Chiral indolo[3,2-b]carbazole derivatives, processes for their preparation and use thereof

Abstract

This invention discloses a chiral indodo[3,2-b]carbazole derivative, its preparation method, and its applications. The structure of the chiral indodo[3,2-b]carbazole derivative is shown in formula (3): (3) where Ar is hydrogen, 7-methyl, 5-methyl, 5-bromine, or 5-chloro; R1 is at least one of phenyl, 4-methylphenyl, 4-chlorophenyl, or tert-butyl-substituted phenyl; X is O, S, or N; R2 is a substituent connected to X, selected from at least one of benzyl, substituted benzyl, C1-C6 straight-chain or branched alkyl, C3-C8 cycloalkyl, carbazole, or substituted carbazole. This invention is the first to directly construct a chiral indodo[3,2-b]carbazole skeleton through a chiral phosphoric acid catalytic strategy. The method has mild reaction conditions, is simple to operate in a one-pot process, and is suitable for nucleophiles with oxygen, sulfur, and nitrogen centers. The obtained new compound has a rigid non-planar fused π-conjugated skeleton, a benzyl chiral center, significant optical rotation, and high enantiomeric purity.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis and chiral optoelectronic functional materials technology, specifically relating to a chiral indodo[3,2-b]carbazole derivative, its preparation method, and its application. Background Technology

[0002] Indolo[3,2-b]carbazole (ICZ) is an important rigid fused nitrogen-containing aromatic heterocyclic skeleton with excellent π-conjugation properties, high thermal stability, and charge transport performance. It has potential applications in organic electroluminescence, thermally activated delayed fluorescence, semiconductors, and chiral optoelectronic functional materials. Some ICZ derivatives also exhibit aromatic hydrocarbon acceptor-related biological activities (see...). Chem.Rev. 2018, 118 9058-9128; J.Am.Chem.Soc. 2005, 127 614-618; J.Am.Chem.Soc. 2007, 129 9125-9136; J.Natl.CancerInst. 1994, 86 (1758-1765).

[0003] The synthesis of existing ICZ derivatives mainly relies on methods such as Fischer indoleation, Cadogan cyclization, transition metal-catalyzed cyclization, or stepwise condensation (see...). J.Org.Chem. 1963, 28 2930-2931; Org.Lett. 2019, 21 (166-169). The above methods usually yield planar, achiral fused-ring products, making it difficult to achieve stereoinduction while constructing the ICZ framework; existing chiral systems related to ICZ mostly rely on the introduction of peripheral chiral groups or self-assembly, rather than direct asymmetric construction of the ICZ framework (see [link to article]). J. Lumin. 2024, 266 Therefore, developing a catalytic asymmetric synthesis method capable of directly constructing the chiral indolo[3,2-b]carbazole skeleton is of great significance. Summary of the Invention

[0004] One of the objectives of this invention is to provide a class of chiral indolo[3,2-b]carbazole derivatives with a rigid nonplanar fused π-conjugated framework and a benzylic chiral center, which solves the problems of complex preparation methods and cumbersome operation processes in existing methods.

[0005] The present invention also aims to provide a method for preparing the above-mentioned chiral indolo[3,2-b]carbazole derivative and its use in chiral optoelectronic functional materials; the method utilizes chiral phosphoric acid to catalyze a dimerization-triggered cascade reaction between the 3-(arylethynyl)-1H-indole derivative and a nucleophilic reagent to construct a seven-ring skeleton in one pot and simultaneously introduce a benzylic chiral center.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows: a chiral indodo[3,2-b]carbazole derivative, the structure of which is shown in formula (3): (1) Wherein, Ar is hydrogen, 7-methyl, 5-methyl, 5-bromine, or 5-chloro; R1 is at least one of phenyl, 4-methylphenyl, 4-chlorophenyl, or tert-butyl-substituted phenyl; X is O, S, or N; R2 is a substituent connected to X, selected from at least one of benzyl, substituted benzyl, C1-C6 straight-chain or branched alkyl, C3-C8 cycloalkyl, carbazolyl, or substituted carbazolyl.

[0007] Another technical solution of the present invention is implemented as follows: a method for preparing a chiral indolo[3,2-b]carbazole derivative, using the 3-(arylethynyl)-1H-indole derivative shown in formula (1) and the nucleophile shown in formula (2) as raw materials, a dimerization-triggered cascade reaction is carried out in the presence of a chiral phosphoric acid catalyst to obtain the chiral indolo[3,2-b]carbazole derivative shown in formula (3), the reaction formula of which is as follows:

[0008] The nucleophile is selected from alcohols, thiols, carbazoles or their derivatives.

[0009] Preferably, the specific method is as follows: the 3-(arylethynyl)-1H-indole derivative shown in formula (1), the nucleophile shown in formula (2) and the chiral phosphoric acid catalyst are dissolved in an organic solvent under an inert atmosphere and reacted at 10-35°C for 48-96 h. After the reaction is completed, the chiral indolo[3,2-b]carbazole derivative shown in formula (3) is obtained by purification.

[0010] Preferably, the molar concentration of the 3-(arylethynyl)-1H-indole derivative in the reaction system is 0.02~0.08 mol / L.

[0011] Preferably, the molar ratio of the 3-(arylethynyl)-1H-indole derivative to the nucleophile is 1:(2~5).

[0012] Preferably, the molar ratio of the 3-(arylethynyl)-1H-indole derivative to the chiral phosphoric acid catalyst is 1:(0.05~0.15).

[0013] Preferably, the organic solvent is selected from at least one of a mixed solvent of dichloromethane and toluene in a volume ratio of 1:(0.8~1.2), carbon tetrachloride, or acetonitrile.

[0014] Preferably, the nucleophile is selected from at least one of benzyl alcohols, C1-C6 fatty alcohols, C3-C8 cycloalcohols, C1-C6 alkyl thiols, C3-C8 cycloalkyl thiols, carbazole, or substituted carbazole.

[0015] The third technical solution of this invention is achieved as follows: the application of a chiral indodo[3,2-b]carbazole derivative in the preparation of chiral optoelectronic functional materials.

[0016] Preferably, the chiral optoelectronic functional material is selected from at least one of circularly polarized light-emitting materials, organic electroluminescent materials, organic semiconductor materials, or chiral recognition materials.

[0017] Compared with existing technologies, this invention is the first to directly construct a chiral indolo[3,2-b]carbazole skeleton through a chiral phosphoric acid catalytic strategy. The method has mild reaction conditions, is simple to operate in a one-pot process, and is suitable for nucleophiles with oxygen, sulfur, and nitrogen centers. The resulting chiral indolo[3,2-b]carbazole derivative has a rigid non-planar fused π-conjugated skeleton, a benzylic chiral center, significant optical rotation properties, and high enantiomeric purity. It can be protected as an independent compound and is also suitable for further development as a chiral photoelectric functional molecular skeleton.

[0018] Furthermore, by applying the chiral indodo[3,2-b]carbazole derivative of this invention to the preparation of chiral optoelectronic functional materials, the application of the chiral indodo[3,2-b]carbazole derivative is effectively extended, given that the ICZ framework has already shown excellent application potential in the field of organic electronic materials, and the chiral nonplanar π system has further application potential in the field of chiral optoelectronics. This also lays a solid foundation for future research on chiral optoelectronic functional materials. Attached Figure Description

[0019] Figure 1 is a schematic diagram of the liquid chromatography of the chiral indolo[3,2-b]carbazole derivative obtained in Example 1 of the present invention; wherein: Figure a is the HPLC chromatogram of the racemic indodo[3,2-b]carbazole derivative; Figure b is the chiral HPLC chromatogram of the chiral indodo[3,2-b]carbazole derivative monomer; Figure 2 is a schematic diagram of the liquid chromatography of the chiral indodo[3,2-b]carbazole derivative obtained in Example 2 of the present invention; wherein: Figure a is the HPLC chromatogram of the racemic indodo[3,2-b]carbazole derivative; Figure b is the chiral HPLC chromatogram of the chiral indodo[3,2-b]carbazole derivative monomer; Figure 3 is a schematic diagram of the liquid chromatography of the chiral indodo[3,2-b]carbazole derivative obtained in Example 3 of the present invention; wherein: Figure a is the HPLC chromatogram of the racemic indodo[3,2-b]carbazole derivative; Figure b is the chiral HPLC chromatogram of the chiral indodo[3,2-b]carbazole derivative monomer; Figure 4 is a schematic diagram of the liquid chromatography of the chiral indodo[3,2-b]carbazole derivative obtained in Example 4 of the present invention; wherein: Figure a is the HPLC chromatogram of the racemic indodo[3,2-b]carbazole derivative; Figure b is the chiral HPLC chromatogram of the chiral indodo[3,2-b]carbazole derivative monomer; Figure 5 is a schematic diagram of the liquid chromatography of the chiral indolo[3,2-b]carbazole derivative obtained in Example 5 of the present invention; wherein: Figure a is the HPLC chromatogram of the racemic indodo[3,2-b]carbazole derivative; Figure b is the chiral HPLC chromatogram of the chiral indodo[3,2-b]carbazole derivative monomer; Figure 6 is a schematic diagram of the liquid chromatography of the chiral indodo[3,2-b]carbazole derivative obtained in Example 6 of the present invention; wherein: Figure a is the HPLC chromatogram of the racemic indodo[3,2-b]carbazole derivative; Figure b is the chiral HPLC chromatogram of the chiral indodo[3,2-b]carbazole derivative monomer; Figure 7 is a schematic diagram of the liquid chromatography of the chiral indodo[3,2-b]carbazole derivative obtained in Example 7 of the present invention; wherein: Figure a is the HPLC chromatogram of the racemic indodo[3,2-b]carbazole derivative; Figure b is the chiral HPLC chromatogram of the chiral indodo[3,2-b]carbazole derivative monomer; Figure 8 is a schematic diagram of the liquid chromatography of the chiral indolo[3,2-b]carbazole derivative obtained in Example 8 of the present invention; wherein: Figure a is the HPLC chromatogram of the racemic indodo[3,2-b]carbazole derivative; Figure b is the chiral HPLC chromatogram of the chiral indodo[3,2-b]carbazole derivative monomer; Figure 9 is a schematic diagram of the liquid chromatography of the chiral indolo[3,2-b]carbazole derivative obtained in Example 9 of the present invention; wherein: Figure a is the HPLC chromatogram of the racemic indodo[3,2-b]carbazole derivative; Figure b is the chiral HPLC chromatogram of the chiral indodo[3,2-b]carbazole derivative monomer; Figure 10 is a schematic diagram of the liquid chromatography of the chiral indolo[3,2-b]carbazole derivative obtained in Example 10 of the present invention; wherein: Figure a is the HPLC chromatogram of the racemic indodo[3,2-b]carbazole derivative; Figure b is the chiral HPLC chromatogram of the chiral indodo[3,2-b]carbazole derivative monomer; Figure 11 The ultraviolet (UV) spectra of chiral indodo[3,2-b]carbazole derivatives obtained in Examples 1 and 9 of the present invention; Figure 12 Fluorescence (PL) spectra of chiral indodo[3,2-b]carbazole derivatives obtained in Examples 1 and 9 of the present invention; Figure 13 The circular dichroism (CD) spectra of chiral indodo[3,2-b]carbazole derivatives obtained in Examples 1 and 9 of this invention are shown. Figure 14 The circular polarization (CPL) spectra of the chiral indodo[3,2-b]carbazole derivatives obtained in Examples 1 and 9 of this invention are shown. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of this invention clearer, the present application will be further described in detail below with reference to the accompanying drawings. The described embodiments should not be regarded as limitations on the present invention. All other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0021] It should be noted that all raw materials or reagents in the embodiments of the present invention were purchased on the market or prepared according to conventional methods known to those skilled in the art.

[0022] In the following examples, the general formula of the target chiral indodo[3,2-b]carbazole derivative is shown in formula (3): (3) Wherein, Ar is hydrogen, 7-methyl, 5-methyl, 5-bromine, or 5-chloro; R1 is at least one of phenyl, 4-methylphenyl, 4-chlorophenyl, or tert-butyl-substituted phenyl; X is O, S, or N; R2 is a substituent connected to X, selected from at least one of benzyl, substituted benzyl, C1-C6 straight-chain or branched alkyl, C3-C8 cycloalkyl, carbazolyl, or substituted carbazolyl.

[0023] The following examples use the following general method to prepare the target product: using the 3-(arylethynyl)-1H-indole derivative shown in formula (1) and the nucleophile shown in formula (2) as raw materials, the reaction is carried out in the presence of a chiral phosphoric acid catalyst to obtain the chiral indolo[3,2-b]carbazole derivative shown in formula (3), the reaction formula of which is as follows:

[0024] The definitions of Ar, R1, X, and R2 are the same as before.

[0025] The general operating procedure is as follows: under an inert atmosphere, the 3-(arylethynyl)-1H-indole derivative, nucleophile and chiral phosphoric acid catalyst shown in formula (1) are added to the reactor, followed by the addition of organic solvent. The temperature is controlled at 10-35℃ and the reaction is carried out for 48-96 hours. After the reaction is completed, the solvent is removed under reduced pressure and the target product is obtained by column chromatography purification.

[0026] Preferably, the concentration of the 3-(arylethynyl)-1H-indole derivative shown in formula (1) in the reaction system is 0.02~0.08 mol / L, the molar ratio of the 3-(arylethynyl)-1H-indole derivative shown in formula (1) to the nucleophile is 1:(2~5), and the molar ratio of the 3-(arylethynyl)-1H-indole derivative shown in formula (1) to the chiral phosphoric acid catalyst is 1:(0.05~0.15); the organic solvent is selected from a mixed solvent of dichloromethane / toluene with a volume ratio of 1:(0.8~1.2), carbon tetrachloride, or acetonitrile.

[0027] The following are specific embodiments. Example 1 The chiral indolo[3,2-b]carbazole derivative shown in structural formula 3a is prepared by the following method: The compound shown in structural formula 1a (0.50 mmol), benzyl alcohol (1.50 mmol), and chiral phosphoric acid (0.050 mmol) were added to a Krüger flask equipped with a magnetic flask. After evacuation and nitrogen purging, 10.0 mL of a mixed solvent of dichloromethane and toluene in a volume ratio of 1:1 was added, followed by 250 mg of anhydrous calcium sulfate. The reaction system was then placed in a temperature-controlled device at 10 °C and reacted for 96 h. The reaction was monitored by TLC plate. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain the chiral indolo[3,2-b]carbazole derivative (white solid, 90 mg, 69%) shown in structural formula 3a. The chemical reaction formula of this method is as follows:

[0028] The chiral indodo[3,2-b]carbazole derivatives represented by structural formula 3a were detected by nuclear magnetic resonance, melting point, infrared spectroscopy, and high-resolution mass spectrometry. The high-performance liquid chromatography (HPLC) detection data are as follows: The melting point test result is: 134-135℃. The infrared detection results are as follows: IR (KBr): 3436, 3058, 2925, 1467, 1024, 744 cm⁻¹ -1 The results of the nuclear magnetic resonance imaging (NMR) examination are as follows: 1 HNMR (400MHz, Chloroform-d) δ9.26 (s, 1H), 8.15 (d, J =7.9Hz, 1H), 7.93 (s, 1H), 7.89 (d, J =7.9Hz, 1H, 7.47–7.44 (m, 2H), 7.39–7.31 (m, 12H), 7.28 (d, J =7.9Hz, 2H), 7.24–7.17 (m, 3H), 7.09–7.05 (m, 2H), 7.00 (s, 1H), 4.99 (s, 2H), 4.76 (d, J =11.6Hz, 1H), 4.65 (d, J =11.6Hz, 1H). 13 CNMR (101MHz, Chloroform-d) δ141.27, 141.06, 140.05, 138.81, 137.77, 135.08, 134.04, 129.06, 128.82, 128.68, 128.63, 128.41, 128.15, 128 .01, 127.57, 126.70, 125.71, 123.36, 123.14, 122.69, 122.53, 122.43, 121.42, 119.16, 118.70, 114.82, 114.08, 110.80, 110.59, 71.92, 34.64. The high-resolution mass spectrometry detection results are as follows: HRMS (ESI) m / z: [M+Na] + calcdforC 39 H 30 N2ONa565.2251; found565.2246. The results of high-performance liquid chromatography detection and optical rotation values ​​are as follows: , HPLC (DaicelChiralpakIA, i -PrOH / hexane=20 / 80, flowrate0.8mL / min, λ=230nm): t1(minor)=7.5min, t2(major)=11.6min. Example 2 The chiral indolo[3,2-b]carbazole derivative as shown in structural formula 3b is prepared by the following method: The compound shown in structural formula 1a (0.50 mmol), 2-bromobenzyl alcohol (1.50 mmol), and chiral phosphoric acid (0.050 mmol) were added to a Krüger flask equipped with a magnetic flask. After evacuation and nitrogen purging, 10.0 mL of a mixed solvent of dichloromethane and toluene in a volume ratio of 1:1 was added, followed by 250 mg of anhydrous calcium sulfate. The reaction system was then placed in a temperature-controlled device at 10 °C and reacted for 96 h. The reaction was monitored by TLC plate. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain the chiral indolo[3,2-b]carbazole derivative (white solid, 80 mg, 53%) shown in structural formula 3b. The chemical reaction formula of this method is as follows:

[0029] The data obtained by nuclear magnetic resonance, melting point, infrared spectroscopy, high-resolution mass spectrometry, and high-performance liquid chromatography of the chiral indodo[3,2-b]carbazole derivative represented by structural formula 3b are as follows: The melting point test result is: 216-217℃ The infrared detection results are as follows: IR (KBr): 3432, 3045, 2925, 1267, 1123, 756 cm⁻¹ -1 . The results of the nuclear magnetic resonance imaging (NMR) examination are as follows: 1 HNMR (400MHz, Chloroform-d) δ9.30 (s, 1H), 8.21 (d, J =8.0Hz, 1H), 8.01 (s, 1H), 7.99 (s, 1H), 7.62 (s, 1H), 7.57 (d, J =7.3Hz, 2H), 7.43 (d, J =8.6Hz, 6H), 7.38–7.31 (m, 4H), 7.30 (d, J =8.4Hz, 4H), 7.23–7.12 (m, 3H), 7.10 (s, 1H), 5.05 (s, 2H), 4.84 (s, 2H). 13CNMR (101MHz, Chloroform-d) δ141.23, 141.02, 139.69, 137.02, 135.02, 133.97, 133.03, 130.81, 129.69, 129.00, 128.60, 128.35, 128.06, 127 .68, 127.49, 126.64, 125.65, 124.35, 123.29, 123.11, 122.63, 122.49, 122.37, 121.32, 119.12, 118.64, 113.69, 110.75, 110.51, 71.75, 34.61. The high-resolution mass spectrometry detection results are as follows: HRMS (ESI) m / z: [M+H] + calcdforC 39 H 29 BrN2OH621.1536; found621.1532. The results of high-performance liquid chromatography detection and optical rotation values ​​are as follows: , HPLC (DaicelChiralpakIA, i -PrOH / hexane=20 / 80, flowrate0.8mL / min, λ=230nm): t1(minor)=7.1min, t2(major)=12.2min. Example 3 The chiral indolo[3,2-b]carbazole derivative as shown in structural formula 3c is prepared by the following method: The compound shown in structural formula 1a (0.50 mmol), ethanol (1.50 mmol), and chiral phosphoric acid (0.050 mmol) were added to a Krüger flask equipped with a magnetic flask. After evacuation and nitrogen purging, 10.0 mL of a mixed solvent of dichloromethane and toluene in a volume ratio of 1:1 was added, along with 250 mg of anhydrous calcium sulfate. The reaction system was then placed in a temperature-controlled environment at 10 °C and reacted for 96 h. The reaction was monitored by TLC. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain the chiral indolo[3,2-b]carbazole derivative (white solid, 80 mg, 67%) shown in structural formula 3c. The chemical reaction formula of this method is as follows:

[0030] The data obtained by nuclear magnetic resonance, melting point, infrared spectroscopy, high-resolution mass spectrometry, and high-performance liquid chromatography of the chiral indodo[3,2-b]carbazole derivative represented by structural formula 3c are as follows: The melting point test result is: 177-178℃ The infrared detection results are as follows: IR (KBr): 3124, 2953, 1510, 1414, 977, 895 cm⁻¹ -1 . The results of the nuclear magnetic resonance imaging (NMR) examination are as follows: 1 HNMR (400MHz, Chloroform-d) δ9.38 (s, 1H), 8.19 (d, J =7.9Hz, 1H), 8.10 (d, J =8.0Hz, 1H), 7.95 (s, 1H), 7.55 (d, J =7.3Hz, 2H), 7.50–7.36 (m, 6H), 7.34 (d, J =7.3Hz, 3H), 7.30 (d, J =10.0Hz, 3H), 7.17 (s, 2H), 6.95 (s, 1H), 5.02 (s, 2H), 3.87–3.73 (m, 2H), 1.42 (t, J =7.2Hz, 3H). 13 CNMR (101MHz, Chloroform-d) δ141.21, 140.99, 140.17, 138.77, 134.97, 133.98, 128.97, 128.61, 128.33, 127.95, 127.53, 126 .60, 125.59, 123.39, 123.02, 122.61, 122.38, 121.12, 119.09, 118.56, 114.69, 114.47, 110.75, 110.48, 65.71, 34.54, 15.62. The high-resolution mass spectrometry detection results are as follows: HRMS (ESI) m / z: [M+K] + calcdforC 34 H 28 N2OK519.1833; found519.1827. The results of high-performance liquid chromatography detection and optical rotation values ​​are as follows: , HPLC (DaicelChiralpakIA, i -PrOH / hexane=20 / 80, flowrate0.8mL / min, λ=230nm): t1(minor)=7.1min, t2(major)=10.5min. Example 4 The chiral indolo[3,2-b]carbazole derivative shown in structural formula 3d is prepared by the following method: The compound shown in structural formula 1a (0.50 mmol), 3-pentanol (1.50 mmol), and chiral phosphoric acid (0.050 mmol) were added to a Kreutz flask equipped with a magnetic flask. After evacuation and nitrogen purging, 10.0 mL of carbon tetrachloride solvent was added. The reaction system was then placed in a temperature-controlled device at 35 °C and reacted for 48 h. The reaction was monitored by TLC plate. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain the chiral indolo[3,2-b]carbazole derivative (white solid, 80 mg, 64%) shown in structural formula 3d. The chemical reaction formula for this method is:

[0031] The data obtained by nuclear magnetic resonance, melting point, infrared spectroscopy, high-resolution mass spectrometry, and high-performance liquid chromatography of the chiral indodo[3,2-b]carbazole derivative represented by structural formula 3d are as follows: The melting point test result is: 178-179℃ The infrared detection results are: 3357, 2842, 1320, 923, 648, 546 cm. -1 . The results of the nuclear magnetic resonance imaging (NMR) examination are as follows: 1 HNMR (400MHz, Acetone-d6) δ10.43 (s, 1H), 9.95 (s, 1H), 8.35 (d, J =8.1Hz, 1H), 8.10 (d, J =8.0Hz, 1H), 7.59 (t, J =7.6Hz, 3H), 7.53 (d, J =8.1Hz, 1H), 7.41–7.28 (m, 5H), 7.29–7.20 (m, 4H), 7.16–7.12 (m, 2H), 7.04 (t, J =7.5Hz, 1H), 5.06 (s, 2H), 3.65 (p, J =5.6Hz, 1H), 2.07 (p, J =2.2Hz, 1H), 1.96–1.87 (m, 1H), 1.80 (dtd, J =9.5, 7.3, 3.6Hz, 1H), 1.57 (h, J =6.9Hz, 2H), 1.05 (t, J =7.4Hz, 3H), 0.66 (t, J =7.5Hz, 3H). 13CNMR (101MHz, Acetone-d6) δ141.91, 141.80, 141.50, 139.54, 135.50, 134.37, 128.41, 128.18, 128.12, 127.18, 126.98, 125.97, 125.32, 1 25.22, 123.41, 123.06, 122.67, 122.32, 122.08, 120.59, 118.11, 115 .96, 114.48, 110.67, 80.40, 76.69, 33.75, 25.73, 24.40, 8.85, 8.47. The high-resolution mass spectrometry detection results are as follows: HRMS (ESI) m / z: [M+H] + calcdforC 37 H 34 N2OH 523.2744; found 523.2738. The results of high-performance liquid chromatography detection and optical rotation values ​​are as follows: , HPLC (DaicelChiralpakIA, i -PrOH / hexane=20 / 80, flowrate0.8mL / min, λ=230nm): t1(minor)=5.9min, t2(major)=7.9min. Example 5 The chiral indolo[3,2-b]carbazole derivative shown in structural formula 3e is prepared by the following method: The compound shown in structural formula 1a (0.50 mmol), cyclohexanol (1.50 mmol), and chiral phosphoric acid (0.050 mmol) were added to a Kreutz flask equipped with a magnetic flask. After evacuation and nitrogen purging, 10.0 mL of carbon tetrachloride solvent was added. The reaction system was then placed in a temperature-controlled device at 35 °C and reacted for 48 h. The reaction was monitored by TLC plate. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain the chiral indolo[3,2-b]carbazole derivative (white solid, 60 mg, 46%) shown in structural formula 3e. The chemical reaction formula for this method is:

[0032] The data obtained by nuclear magnetic resonance, melting point, infrared spectroscopy, high-resolution mass spectrometry, and high-performance liquid chromatography of the chiral indodo[3,2-b]carbazole derivative represented by structural formula 3e are as follows: The melting point test result is: 143-144℃ The infrared detection results are: 3235, 3159, 1641, 1208, 668, 621 cm. -1 . The results of the nuclear magnetic resonance imaging (NMR) examination are as follows: 1 HNMR (400MHz, Chloroform-d) δ9.39 (s, 1H), 8.12 (d, J =7.9Hz, 1H), 8.04 (s, 1H), 8.03 (s, 1H), 7.46 (d, J =7.2Hz, 2H), 7.41–7.30 (m, 6H), 7.30–7.21 (m, 5H), 7.18 (d, J =6.8Hz, 1H), 7.14–7.10 (m, 2H), 7.08 (d, J =4.5Hz, 1H), 4.95 (s, 2H), 3.59 (tt, J =9.0, 3.8Hz, 1H), 2.30–2.15 (m, 1H), 1.85–1.74 (m, 2H), 1.65 (d, J =9.9Hz, 2H), 1.48 (d, J =3.9Hz, 2H), 1.23 (s, 2H), 1.11 (d, J =3.2Hz, 1H). 13 CNMR (101MHz, Chloroform-d) δ141.31, 140.95, 140.85, 138.92, 134.99, 134.47, 129.01, 128.60, 128.40, 127.76, 127.55, 126.61, 125.56, 123. 53, 122.92, 122.69, 122.42, 120.98, 119.16, 118.51, 115.45, 114.38, 1 10.84, 110.52, 76.47, 76.22, 34.61, 33.32, 31.56, 25.87, 24.15, 24.05. The high-resolution mass spectrometry detection results are as follows: HRMS (ESI) m / z: [M+Na] + calcdforC 38 H 34 N2ONa557.2563; found557.2552. The results of high-performance liquid chromatography detection and optical rotation values ​​are as follows: , HPLC (DaicelChiralpakIA, i-PrOH / hexane=20 / 80, flowrate0.8mL / min, λ=230nm): t1(minor)=5.6min, t2(minor)=7.9min. Example 6 The chiral indolo[3,2-b]carbazole derivative shown in structural formula 3f is prepared by the following method: The compound shown in structural formula 1b (0.50 mmol), isopropanol (1.50 mmol), and chiral phosphoric acid (0.050 mmol) were added to a Kreutz flask equipped with a magnetic flask. After evacuation and nitrogen purging, 10.0 mL of carbon tetrachloride solvent was added. The reaction system was then placed in a temperature-controlled device at 35 °C and reacted for 48 h. The reaction was monitored by TLC plate. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain the chiral indolo[3,2-b]carbazole derivative (white solid, 60 mg, 46%) shown in structural formula 3f. The chemical reaction formula for this method is:

[0033] The data obtained by nuclear magnetic resonance, melting point, infrared spectroscopy, high-resolution mass spectrometry, and high-performance liquid chromatography of the chiral indodo[3,2-b]carbazole derivative shown in structural formula 3f are as follows: The melting point test result is: 159-160℃ The infrared detection results are: 3269, 1250, 1168, 1014, 721, 708 cm. -1 . The results of the nuclear magnetic resonance imaging (NMR) examination are as follows: 1 HNMR (400MHz, DMSO-d6) δ10.69 (s, 1H), 10.27 (s, 1H), 8.13 (d, J =8.2Hz, 1H), 7.87 (d, J =8.0Hz, 1H), 7.43 (d, J =7.7Hz, 2H), 7.36–7.12 (m, 9H), 7.11 (d, J =5.9Hz, 2H), 6.96 (t, J =7.6Hz, 1H), 6.88 (t, J =7.6Hz, 1H), 5.14 (s, 2H), 3.73 (q, J =6.2Hz, 1H), 2.58 (d, J =10.1Hz, 6H), 1.38 (d, J =6.0Hz, 3H), 1.02 (d, J=6.2Hz, 3H). 13 CNMR (101MHz, DMSO-d6) δ142.19, 141.01, 140.60, 136.47, 128.83, 128.55, 127.44, 127.29, 126.30, 126.21, 122.43, 121 .88, 121.04, 120.46, 119.93, 119.82, 118.75, 118.08, 115.56, 115.10, 75.45, 69.63, 33.73, 23.57, 22.04, 17.99, 17.62. The high-resolution mass spectrometry detection results are as follows: HRMS (ESI) m / z: [M+Na] + calcdforC 37 H 34 N2ONa545.2563; found545.2563. The results of high-performance liquid chromatography detection and optical rotation values ​​are as follows: , HPLC (DaicelChiralpakIA, i -PrOH / hexane=20 / 80, flowrate0.8mL / min, λ=230nm): t1(minor)=12.6min, t2(major)=25.0min. Example 7 The chiral indolo[3,2-b]carbazole derivative with structural formula 3g was prepared by the following method: The compound shown in structural formula 1a (0.50 mmol), n-propylthiol (1.50 mmol), and chiral phosphoric acid (0.050 mmol) were added to a Kirschner flask equipped with a magnetic flask. After evacuation and nitrogen purging, 10.0 mL of acetonitrile solvent was added. The reaction system was then placed in a temperature-controlled device at 35 °C and reacted for 48 h. The reaction was monitored by TLC plate. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain the chiral indolo[3,2-b]carbazole derivative (white solid, 70 mg, 66%) shown in structural formula 3g. The chemical reaction formula of this method is as follows:

[0034] The data obtained by nuclear magnetic resonance, melting point, infrared spectroscopy, high-resolution mass spectrometry, and high-performance liquid chromatography of the chiral indodo[3,2-b]carbazole derivative with structural formula 3g are as follows: The melting point test result is: 166-167℃ The infrared detection results are: 3635, 3359, 1648, 1242, 764, 729 cm. -1 . The results of the nuclear magnetic resonance imaging (NMR) examination are as follows: 1 HNMR (400MHz, Chloroform-d) δ9.84 (s, 1H), 8.20 (d, J =8.2Hz, 1H), 8.14 (d, J =8.3Hz, 1H), 7.88 (s, 1H), 7.54 (d, J =7.9Hz, 2H), 7.42–7.35 (m, 6H), 7.23 (d, J =8.7Hz, 6H), 7.13 (d, J =7.8Hz, 2H), 6.89 (s, 1H), 4.95 (s, 2H), 2.47 (dt, J =13.4, 6.8Hz, 1H), 2.30–2.21 (m, 1H), 1.52 (q, J =7.4Hz, 2H), 0.83 (t, J =7.6Hz, 3H). 13 CNMR (101MHz, Chloroform-d) δ141.19, 140.95, 139.06, 138.66, 135.24, 135.12, 128.99, 128.80, 128.45, 128.30, 127.48, 126.6 2, 125.69, 125.59, 123.39, 122.75, 122.39, 121.70, 119.11, 118.77, 114.64, 113.34, 110.82, 48.56, 34.60, 34.51, 22.39, 13.47. The high-resolution mass spectrometry detection results are as follows: HRMS (ESI) m / z: [M+Na] + calcdforC 35 H 30 N2SNa533.2022; found533.2011. The results of high-performance liquid chromatography detection and optical rotation values ​​are as follows: , HPLC (DaicelChiralpakIA, i -PrOH / hexane=20 / 80, flowrate0.8mL / min, λ=230nm): t1(minor)=7.3min, t2(major)=12.2min. Example 8 The chiral indolo[3,2-b]carbazole derivative with structural formula 3h was prepared by the following method: The compound shown in structural formula 1a (0.50 mmol), cyclopentylthiol (1.50 mmol), and chiral phosphoric acid (0.050 mmol) were added to a Kreutz flask equipped with a magnetic flask. After evacuation and nitrogen purging, 10.0 mL of acetonitrile solvent was added. The reaction system was then placed in a temperature-controlled device at 35 °C and reacted for 48 h. The reaction was monitored by TLC plate. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain the chiral indolo[3,2-b]carbazole derivative (white solid, 60 mg, 51%) shown in structural formula 3h. The chemical reaction formula of this method is as follows:

[0035] The data obtained by nuclear magnetic resonance, melting point, infrared spectroscopy, high-resolution mass spectrometry, and high-performance liquid chromatography of the chiral indodo[3,2-b]carbazole derivative with structural formula 3h are as follows: The melting point test result is: 169-171℃ The infrared detection results are: 3575, 3128, 1688, 1046, 984, 783 cm. -1 . The results of the nuclear magnetic resonance imaging (NMR) examination are as follows: 1 HNMR (400MHz, Chloroform-d) δ9.89 (s, 1H), 8.23 ​​(d, J =8.1Hz, 1H), 8.13 (d, J =8.1Hz, 1H), 7.86 (s, 1H), 7.52 (d, J =7.7Hz, 2H), 7.47 (d, J =7.9Hz, 1H), 7.40 (d, J =7.3Hz, 1H), 7.35–7.29 (m, 4H), 7.29–7.20 (m, 5H), 7.18–7.10 (m, 3H), 6.92 (s, 1H), 5.00–4.88 (m, 2H), 2.83 (p, J =7.2Hz, 1H), 1.89–1.72 (m, 2H), 1.72–1.55 (m, 3H), 1.39–1.25 (m, 3H). 13CNMR (101MHz, Chloroform-d) δ141.22, 140.99, 139.08, 138.70, 135.50, 135.17, 129.00, 128.78, 128.47, 128.33, 127.39, 126.64, 125.68, 1 25.57, 123.46, 122.82, 122.73, 122.40, 121.46, 119.17, 118.78, 114. 56, 113.95, 110.90, 110.84, 48.85, 44.37, 34.55, 32.78, 24.96, 24.78. The high-resolution mass spectrometry detection results are as follows: HRMS (ESI) m / z: [M+Na] + calcdforC 37 H 32 N2SNa559.2178; found559.2176. High performance liquid chromatography detection and optical rotation values ​​are: , HPLC (DaicelChiralpakIA, i -PrOH / hexane=20 / 80, flowrate0.8mL / min, λ=230nm): t1(minor)=6.7min, t2(major)=12.1min. Example 9 The chiral indolo[3,2-b]carbazole derivative as shown in structural formula 3i is prepared by the following method: The compound shown in structural formula 1a (0.50 mmol), carbazole (1.50 mmol), and chiral phosphoric acid (0.050 mmol) were added to a Kirschner flask equipped with a magnetic stirrup. After evacuation and nitrogen purging, 10.0 mL of dichloromethane and toluene in a 1:1 volume ratio were added. The reaction system was then placed in a temperature-controlled environment at 35 °C for 48 h, monitored by TLC. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated by column chromatography (petroleum ether: dichloromethane = 2:1) to obtain the chiral indolo[3,2-b]carbazole derivative (white solid, 90 mg, 57%) shown in structural formula 3i. The chemical reaction formula of this method is as follows:

[0036] The data obtained by nuclear magnetic resonance, melting point, infrared spectroscopy, high-resolution mass spectrometry, and high-performance liquid chromatography of the chiral indodo[3,2-b]carbazole derivative shown in structural formula 3i are as follows: The melting point test result is: 165-168℃ The infrared detection results are: 3124, 3360, 1289, 872, 812, 604 cm. -1 . The results of the nuclear magnetic resonance imaging (NMR) examination are as follows: 1 HNMR (400MHz, Chloroform-d) δ8.46 (s, 1H), 8.23–8.17 (m, 2H), 8.10 (d, J =8.0Hz, 1H), 8.04 (s, 1H), 7.95 (d, J =8.1Hz, 1H), 7.43 (td, J =9.0, 6.8Hz, 6H), 7.34-7.30 (m, 8H), 7.27-7.21 (m, 4H), 7.05 (q, J =7.8Hz, 2H), 6.89 (d, J =7.9Hz, 2H), 6.79 (d, J =8.1Hz, 1H), 5.01 (q, J =5.2Hz, 2H). 13 CNMR (101MHz, Chloroform-d) δ141.18, 140.82, 138.49, 137.93, 135.12, 13 4.54, 131.40, 129.55, 129.01, 128.75, 128.36, 128.28, 127.80, 126.67, 126 .22, 125.73, 125.55, 123.82, 123.03, 122.97, 122.24, 121.50, 120.51, 120. 11, 119.75, 119.36, 118.79, 115.44, 112.67, 110.74, 110.31, 60.56, 34.54. The high-resolution mass spectrometry detection results are as follows: HRMS (ESI) m / z: [M+H] + calcdforC 44 H 31 N3H602.2591; found602.2586. High performance liquid chromatography detection and optical rotation values ​​are: , HPLC (DaicelChiralpakIA, i -PrOH / hexane=30 / 70, flowrate1.0mL / min, λ=230nm): t1(minor)=8.7min, t2(major)=21.1min. Example 10 The chiral indolo[3,2-b]carbazole derivative as shown in structural formula 3j is prepared by the following method: The compound shown in structural formula 1a (0.50 mmol), 2-phenylcarbazole (1.50 mmol), and chiral phosphoric acid (0.050 mmol) were added to a Kirschner flask equipped with a magnetic flask. After evacuation and nitrogen purging, 10.0 mL of a solvent mixture of dichloromethane and toluene in a 1:1 volume ratio was added. The reaction system was then placed in a temperature-controlled environment at 35 °C and reacted for 48 h. The reaction was monitored by TLC. After the reaction was complete, the solvent was removed under reduced pressure, and the mixture was separated by column chromatography (petroleum ether: dichloromethane = 2:1) to obtain the chiral indolo[3,2-b]carbazole derivative (white solid, 100 mg, 66%) shown in structural formula 3j. The chemical reaction formula of this method is as follows:

[0037] The data obtained by nuclear magnetic resonance, melting point, infrared spectroscopy, high-resolution mass spectrometry, and high-performance liquid chromatography of the chiral indodo[3,2-b]carbazole derivative shown in structural formula 3j are as follows: The melting point test result is: 153-154℃ The infrared detection results are: 3404, 3211, 1447, 1336, 868, 709 cm. -1 . The results of the nuclear magnetic resonance imaging (NMR) examination are as follows: 1 HNMR (400MHz, Chloroform-d) δ8.87 (d, J =8.3Hz, 1H), 8.68 (d, J =7.9Hz, 1H), 8.55 (s, 1H), 8.04 (d, J =7.8Hz, 1H), 8.00 (s, 1H), 7.89–7.74 (m, 2H), 7.70 (t, J =7.1Hz, 1H), 7.62 (d, J =9.3Hz, 1H), 7.52–7.33 (m, 7H), 7.33–7.25 (m, 6H), 7.25–7.10 (m, 7H), 7.02–6.92 (m, 3H), 6.71 (d, J =8.1Hz, 1H), 5.03–4.89 (m, 2H). 13CNMR (101MHz, Chloroform-d) δ141.23, 140.88, 138.52, 135.22, 134.76, 12 9.75, 129.25, 129.18, 129.10, 128.91, 128.36, 127.73, 127.13, 126.77, 125 .86, 125.67, 124.80, 123.37, 123.22, 123.04, 122.99, 122.57, 122.32, 120. 59, 119.50, 118.94, 115.73, 112.51, 111.45, 110.82, 110.44, 60.94, 34.62. The high-resolution mass spectrometry detection results are as follows: HRMS (ESI) m / z: [M+Na] + calcdforC 50 H 35 N3Na700.2723; found700.2722. High performance liquid chromatography detection and optical rotation values ​​are: , HPLC (DaicelChiralpakIA, i -PrOH / hexane=20 / 80, flowrate0.8mL / min, λ=230nm): t1(minor)=8.4min, t2(major)=14.9min. Results Analysis As can be seen from Examples 1-10, Figures 1-10 and Table 1, the method of the present invention is applicable to a variety of oxygen-, sulfur-, and nitrogen-containing nucleophiles and 3-(arylethynyl)-1H-indole substrates with different substitutions, and can stably obtain the target chiral indolo[3,2-b]carbazole derivative.

[0038] The obtained products were characterized by melting point, infrared, nuclear magnetic resonance, high-resolution mass spectrometry and chiral chromatography, confirming that the structure was correct. The yield was 16%~72%, and the enantiomeric excess value was up to 99%ee, indicating that the method of the present invention has good substrate universality and high stereoselectivity. At the same time, these new compounds have a rigid non-planar fused π-conjugated framework and a stable chiral center, which can be used as candidate frameworks for chiral optoelectronic functional materials, circularly polarized light-emitting materials, organic semiconductor materials and chiral recognition molecules.

[0039] Table 1 shows the synthesis results of other chiral indodo[3,2-b]carbazole derivatives under the same conditions as in Example 1.

[0040] The detection data for compounds with structural formulas 3k, 3m, and 3o shown in the table are as follows: The detection data for the structural 3K is: mp: 171-172℃; ; IR (KBr): 30461350, 1232, 1178, 641, 585cm -1 ; 1 HNMR (400MHz, DMSO-d6) δ11.08 (s, 1H), 10.53 (s, 1H), 8.16 (s, 1H), 7.86 (s, 1H), 7.48 (dd, J =8.0, 3.7Hz, 3H), 7.40–7.36 (m, 1H), 7.34–7.29 (m, 3H), 7.28–7.22 (m, 4H), 7.16 (d, J =7.9Hz, 3H), 6.94 (s, 1H), 4.96 (s, 2H), 3.73 (p, J =6.1Hz, 1H), 2.38 (s, 6H), 1.36 (d, J =6.0Hz, 3H), 1.08 (d, J =6.3Hz, 3H). 13 CNMR (101MHz, DMSO-d6) δ142.09, 140.31, 140.22, 140.05, 136.18, 128.84, 128.60, 128.50, 127.48, 127.29, 126.92, 126.77, 126. 74, 126.55, 126.36, 122.83, 122.68, 122.48, 121.23, 120.17, 115.03, 114.96, 111.04, 69.60, 55.39, 33.96, 23.55, 21.87, 21.83. HRMS (ESI) m / z: [M+Na] + calcdforC 37 H 34 N2ONa545.2562; found545.2563; HPLC (Daicel Chiralpakia, i -PrOH / hexane=20 / 80, flowrate0.8mL / min, λ=230nm): t1(minor)=5.5min, t2(major)=6.0min. The test data for the 3m structure is: mp: 121-122℃; , 91%ee); IR (KBr): 3046, 2143, 1321, 1178, 852, 729cm -1 ; 1 HNMR (400MHz, Chloroform-d) δ9.47 (s, 1H), 8.23 ​​(dd, J =31.5, 8.2Hz, 2H), 7.97 (s, 1H), 7.57–7.44 (m, 6H), 7.35 (d, J =7.9Hz, 2H), 7.30–7.21 (m, 3H), 7.19 (d, J =7.7Hz, 3H), 7.13 (s, 1H), 5.01 (s, 2H), 3.99 (dt, J =12.2, 6.1Hz, 1H), 2.39 (d, J =10.0Hz, 6H), 1.53 (d, J =6.1Hz, 3H), 1.32 (d, J =6.4Hz, 3H). 13 CNMR (101MHz, Chloroform-d) δ141.30, 140.99, 137.74, 137.51, 136.15, 135.80, 134.95, 134.43, 129.70, 129.34, 128.29, 127.53, 125.5 5, 123.57, 122.92, 122.77, 122.46, 121.01, 119.17, 118.53, 115.40, 114.71, 110.80, 110.46, 70.38, 34.22, 23.35, 21.66, 21.20, 21.13. HRMS (ESI) m / z: [M+Na] + calcdforC 37 H 34 N2ONa545.2563;found545.2545; HPLC (Daicel Chiralpakia, i -PrOH / hexane=20 / 80, flowrate0.8mL / min, λ=230nm): t1(minor)=5.5min, t2(major)=7.3min. The detection data for structural type 3O is: mp: 157-158℃; , 87%ee); IR (KBr): 3212, 2120, 1623, 1105, 983, 643cm-1 ; 1 HNMR (400MHz, Chloroform-d) 1 HNMR (400MHz, Chloroform-d) δ9.46 (s, 1H), 8.10 (dd, J =12.9, 8.0Hz, 2H), 7.89 (s, 1H), 7.47–7.43 (m, 2H), 7.42–7.34 (m, 4H), 7.34–7.24 (m, 5H), 7.23–7.08 (m, 5H), 7.07 (s, 1H), 4.95 (d, J =3.1Hz, 2H), 1.31 (s, 9H). 13 CNMR (101MHz, Chloroform-d) δ141.75, 141.31, 141.09, 138.94, 134.91, 134.79, 129.03, 128.55, 128.38, 127.53, 127.35, 126.63, 12 5.57, 125.51, 123.63, 122.77, 122.67, 122.43, 119.60, 119.26, 118.58, 118.43, 113.88, 110.84, 110.55, 76.26, 72.76, 34.60, 28.48. HRMS (ESI) m / z: [M+Na] + calcdforC 36 H 32 N2ONa531.2407;found531.2406; HPLC (Daicel Chiralpakia, i -PrOH / hexane=20 / 80, flowrate0.8mL / min, λ=230nm): t1(minor)=5.7min, t2(major)=8.2min. Other structurally similar compounds can be prepared and characterized using the methods described above, and will not be repeated here.

[0041] Furthermore, the embodiments of the present invention also provide the application of the chiral indodo[3,2-b]carbazole derivatives obtained in the above specific embodiments in the preparation of chiral optoelectronic functional materials, wherein the chiral optoelectronic functional materials are selected from circularly polarized light-emitting materials, organic electroluminescent materials, organic semiconductor materials or chiral recognition materials.

[0042] Since the ICZ framework has already shown excellent application potential in the field of organic electronic materials, the chiral nonplanar π system has further application potential in the field of chiral optoelectronics.

[0043] Specifically, the chiral indodo[3,2-b]carbazole derivative with structural formula 3a prepared in Example 1 and the chiral indodo[3,2-b]carbazole derivative with structural formula 3i prepared in Example 9 were detected by ultraviolet (UV), fluorescence (PL), circular dichroism (CD), and circular polarization spectroscopy (CPL). The chiral indolo[3,2-b]carbazole derivatives represented by structural formulas 3a and 3i were subjected to ultraviolet spectroscopy for detection, as follows: Figure 11 As shown, through analysis Figure 11 It can be seen that the ultraviolet-visible absorption spectrum shows characteristic absorption peaks at 276, 336 and about 403 nm.

[0044] Fluorescence spectroscopy was performed on the chiral indolo[3,2-b]carbazole derivatives shown in structural formulas 3a and 3i, respectively, as follows: Figure 12 As shown, through analysis Figure 12 It can be seen that the fluorescence spectrum shows a broad emission band in the range of 394-467 nm, with the main absorption peaks located near 404 and 434 nm.

[0045] The chiral indolo[3,2-b]carbazole derivatives represented by structural formulas 3a and 3i were subjected to CD and CPL spectral analysis, respectively, as detailed below. Figure 13 and Figure 14 As shown, through analysis Figure 13 and Figure 14 It can be seen that the enantiomers such as R / S-3a and R / S-3i exhibit mirror-symmetric circular dichroism, confirming the persistent optical activity in the ground state.

[0046] Furthermore, circular polarization spectral measurements of R / S-3i revealed a significant asymmetric emission signal. The value is 1.5 × 10 -4 .

[0047] In summary, this invention is the first to directly construct a chiral indolo[3,2-b]carbazole skeleton via a chiral phosphoric acid catalytic strategy. This method features mild reaction conditions, a simple one-pot operation, and applicability to nucleophiles with oxygen, sulfur, and nitrogen centers. The resulting chiral indolo[3,2-b]carbazole derivative possesses a rigid, nonplanar fused π-conjugated skeleton, a benzylic chiral center, significant optical rotation, and high enantiomeric purity. It can be protected as an independent compound or is suitable for further development as a chiral photoelectric functional molecular framework.

[0048] Furthermore, by applying the chiral indodo[3,2-b]carbazole derivative of this invention to the preparation of chiral optoelectronic functional materials, the application of the chiral indodo[3,2-b]carbazole derivative is effectively extended, given that the ICZ framework has already shown excellent application potential in the field of organic electronic materials, and the chiral nonplanar π system has further application potential in the field of chiral optoelectronics. This also lays a solid foundation for future research on chiral optoelectronic functional materials.

[0049] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A chiral indolo[3,2-b]carbazole derivative, characterized in that, Its structure is shown in equation (3): （3） Wherein, Ar is hydrogen, 7-methyl, 5-methyl, 5-bromine, or 5-chloro; R1 is at least one of phenyl, 4-methylphenyl, 4-chlorophenyl, or tert-butyl-substituted phenyl; X is O, S, or N; R2 is a substituent connected to X, selected from at least one of benzyl, substituted benzyl, C1-C6 straight-chain or branched alkyl, C3-C8 cycloalkyl, carbazolyl, or substituted carbazolyl.

2. The method for preparing the chiral indolo[3,2-b]carbazole derivative according to claim 1, characterized in that, Using the 3-(arylethynyl)-1H-indole derivative shown in formula (1) and the nucleophile shown in formula (2) as raw materials, a dimerization-triggered cascade reaction was carried out in the presence of a chiral phosphoric acid catalyst to obtain the chiral indolo[3,2-b]carbazole derivative shown in formula (3), the reaction formula of which is as follows: The nucleophile is selected from alcohols, thiols, carbazoles or their derivatives.

3. The method for preparing the chiral indolo[3,2-b]carbazole derivative according to claim 2, characterized in that, The specific method is as follows: the 3-(arylethynyl)-1H-indole derivative shown in formula (1), the nucleophile shown in formula (2) and the chiral phosphoric acid catalyst are dissolved in an organic solvent under an inert atmosphere and reacted at 10-35℃ for 48-96h. After the reaction is completed, the chiral indolo[3,2-b]carbazole derivative shown in formula (3) is obtained by purification.

4. The method for preparing the chiral indolo[3,2-b]carbazole derivative according to claim 2 or 3, characterized in that, The molar concentration of the 3-(arylethynyl)-1H-indole derivative in the reaction system is 0.02~0.08 mol / L.

5. The method for preparing the chiral indolo[3,2-b]carbazole derivative according to claim 4, characterized in that, The molar ratio of the 3-(arylethynyl)-1H-indole derivative to the nucleophile is 1:(2~5).

6. The method for preparing the chiral indolo[3,2-b]carbazole derivative according to any one of claims 4, characterized in that, The molar ratio of the 3-(arylethynyl)-1H-indole derivative to the chiral phosphoric acid catalyst is 1:0.05~0.

15.

7. The method for preparing the chiral indolo[3,2-b]carbazole derivative according to claim 4, characterized in that, The organic solvent is selected from at least one of a mixed solvent of dichloromethane and toluene in a volume ratio of 1:(0.8~1.2), carbon tetrachloride, or acetonitrile.

8. The method for preparing the chiral indolo[3,2-b]carbazole derivative according to claim 5, characterized in that, The nucleophile is selected from at least one of benzyl alcohols, C1-C6 fatty alcohols, C3-C8 cyclic alcohols, C1-C6 alkyl thiols, C3-C8 cycloalkyl thiols, carbazole, or substituted carbazole.

9. The use of a chiral indodo[3,2-b]carbazole derivative according to any one of claims 1-8 in the preparation of chiral optoelectronic functional materials.

10. The application according to claim 9, characterized in that, The chiral optoelectronic functional material is selected from at least one of circularly polarized light-emitting materials, organic electroluminescent materials, organic semiconductor materials, or chiral recognition materials.

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