Chiral additives of binaphthyl bridged biphenyl heterocyclic rings, methods of making and circularly polarized luminescent liquid crystals

Abstract

The present application relates to the technical field of organic functional materials, in particular to binaphthyl bridged diphenyl heterocyclic chiral additive, its preparation method and circularly polarized luminescent liquid crystal. The additive takes axially chiral binaphthyl as the core, introduces diphenyl furan / thiophene unit through Suzuki-Miyaura coupling, has definite structure and excellent thermal stability. The preparation route takes 3,3'-diiodo-2,2'-dimethoxy binaphthyl and diphenyl heterocyclic boronic acid as raw materials, has simple reaction steps, mild reaction conditions and good yield. When the additive is doped in nematic liquid crystal E7 at 0.5wt%-2wt%, cholesteric liquid crystal can be efficiently induced to form, and typical fingerprint texture is presented; the obtained circularly polarized luminescent liquid crystal realizes significant chiral amplification, the CPL signal is improved by about 1000 times, and has good application prospect in circularly polarized luminescent devices.

Description

Technical Field

[0001] This invention relates to the field of organic functional materials technology, specifically to binaphthalene-bridged biphenyl heterocyclic chiral additives and their preparation methods, and circularly polarized luminescent liquid crystals. Background Technology

[0002] Chiral liquid crystals, due to their unique helical supramolecular structure, exhibit characteristics such as spontaneous polarization, selective reflection of circularly polarized light, and amplification of chiral signals, making them valuable for applications in high-contrast displays, 3D displays, and circularly polarized light-emitting (CPL) devices. Cholesteric liquid crystals are the most representative chiral liquid crystals, formed by inducing the addition of chiral additives to nematic liquid crystals, offering advantages such as simple preparation, tunable helical structure, and excellent optical properties.

[0003] Chiral additives are core components determining the chiral induction ability, optical asymmetry, and luminescence properties of cholesteric liquid crystals. In the design of chiral additives, axially chiral binaphthol and its derivatives are widely used due to their stable optical activity and strong chiral induction ability. Previous studies have shown that binaphthol derivatives can act as chiral dopants to induce the formation of a cholesteric phase in achiral liquid crystals and generate amplified circularly polarized luminescence signals. However, most reported binaphthol-based chiral additives are combined with rod-shaped molecules or aggregated luminescent groups. These chiral additives have the following problems: firstly, high doping levels easily disrupt the original phase state and physicochemical properties of the liquid crystal; secondly, the chiral amplification effect is weak, and the circularly polarized luminescence asymmetry factor (g) is low. lum The fluorescence quantum yield is generally below 0.2, which is insufficient to meet the requirements of high-performance devices; thirdly, it is difficult to balance fluorescence quantum yield and chiral induction ability, and thermal stability is insufficient. Summary of the Invention

[0004] To address the aforementioned problems, this invention provides a binaphthalene-bridged dibenzoheterocyclic chiral additive, its preparation method, and a circularly polarized luminescent liquid crystal. Using chiral binaphthalene as the central core, a dibenzoheterocyclic unit is introduced, exhibiting a well-defined structure, strong chiral induction ability, high fluorescence quantum yield, and excellent thermal stability. In the dibenzoheterocyclic ring, the five-membered heteroaromatic ring has a high electron cloud density, promoting ordered self-assembly of molecules, effectively enhancing molecular stability and providing a high charge transport rate, while also possessing unique optical properties and superior electrical conductivity. Multiple modification sites on the dibenzoheterocyclic ring regulate chiral induction and luminescence properties. This solves the problems of existing chiral additives, such as high doping levels, easy destruction of liquid crystal phase and physicochemical properties, weak chiral amplification effect, low luminescence asymmetry factor, and difficulty in simultaneously achieving high fluorescence quantum yield and chiral induction ability.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: The first objective of this invention is to provide a binatidine-bridged bibenzidine-heterocyclic chiral additive, the structure of which is shown below: .

[0006] Where X is O or S. * indicates the presence of chirality on the binaphthyl axis, indicating that there are two configurations, R and S.

[0007] In a preferred embodiment of the present invention, when X is O, the binaphthalene-bridged bibenzyl heterocyclic chiral additive has one of the following structures: ; The asterisk (*) indicates that the binaphthyl axis is chiral and has either an R or S configuration.

[0008] In a preferred embodiment of the present invention, when X is S, the binaphthalene-bridged bibenzyl heterocyclic chiral additive has one of the following structures: ; The asterisk (*) indicates that the binaphthyl axis is chiral and has either an R or S configuration.

[0009] A second objective of this invention is to provide a method for preparing the above-mentioned naphthalene-bridged dibenzohexacyclic chiral additive, comprising the following steps: Using 3,3'-diiodo-2,2'-dimethoxy-1,1'-binaphthyl, dibenzofuran boronic acid, or dibenzothiophene boronic acid as raw materials, a Suzuki-Miyaura cross-coupling reaction was carried out to obtain a binaphthyl-bridged dibenzoheterocyclic chiral additive.

[0010] In a preferred embodiment of the present invention, dibenzofuranboronic acid is 1-boronic fluorene, 2-boronic fluorene, dibenzo[b,d]furan-3-ylboronic acid, or 4-boronic fluorene.

[0011] In a preferred embodiment of the present invention, dibenzothiophene boric acid is dibenzo[b,d]thiophene-1-ylboronic acid, 2-boronic acid thiofluorene, 3-boronic acid thiofluorene, or 4-boronic acid thiofluorene.

[0012] In a preferred embodiment of the present invention, the molar ratio of 3,3'-diiodo-2,2'-dimethoxy-1,1'-binaphthylene to dibenzofuran boronic acid or dibenzothiophene boronic acid is 1:3.

[0013] The third objective of this invention is to provide a circularly polarized luminescent liquid crystal, which comprises a nematic liquid crystal and a chiral additive, wherein the chiral additive is the aforementioned binaphthalene-bridged bibenzyl heterocyclic chiral additive.

[0014] In a preferred embodiment of the present invention, the mass doping fraction of the chiral additive is 0.5wt% to 2wt% based on the nematic liquid crystal.

[0015] Compared with the prior art, the beneficial effects of the present invention are: 1. This invention provides a binaphthalene-bridged dibenzoheterocyclic chiral additive. Using chiral binaphthalene as the central core, a dibenzoheterocyclic unit is introduced, exhibiting a well-defined structure, strong chiral induction ability, high fluorescence quantum yield, and excellent thermal stability. In the dibenzoheterocyclic ring, the five-membered heteroaromatic ring has a high electron cloud density, promoting easier molecular arrangement and stacking to form ordered self-assembly. This not only effectively enhances molecular stability but also imparts a high charge transport rate, along with unique optical properties and superior electrical conductivity. The dibenzoheterocyclic ring has multiple modification sites, allowing for the modulation of chiral induction and luminescence properties. The chiral additive has a simple synthetic procedure, and the binary cholesteric phase liquid crystal, co-assembled with E7 to form a chiral supramolecular system, exhibits a high asymmetric luminescence factor, thus solving the problem of generally low luminescence asymmetric factors in existing circularly polarized luminescent organic small molecules. Chiral additives can efficiently induce the formation of cholesteric liquid crystals from nematic liquid crystals at low doping levels. The additives have a fluorescence quantum yield of up to 81% and excellent chiral induction ability, and both CD and CPL signals are amplified. This solves the problems of existing chiral additives, such as high doping levels, easy destruction of liquid crystal phase and physicochemical properties, weak chiral amplification effect, low luminescence asymmetry factor, and difficulty in balancing fluorescence quantum yield and chiral induction ability.

[0016] 2. This invention provides chiral binaphthyl-bridged dibenzofuran derivatives. Using chiral binaphthyl as the central core, a series of chiral additives, DBFBn, are synthesized via Suzuki-Miyaura cross-coupling of external dibenzofuran disk-shaped units. The thermal decomposition temperatures of this series of molecules are all above 350℃, exhibiting good thermal stability. When added as a chiral additive at a 1% ratio to E7 liquid crystal, it induces a highly ordered supramolecular helical structure in the nematic liquid crystal. POM testing results show that they all exhibit the characteristic texture of chiral liquid crystals—fingerprint texture; and R The DBFB3 compound exhibits a high absolute quantum yield of 69% in dichloromethane solution, indicating its potential as a promising luminescent material. The DBFBn series compounds and their binary cholesteric liquid crystal compounds demonstrate significant chiral signals in circular dichroism and circularly polarized fluorescence spectroscopy. The doped compounds show chiral amplification in both CD and CPL spectra, with the binary compounds exhibiting approximately 1000 times greater CPL signal compared to the undoped form. lum The l-value can reach as high as 0.485, which is relatively high among luminescence asymmetry factors. This provides a new strategy for the development of chiral liquid crystal devices.

[0017] 3. This invention provides chiral binaphthylene-bridged dibenzothiophene derivatives. Using chiral binaphthylene as the central core, a series of chiral additives are synthesized through Suzuki-Miyaura cross-coupling of external dibenzothiophene disk-shaped liquid crystal units. The DBTBn series compounds all exhibit thermal decomposition temperatures above 370℃ and good thermal stability. When added as chiral additives at a 1% ratio to E7 liquid crystal, they induce a highly ordered supramolecular helical structure in the nematic liquid crystal. POM testing results show that they all exhibit the characteristic texture—fingerprint texture—of chiral liquid crystals. DSC and XRD results indicate that the addition of these additives has little impact on the physicochemical properties and mesocrystalline range of the original substances, all exhibiting a wide mesocrystalline range of room-temperature chiral nematic mesophase. This suggests that these compounds have potential application value as additives in the liquid crystal field. R The DBTB1 compound exhibits a high absolute quantum yield of 81% for fluorescence. The DBTBn series compounds and their binary cholesteric liquid crystal compounds demonstrate significant chiral signals in circular dichroism and circularly polarized fluorescence spectroscopy. The doped compounds show chiral amplification in both CD and CPL spectra, with the CPL signal of the binary compounds being approximately 1000 times greater than that of the undoped compounds. lum The value can reach as high as 0.501, indicating that this series of compounds shows promise as a promising optoelectronic material. Attached Figure Description

[0018] Figure 1 For the present invention R -DBFBn and R -Thermogravimetric analysis curves of DBTBn series compounds.

[0019] Figure 2 The images show polarization textures of different binary cholesteric phase liquid crystals according to the present invention. Figure 2 Figure (A) is R The polarization texture of DBFB1-E7, (B) figure is shown. R The polarization texture of DBFB2-E7, (C) figure is shown. R The polarization texture of DBFB3-E7, (D) figure is shown. R The polarization texture pattern of DBFB4-E7, (E) figure is shown. R The polarization texture pattern of DBTB1-E7, (F) is shown in Figure 1. R The polarization texture pattern of DBTB2-E7, (G) figure is shown. R The polarization texture pattern of DBTB3-E7, (H) figure is shown. R -DBTB4-E7 polarized texture pattern.

[0020] Figure 3 For the present invention R -DBFBn and R- Fluorescence emission pattern of DBTBn series chiral additives in thin film state.

[0021] Figure 4 This is a fluorescence emission diagram of different binary cholesteric liquid crystals in thin film state according to the present invention.

[0022] Figure 5 For the present invention R / S -Circularly polarized emission diagrams of DBFBn series compounds and E7-doped binary cholesteric liquid crystals in thin film state.

[0023] Figure 6 For the present invention R / S -Circularly polarized emission diagrams of DBTBn series compounds and E7-doped binary cholesteric liquid crystals in thin film state.

[0024] Figure 7 This is a diagram showing the asymmetry factor of the binary cholesteric liquid crystal in the thin film state according to the present invention. Detailed Implementation

[0025] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0026] It should be noted that the technical terms used in this invention are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of this invention. Unless otherwise specified, all raw materials, reagents, instruments and equipment used in the following embodiments of this invention can be purchased from the market or prepared by existing methods.

[0027] First, this invention provides a binaphthalene-bridged bibenzo[a]heterocyclic chiral additive. The five-membered heteroaromatic rings, such as thiophene and furan, possess high electron cloud density. Their introduction facilitates molecule arrangement and stacking, forming ordered self-assemblies, effectively enhancing molecular stability and providing high charge transport rates. Furthermore, they exhibit unique optical properties and superior electrical conductivity. Dibenzofuran / thiophene has multiple modification sites, allowing for the formation of chiral additives with different substitution positions, thus illustrating the influence of different atoms and substitution positions on the asymmetric luminescence factor of binary cholesteric liquid crystals.

[0028] Secondly, this invention provides a method for preparing the above-mentioned naphthalene-bridged biphenyl heterocyclic chiral additive, comprising the following steps: Using 3,3'-diiodo-2,2'-dimethoxy-1,1'-binaphthyl and dibenzofuran boronic acid as raw materials, a Suzuki-Miyaura cross-coupling reaction was carried out to obtain a binaphthyl-bridged bibenzofuran chiral additive, namely a chiral binaphthyl-bridged bibenzofuran derivative.

[0029] Alternatively, using 3,3'-diiodo-2,2'-dimethoxy-1,1'-binaphthyl and dibenzothiophene boric acid as raw materials, a Suzuki-Miyaura cross-coupling reaction can be carried out to obtain a binaphthyl-bridged dibenzothiophene chiral additive, namely a chiral binaphthyl-bridged dibenzothiophene derivative.

[0030] The specific preparation process of the chiral binatrol-bridged dibenzofuran derivative is as follows: First, binatrol is etherified with iodomethane to generate 3,3'-diiodo-2,2'-dimethoxy-1,1'-binaphthylene, which then reacts with n-butyllithium and iodine to generate iodinated binatrol. Finally, it is prepared by a Suzuki-Miyaura cross-coupling reaction with four dibenzofuran boric acids at different substitution positions to obtain four pairs of chiral isomers. The specific synthetic methods of the above series of related compounds are shown below:

[0031] ; .

[0032] The specific preparation process of the chiral binaphthalene-bridged dibenzothiophene derivative is as follows: Four pairs of chiral compounds with different positions were prepared by Suzuki-Miyaura cross-coupling reaction of 3,3'-diiodo-2,2'-dimethoxy-1,1'-binaphthalene with four dibenzothiophene boric acids at different positions.

[0033] .

[0034] In this invention, a dibenzofuran structure is introduced into a chiral binaphthyl-bridged dibenzofuran derivative. Four pairs of dibenzofuran derivatives (DBFBn) based on chiral binaphthyl-bridged dibenzofurans were designed and synthesized, and used as chiral additives in E7 liquid crystals. Only 1% by mass of DBFBn was sufficient to induce E7 to transform from a classic nematic texture to a fingerprint texture with a helical structure. Furthermore, the CD and CPL thin film spectra of the binary liquid crystal composite DBFBn-E7 both exhibited good mirror symmetry, showing a stronger chiral signal with a signal intensity greater than 1000 times higher than that of DBFBn, and its luminescence asymmetry factor |g lum | Up to 0.485. In dichloromethane solvent, R -DBFB3 has an absolute fluorescence quantum yield of up to 69%.

[0035] In this invention, the chiral binaphthalene-bridged dibenzothiophene derivative is mainly based on the chiral binaphthalene-bridged dibenzofuran derivative, in which a dibenzothiophene structure is introduced to enhance the luminescence properties of the molecule. Four axially chiral molecules, DBTBn, of chiral binaphthalene-bridged dibenzothiophene were designed and synthesized, and a binary cholesteric liquid crystal composite, DBTBn-E7, was prepared. Similarly, only 1% by mass of DBTBn was sufficient to induce E7 to transform from a schlieren texture to a fingerprint texture. The CD and CPL thin film spectra of the binary liquid crystal composite DBTBn-E7 both exhibit good mirror symmetry, showing a stronger chiral signal, with a signal intensity approximately 1000 times higher than that of DTPBn. Its luminescence asymmetry factor |g lum | Up to 0.501. R -DBTB1 exhibits an absolute fluorescence quantum yield of up to 81% in dichloromethane solution.

[0036] Finally, the present invention provides a circularly polarized light-emitting liquid crystal, namely a cholesteric liquid crystal, which comprises a nematic liquid crystal and a chiral additive. The chiral additive is the above-mentioned chiral binaphthyl-bridged dibenzofuran / thiophene derivative. The mass doping fraction of the chiral additive is 0.5wt%~2wt% based on the nematic liquid crystal.

[0037] The following specific examples will provide further explanation.

[0038] In this invention, the English abbreviation for N,N-dimethylformamide is DMF, the English abbreviation for dichloromethane is DCM, and the English abbreviation for petroleum ether is PE.

[0039] Example 1 A sort of( R )-3,3'-diiodo-2,2'-dimethoxy-1,1'-binaphthyl R The method for synthesizing -9 includes the following steps: S1、( R )-2,2'-dimethoxy-1,1'-binaphthyl R Synthesis of -8: In a 250 mL round-bottom flask, weigh out 5.0 g of (equivalent to 17.46 mmol) R 9.92 g of 1-binaphthol, 9.92 g of CH3I (equivalent to 69.89 mmol), and 14.48 g of K2CO3 (equivalent to 104.78 mmol) were dissolved in 90 mL of DMF and reacted at 60 °C for 24 h. After the reaction was complete, 200 mL of ice was added to a clean 500 mL beaker. The reaction mixture from the round-bottom flask was then poured into the beaker, and 2 M dilute hydrochloric acid was added dropwise while stirring continuously until the pH became acidic. The mixture was then filtered through a Buchner funnel lined with double-layered filter paper to obtain a white solid, which is the compound. R-8, yield was 5.33g, with a yield rate of 97%.

[0040] compound R The NMR data for -8 are as follows: 1 H NMR (400MHz, CDCl3) δ 8.00 (d, J = 9.0 Hz, 2H), 7.89 (d, J = 8.2 Hz, 2H), 7.48 (d, J = 9.0 Hz, 2H), 7.34 (t, J = 7.4 Hz, 2H),7.27 – 7.20 (m, 2H), 7.15 (d, J = 8.5 Hz, 2H), 3.78 (s, 6H).

[0041] S2、( R )-3,3'-diiodo-2,2'-dimethoxy-1,1'-binaphthyl R Synthesis of -9: In a 100 mL reaction tube, weigh out 3.0 g of the solution, equivalent to 9.54 mmol. R -8, add 3 mL of THF to dissolve it completely. Under argon protection, slowly inject 3.0 mL of N,N,N',N'-tetramethylethylenediamine (equivalent to 21.00 mmol) into the reaction tube at room temperature. After reacting for 10 min, slowly add 20.5 mL of N,N,N',N'-tetramethylethylenediamine (equivalent to 38.16 mmol) using a syringe. n After reacting with BuLi for 6 hours, 9.69 g of I₂ (equivalent to 38.16 mmol) was added at -78 °C, and the reaction was allowed to proceed for 12 hours at room temperature. After the reaction was complete, the mixture was extracted with saturated Na₂SO₃ and ethyl acetate. The organic phase was dried over anhydrous MgSO₄, concentrated under reduced pressure, and dried again. Finally, silica gel column chromatography was performed (eluent: V). DCM :V PE (1:6) After separation and purification, recrystallization with anhydrous ethanol and ethyl acetate yielded a pale yellow solid, which is the compound. R -9, yield was 3.05g, yield rate was 56%.

[0042] compound R The NMR data for -9 are as follows: 1 H NMR (400MHz, CDCl3) δ 8.55 (s, 2H), 7.80(d, J = 8.2 Hz, 2H), 7.41 (t, J = 7.5 Hz, 2H), 7.32 – 7.23 (m, 2H), 7.09 (d,J =8.4 Hz, 2H), 3.43 (s, 6H).

[0043] Example 2 A sort of( S )-3,3'-diiodo-2,2'-dimethoxy-1,1'-binaphthyl S The method for synthesizing -9 includes the following steps: S1、( S )-2,2'-dimethoxy-1,1'-binaphthyl S Synthesis of -8: In a 250 mL round-bottom flask, weigh out 5.0 g of (equivalent to 17.46 mmol) S 9.92 g of 1-binaphthol, equivalent to 69.89 mmol of CH3I, and 14.48 g of K2CO3, equivalent to 104.78 mmol, were dissolved in 90 mL of DMF and reacted at 60 °C for 24 h. After the reaction was complete, 200 mL of ice was added to a clean 500 mL beaker. The reaction mixture from the round-bottom flask was then poured into the beaker, and 2 M dilute hydrochloric acid was added dropwise while stirring continuously until the pH became acidic. The mixture was then filtered through a Buchner funnel lined with double-layered filter paper. The resulting white solid was the product. S -8, yield was 5.38g, with a yield rate of 98%.

[0044] S2、( S )-3,3'-diiodo-2,2'-dimethoxy-1,1'-binaphthyl S Synthesis of -9: In a 100 mL reaction tube, weigh out 3.0 g of the solution, equivalent to 9.54 mmol. S -8, add 3 mL of THF to dissolve it completely. Under argon protection, slowly inject 3.0 mL of N,N,N',N'-tetramethylethylenediamine (equivalent to 21.00 mmol) into the reaction tube at room temperature. After reacting for 10 min, slowly add 20.5 mL of N,N,N',N'-tetramethylethylenediamine (equivalent to 38.16 mmol) using a syringe. n After reacting with BuLi for 6 hours, 9.69 g of I₂ (equivalent to 38.16 mmol) was added at -78 °C, and the reaction was continued at room temperature for 12 hours. After the reaction was complete, the mixture was extracted with saturated Na₂SO₃ and ethyl acetate. The organic phase was dried over anhydrous MgSO₄, concentrated under reduced pressure, and dried again. Finally, silica gel column chromatography was performed (eluent: V). DCM :V PE (1:6) After separation and purification, recrystallization with anhydrous ethanol and ethyl acetate yielded a pale yellow solid, which is the compound. S -9, yield was 2.81g, yield rate was 52%.

[0045] Example 3 A sort of( R )-1,1'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]furan R -DBFB1, its structure is as follows: The above R The synthesis method of -DBFB1 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. R -9. 224.7 mg (equivalent to 1.05 mmol of 1-boronic acid fluorene), 1.8 g (equivalent to 5.25 mmol of Cs₂CO₃), and 122.5 mg (equivalent to 0.11 mmol of Pd(PPh₃)₄) were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:6, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. R -DBFB1, yield was 147.8 mg, with a yield of 65%.

[0046] compound R The characterization data for -DBFB1 is as follows: 1 H NMR (400MHz, CDCl3) δ 8.58 (s, 2H),8.28 – 8.22 (m, 2H), 8.12 (s, 2H), 8.01 – 7.87 (m, 8H), 7.52 – 7.43 (m, 6H),7.32 (d, J = 3.7 Hz, 4H), 3.25 (s, 6H). 13C NMR (150MHz, CDCl3) δ 134.21,134.12, 135.89 – 131.13, 132.62, 135.89 – 126.91, 135.89 – 126.83, 135.89 –126.22, 218.33 – 125.69, 125.13, 124.35, 123.76, 122.51, 122.33, 111.50,111.20, 110.78, 110.22, 60.77, 53.47. HRMS(MALDI) calcd for C 46 H 30 O4Na [M+Na] + 669.2037, found 669.2040.

[0047] Example 4 A sort of( S )-1,1'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]furan S -DBFB1, its structure is as follows: .

[0048] The above S The synthesis method of -DBFB1 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. S -9. 224.7 mg (equivalent to 1.05 mmol of 1-boronic acid fluorene), 1.8 g (equivalent to 5.25 mmol of Cs₂CO₃), and 122.5 mg (equivalent to 0.11 mmol of Pd(PPh₃)₄) were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:6, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. S -DBFB1, yield was 143.5 mg, with a yield of 63%.

[0049] Example 5 A sort of( R)-2,2'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]furan R -DBFB2, its structure is as follows: .

[0050] The above R The synthesis method of -DBFB2 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. R -9. 224.7 mg (equivalent to 1.05 mmol) of fluorene 2-borate, 1.8 g (equivalent to 5.25 mmol) of Cs₂CO₃, and 122.5 mg (equivalent to 0.11 mmol) of Pd(PPh₃)₄ were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:6, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. R -DBFB2, yield was 174.5 mg, with a yield of 76%.

[0051] compound R The representation data for -DBFB2 is as follows: 1 H NMR (400MHz, CDCl3) δ 8.38 (s, 2H), 8.09 (s, 2H), 8.02 (d, J = 7.7 Hz, 2H), 7.97 (d, J = 8.2 Hz, 2H), 7.89 (d, J = 8.5Hz, 2H), 7.67 (d, J = 8.5 Hz, 2H), 7.61 (d, J = 8.2 Hz, 2H), 7.50 – 7.45 (m, 4H), 7.37 (t, J = 7.5 Hz, 2H), 7.31 (s, 4H), 3.22 (s, 6H). 13C NMR (150MHz, CDCl3) δ156.63, 155.72, 154.14, 135.00, 133.68, 130.88, 128.82, 128.11, 127.27,126.38, 126.09, 125.85, 125.18, 124.40, 122.86, 121.51, 120.89, 111.79,111.48, 60.62, 53.62. HRMS(MALDI) calcd for C 46 H 30 O4Na [M+Na] + 669.2037, found669.2038.

[0052] Example 6 A sort of( S )-2,2'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]furan S -DBFB2, its structure is as follows: .

[0053] The above S The synthesis method of -DBFB2 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. S -9. 224.7 mg (equivalent to 1.05 mmol) of fluorene 2-borate, 1.8 g (equivalent to 5.25 mmol) of Cs₂CO₃, and 122.5 mg (equivalent to 0.11 mmol) of Pd(PPh₃)₄ were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:6, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. S -DBFB2, yield was 179.1 mg, with a yield of 78%.

[0054] Example 7 A sort of( R )-3,3'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]furan R-DBFB3, its structure is as follows: .

[0055] The above R The synthesis method of -DBFB3 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. R -9. 224.7 mg (equivalent to 1.05 mmol) of dibenzo[b,d]furan-3-ylboronic acid, 1.8 g (equivalent to 5.25 mmol) of Cs₂CO₃, and 122.5 mg (equivalent to 0.11 mmol) of Pd(PPh₃)₄ were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum drying oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:6, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. R -DBFB3, yield was 185.7 mg, with a yield of 81%.

[0056] compound R The representation data for -DBFB3 is as follows: 1 H NMR (400MHz, CDCl3) δ 8.10 (s, 2H), 8.04 (d, J = 11.2 Hz, 4H), 7.99 (dd, J = 14.6, 7.9 Hz, 4H), 7.81 (d, J = 7.9Hz, 2H), 7.61 (d, J = 8.2 Hz, 2H), 7.50 – 7.43 (m, 4H), 7.38 (t, J = 7.4 Hz, 2H), 7.34 – 7.28 (m, 4H), 3.24 (s, 6H). 13C NMR (150MHz, CDCl3) δ 156.65,156.48, 154.06, 138.21, 134.76, 133.72, 130.90, 128.19, 127.19, 126.52,126.11, 125.83, 125.20, 124.36, 124.17, 123.37, 122.83, 120.72, 120.37,112.44, 111.75, 60.69, 53.47. HRMS(MALDI) calcd for C 46 H 30 O4Na [M+Na] + 669.2037, found 669.2041.

[0057] Example 8 A sort of( S )-3,3'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]furan S -DBFB3, its structure is as follows: .

[0058] The above S The synthesis method of -DBFB3 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. S -9. 224.7 mg (equivalent to 1.05 mmol) of dibenzo[b,d]furan-3-ylboronic acid, 1.8 g (equivalent to 5.25 mmol) of Cs₂CO₃, and 122.5 mg (equivalent to 0.11 mmol) of Pd(PPh₃)₄ were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum drying oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:6, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. S -DBFB3, yield was 174.5 mg, with a yield of 76%.

[0059] Example 9 A sort of( R)-4,4'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]furan R -DBFB4, its structure is as follows: .

[0060] The above R The synthesis method of -DBFB4 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. R -9. 224.7 mg (equivalent to 1.05 mmol) of fluorene 4-borate, 1.8 g (equivalent to 5.25 mmol) of Cs₂CO₃, and 122.5 mg (equivalent to 0.11 mmol) of Pd(PPh₃)₄ were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:6, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. R -DBFB4, yield was 162.4 mg, with a yield of 71%.

[0061] compound R The representation data for -DBFB4 is as follows: 1 H NMR (400MHz, CDCl3) δ 8.30 (s, 2H), 8.02 (s, 6H), 7.83 (d, J = 7.4 Hz, 2H), 7.54 (d, J = 8.1 Hz, 2H), 7.48 (t, J = 7.6Hz, 8H), 7.42 – 7.35 (m, 4H), 3.30 (s, 6H). 13C NMR (151MHz, CDCl3) δ 155.16,153.62, 152.90, 133.06, 130.58, 129.53, 128.80, 127.77, 127.21, 126.07,125.55, 124.92, 124.50, 123.98, 123.35, 122.34, 121.73, 119.63, 118.85,110.80, 52.55. HRMS(MALDI) calcd for C 46 H 30 O4[M] + 669.2041, found 669.2040.

[0062] Example 10 A sort of( S )-4,4'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]furan S -DBFB4, its structure is as follows: .

[0063] The above S The synthesis method of -DBFB4 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. S -9. 224.7 mg (equivalent to 1.05 mmol) of fluorene 4-borate, 1.8 g (equivalent to 5.25 mmol) of Cs₂CO₃, and 122.5 mg (equivalent to 0.11 mmol) of Pd(PPh₃)₄ were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:6, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. S -DBFB4, yield was 159.5 mg, with a yield of 70%.

[0064] Example 11 A sort of( R )-1,1'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]thiophene R-DBTB1, its structure is as follows: .

[0065] The above R The synthesis method of DBTB1 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. R -9. 224.7 mg (equivalent to 1.05 mmol) of dibenzo[b,d]thiophene-1-ylboronic acid, 1.8 g (equivalent to 5.25 mmol) of Cs₂CO₃, and 49.6 mg (equivalent to 0.07 mmol) of PdCl₂(PPh₃)₂ were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was cooled to room temperature and extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum drying oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:4, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. R -DBTB1, yield was 121.5 mg, with a yield of 51%.

[0066] compound R The characterization data for -DBTB1 is as follows: 1 H NMR (400MHz, CDCl3) δ 8.21 (d, J = 8.4Hz, 6H), 7.95 (d, J = 8.0 Hz, 2H), 7.81 (d, J = 7.1 Hz, 2H), 7.70 (d, J = 7.3 Hz, 2H), 7.59 (t, J = 7.5 Hz, 2H), 7.50 – 7.37 (m, 10H), 3.19 (s, 6H). 13C NMR (150MHz, CDCl3) δ 153.02, 139.04, 138.70, 134.85, 133.11, 132.92, 132.55, 129.72,129.45, 127.19, 125.74, 124.77, 124.13, 123.63, 123.29, 121.69, 120.67,119.59, 60.00, 52.41. HRMS(MALDI) calcd for C 46 H 30 O2S2Na [M+Na] + 701.1580, found701.1582.

[0067] Example 12 A sort of( S )-1,1'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]thiophene S -DBTB1, its structure is as follows: .

[0068] The above S The synthesis method of DBTB1 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. S -9. 224.7 mg (equivalent to 1.05 mmol) of dibenzo[b,d]thiophene-1-ylboronic acid, 1.8 g (equivalent to 5.25 mmol) of Cs₂CO₃, and 49.6 mg (equivalent to 0.07 mmol) of PdCl₂(PPh₃)₂ were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was cooled to room temperature and extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum drying oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:4, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. S -DBTB1, yield was 125.6 mg, with a yield of 52%.

[0069] Example 13 A sort of( R)-2,2'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]thiophene R -DBTB2, its structure is as follows: .

[0070] The above R The synthesis method of DBTB2 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. R -9. 224.7 mg (equivalent to 1.05 mmol of thiofluorene 2-boronate), 1.8 g (equivalent to 5.25 mmol of Cs₂CO₃), and 81.6 mg (equivalent to 0.11 mmol of Pd(PPh₃)₄) were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was cooled to room temperature and extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum drying oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:4, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. R -DBTB2, yield was 171.7 mg, with a yield of 72%.

[0071] compound R The characterization data for -DBTB2 is as follows: 1 H NMR (400MHz, CDCl3) δ 8.59 (s, 2H),8.29 – 8.23 ​​(m, 2H), 8.13 (s, 2H), 8.02 – 7.87 (m, 8H), 7.48 (t, J = 6.7 Hz, 6H), 7.33 (d, J = 3.8 Hz, 4H), 3.26 (s, 6H). 13C NMR (150MHz, CDCl3) δ 153.10,138.74, 137.52, 134.81, 134.60, 134.32, 133.80, 132.65, 129.82, 127.27,127.08, 125.78, 125.39, 125.05, 124.82, 124.14, 123.42, 121.88, 121.57,121.15, 120.73, 59.78, 52.56. HRMS(MALDI) calcd for C 46 H 30 O2S2[M] + 678.1687, found 678.1681.

[0072] Example 14 A sort of( S )-2,2'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]thiophene S -DBTB2, its structure is as follows: .

[0073] The above S The synthesis method of DBTB2 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. S -9. 224.7 mg (equivalent to 1.05 mmol of thiofluorene 2-boronate), 1.8 g (equivalent to 5.25 mmol of Cs₂CO₃), and 81.6 mg (equivalent to 0.11 mmol of Pd(PPh₃)₄) were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was cooled to room temperature and extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum drying oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:4, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. S -DBTB2, yield was 176.3 mg, with a yield of 73%.

[0074] Example 15 A sort of( R)-3,3'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]thiophene R -DBTB3, its structure is as follows: .

[0075] The above R The synthesis method of DBTB3 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. R -9. 224.7 mg (equivalent to 1.05 mmol of thiofluorene 3-boronate), 1.8 g (equivalent to 5.25 mmol of Cs₂CO₃), and 81.6 mg (equivalent to 0.11 mmol of Pd(PPh₃)₄) were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was cooled to room temperature and extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum drying oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:4, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. R -DBTB3, yield was 191.2 mg, with a yield of 80%.

[0076] compound R The characterization data for DBTB3 is as follows: 1 H NMR (400MHz, CDCl3) δ 8.31 (s, 2H),8.26 (d, J = 8.2 Hz, 2H), 8.21 (d, J = 4.8 Hz, 2H), 8.11 (s, 2H), 7.97 (d, J = 8.1Hz, 2H), 7.94 – 7.86 (m, 4H), 7.53 – 7.42 (m, 6H), 7.36 – 7.27 (m, 4H), 3.24(s, 6H). 13C NMR (150MHz, CDCl3) δ 154.08, 139.73, 137.56, 135.40, 134.64,133.76, 130.85, 128.20, 126.77, 126.54, 126.06, 125.82, 125.23, 124.51,123.39, 122.91, 121.70, 121.40, 60.82, 53.62. HRMS(MALDI) calcd for C 46 H 30 O2S2[M] + 678.1687, found 678.1682.

[0077] Example 16 A sort of( S )-3,3'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]thiophene S -DBTB3, its structure is as follows: .

[0078] The above S The synthesis method of DBTB3 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. S -9. 224.7 mg (equivalent to 1.05 mmol of thiofluorene 3-boronate), 1.8 g (equivalent to 5.25 mmol of Cs₂CO₃), and 81.6 mg (equivalent to 0.11 mmol of Pd(PPh₃)₄) were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was cooled to room temperature and extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum drying oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:4, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. S -DBTB3, yield was 186.4 mg, with a yield of 78%.

[0079] Example 17 A sort of( R )-4,4'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]thiophene R-DBTB4, its structure is as follows: .

[0080] The above R The synthesis method of -DBTB4 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. R -9. 224.7 mg (equivalent to 1.05 mmol) of thiofluorene 4-boronate, 1.8 g (equivalent to 5.25 mmol) of Cs₂CO₃, and 81.6 mg (equivalent to 0.11 mmol) of Pd(PPh₃)₄ were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was cooled to room temperature and extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:4, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. R -DBTB4, yield was 183.0 mg, with a yield of 76%.

[0081] compound R The characterization data for -DBTB4 is as follows: 1 H NMR (400MHz, CDCl3) δ 8.10 (s, 2H),8.01 (dt, J = 14.3, 9.3 Hz, 8H), 7.81 (d, J = 8.0 Hz, 2H), 7.61 (d, J = 8.2 Hz, 2H), 7.47 (dd, J = 17.8, 9.7 Hz, 4H), 7.38 (t, J = 7.1 Hz, 2H), 7.30 (s, 4H), 3.24 (s, 6H). 13C NMR (151MHz, CDCl3) δ 153.02, 139.04, 138.70, 134.85, 133.11,132.92, 132.55, 129.72, 129.52, 127.19, 125.70, 124.82, 124.13, 123.63,123.29, 121.69, 120.67, 119.59, 60.06, 52.58. HRMS(MALDI) calcd for C 46 H 30 O2S2[M] + 678.1687, found 678.1683.

[0082] Example 18 A sort of( S )-4,4'-(2,2'-dimethoxy-[1,1'-binaphthyl]-3,3'-diyl)dibenzo[b,d]thiophene S -DBTB4, its structure is as follows: .

[0083] The above S The synthesis method of -DBTB4 includes the following steps: In a 50 mL reaction tube, weigh 200.0 mg, equivalent to 0.35 mmol. S -9. 224.7 mg (equivalent to 1.05 mmol) of thiofluorene 4-boronate, 1.8 g (equivalent to 5.25 mmol) of Cs₂CO₃, and 81.6 mg (equivalent to 0.11 mmol) of Pd(PPh₃)₄ were added to a reaction tube in 12 mL of a 1:2 mixture of H₂O and THF using a syringe. The reaction was carried out at 75 °C for 48 h under argon protection. After the reaction was complete, the mixture was cooled to room temperature and extracted three times with saturated NaCl solution and dichloromethane. The combined organic phases were dried over anhydrous MgSO₄, concentrated under reduced pressure, and the crude product was dried in a vacuum oven. Finally, silica gel column chromatography (eluent: V) was performed. DCM :V PE The mixture was separated and purified using a ratio of 1:4, and then recrystallized from anhydrous ethanol and ethyl acetate to obtain a white solid, which is the compound. S -DBTB4, yield was 182.3 mg, with a yield of 76%.

[0084] The derivatives obtained in Examples 3 to 18 were characterized in terms of structure and properties.

[0085] This invention uses thermogravimetric analysis (TGA) to... R -DBFBn andR The thermal stability of the -DBTBn series compounds was analyzed in the range of 550 °C. Figure 1 For the present invention R -DBFBn and R -Thermogravimetric analysis curves of the DBTBn series compounds. (From...) Figure 1 It can be seen that, R -DBFBn series compounds, i.e. R -DBFB1~ R -DBFB4 all exhibited temperatures above 350℃ at 5% weight loss, indicating its relatively high thermal stability. Furthermore, the temperatures at 5% weight loss varied significantly among the four compounds. R -DBFB2 and R The temperature difference of 24℃ between DBFB4 and DBFB4 may be due to the 4th position. R -DBFB4 has relatively high steric hindrance, making it relatively unstable. Furthermore, R The DBTBn series compounds all maintained temperatures above 370℃ after a 5% weight loss, indicating relatively high thermal stability. Furthermore, the temperatures at which the four compounds reached a 5% weight loss varied considerably. R -DBTB3 and R The temperature difference of 35℃ between DBTB4 and DBTB4 may be due to... R The steric hindrance of the -DBTB4 compound leads to its relative instability. This indicates that positional isomerism in the compound has a certain impact on its thermal stability.

[0086] Next, this invention investigates the mesocrystalline properties of DBFBn and DBTBn series compounds, using them as chiral additives and doping them with E7 liquid crystal at a mass ratio of 1% to form cholesteric liquid crystals. The binary cholesteric compound is placed on a glass slide and heated using a hot stage to make it an isotropic liquid. This temperature is maintained for 1-2 minutes, followed by slow cooling to room temperature. Since E7 is a room-temperature liquid crystal, only the polarized texture of the binary cholesteric compound at 30°C is shown.

[0087] Figure 2 The images show polarization textures of different binary cholesteric phase liquid crystals according to the present invention. Figure 2 Figure (A) is R The polarization texture of DBFB1-E7, (B) figure is shown. R The polarization texture of DBFB2-E7, (C) figure is shown. R The polarization texture of DBFB3-E7, (D) figure is shown. R The polarization texture pattern of DBFB4-E7, (E) figure is shown. R The polarization texture pattern of DBTB1-E7, (F) is shown in Figure 1. R The polarization texture pattern of DBTB2-E7, (G) figure is shown. RThe polarization texture pattern of DBTB3-E7, (H) figure is shown. R -Polarized texture pattern of DBTB4-E7. (From...) Figure 2 It can be seen that the cholesteric compounds obtained after adding chiral additives all exhibit obvious chiral characteristic textures—fingerprint textures—and the four compounds with different substitution positions have no significant effect on their polarization texture, indicating that positional isomerism has little impact on the self-assembly mode of chiral additives. Compared with the DBFBn series, the DBTBn series compounds are more rigid, and a small amount can achieve significant effects when used as chiral additives.

[0088] To investigate the effects of four different substitution positions on the photophysical properties of the compound, four... R -DBFBn and four types R -DBTB chiral compounds were dissolved in dichloromethane to prepare solutions with a concentration of 1×10⁻⁶. -5 mol -1 L -1 The luminescence properties of a dilute solution were analyzed by fluorescence emission spectroscopy in thin film form.

[0089] Figure 3 For the present invention R -DBFBn and R - Fluorescence emission diagram of DBTBn series chiral additives in thin film state. (Source: [Insert source here]) Figure 3 It can be seen that the solution fluorescence emission spectrum was measured at an excitation wavelength of 275 nm. R -DBFB1 has a maximum emission peak at 378nm. R -DBFB2 has a maximum emission peak at 370 nm. R -DBFB3 has a maximum emission peak at 383nm. R DBFB4 exhibits a maximum emission peak at 379 nm. This is in contrast to its performance in the thin-film state (excitation at 275 nm). R -DBFB1 has a maximum emission peak at 380nm. R -DBFB2 has a maximum emission peak at 377nm. R -DBFB3 has a maximum emission peak at 387nm. R -DBFB4 exhibits a maximum emission peak at 383 nm, with a slight redshift relative to solution. This may be due to increased effective conjugation in the aggregated state, leading to enhanced fluorescence. Of these four compounds... R -DBFB3 has an absolute quantum yield of up to 69%. R -DBTB1 has a maximum emission peak at 344nm. R -DBTB2 has a maximum emission peak at 370nm. R -DBTB3 has a maximum emission peak at 370nm.R -DBTB4 exhibits a maximum emission peak at 363 nm. Compared to solution, in the thin film state (λ... em =300nm) R -DBTB1 has a maximum emission peak at 382nm. R -DBTB2 has a maximum emission peak at 382nm. R -DBTB3 has a maximum emission peak at 394nm. R -DBTB4 exhibits a maximum emission peak at 381 nm, with a slight redshift relative to solution. This may be due to increased effective conjugation in the aggregated state, leading to enhanced fluorescence. Of these four compounds... R -DBTB1 has an absolute quantum yield of up to 81%.

[0090] Figure 4 This is a fluorescence emission diagram of different binary cholesteric liquid crystals in thin film state according to the present invention. Figure 4 It can be seen that under 275nm excitation, R The maximum emission peak of the -DBFB1-E7 cholesteric liquid crystal composite film fluorescence is located at 386 nm. R -DBFB2-E7 R -DBFB3-E7 R The maximum emission peaks of -DBFB4-E7 are all located at 387 nm. The fluorescence emission of the binary cholesteric liquid crystal in thin film state is slightly red-shifted compared to that of the chiral additive. Under 280 nm excitation, R The maximum emission peak of the -DBTB1-E7 cholesteric liquid crystal composite film is located at 379 nm. R -DBTB2-E7 and R The maximum emission peak of the DBTB4-E7 is located at 387nm. R The maximum emission peak of -DBTB3-E7 is located at 388 nm.

[0091] Meanwhile, this invention further explores the circularly polarized luminescence properties of chiral additives and binary cholesteric liquid crystal compounds in thin film state.

[0092] Figure 5 For the present invention R / S -Circularly polarized emission diagrams of DBFBn series compounds and E7-doped binary cholesteric liquid crystals in thin film state. Figure 5 It can be seen that, R / SNo significant CPL signal was detected in the thin film state of the DBFBn series compounds. The CPL spectra of the binary cholesteric liquid crystal compounds showed a distinct mirror-symmetric emission peak around 398 nm, the position of which coincided with the position of the maximum emission peak of fluorescence. Compared to chiral additive compounds, the chiral signal intensity of the binary cholesteric liquid crystal was amplified by approximately 1000 times.

[0093] Figure 6 For the present invention R / S -Circularly polarized emission diagrams of DBTBn series compounds and E7-doped binary cholesteric liquid crystals in thin film state. Figure 6 It can be seen that, R / S No obvious CPL signal was detected in the thin film state of the DBTBn series compounds. The CPL spectra of the four pairs of binary cholesteric liquid crystal compounds showed obvious mirror-symmetric emission peaks at around 394 nm, and the position of the maximum emission peaks matched the position of the maximum fluorescence emission peaks. Compared with chiral additive compounds, the chiral signal intensity of the binary cholesteric liquid crystals was amplified by about 1000 times.

[0094] Figure 7 This is a statistical diagram of the asymmetry factor of the binary cholesteric liquid crystal in the thin film state according to the present invention. Figure 7 It can be seen that DBFB1 has a maximum of |g lum | Value is 0.355, DBFB2 maximum | g lum The value is 0.471, and DBFB3 is at its maximum. lum The value is 0.470, and DBFB4 has the maximum value of g. lum The value is 0.485. DBFB4 maximum |g lum The value exceeds that of most purely organic materials by 10. -5 Up to 10 -2 of |g lum The range is relatively high, even among CPL materials. DBTB1 has the largest value in terms of g. lum | Value is 0.501, DBTB2 maximum | g lum The value is 0.375, and DBTB3 has the maximum value. lum The value is 0.481, and DBTB4 has the maximum value of 0.481. lum The value is 0.455. DBTB4 in 4 pairs of binary cholesteric liquid crystal compounds | g lum The value can reach as high as 0.501, exceeding that of most purely organic materials. -5 Up to 10 -2 of |g lum │Scope, ranking among the top CPL materials.

[0095] It should be noted that when numerical ranges are involved in this invention, it should be understood that both endpoints of each numerical range, as well as any value between the two endpoints, can be selected. Since the steps and methods used are the same as in the embodiments, preferred embodiments are described here to avoid redundancy. Although preferred embodiments of this invention have been described, those skilled in the art, once they understand the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended scope of protection is intended to be interpreted as including the preferred embodiments and all changes and modifications falling within the scope of this invention.

[0096] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of protection of this invention and its equivalents, this invention also intends to include these modifications and variations.

Claims

1. A binatidine-bridged biphenyl heterocyclic chiral additive, characterized in that, The structure of the binaphthalene-bridged biphenyl heterocyclic chiral additive is shown below: ； Where X is O or S; * indicates that the binaphthyl axis is chiral and has an R configuration or an S configuration.

2. The binaphthalene-bridged biphenyl heterocyclic chiral additive according to claim 1, characterized in that, When X is O, the naphthalene-bridged biphenyl heterocyclic chiral additive has one of the following structures: ； The asterisk (*) indicates that the binaphthyl axis is chiral and has either an R or S configuration.

3. The binaphthalene-bridged biphenyl heterocyclic chiral additive according to claim 1, characterized in that, When X is S, the naphthalene-bridged biphenyl heterocyclic chiral additive has one of the following structures: ； The asterisk (*) indicates that the binaphthyl axis is chiral and has either an R or S configuration.

4. A method for preparing a binaphthalene-bridged biphenyl heterocyclic chiral additive according to any one of claims 1 to 3, characterized in that, Includes the following steps: Using 3,3'-diiodo-2,2'-dimethoxy-1,1'-binaphthyl, dibenzofuran boronic acid, or dibenzothiophene boronic acid as raw materials, a Suzuki-Miyaura cross-coupling reaction was carried out to obtain a binaphthyl-bridged dibenzoheterocyclic chiral additive.

5. The method for preparing the binaphthalene-bridged biphenyl heterocyclic chiral additive according to claim 4, characterized in that, Dibenzofuran boronic acid is 1-boronic acid fluorene, 2-boronic acid fluorene, dibenzo[b,d]furan-3-ylboronic acid, or 4-boronic acid fluorene.

6. The method for preparing the binaphthalene-bridged biphenyl heterocyclic chiral additive according to claim 4, characterized in that, Dibenzothiophene boric acid is dibenzo[b,d]thiophene-1-ylboronic acid, 2-boronic acid thiofluorene, 3-boronic acid thiofluorene, or 4-boronic acid thiofluorene.

7. The method for preparing the binaphthalene-bridged biphenyl heterocyclic chiral additive according to claim 4, characterized in that, The molar ratio of 3,3'-diiodo-2,2'-dimethoxy-1,1'-binaphthylene to dibenzofuran boronic acid or dibenzothiophene boronic acid is 1:

3.

8. A circularly polarized light-emitting liquid crystal, characterized in that, The circularly polarized luminescent liquid crystal comprises a nematic liquid crystal and a chiral additive, wherein the chiral additive is the binatidine-bridged bibenzyl heterocyclic chiral additive as described in any one of claims 1 to 3.

9. The circularly polarized light-emitting liquid crystal according to claim 8, characterized in that, For nematic liquid crystals, the mass doping fraction of chiral additives is 0.5wt%~2wt%.

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