Compounds with high solid-state circularly polarized luminescent activity and methods of synthesis and use thereof

Abstract

This invention belongs to the field of chiral luminescent materials technology, specifically relating to a compound with high solid-state circularly polarized luminescence activity, its synthesis method, and its application. The synthesis method of the compound is as follows: first, a pre-chiral diynyl[2.2] p-cycloaromatic hydrocarbon and benzyl azide undergo an asymmetric azido-yne cycloaddition desymmetry reaction under the action of a catalyst and a chiral ligand to obtain a chiral product. Then, the chiral product is mixed with 1-iodopyrene and subjected to a Sonogashira cross-coupling reaction under the catalysis of Pd(PPh3)4 and CuI to obtain the final product. This synthesis route is simple, efficient, and highly enantioselective. The final product obtained is a planar chiral compound with high solid-state circularly polarized luminescence performance, which can be used to produce solid-state circularly polarized luminescent materials, such as solid-state circularly polarized organic light-emitting diodes, 3D display devices, or optical information encryption materials.

Description

Technical Field

[0001] This invention belongs to the field of chiral luminescent materials technology, specifically relating to a compound with high solid-state circularly polarized luminescence activity, its synthesis method, and its applications. Background Technology

[0002] Circularly polarized emission (CPL) refers to the phenomenon where a chiral luminescent material, upon excitation, directly emits left- or right-handed circularly polarized light. Circularly polarized luminescent materials exhibit enormous application potential in fields such as 3D displays, optical information storage and encryption, chiral sensing, and spintronics. Among numerous chiral luminescent systems, small-molecule organic compounds possessing both high luminescence asymmetry factor (glume) and high fluorescence quantum yield (ΦF), especially materials that can maintain excellent performance in the solid state, are key to realizing high-performance device applications.

[0003] Planar chiral [2.2]-cyclic aromatic hydrocarbons (PCPs) are considered excellent functional molecules for constructing CPL materials due to their rigid chiral framework, stable configuration, and unique photoelectric properties. However, how to efficiently and selectively synthesize specific PCP derivatives with well-defined structures, tunable functions, and excellent solid-state CPL performance remains a challenge. Therefore, developing a synthetic method for efficiently preparing high-performance solid-state CPL-active PCP compounds has important theoretical significance and application value. Summary of the Invention

[0004] To address the aforementioned shortcomings, this invention discloses a compound with high solid-state circularly polarized luminescence activity, its synthesis method, and its applications. By combining asymmetric catalysis and coupling reaction, a planar chiral compound with high solid-state circularly polarized luminescence performance can be obtained with high yield and high enantioselectivity. Furthermore, the planar chiral compound can be used to produce solid-state circularly polarized luminescent materials.

[0005] This invention is achieved using the following technical solution:

[0006] A compound exhibiting high solid-state circularly polarized luminescence activity has the following structural formula:

[0007] .

[0008] The method for synthesizing the compound with high solid-state circularly polarized luminescence activity includes the following steps:

[0009] (1) Under argon protection, the catalyst and chiral ligand were added to the solvent and stirred at room temperature for 1 h to obtain a catalytic system; a mixture of pre-chiral diynyl[2.2]-cyclic aromatic hydrocarbon, azide compound and base was dissolved in the solvent to obtain a mixture, which was then added to the catalytic system and stirred at 0-40°C for 2-6 h. After the reaction was completed, the reaction mixture was diluted with dichloromethane (DCM) and filtered through a diatomaceous earth pad to obtain filtrate A. The residue of filtrate A after vacuum concentration was purified by silica gel column chromatography to obtain a chiral product; the catalyst was any one of Cu(OAc)2 (copper acetate), Cu(HFA)2, Cu(OTf)2, CuTC, CuCl (cuprous chloride), CuBr (cuprous bromide);

[0010] This step involves using a prechiral diynyl[2.2] p-cyclic aromatic hydrocarbon as the starting material, and reacting with benzyl azide in a catalytic system composed of a catalyst and a chiral ligand to undergo an asymmetric azido-alkyne cycloaddition (CuAAC) desymmetry reaction. Based on the prechiral substrate, a single-configuration planar chiral intermediate is obtained, successfully constructing the core planar chiral skeleton of the compound and introducing a terminal alkyne "handle" that can be further derivatized.

[0011] (2) Under argon protection, the chiral product obtained in step (1), 1-iodopyrene, Pd(PPh3)4, CuI and triethylamine were added to the solvent in sequence and mixed evenly. The mixture was then stirred at 20-80°C for 6-24 hours. After the reaction was completed, the reaction mixture was diluted with dichloromethane (DCM) and filtered through a diatomaceous earth pad to obtain filtrate B. The residue of filtrate B after vacuum concentration was purified by silica gel column chromatography to obtain a yellow solid product, namely the compound with high solid-state circular polarization luminescence activity.

[0012] This step utilizes a module to undergo a Sonogashira cross-coupling reaction between its terminal alkyne group and a derivative of the strongly luminescent pyrene group (1-iodopyrene) under the catalysis of Pd(PPh3)4 and CuI to obtain the final target product with a single configuration, while completely maintaining the chiral purity obtained in the first step.

[0013] The structural formula of the prochiral diynyl[2.2]-p-cycloarane is:

[0014] ;

[0015] The azide compound is a benzyl azide compound with the structural formula: Bn-N3;

[0016] The chiral ligand is a ligand having any of the following structures:

[0017] ;

[0018] The structure of the chiral product is as follows:

[0019] .

[0020] Furthermore, the solvent is any one of DCE (dichloroethane), acetonitrile, DCM (dichloromethane), THF (tetrahydrofuran), and toluene.

[0021] Furthermore, the base is any one of DIPEA (N,N-diisopropylethylamine), NaOAc (sodium acetate), t-BuOK (potassium tert-butoxide), and Et3N (triethylamine).

[0022] Further, in step (1), the molar ratio of the prochiral diynyl group [2.2] to the cyclic aromatic hydrocarbon, the catalyst, and the chiral ligand is 1:(0.025~0.1):(0.025~0.1); the equivalence ratio of the azide compound to the prochiral diynyl group [2.2] to the cyclic aromatic hydrocarbon is 1:(1.2~2.0); and the equivalence ratio of the base to the prochiral diynyl group [2.2] to the cyclic aromatic hydrocarbon is 1:(1.0~2.0).

[0023] Further, in step (1), the molar ratio of the prochiral diyne [2.2] to the cycloaromatic hydrocarbon, azide compound, catalyst, chiral ligand and base is 1:1.2:0.1:0.1:1.2; and 0.5 to 1.0 mL of solvent is added to each 0.1 mmol of prochiral diyne [2.2] to the cycloaromatic hydrocarbon.

[0024] Furthermore, in step (2), the molar ratio of the chiral product, 1-iodopyrene, Pd(PPh3)4 and CuI is 1:1.2:0.03:0.05; 0.5 mL of Et3N and 1 mL of solvent are added for every 0.1 mmol of chiral product.

[0025] The compound with high solid-state circularly polarized light-emitting activity can be used to produce solid-state circularly polarized light-emitting materials, such as solid-state circularly polarized organic light-emitting diodes (CP-OLEDs), 3D display devices, or optical information encryption materials.

[0026] Compared with existing technologies, this technical solution has the following advantages:

[0027] 1. The compound with high solid-state circularly polarized luminescence activity provided by this invention has been experimentally verified to have a circularly polarized luminescence asymmetry factor (g) in the solid-state thin film state. lum ) reached 2.7×10 -3 Meanwhile, the fluorescence quantum yield (ΦF) is as high as 0.59, which is a high g lumThe property of maintaining high ΦF is rare in solid-state small molecule CPL materials, indicating that the compound has good application value in the field of solid-state optoelectronic devices.

[0028] 2. The synthetic method described in this invention employs a strategy of desymmetry to construct a chiral core and modular coupling to introduce functional groups. The first step, the asymmetric CuAAC reaction for constructing the chiral core, is characterized by high efficiency and extremely high enantioselectivity (>99% ee), and is the key to constructing the chiral center. The second step, the Sonogashira coupling for modular coupling to introduce functional groups, utilizes a pre-reserved "handle" to precisely introduce a strongly luminescent pyrene group, while maintaining the chiral purity of the final product. The entire synthetic route is simple, has high yield, and precise stereochemical control.

[0029] 3. The compound obtained by this invention has excellent solid-state CPL performance, making it a candidate light-emitting material for developing high-efficiency, high-performance solid-state CP-OLED and other devices, and it has great application value in next-generation display and encryption technologies. Attached Figure Description

[0030] Figure 1 This is a schematic diagram of the organic synthesis route of step (1) in the synthesis method described in Example 1.

[0031] Figure 2 This is a schematic diagram of the organic synthesis route of step (2) in the synthesis method described in Example 1.

[0032] Figure 3 This is the proton NMR spectrum of the compound with high solid-state circularly polarized luminescence activity described in Example 1.

[0033] Figure 4 This is the carbon NMR spectrum of the compound with high solid-state circularly polarized luminescence activity described in Example 1.

[0034] Figure 5 This is a high-resolution mass spectrum of the compound with high solid-state circularly polarized luminescence activity described in Example 1.

[0035] Figure 6 This is the HPLC spectrum of the racemic sample of the compound with high solid-state circularly polarized luminescence activity described in Example 1.

[0036] Figure 7 The image shows the HPLC spectrum of the chiral sample of the compound with high solid-state circularly polarized luminescence activity described in Example 1.

[0037] Figure 8 This is the 1H NMR spectrum of the chiral product described in Example 4.

[0038] Figure 9 This is the carbon NMR spectrum of the chiral product described in Example 4.

[0039] Figure 10 This is a high-resolution mass spectrum of the chiral product described in Example 4.

[0040] Figure 11 This is a crystal structure diagram of the chiral product described in Example 4.

[0041] Figure 12 This is the racemic HPLC chromatogram of the chiral product described in Example 4.

[0042] Figure 13 This is the HPLC chromatogram of the chiral sample of the chiral product described in Example 4.

[0043] Figure 14 The emission spectra of the compound with high solid-state circularly polarized luminescence activity described in the experimental examples are in DCM and pure films.

[0044] Figure 15 shows the circular dichroism (CPL) spectra of the compound with high solid-state circular polarization luminescence activity and its enantiomers described in the experimental examples in DCM and pure films.

[0045] Figure 16 The glum value-wavelength curves of the compound and its enantiomer with high solid-state circularly polarized luminescence activity described in the experimental examples in DCM and pure films.

[0046] Figure 17 The fluorescence lifetime decay curve of the compound with high solid-state circularly polarized luminescence activity described in the experimental example in the pure film.

[0047] Figure 18 The circular dichroism (CD) spectra of the compound and its enantiomer with high solid-state circular polarization luminescence activity described in the experimental examples are in a pure film. Detailed Implementation

[0048] The following examples further illustrate the present invention, but are not intended to limit the invention. Specific experimental conditions and methods not specified in the following examples are generally conventional methods well known to those skilled in the art. Nuclear magnetic resonance (NMR) spectra were acquired on a Bruker DPX 500 (500 MHz) instrument. ¹H NMR (500 MHz) chemical shifts were taken with tetramethylsilane (TMS: δ = 0 ppm) as a reference. ¹³C NMR (125 MHz) chemical shifts were taken using CDCl3 as an internal standard (CDCl3: δ = 77.0 ppm). High-resolution mass spectrometry (HRMS) was performed using an Agilent 6224 TOF mass spectrometer equipped with an electrospray ionization (ESI) source. X-ray single-crystal diffraction data were acquired using a Bruker D8 VENTURE instrument. Photoluminescence spectra and transient PL decay characteristics were recorded using an Edinburgh Instruments FLS1000 spectrometer. Circularly polarized luminescence (CPL) signals were measured using a JASCO CPL-300 spectrometer. Circular dichroism (CD) signals were measured using a JASCO J-1700 spectrometer. Chiral high-performance liquid chromatography (HPLC) chromatograms were acquired using a Shimadzu LC-20A system. Optical rotation was determined using an Insmark IP-digi300 autorotometer with CHCl3 solution and a sample concentration of 0.1 g / 100 mL. Unless otherwise specified, all reagents and anhydrous solvents were purchased from commercial suppliers (Bide Pharmatech, Aladdin, Energy Chemical, Adamas-beta, and Beijing Innokai) and used directly without further purification. Toluene was purified and dried according to standard methods before use. Both routine and catalytic reactions were carried out in colorless Schlenk reaction tubes under an inert argon atmosphere.

[0049] Example 1: A method for synthesizing the compound with high solid-state circularly polarized luminescence activity, comprising the following steps:

[0050] (1) such as Figure 1As shown, under argon protection, 0.01 mmol of CuBr and 0.01 mmol of chiral ligand were added to 0.5 mL of THF and stirred at room temperature for 1 h to obtain a catalytic system; 0.1 mmol of prochiral diynyl[2.2] p-cycloaromatic, 0.15 mmol of benzyl azide (structural formula: Bn-N3) and 0.12 mmol of Et3N were dissolved in 0.5 mL of THF to obtain a mixture, which was then added to the catalytic system and stirred at 25 °C for 4 h. After the reaction was completed, the reaction mixture was diluted with 5 mL of dichloromethane, filtered through a diatomaceous earth pad and the filter cake was washed with 15 mL of dichloromethane. The filtrates were combined to obtain filtrate A. The residue of filtrate A after vacuum concentration was purified by silica gel column chromatography (eluent: dichloromethane) to obtain a yellow solid product, which is the chiral product. The yield was determined to be 35.4 mg, with a yield of 91% and 99% ee.

[0051] (2) such as Figure 2 As shown, under argon protection, 0.1 mmol of the chiral product obtained in step (1), 0.12 mmol of 1-iodopyrene, 0.003 mmol of Pd(PPh3)4, 0.005 mmol of CuI and 0.5 mL of Et3N were added sequentially to 1 mL of THF and mixed evenly. The mixture was then stirred at 25 °C for 12 h. After the reaction was completed, the reaction mixture was diluted with 5 mL of dichloromethane, filtered through a diatomaceous earth pad, and the filter cake was washed with 15 mL of dichloromethane. The filtrates were combined to obtain filtrate B. The residue of filtrate B after vacuum concentration was purified by silica gel column chromatography to obtain a yellow solid product, which is the compound with high solid-state circular polarization luminescence activity. The yield was determined to be 56.0 mg, with a yield of 95%, >99% ee.

[0052] The structural formula of the prochiral diynyl[2.2]-p-cycloarane is:

[0053] ;

[0054] The chiral ligand is:

[0055] ;

[0056] The structure of the chiral product is as follows:

[0057] ;

[0058] The structural formula of the compound exhibiting high solid-state circularly polarized luminescence activity is:

[0059] .

[0060] The obtained compound exhibiting high solid-state circularly polarized luminescence activity was characterized, and its proton NMR spectrum was obtained (see...). Figure 3 ), 1 H NMR (500 MHz, CDCl3): δ = 8.75 (d, J = 9.1 Hz, 1H), 8.28 – 8.15(m, 5H), 8.12 – 8.01 (m, 3H), 7.55 (s, 1H), 7.44 – 7.35 (m, 3H), 7.33 (d, J =1.2 Hz, 1H), 7.31 (s, 1H), 7.15 (dd, J = 7.8, 1.6 Hz, 1H), 6.89 (d, J = 1.5Hz, 1H), 6.82 (d, J = 1.1 Hz, 1H), 6.65 – 6.59 (m, 2H), 6.56 (dd, J = 7.8,1.5 Hz, 1H), 5.63 (s, 2H), 3.96 – 3.87 (m, 1H), 3.84 – 3.75 (m, 1H), 3.45 – 3.35 (m, 1H), 3.18 – 3.05 (m, 2H), 3.04 – 2.92 (m, 2H), 2.90 – 2.83 (m, 1H) ppm; C NMR spectrum (see...) Figure 4 ), 13 C NMR (125 MHz, CDCl3): δ = 148.4, 142.01, 139.8,139.7, 137.3, 137.0, 135.1, 134.8, 133.3, 132.8, 131.7, 131.3, 131.08,131.05, 130.82, 130.80, 130.3, 129.6, 129.1, 128.7, 128.4, 128.0, 127.9,127.2, 126.2, 125.6, 125.4, 124.9, 124.57, 124.55, 124.4, 121.5, 118.4, 95.6, 91.8, 54.1, 34.3, 34.20, 34.17, 34.1 ppm; HRMS (ESI) Precise Mass Calculation C 43 H 32 N3 [M+H] + : 590.2591, Measured value: 590.2593 (see Figure 5 ); Specific rotation [α] D 20= +20.25 (c = 0.1, CHCl3); Enantiomer excess (ee) was analyzed by HPLC using a Daicel Chiralpak IA column, n-hexane / isopropanol = 90 / 10, flow rate 1.0 mL / min, detection wavelength λ = 254 nm, temperature = 35 °C, minor isomer retention time t(minor) = 32.61 min, major isomer retention time t(major) = 34.94 min (see...) Figure 6 and Figure 7 ).

[0061] Example 2: A method for synthesizing the compound with high solid-state circularly polarized luminescence activity, comprising the following steps:

[0062] (1) Under argon protection, 0.025 mmol of CuBr and 0.025 mmol of chiral ligand were added to 0.25 mL of THF and stirred at room temperature for 1 h to obtain a catalytic system; 0.1 mmol of prochiral diynyl[2.2] p-cycloaromatic, 0.12 mmol of benzyl azide (structural formula: Bn-N3) and 0.10 mmol of Et3N were dissolved in 0.25 mL of THF to obtain a mixture, which was then added to the catalytic system and stirred at 0 °C for 6 h. After the reaction was completed, the reaction mixture was diluted with 5 mL of dichloromethane, filtered through a diatomaceous earth pad and the filter cake was washed with 15 mL of dichloromethane. The filtrates were combined to obtain filtrate A. The residue of filtrate A after vacuum concentration was purified by silica gel column chromatography (eluent was dichloromethane) to obtain a yellow solid product, which was the chiral product. The yield was determined to be 90% and 98% ee.

[0063] (2) Under argon protection, 0.1 mmol of the chiral product obtained in step (1), 0.12 mmol of 1-iodopyrene, 0.003 mmol of Pd(PPh3)4, 0.005 mmol of CuI and 0.5 mL of Et3N were added sequentially to 1 mL of THF and mixed evenly. The mixture was then stirred at 20 °C for 24 h. After the reaction was completed, the reaction mixture was diluted with 5 mL of dichloromethane, filtered through a diatomaceous earth pad, and the filter cake was washed with 15 mL of dichloromethane. The filtrates were combined to obtain filtrate B. The residue of filtrate B after vacuum concentration was purified by silica gel column chromatography to obtain a yellow solid product, which is the compound with high solid-state circular polarization luminescence activity. The yield was determined to be 92% and 99% ee.

[0064] The structural formula of the prochiral diynyl[2.2]-p-cycloarane is:

[0065] ;

[0066] The chiral ligand is:

[0067] ;

[0068] The structure of the chiral product is as follows:

[0069] ;

[0070] The structural formula of the compound exhibiting high solid-state circularly polarized luminescence activity is:

[0071] .

[0072] Example 3: A method for synthesizing the compound with high solid-state circularly polarized luminescence activity, comprising the following steps:

[0073] (1) Under argon protection, 0.08 mmol of CuBr and 0.08 mmol of chiral ligand were added to 0.3 mL of THF and stirred at room temperature for 1 h to obtain a catalytic system; 0.1 mmol of prochiral diynyl[2.2] p-cyclic aromatic hydrocarbon, 0.2 mmol of benzyl azide compound (structural formula: Bn-N3) and 0.2 mmol of Et3N were dissolved in 0.5 mL of THF to obtain a mixture, which was then added to the catalytic system and stirred at 40 °C for 2 h. After the reaction was completed, the reaction mixture was diluted with 5 mL of dichloromethane, filtered through a diatomaceous earth pad and the filter cake was washed with 15 mL of dichloromethane. The filtrates were combined to obtain filtrate A. The residue of filtrate A after vacuum concentration was purified by silica gel column chromatography (eluent was dichloromethane) to obtain a yellow solid product, which was the chiral product. The yield was determined to be 88% and 95% ee.

[0074] (2) Under argon protection, 0.1 mmol of the chiral product obtained in step (1), 0.12 mmol of 1-iodopyrene, 0.003 mmol of Pd(PPh3)4, 0.005 mmol of CuI and 0.5 mL of Et3N were added sequentially to 1 mL of THF and mixed evenly. The mixture was then stirred at 80 °C for 6 h. After the reaction was completed, the reaction mixture was diluted with 5 mL of dichloromethane, filtered through a diatomaceous earth pad, and the filter cake was washed with 15 mL of dichloromethane. The filtrates were combined to obtain filtrate B. The residue of filtrate B after vacuum concentration was purified by silica gel column chromatography to obtain a yellow solid product, which is the compound with high solid-state circular polarization luminescence activity. The yield was determined to be 90% and 96% ee.

[0075] The structural formula of the prochiral diynyl[2.2]-p-cycloarane is:

[0076] ;

[0077] The chiral ligand is:

[0078] ;

[0079] The structure of the chiral product is as follows:

[0080] ;

[0081] The structural formula of the compound exhibiting high solid-state circularly polarized luminescence activity is:

[0082] .

[0083] Example 4: The gram-scale reaction synthesis of the chiral product described in step (1) of Example 1 is as follows:

[0084] Under argon protection, 57.4 mg of CuBr and 204.2 mg of chiral ligand (L1) were added to 10 mL of THF and stirred at room temperature for 1 h to obtain a catalytic system. 1024.5 mg of a prochiral diynyl[2.2]-p-cyclic aromatic hydrocarbon, 798.9 mg of a benzyl azide compound (structural formula: Bn-N3), and 1.2 equivalents of Et3N were dissolved in 30 mL of THF to obtain a mixture. This mixture was then added to the catalytic system, and the reaction was stirred at 25 °C for 24 h. After the reaction, the reaction mixture was diluted with 20 mL of dichloromethane, filtered through a diatomaceous earth mat, and the filter cake was washed with 40 mL of dichloromethane. The filtrates were combined to obtain filtrate A. The residue of filtrate A after vacuum concentration was purified by silica gel column chromatography (dichloromethane / ethyl acetate = 50 / 1, v / v) to obtain a yellow solid product, which was the chiral product. The yield was determined to be 1432.3 mg, with a yield of 92%, >99%. ee.

[0085] The obtained chiral product was characterized, and its proton NMR spectrum was obtained (see...). Figure 8 ), 1H NMR (500 MHz, CDCl3): δ = 7.53 (s, 1H), 7.44 – 7.35 (m, 3H), 7.33 (d, J = 1.4 Hz, 1H), 7.31(s, 1H), 7.00 (dd, J = 7.8, 1.7 Hz, 1H), 6.82 (d, J = 1.7 Hz, 1H), 6.60 (s,1H), 6.54 – 6.46 (m, 3H), 5.63 (s, 2H), 3.77 – 3.69 (m, 1H), 3.63 – 3.55 (m,1H), 3.28 (s, 1H), 3.27 – 3.19 (m, 1H), 3.06 – 2.97 (m, 1H), 2.97 – 2.84 (m, 3H), 2.83 – 2.75 (m, 1H) ppm; C NMR spectrum (see Figure 9 ), 13 C NMR (125 MHz, CDCl3): δ = 148.3, 142.7, 139.7, 139.5, 137.4, 137.1, 135.1, 134.8, 133.1, 132.8, 131.1, 130.7, 130.0, 129.2, 128.7, 127.9, 123.5, 121.4, 84.0, 80.1, 54.1, 34.2, 34.1, 33.8, 33.6 ppm; HRMS (ESI) precise mass calculation C 27 H 24 N3 [M+H] + 390.1965, measured value: 390.1961 (see Figure 10 ); Specific rotation [α] D 20 = +56.47 (c = 0.1, CHCl3); X-ray diffraction single crystal of the chiral product, X-ray single crystal structure data are stored at Cambridge Crystallographic Data Center (CCDC2541919), diffraction data were collected using Ga-Kα radiation (λ = 1.34138 Å) and Bruker D8 VENTURE, crystal structure (see Figure 11), detailed information is shown in Table 1; enantiomeric excess (ee) was analyzed by HPLC using a Daicel Chiralpak IA column, hexane / isopropanol = 90 / 10, flow rate 1.0 mL / min, detection wavelength λ = 254 nm, temperature = 35 °C, minor isomer retention time t(minor) = 18.59 min, major isomer retention time t(major) = 21.76 min (see Figure 12 and Figure 13 ).

[0086] Table 1 Crystal structure information of chiral products

[0087]

[0088] Example 5: Chiral products were prepared according to step (1) of the synthesis method described in Example 1, using different chiral ligands. The results are shown in Table 2. The results show that the same chiral product can be obtained using the chiral ligands described in this invention.

[0089] Table 2 Results using different chiral ligands

[0090]

[0091] Example 6: Chiral products were prepared according to step (1) of the synthesis method described in Example 1, using different catalysts. The results are shown in Table 3. The results show that the same chiral product can be obtained using the catalysts described in this invention.

[0092] Table 3 Results using different catalysts

[0093]

[0094] Example 7: Chiral products were prepared according to step (1) of the synthesis method described in Example 1, using different solvents. The results are shown in Table 4. The results show that the same chiral product can be obtained using the solvents described in this invention.

[0095] Table 4 Results using different solvents

[0096]

[0097] Example 8: Chiral products were prepared according to step (1) of the synthesis method described in Example 1, using different bases. The results are shown in Table 5. The results show that the same chiral product can be obtained by using the bases described in this invention.

[0098] Table 5 Results using different bases

[0099]

[0100] Experimental Example: The compound with high solid-state circularly polarized luminescence activity obtained in Example 1 was labeled (S)-a, and its enantiomer was labeled (R)-a (obtained by using enantiomers or by chemical conversion of (S)-a using the same method); (S)-a and (R)-a were respectively prepared into uniform solid films, and then their photophysical properties and chiral optical properties were tested, specifically including the following:

[0101] (1) Solid-state fluorescence spectrum: The fluorescence emission spectrum of the (S)-a solid film was measured using a fluorescence spectrometer (see Figure 14 Its maximum emission wavelength (λem) is located at approximately 499 nm, emitting green light with a relatively wide half-peak.

[0102] (2) Solid-state circularly polarized luminescence (CPL) performance: Tested using a circularly polarized luminescence spectrometer, the results are as follows: Figure 15 The solid-state CPL spectra of (S)-a and (R)-a show a perfect mirror relationship. (S)-a exhibits a negative CPL signal near 512 nm. Its luminescence asymmetry factor (g) was calculated. lum ) Spectrum (see Figure 16 It reaches its minimum value at 512 nm, g lum = -2.7×10 -3 This value indicates that the compound exhibits a significant chiral luminescence signal in the solid state.

[0103] (3) Fluorescence quantum yield and lifetime: The absolute fluorescence quantum yield Φ of the (S)-a solid film was measured. F = 0.59, its fluorescence decay curve (see Figure 17 After fitting, the luminescence lifetime τ = 12.38 ns, with high Φ F The value highlights its high energy conversion efficiency as a luminescent material.

[0104] (4) Solid-state circular dichroism (CD) spectrum: The CD spectra of (S)-a and (R)-a solid films were tested (see Figure 18 Both exhibit approximately equal intensity but opposite signs of the Cotton effect near 283 nm and 329 nm.

[0105] In summary, the compound with high solid-state circularly polarized light emission activity described in this invention simultaneously possesses a high circularly polarized light emission asymmetry factor and fluorescence quantum yield in the solid state. This excellent combination of properties makes it an excellent candidate material for fabricating high-performance solid-state chiral light-emitting devices.

[0106] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A compound exhibiting high solid-state circularly polarized luminescence activity, characterized in that: The structural formula of the compound is: 。 2. The method for synthesizing the compound with high solid-state circularly polarized luminescence activity as described in claim 1, characterized in that: Includes the following steps: (1) Under argon protection, the catalyst and chiral ligand were added to the solvent and stirred at room temperature for 1 h to obtain a catalytic system; a mixture of pre-chiral diynyl[2.2]-cyclic aromatic hydrocarbon, azide compound and base was dissolved in the solvent to obtain a mixture, which was then added to the catalytic system and stirred at 0-40°C for 2-6 h. After the reaction was completed, the reaction mixture was diluted with dichloromethane (DCM) and filtered through a diatomaceous earth pad to obtain filtrate A. The residue of filtrate A after vacuum concentration was purified by silica gel column chromatography to obtain the chiral product; the catalyst is any one of Cu(OAc)2, Cu(HFA)2, Cu(OTf)2, CuTC, CuCl and CuBr. (2) Under argon protection, the chiral product obtained in step (1), 1-iodopyrene, Pd(PPh3)4, CuI and triethylamine were added to the solvent in sequence and mixed evenly. The mixture was then stirred at 20-80°C for 6-24 hours. After the reaction was completed, the reaction mixture was diluted with dichloromethane and filtered through a diatomaceous earth pad to obtain filtrate B. The residue of filtrate B after vacuum concentration was purified by silica gel column chromatography to obtain a yellow solid product, namely the compound with high solid-state circular polarization luminescence activity. The structural formula of the prochiral diynyl[2.2]-p-cycloarane is: ； The azide compound is a benzyl azide compound with the structural formula: Bn-N3; The chiral ligand is a ligand having any of the following structures: ； The structure of the chiral product is as follows: 。 3. The synthesis method according to claim 2, characterized in that: The solvent is any one of DCE, acetonitrile, DCM, THF, and toluene.

4. The synthesis method according to claim 2, characterized in that: The alkali is any one of DIPEA, NaOAc, t-BuOK, and Et3N.

5. The synthesis method according to claim 2, characterized in that: In step (1), the molar ratio of the prochiral diynyl group [2.2] to the cyclic aromatic hydrocarbon, the catalyst, and the chiral ligand is 1:(0.025~0.1):(0.025~0.1); the equivalence ratio of the azide compound to the prochiral diynyl group [2.2] to the cyclic aromatic hydrocarbon is 1:(1.2~2.0); and the equivalence ratio of the base to the prochiral diynyl group [2.2] to the cyclic aromatic hydrocarbon is 1:(1.0~2.0).

6. The synthesis method according to claim 5, characterized in that: In step (1), the molar ratio of the prochiral diyne [2.2] to the cycloaromatic hydrocarbon, azide compound, catalyst, chiral ligand and base is 1:1.2:0.1:0.1:1.2; 0.5 to 1.0 mL of solvent is added to each 0.1 mmol of prochiral diyne [2.2] to the cycloaromatic hydrocarbon.

7. The synthesis method according to claim 6, characterized in that: In step (2), the molar ratio of the chiral product, 1-iodopyrene, Pd(PPh3)4 and CuI is 1:1.2:0.03:0.05; 0.5 mL of triethylamine and 1 mL of solvent are added for every 0.1 mmol of chiral product.

8. The application of the compound with high solid-state circularly polarized luminescence activity as described in claim 1, characterized in that: The compound is used to produce solid-state circularly polarized light-emitting materials.

9. The application according to claim 8, characterized in that: The compound is used to produce solid-state circularly polarized organic light-emitting diodes, 3D display devices, or optical information encryption materials.

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