performance. Although studies have reported cases of CPL on / off control through light, the asymmetric emission factors (glum) of these materials are generally low (glum < 0.01), making it difficult to meet the demand for high-performance CPL materials in practical applications. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention provides a circularly polarized luminescent material, a preparation method and a method for reversibly switching circularly polarized luminescence. The circularly polarized luminescent material prepared by the present invention has both high glum and light-controlled on / off, which can not only break through the limitations of existing technologies, but also provide more efficient and flexible technical solutions for optical devices, display technology, information storage and biological imaging.

[0006] The present invention is specifically implemented through the following technical solutions.

[0007] The present invention provides a method for preparing a circularly polarized luminescent material, comprising the following steps: Under a protective gas atmosphere, the reaction raw materials DTE and [6] helixene-2Br, palladium catalyst, ligand, phase transfer catalyst and inorganic base were dissolved in a solvent, and circularly polarized luminescent materials were prepared through Suzuki-Miyaura coupling reaction.

[0008] Wherein, DTE is 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), or 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane).

[0009] Preferably, the molar ratio of DTE to [6] helixene-2Br is 1:1, the molar ratio of DTE to palladium catalyst is 1.25 mmol: 0.1~0.3 mmol, the molar ratio of DTE to ligand is 1.25 mmol: 0.2~0.5 mmol, the molar ratio of DTE to phase transfer catalyst is 1.25 mmol: 0.2~0.5 mmol, and the molar ratio of DTE to inorganic base is 1.25 mmol: 20~50 mmol.

[0010] Preferably, the reaction temperature of the Suzuki-Miyaura coupling reaction is 70-90 °C, and the reaction time is 3-5 days.

[0011] Preferably, the palladium catalyst is at least one of PdCl2, PdCl2(dppf)CH2Cl2 or Pd2(dba)3, the ligand is SPhos (2-dicyclohexylphosphine-2′,6′-dimethoxybiphenyl), the phase transfer catalyst is TBAB (tetrabutylammonium bromide), the inorganic base is K2CO3, and the solvent is a mixed solvent of toluene and water, with a volume ratio of toluene to water of 25-35 mL:4-5 mL.

[0012] Preferably, after the Suzuki-Miyaura coupling reaction is completed, the reaction system is concentrated, the precipitate is dissolved in an organic solvent, then washed with brine, the organic layer is collected, dried and the solvent of the organic layer is removed, and the product is purified by silica gel column chromatography, and the eluent is a mixture of petroleum ether and dichloromethane in a volume ratio of 10:1 to 3:1 to obtain a circularly polarized luminescent material.

[0013] Preferably, when DTE is 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), the circularly polarized luminescent material after purification by silica gel column chromatography is m -[2+2] and m -[3+3].

[0014] m The chemical structure of -[2+2] is: .

[0015] m The chemical structure of -[3+3] is: .

[0016] Will m -[2+2] was separated by chiral chromatography using a mobile phase consisting of a mixed solution of n-hexane, tetrahydrofuran, and ethanol in a volume ratio of 92:5:3. Enantiomers were obtained at retention times of 9.4 min and 12.2 min, respectively. m -[2+2]- PP and enantiomers m -[2+2]- MM .

[0017] Will m -[3+3] was separated by chiral chromatography using a mobile phase consisting of a mixed solution of n-hexane, dichloromethane, and ethanol in a volume ratio of 90:6:4. Enantiomers were obtained at retention times of 11.4 min, 12.8 min, and 16.5 min, respectively. m -[3+3]- MMM and m -[3+3]- MMP mixture m -[3+3]- MMM+MMP, Enantiomers m -[3+3]- PPM and enantiomers m -[3+3]- PPP.

[0018] Preferably, when DTE is 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), the circularly polarized luminescent material after purification by silica gel column chromatography is p -[2+2] and p -[3+3]; p The chemical structure of -[2+2] is: .

[0019] p The chemical structure of -[3+3] is: .

[0020] Will p -[2+2] was separated by chiral chromatography using a mobile phase consisting of a mixed solution of n-hexane, dichloromethane, and ethanol in a volume ratio of 90:5:5. The enantiomers were finally obtained at retention times of 9.0 min and 11.6 min, respectively. p-[2+2]- PP and p -[2+2]- MM .

[0021] Will p -[3+3] was separated by chiral chromatography using a mobile phase consisting of a mixed solution of n-hexane, dichloromethane, and ethanol in a volume ratio of 85:10:5. The enantiomers were finally obtained at a retention time of 4.1 min to 6 min. p -[3+3]- MMM 、 p -[3+3]- MMP and p -[3+3]- PPM The enantiomers were obtained at 6.5 min. p -[3+3]- PPP .

[0022] The synthesis method of DTE comprises the following steps: S1. Under protective atmosphere, using m-xylene as solvent, in the presence of palladium catalyst, ligand 2,2'-bipyridine and inorganic base Ag2CO3, 3,3'-(3,3,4,4,5,5-hexafluoro-1-cyclopentene-1,2-diyl)bis[2-methylthiophene] was reacted with m-bromoiodobenzene or p-bromoiodobenzene to prepare 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene) or 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene), respectively.

[0023] S2. Under protective atmosphere, using toluene as solvent, in the presence of palladium catalyst and inorganic base potassium acetate, 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene) or 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene) is reacted with diboronic acid pinacol ester to prepare DTE1: 2,2'-((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) respectively. and DTE2: 2,2′-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane).

[0024] Preferably, in S1, the molar ratio of 3,3′-(3,3,4,4,5,5-hexafluoro-1-cyclopentene-1,2-diyl)bis[2-methylthiophene] to m-bromoiodobenzene or p-bromoiodobenzene is 5:11-22, the molar ratio of Ag2CO3 to m-bromoiodobenzene or p-bromoiodobenzene is 1:1, the molar ratio of the palladium catalyst to 2,2′-bipyridine is 1:1, and the molar ratio of the palladium catalyst to 3,3′-(3,3,4,4,5,5-hexafluoro-1-cyclopentene-1,2-diyl)bis[2-methylthiophene] is 4-8:5. The reaction temperature is 120°C-140°C, and the reaction is stirred for 24-72 hours.

[0025] Preferably, in S2, the molar ratio of 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene) or 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene) to diboric acid pinacol ester is 1:2~4; the molar ratio of potassium acetate to diboric acid pinacol ester is 2~4:1~2; the molar ratio of palladium catalyst to 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene) or 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene) is 0.1~0.2:1; the reaction temperature is 90°C~110°C, and the reaction time is 8~16 hours.

[0026] Preferably, in S1 and S2, the palladium catalyst is selected from at least one of PdCl2, PdCl2(dppf)CH2Cl2 or Pd2(dba)3.

[0027] The present invention also provides a method for reversibly switching circularly polarized luminescence, which achieves reversible switching of circularly polarized luminescence through light stimulation, comprising the following steps: Applying 365 nm light to the circularly polarized luminescent material to convert it from an open-ring conformation to a closed-ring conformation, thereby turning off the circularly polarized luminescence; Applying 520 nm light to the closed-ring conformation material will restore it to the open-ring conformation and turn on circularly polarized luminescence; The asymmetric emission factor of the open-ring conformation is greater than 0.01.

[0028] The ring-opening conformation (except p -[2+2]) retains more than 90% of the initial value after at least 10 cycles of switching.

[0029] The present invention provides a light-switchable circularly polarized luminescent material composition, characterized in that it comprises the m -[2+2], m -[3+3], p -[2+2] orp -[3+3], or its chirally separated enantiomers.

[0030] Compared with the prior art, the present invention has the following beneficial effects: The present invention prepares a circularly polarized luminescent material. The reaction raw materials DTE and [6] helixene-2Br, a palladium catalyst, a ligand, a phase transfer catalyst and an inorganic base are dissolved in a solvent, and the circularly polarized luminescent material is prepared through a Suzuki-Miyaura coupling reaction; wherein DTE is 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), or 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane). The circularly polarized luminescent material prepared by the present invention has both a high asymmetric emission factor and a light-controlled on / off characteristic, which is specifically embodied in:

[0031] Through light stimulation, CPL switching can be achieved without direct contact with the material, demonstrating remote control. The material exhibits a high asymmetric emission factor (>0.01). The material responds rapidly to light stimulation, with significant changes in the CPL signal and excellent reversibility.

[0032] This invention not only breaks through the limitations of existing technologies, but also provides more efficient and flexible technical solutions for fields such as optical devices, display technology, information storage and biological imaging, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is the synthetic reaction formula for preparing 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene) in Example 1.

[0034] Figure 2 The synthetic reaction formula for preparing 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) according to Example 1 is shown.

[0035] Figure 3 Prepared as Example 1 m -[2+2] and m -[3+3] synthesis reaction formula.

[0036] Figure 4This is the H NMR spectrum of 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene) prepared in Example 1.

[0037] Figure 5 This is the H NMR spectrum of 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) prepared in Example 1.

[0038] Figure 6 Prepared in Example 1 m -[2+2] H NMR spectrum.

[0039] Figure 7 Prepared in Example 1 m -[3+3] H NMR spectrum.

[0040] Figure 8 Prepared in Example 1 m -[2+2] high-resolution mass spectrometry.

[0041] Figure 9 Prepared in Example 1 m -[3+3] high-resolution mass spectrometry.

[0042] Figure 10 Prepared in Example 1 m Schematic diagram of the -[2+2] conformation and CPL switching.

[0043] Figure 11 Prepared in Example 1 m Schematic diagram of the conformation and CPL switching of -[3+3].

[0044] Figure 12 Prepared in Example 1 m -[2+2] reversible cyclic switching test between "open ring" and "closed ring" conformations.

[0045] Figure 13 Prepared in Example 1 m -[3+3] reversible cyclic switching test between "open ring" and "closed ring" conformations.

[0046] Figure 14 Prepared in Example 1 m -[2+2] circularly polarized luminescence spectrum, including the on and off of circularly polarized luminescence.

[0047] Figure 15 Prepared in Example 1 m -[3+3] circularly polarized luminescence spectrum, including the on and off of circularly polarized luminescence.

[0048] Figure 16 Prepared in Example 1 m -[2+2] asymmetric emission factor.

[0049] Figure 17 Prepared in Example 1 m -[3+3] asymmetric emission factor. DETAILED DESCRIPTION

[0050] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention is further described below with reference to specific examples and accompanying drawings. However, the examples are not intended to limit the present invention. The experimental methods and detection methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0051] The present invention provides a method for preparing a circularly polarized luminescent material, comprising the following steps: Under a protective gas atmosphere, the reaction raw materials DTE and [6] helixene-2Br, palladium catalyst, ligand, phase transfer catalyst and inorganic base were dissolved in a solvent, and circularly polarized luminescent materials were prepared through Suzuki-Miyaura coupling reaction.

[0052] Wherein, DTE is 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), or 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane).

[0053] When DTE is 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), the circularly polarized luminescent material after purification by silica gel column chromatography is m -[2+2] and m -[3+3].

[0054] When DTE is 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), the circularly polarized luminescent material after purification by silica gel column chromatography is p -[2+2] and p -[3+3].

[0055] External stimulation: by remotely applying external optical cycle stimulation (365 nm and 520 nm), m -[2+2] and m -[3+3], p -[2+2] and p The molecular conformation of -[3+3] can be reversibly switched between "closed ring" and "open ring".

[0056] Performance switching: Under the cycle of external light (365 nm and 520 nm), m -[2+2] and m -[3+3], p -[2+2] and p -[3+3] CPL reversibly switches between “off” and “on” states.

[0057] The present invention will be specifically described below through the following examples.

[0058] Example 1 1) Preparation of 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene), the synthetic route is as follows Figure 1 shown.

[0059] Under a nitrogen atmosphere, the catalyst PdCl2 (5.45 mmol) and the ligand 2,2'-bipyridine (5.45 mmol, forming a catalytically active palladium complex with PdCl2) were added. Subsequently, dry m-xylene (8.5 mL) was added, and the mixture was heated at 70°C for 30 minutes. Next, the reactant 3,3′-(3,3,4,4,5,5-hexafluoro-1-cyclopentene-1,2-diyl)bis[2-methylthiophene] (5 mmol), the reactant m-bromoiodobenzene (16.35 mmol), the inorganic base Ag2CO3 (16.35 mmol, to assist in deprotonation and capture halogens, driving the reaction), and dry m-xylene solvent (10 mL) were added in sequence. The mixture was heated to 130°C and stirred for 48 hours to perform the C–H arylation reaction. After the reaction, the mixture was cooled to room temperature and filtered through a layer of silica gel with dichloromethane (DCM). The solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether, PE) to obtain 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene) as a white solid (yield 42%). Figure 4 shown.

[0060] 2) Preparation of 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), the synthetic route is as follows: Figure 2 shown.

[0061] Under nitrogen atmosphere, the reactant 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene) (1 mmol), the reactant pinacol diboronate (3 mmol), the inorganic base potassium acetate (KOAc, 6 mmol) and the catalyst PdCl2(dppf)CH2Cl2 (0.1 mmol) were suspended in 24 mL of toluene solvent. The reaction mixture was heated to 90°C and maintained for 12 hours to perform the Suzuki-Miyaura coupling reaction. After the reaction was completed, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / dichloromethane, PE / DCM: 2 / 1 to 1 / 2) to obtain DTE1 as a colorless solid (yield 92%). H NMR spectrum as shown Figure 5 shown.

[0062] 3) m -[2+2] and m -[3+3] preparation, the synthetic route is as follows Figure 3 shown.

[0063] Under nitrogen atmosphere, reactant [6] helixene-2Br (1.25 mmol), reactant 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (1.25 mmol), catalyst Pd2(dba)3 (0.2 mmol), ligand SPhos (0.4 mmol), phase transfer catalyst TBAB (0.4 mmol), inorganic base K2CO3 (37.5 mmol), toluene solvent (630 mL) and water (90 mL) were added in sequence and degassed three times by freeze-thaw cycle method. The reaction mixture was stirred at 80 ° C for 4 days to carry out Suzuki-Miyaura coupling reaction. After the reaction was completed, the mixture was concentrated under reduced pressure, and the collected precipitate was dissolved with dichloromethane (DCM) and washed with brine. The organic layer was dried over Na2SO4 and the solvent was evaporated. The residue was purified by silica gel column chromatography (petroleum ether / dichloromethane, PE / DCM = 10 / 1 to 3 / 1) to give m -[2+2] (yield: 11%) and m -[3+3] (yield: 9%), all as white solids.

[0064] 4) m -[2+2] chiral separation A CHIRAL EnantoRak column was used for separation. The column had an inner diameter of 4.6 mm, a column length of 250 mm, a filler particle size of 5 μm, and a mobile phase of a mixed solution of n-hexane: tetrahydrofuran: ethanol = 92:5:3. The enantiomers were finally obtained at retention times of 9.4 min and 12.2 min, respectively. m -[2+2]- PP and m -[2+2]- MM .

[0065] 5) m -Chiral separation of [3+3] A CHIRAL EnantoRak column was used for separation. The column had an inner diameter of 4.6 mm, a column length of 250 mm, a filler particle size of 5 μm, and a mobile phase consisting of a mixture of n-hexane: dichloromethane: ethanol = 90:6:4. The enantiomers were finally obtained at retention times of 11.4 min, 12.8 min, and 16.5 min, respectively. m -[3+3]- MMM+MMP ( m -[3+3]- MMM and m -[3+3]- MMP mixture of m -[3+3]- PPM and m -[3+3]- PPP .

[0066] 6) m -[2+2] and m -[3+3] CPL on / off First, irradiate with 365 nm light m -[2+2] and m -[3+3], molecules that acquire a closed-ring conformation and have CPL in the "off" state m -[2+2]- PP -c, m -[2+2]- MM -c 、m -[3+3]- PPP -c, m -[3+3]- PPM -c and m -[3+3]- MMM+ MMP-c, respectively test the CPL signal of the above closed-loop conformation molecules; then use 520 nm light to irradiate the above molecules to restore them to the open-loop conformation and the CPL is in the "on" state m -[2+2]- PP 、 m -[2+2]- MM, m -[3+3]- PPP 、 m -[3+3]- PPM and m -[3+3]- MMM+MMP , respectively tested the CPL signals of the above-mentioned open-ring conformation molecules.

[0067] Example 2 1) Preparation of 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene) Under a nitrogen atmosphere, the catalyst PdCl2 (5.45 mmol) and the ligand 2,2'-bipyridine (5.45 mmol) were added. Subsequently, dry m-xylene (8.5 mL) was added, and the mixture was heated at 70 °C for 30 minutes. Next, the reactant 3,3′-(3,3,4,4,5,5-hexafluoro-1-cyclopentene-1,2-diyl)bis[2-methylthiophene] (5 mmol), the reactant p-bromoiodobenzene (16.35 mmol), the inorganic base Ag2CO3 (16.35 mmol), and dry m-xylene solvent (10 mL) were added sequentially. The mixture was heated to 130 °C and stirred for 48 hours to perform the C–H arylation reaction. After completion of the reaction, the mixture was cooled to room temperature and filtered through a layer of silica gel with dichloromethane (DCM). The solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether, PE) to give 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene) as a white solid (yield 41%).

[0068] 2) Preparation of 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) Under a nitrogen atmosphere, the reactant 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene) (1 mmol), the reactant pinacol diboronate (3 mmol), the inorganic base potassium acetate (KOAc, 6 mmol), and the catalyst PdCl2(dppf)CH2Cl2 (0.1 mmol) were suspended in 24 mL of toluene. The reaction mixture was heated to 90 °C for 12 hours to perform the Suzuki-Miyaura coupling reaction. After completion of the reaction, the solvent was removed under reduced pressure and the crude product was purified by silica gel column chromatography (petroleum ether / dichloromethane, PE / DCM: 2 / 1 to 1 / 2) to obtain 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), abbreviated as DTE2, as a colorless solid (yield 90%).

[0069] 3) p -[2+2] and p Preparation of -[3+3] Under nitrogen atmosphere, reactant [6] helixene-2Br (1.25 mmol), reactant 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (1.25 mmol), catalyst Pd2(dba)3 (0.2 mmol), ligand SPhos (0.4 mmol), phase transfer catalyst TBAB (0.4 mmol), inorganic base K2CO3 (37.5 mmol), toluene solvent (630 mL) and water (90 mL) were added in sequence and degassed three times by freeze-thaw cycle method. The reaction mixture was stirred at 80 °C for 4 days to perform Suzuki-Miyaura coupling reaction. After the reaction was completed, the mixture was concentrated under reduced pressure, and the collected precipitate was dissolved with dichloromethane (DCM) and washed with brine. The organic layer was dried over Na2SO4 and the solvent was evaporated. The residue was purified by silica gel column chromatography (petroleum ether / dichloromethane, PE / DCM = 10 / 1 to 3 / 1) to give p -[2+2] (yield: 11%) and p -[3+3] (yield: 7%), all as white solids.

[0070] 4) p -[2+2] chiral separation A CHIRAL EnantoRak column was used for separation. The column had an inner diameter of 4.6 mm, a column length of 250 mm, a filler particle size of 5 μm, and a mobile phase of a mixed solution of n-hexane: dichloromethane: ethanol = 90:5:5. The enantiomers were finally obtained at retention times of 9.0 min and 11.6 min, respectively. p -[2+2]- PP and p -[2+2]- MM .

[0071] 5) p -Chiral separation of [3+3] A CHIRAL EnantoRak column was used for separation. The column had an inner diameter of 4.6 mm, a column length of 250 mm, a filler particle size of 5 μm, and a mobile phase of a mixed solution of n-hexane: dichloromethane: ethanol = 85:10:5. The final product was obtained at a retention time of 4.1-6 min. p -[3+3]- MMM 、 p -[3+3]- MMP and p -[3+3]- PPM The enantiomer was obtained at a retention time of 6.5 min. p -[3+3]- PPP .

[0072] 6) p -[2+2] and p -[3+3] CPL switching test First, irradiate with 365 nm light p -[2+2] and p -[3+3], molecules that acquire a closed-ring conformation and have CPL in the "off" state p -[2+2]- PP -c, p -[2+2]- MM -c and p -[3+3]- PPP -c, respectively test the CPL signal of the above closed-loop conformation molecules; then use 520 nm light to irradiate the above molecules to restore them to the open-loop conformation and the CPL is in the "on" state p -[2+2]- PP 、 p -[2+2]- MM, p -[3+3]- PPP , respectively tested the CPL signals of the above-mentioned open-ring conformation molecules.

[0073] m -[2+2] H NMR spectrum is as follows Figure 6 As shown, m -[3+3] H NMR spectrum is as follows Figure 7 As shown, m -[2+2] high-resolution mass spectrometry Figure 8 shown. m -[3+3] high-resolution mass spectrometry Figure 9 shown.

[0074] m The conformation of -[2+2] and the schematic diagram of CPL switching are shown in Figure 10 As shown, m The conformation of -[3+3] and the schematic diagram of CPL switching are shown in Figure 11 As shown. Similarly, p -[2+2] and p The -[3+3] conformation also has a similar relationship with CPL switching as above, that is, by remotely applying external light cycle stimulation (365 nm and 520 nm), m -[2+2], m -[3+3], p -[2+2] and p The molecular conformation of -[3+3] can be reversibly switched between "closed ring" and "open ring". Under the cyclic irradiation of external light (365 nm and 520 nm), m -[2+2], m -[3+3], p -[2+2] and p -[3+3] CPL reversibly switches between “off” and “on” states.

[0075] Figure 12 for m -[2+2] reversible cyclic switching test between "open ring" and "closed ring" conformations. Figure 12 Visible, characterized by UV-visible absorption spectroscopy m The reversible switching of -[2+2] between “open loop” and “closed loop” showed no obvious fatigue degradation after 100 cycles.

[0076] Figure 13 for m -[3+3] reversible cyclic switching test between "open ring" and "closed ring" conformations. Figure 13 Visible, characterized by UV-visible absorption spectroscopy m -[3+3] reversibly switches between “open loop” and “closed loop” without showing obvious fatigue degradation after 100 cycles.

[0077] Figure 14 form -[2+2] circularly polarized luminescence spectrum, including the on and off of circularly polarized luminescence. Figure 14 It can be seen that after irradiation with 365 nm light, the "closed ring" conformation molecule is formed. m The CPL signal of -[2+2]-c is "off"; after irradiation with 520 nm light, the "open ring" conformation of the molecule is formed m -[2+2]'s CPL signal is "on".

[0078] Figure 15 for m -[3+3] circularly polarized luminescence spectrum, including the on and off of circularly polarized luminescence. Figure 15 It can be seen that after irradiation with 365 nm light, the "closed ring" conformation molecule is formed. m The CPL signal of -[3+3]-c is "off"; after irradiation with 520 nm light, the "open ring" conformation of the molecule is formed m -[3+3]'s CPL signal is "on".

[0079] Figure 16 for m -[2+2] asymmetric emission factor. Figure 16 visible, m -[2+2] enantiomers m -[2+2]- PP and m -[2+2]- MM The absolute values ​​of the asymmetry factors are all greater than 0.011.

[0080] Figure 17 for m -[3+3] asymmetric emission factor. Figure 17 visible, m -[3+3] enantiomer m -[3+3]- PPP The absolute value of the asymmetry factor is approximately 0.013.

[0081] Example 3 1) Preparation of 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene): Under a nitrogen atmosphere, the catalyst PdCl2 (4 mmol) and the ligand 2,2'-bipyridine (4 mmol, forming a catalytically active palladium complex with PdCl2) were added. Subsequently, dry m-xylene (8.5 mL) was added, and the mixture was heated at 70°C for 30 minutes. Next, the reactant 3,3′-(3,3,4,4,5,5-hexafluoro-1-cyclopentene-1,2-diyl)bis[2-methylthiophene] (5 mmol), the reactant m-bromoiodobenzene (11 mmol), the inorganic base Ag2CO3 (11 mmol, to assist in deprotonation and capture halogens, driving the reaction), and dry m-xylene solvent (10 mL) were added in sequence. The mixture was heated to 120°C and stirred for 72 hours to perform the C–H arylation reaction. After the reaction, the mixture was cooled to room temperature and filtered through a layer of silica gel with dichloromethane (DCM). The solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether, PE) to obtain 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene) as a white solid (yield 43%). The H NMR spectrum was similar to that of Example 1.

[0082] 2) Preparation of 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane): Under a nitrogen atmosphere, the reactant 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene) (1 mmol), the reactant pinacol diboronate (2 mmol), the inorganic base potassium acetate (KOAc, 4 mmol), and the catalyst PdCl2(dppf)CH2Cl2 (0.2 mmol) were suspended in 24 mL of toluene. The reaction mixture was heated to 110°C for 16 hours to perform a Suzuki-Miyaura coupling reaction. After completion of the reaction, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / dichloromethane, PE / DCM: 2 / 1 to 1 / 2) to obtain DTE1 as a colorless solid (yield 92.5%). The H NMR spectrum was similar to that of Example 1.

[0083] 3) m -[2+2] and m Preparation of -[3+3]: Under nitrogen atmosphere, reactant [6] helixene-2Br (1.25 mmol), reactant 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (1.25 mmol), catalyst Pd2(dba)3 (0.1 mmol), ligand SPhos (0.2 mmol), phase transfer catalyst TBAB (0.2 mmol), inorganic base K2CO3 (20 mmol), toluene solvent (630 mL) and water (90 mL) were added in sequence and degassed three times by freeze-thaw cycle method. The reaction mixture was stirred at 80 ° C for 4 days to carry out Suzuki-Miyaura coupling reaction. After the reaction was completed, the mixture was concentrated under reduced pressure, and the collected precipitate was dissolved with dichloromethane (DCM) and washed with brine. The organic layer was dried over Na2SO4 and the solvent was evaporated. The residue was purified by silica gel column chromatography (petroleum ether / dichloromethane, PE / DCM = 10 / 1 to 3 / 1) to give m -[2+2] (yield: 12%) and m -[3+3] (yield: 10%), all as white solids.

[0084] 4) m The chiral separation steps of -[2+2] are the same as those in Example 1.

[0085] 5) m The chiral separation steps of -[3+3] are the same as those in Example 1.

[0086] Example 4 1) Preparation of 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene): Under a nitrogen atmosphere, the catalyst PdCl2 (8 mmol) and the ligand 2,2'-bipyridine (8 mmol, forming a catalytically active palladium complex with PdCl2) were added. Subsequently, dry m-xylene (8.5 mL) was added, and the mixture was heated at 70°C for 30 minutes. Next, the reactant 3,3′-(3,3,4,4,5,5-hexafluoro-1-cyclopentene-1,2-diyl)bis[2-methylthiophene] (5 mmol), the reactant m-bromoiodobenzene (22 mmol), the inorganic base Ag2CO3 (16.35 mmol, to assist in deprotonation and capture halogens, driving the reaction), and dry m-xylene solvent (10 mL) were added in sequence. The mixture was heated to 140°C and stirred for 24 hours to perform the C–H arylation reaction. After the reaction, the mixture was cooled to room temperature and filtered through a layer of silica gel with dichloromethane (DCM). The solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether, PE) to obtain 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene) as a white solid (yield 42.5%). The H NMR spectrum was similar to that of Example 1.

[0087] 2) Preparation of 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane): Under a nitrogen atmosphere, the reactant 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene) (1 mmol), the reactant pinacol diboronate (4 mmol), the inorganic base potassium acetate (KOAc, 8 mmol), and the catalyst PdCl2(dppf)CH2Cl2 (0.1 mmol) were suspended in 24 mL of toluene. The reaction mixture was heated to 100°C for 8 hours to perform a Suzuki-Miyaura coupling reaction. After completion of the reaction, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / dichloromethane, PE / DCM: 2 / 1 to 1 / 2) to obtain DTE1 as a colorless solid (yield 92.7%). The H NMR spectrum was similar to that of Example 1.

[0088] 3) m -[2+2] and m Preparation of -[3+3]: Under nitrogen atmosphere, reactant [6] helixene-2Br (1.25 mmol), reactant 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (1.25 mmol), catalyst Pd2(dba)3 (0.3 mmol), ligand SPhos (0.5 mmol), phase transfer catalyst TBAB (0.5 mmol), inorganic base K2CO3 (50 mmol), toluene solvent (630 mL) and water (90 mL) were added in sequence and degassed three times by freeze-thaw cycle method. The reaction mixture was stirred at 90 ° C for 3 days to carry out Suzuki-Miyaura coupling reaction. After the reaction was completed, the mixture was concentrated under reduced pressure, and the collected precipitate was dissolved with dichloromethane (DCM) and washed with brine. The organic layer was dried over Na2SO4 and the solvent was evaporated. The residue was purified by silica gel column chromatography (petroleum ether / dichloromethane, PE / DCM = 10 / 1 to 3 / 1) to give m -[2+2] (yield: 12%) and m -[3+3] (yield: 10%), all as white solids.

[0089] 4) m The chiral separation steps of -[2+2] are the same as those in Example 1.

[0090] 5) m The chiral separation steps of -[3+3] are the same as those in Example 1.

[0091] The properties of the materials prepared in Examples 3 and 4 are similar to those in Example 1 and will not be described in detail.

[0092] Example 5 1) Preparation of 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene) Under a nitrogen atmosphere, the catalyst PdCl2 (4 mmol) and the ligand 2,2'-bipyridine (4 mmol) were added. Subsequently, dry m-xylene (8.5 mL) was added, and the mixture was heated at 70°C for 30 minutes. Next, the reactant 3,3′-(3,3,4,4,5,5-hexafluoro-1-cyclopentene-1,2-diyl)bis[2-methylthiophene] (5 mmol), the reactant p-bromoiodobenzene (11 mmol), the inorganic base Ag2CO3 (11 mmol), and dry m-xylene solvent (10 mL) were added sequentially. The mixture was heated to 120°C and stirred for 72 hours to perform the C–H arylation reaction. After completion of the reaction, the mixture was cooled to room temperature and filtered through a layer of silica gel with dichloromethane (DCM). The solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether, PE) to give 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene) as a white solid (yield 42%).

[0093] 2) Preparation of 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) Under a nitrogen atmosphere, the reactant 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene) (1 mmol), the reactant pinacol diboronate (2 mmol), the inorganic base potassium acetate (KOAc, 4 mmol), and the catalyst PdCl2(dppf)CH2Cl2 (0.2 mmol) were suspended in 24 mL of toluene. The reaction mixture was heated to 110°C for 16 hours to perform the Suzuki-Miyaura coupling reaction. After completion of the reaction, the solvent was removed under reduced pressure and the crude product was purified by silica gel column chromatography (petroleum ether / dichloromethane, PE / DCM: 2 / 1 to 1 / 2) to give 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), abbreviated as DTE2, as a colorless solid (yield 91%).

[0094] 3) p -[2+2] and p Preparation of -[3+3] Under nitrogen atmosphere, reactant [6] helixene-2Br (1.25 mmol), reactant 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (1.25 mmol), catalyst Pd2(dba)3 (0.1 mmol), ligand SPhos (0.2 mmol), phase transfer catalyst TBAB (0.2 mmol), inorganic base K2CO3 (20 mmol), toluene solvent (630 mL) and water (90 mL) were added in sequence and degassed three times by freeze-thaw cycle method. The reaction mixture was stirred at 80 ° C for 4 days to carry out Suzuki-Miyaura coupling reaction. After the reaction was completed, the mixture was concentrated under reduced pressure, and the collected precipitate was dissolved with dichloromethane (DCM) and washed with brine. The organic layer was dried over Na2SO4 and the solvent was evaporated. The residue was purified by silica gel column chromatography (petroleum ether / dichloromethane, PE / DCM = 10 / 1 to 3 / 1) to give p -[2+2] (yield: 12%) and p -[3+3] (yield: 8%), all were white solids.

[0095] 4) p The chiral separation steps of -[2+2] are the same as those in Example 2.

[0096] 5) p The chiral separation steps of -[3+3] are the same as those in Example 2.

[0097] Example 6 1) Preparation of 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene) Under a nitrogen atmosphere, the catalyst PdCl2 (8 mmol) and the ligand 2,2'-bipyridine (8 mmol) were added. Subsequently, dry m-xylene (8.5 mL) was added, and the mixture was heated at 70°C for 30 minutes. Next, the reactant 3,3′-(3,3,4,4,5,5-hexafluoro-1-cyclopentene-1,2-diyl)bis[2-methylthiophene] (5 mmol), the reactant p-bromoiodobenzene (22 mmol), the inorganic base Ag2CO3 (22 mmol), and dry m-xylene solvent (10 mL) were added sequentially. The mixture was heated to 140°C and stirred for 24 hours to perform the C–H arylation reaction. After completion of the reaction, the mixture was cooled to room temperature and filtered through a layer of silica gel with dichloromethane (DCM). The solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether, PE) to give 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene) as a white solid (yield 42%).

[0098] 2) Preparation of 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) Under a nitrogen atmosphere, the reactant 3,3'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene) (1 mmol), the reactant pinacol diboronate (4 mmol), the inorganic base potassium acetate (KOAc, 8 mmol), and the catalyst PdCl2(dppf)CH2Cl2 (0.1 mmol) were suspended in 24 mL of toluene. The reaction mixture was heated to 100°C for 8 hours to perform the Suzuki-Miyaura coupling reaction. After completion of the reaction, the solvent was removed under reduced pressure and the crude product was purified by silica gel column chromatography (petroleum ether / dichloromethane, PE / DCM: 2 / 1 to 1 / 2) to give 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), abbreviated as DTE2, as a colorless solid (yield 91%).

[0099] 3) p -[2+2] and p Preparation of -[3+3] Under nitrogen atmosphere, reactant [6] helixene-2Br (1.25 mmol), reactant 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (1.25 mmol), catalyst Pd2(dba)3 (0.3 mmol), ligand SPhos (0.5 mmol), phase transfer catalyst TBAB (0.5 mmol), inorganic base K2CO3 (50 mmol), toluene solvent (630 mL) and water (90 mL) were added in sequence and degassed three times by freeze-thaw cycle method. The reaction mixture was stirred at 70 ° C for 5 days to carry out Suzuki-Miyaura coupling reaction. After the reaction was completed, the mixture was concentrated under reduced pressure, and the collected precipitate was dissolved with dichloromethane (DCM) and washed with brine. The organic layer was dried over Na2SO4 and the solvent was evaporated. The residue was purified by silica gel column chromatography (petroleum ether / dichloromethane, PE / DCM = 10 / 1 to 3 / 1) to give p -[2+2] (yield: 11%) and p -[3+3] (yield: 8%), all were white solids.

[0100] 4) p The chiral separation steps of -[2+2] are the same as those in Example 2.

[0101] 5) p The chiral separation steps of -[3+3] are the same as those in Example 2.

[0102] The properties of the materials prepared in Examples 5 and 6 are similar to those in Example 2 and will not be described in detail.

[0103] Obviously, those skilled in the art may make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if such changes and modifications of the present invention fall within the scope of the claims and their equivalents, such changes and modifications are intended to be included.

Claims

1. A method for preparing a circularly polarized luminescent material, characterized in that: The following steps are involved: Under a protective gas atmosphere, the reaction raw materials DTE and [6] helixene-2Br, palladium catalyst, ligand, phase transfer catalyst and inorganic base were dissolved in a solvent and a circularly polarized luminescent material was prepared through a Suzuki-Miyaura coupling reaction. Wherein, DTE is 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), or 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane).

2. The preparation method according to claim 1, characterized in that The molar ratio of DTE to [6]helixene-2Br is 1:1, the molar ratio of DTE to palladium catalyst is 1.25:0.1~0.3, the molar ratio of DTE to ligand is 1.25:0.2~0.5, the molar ratio of DTE to phase transfer catalyst is 1.25:0.2~0.5, and the molar ratio of DTE to inorganic base is 1.25:20~50.

3. The preparation method according to claim 1, characterized in that The reaction temperature of the Suzuki-Miyaura coupling reaction is 70°C~90°C, and the reaction time is 3 days~5 days.

4. The preparation method according to claim 1, characterized in that The palladium catalyst is at least one of PdCl2, PdCl2(dppf)CH2Cl2 or Pd2(dba)3, the ligand is SPhos, the phase transfer catalyst is TBAB, the inorganic base is K2CO3, and the solvent is a mixed solvent of toluene and water, with a volume ratio of toluene to water of 25-35:4-5.

5. The preparation method according to claim 1, characterized in that After the Suzuki-Miyaura coupling reaction is completed, the reaction system is concentrated, the precipitate is dissolved in an organic solvent, and then washed, the organic layer is collected, dried and the solvent of the organic layer is removed, and the product is purified by silica gel column chromatography. The eluent is a mixture of petroleum ether and dichloromethane in a volume ratio of 10:1 to 3:1 to obtain a circularly polarized luminescent material.

6. The preparation method according to claim 5, characterized in that When DTE is 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(3,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), the circularly polarized luminescent material after purification by silica gel column chromatography is m -[2+2] and m -[3+3]; m The chemical structure of -[2+2] is: ; m The chemical structure of -[3+3] is: ; Will m -[2+2] was separated by chiral chromatography using a mobile phase consisting of a mixed solution of n-hexane, tetrahydrofuran, and ethanol in a volume ratio of 92:5:

3. Enantiomers were obtained at retention times of 9.4 min and 12.2 min, respectively. m -[2+2]- PP and enantiomers m -[2+2]- MM ; Will m -[3+3] was separated by chiral chromatography using a mobile phase consisting of a mixed solution of n-hexane, dichloromethane, and ethanol in a volume ratio of 90:6:

4. Enantiomers were obtained at retention times of 11.4 min, 12.8 min, and 16.5 min, respectively. m -[3+3]- MMM and m -[3+3]- MMP mixture m -[3+3]- MMM+MMP, Enantiomers m -[3+3]- PPM and enantiomers m -[3+3]- PPP.

7. The preparation method according to claim 5, characterized in that When DTE is 2,2'-(((perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), the circularly polarized luminescent material after purification by silica gel column chromatography is p -[2+2] and p -[3+3]; p The chemical structure of -[2+2] is: ; p The chemical structure of -[3+3] is: ; Will p -[2+2] was separated by chiral chromatography using a mobile phase consisting of a mixed solution of n-hexane, dichloromethane, and ethanol in a volume ratio of 90:5:

5. Enantiomers were obtained at retention times of 9.0 min and 11.6 min, respectively. p -[2+2]- PP and enantiomers p -[2+2]- MM; Will p -[3+3] was separated using a chiral chromatographic column with a mobile phase consisting of a mixed solution of n-hexane, dichloromethane, and ethanol in a volume ratio of 85:10:

5. Enantiomers were obtained at retention times of 4.1 min to 6 min. p -[3+3]- MMM 、 p -[3+3]- MMP and p -[3+3]- PPM The enantiomer was obtained at a retention time of 6.5 min. p -[3+3]- PPP .

8. A circularly polarized luminescent material, characterized in that: The preparation method according to any one of claims 1 to 7 is used to prepare the compound.

9. A method for reversibly switching circularly polarized light emission, characterized in that: The method of achieving reversible switching of circularly polarized luminescence by light stimulation of a circularly polarized luminescent material comprises the following steps: Applying 365 nm light to the circularly polarized luminescent material of claim 8 to convert the circularly polarized luminescent material from an open-loop conformation to a closed-loop conformation, thereby turning off the circularly polarized luminescence; Applying 520 nm light to the closed-ring conformation material causes the circularly polarized luminescent material to return to the open-ring conformation and turn on circularly polarized luminescence.

10. The method according to claim 9, characterized in that The asymmetric emission factor of the open-ring conformation is >0.01.

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