Red-light nitrogen-thia-bis (9-helicene) as well as synthesis method and application thereof

Abstract

The invention relates to the technical field of helicene compound synthesis processes, in particular to red-light nitrogen-thia-bis (9-helicene) and a synthesis method and application thereof.The red-light nitrogen-thia-bis (9-helicene) is characterized in that benzothiophene-2-boric acid is used as a raw material, 2-bromo-4-(tert-butyl)-1-iodobenzene, a catalyst and anhydrous potassium carbonate are added, and a compound 2 is obtained through heating reaction; taking the compound 2 as a raw material, adding n-butyllithium for reaction, and then adding trimethyl borate to obtain a compound 3; taking the compound 3 as a raw material, adding 1-bromo-3, 6-diiodocarbazole, a catalyst and anhydrous potassium carbonate, and carrying out heating reaction to obtain a compound 4; taking the compound 4 as a raw material, and adding an anhydrous ferric trichloride solution dissolved by nitromethane to obtain a compound 5; the preparation method comprises the following steps: taking a compound 5 as a raw material, adding sodium tert-butoxide, a catalyst and a phosphine ligand, carrying out a heating reaction to obtain a compound 6, i.e., red-light aza-bis (9-helicene), and embedding an anti-aromaticity module into a bis-helicene system to finally obtain the aza-bis (9-helicene) compound with exocarpium citri grandis fluorescence emission.

Description

Technical Field

[0001] The present invention relates to the technical field of the synthesis process of helicene compounds, and particularly relates to a red-light nitrogen-sulfur heterobisnonacene helicene and its synthesis method and application. Background Art

[0002] Chirality is a fundamental property of nature, referring to the property that an object is similar to but non-superimposable on its mirror image. Chirality is ubiquitous from small molecules, macromolecules to the macroscopic material world. In the field of organic small molecules, chirality is mainly divided into central chirality, helical chirality, planar chirality, and axial chirality.

[0003] Helicenes and their derivatives are one of the typical helical chiral compounds, which are unique polycyclic aromatic hydrocarbon compounds with a non-planar helical skeleton formed by ortho-fused benzene or other aromatic rings. Helicene compounds usually exhibit unique chiral optical properties, and the π-conjugated system of helicenes can be extended by introducing other heteroatoms or luminescent groups on their skeletons, which makes it an ideal skeleton for designing and synthesizing compounds with excellent circularly polarized luminescence properties. The helical nanographene structure has attracted great interest due to its unique kinetic behavior and thermodynamic properties, and has broad application prospects in the fields of 3D display, optical switches, and chiral sensing, etc.

[0004] Compared with single helicenes, the synthesis of bishelicenes has higher novelty and provides a design strategy for synthesizing novel helicene topologies. Moreover, the π-conjugation of bishelicenes increases, which is beneficial to the red shift of the fluorescence spectrum and the enhancement of luminescence performance. In addition, studying the chiral luminescence properties of bishelicenes can better study the essence of chirality. However, due to the great difficulty in synthesizing polycyclic aromatic hydrocarbon compounds of bishelicenes, high-performance circularly polarized luminescence bishelicene compounds are even rarer, especially the reports of bishelicene compounds emitting red light or near-infrared light with long-wave emission are relatively rare. And chiral molecules with long-wave emission have received extensive attention in liquid crystal materials, biomedicine, and photodetectors, etc.

[0005] The π-conjugated system with antiaromaticity has received extensive attention as the core skeleton of organic optoelectronic materials. Embedding antiaromatic modules into the π-conjugated system can often obtain near-infrared photophysical properties and multiple redox behaviors. However, the existing methods for synthesizing antiaromatic polycyclic aromatic hydrocarbon compounds are difficult, and the performance of the synthesized products is poor. Summary of the Invention

[0006] Aiming at the above deficiencies of the prior art, the purpose of the present invention is to provide a red-light nitrogen-sulfur heterobisnonacene helicene and its synthesis method and application. The present invention embeds an antiaromatic module into the bishelicene system, and finally obtains a nitrogen-sulfur heterobisnonacene helicene compound with orange-red light fluorescence emission.

[0007] To solve the above technical problems, the present invention adopts the following technical solutions: A synthetic method of red-light nitrogen-sulfur hetero double nonahelicene, comprising the following steps: In a mixed solvent of an organic solvent and water, using benzo[b]thiophene-2-boronic acid as a raw material, under a protective atmosphere, 2-bromo-4-(tert-butyl)-1-iodobenzene, a palladium catalyst and anhydrous potassium carbonate are added thereto, and the reaction is carried out by heating. The iodine in 2-bromo-4-(tert-butyl)-1-iodobenzene undergoes oxidative addition with the palladium catalyst to form an organopalladium intermediate 1. Anhydrous potassium carbonate removes the halogen in the organopalladium intermediate 1 and combines with it to form an organopalladium intermediate 2. After benzo[b]thiophene-2-boronic acid combines with potassium carbonate, it undergoes transmetalation with the organopalladium intermediate 2, the boric acid is removed, the original group connected to the boric acid combines with palladium, and finally compound 2 is obtained through reductive elimination.

[0008] In an organic solvent, using compound 2 as a raw material, under a protective atmosphere, n-butyllithium is added thereto for reaction, and then trimethyl borate is added. N-butyllithium removes the halogen of compound 2, and the carbon anion here attacks trimethyl borate after the halogen is removed, and compound 3 is obtained through subsequent acidification.

[0009] In a mixed solvent of an organic solvent and water, using compound 3 as a raw material, under a protective atmosphere, 1-bromo-3,6-diiodocarbazole, a palladium catalyst and anhydrous potassium carbonate are added thereto, and the reaction is carried out by heating. 1-bromo-3,6-diiodocarbazole undergoes oxidative addition with the palladium catalyst to form an organopalladium intermediate 3. Anhydrous potassium carbonate removes the halogen in the organopalladium intermediate 3 and combines with it to form an organopalladium intermediate 4. After compound 3 combines with potassium carbonate, it undergoes transmetalation with the organopalladium intermediate 4, the boric acid in compound 3 is removed, the original group connected to the boric acid combines with palladium, and finally compound 4 is obtained through reductive elimination.

[0010] In an organic solvent, using compound 4 as a raw material, under a protective atmosphere, an anhydrous iron(III) chloride solution dissolved in nitromethane is added thereto for oxidative dehydrogenation cyclization reaction to obtain compound 5.

[0011] In an organic solvent, using compound 5 as a raw material, under a protective atmosphere, sodium tert-butoxide, a palladium catalyst and a phosphine ligand are added thereto, and the reaction is carried out by heating. First, the halogenated hydrocarbon undergoes oxidative addition with the palladium catalyst, the N-H bond in compound 5 further undergoes oxidative addition with the palladium catalyst, and the base removes the H on the N. Finally, the final product, namely compound 6 red-light nitrogen-sulfur hetero double nonahelicene, is obtained through reductive elimination.

[0012] The synthetic route is: 。

[0013] In the present invention, an antiaromatic module is embedded into the bishelicene system, and the synthesized bishelicene compound has strong stability, good luminescence performance, and strong orange-red light emission in the solid state.

[0014] In a preferred embodiment of the present invention, the mass ratio of benzo[b]thiophene-2-boronic acid to 2-bromo-4-(tert-butyl)-1-iodobenzene is 6.3:10, the mass ratio of the palladium catalyst to benzo[b]thiophene-2-boronic acid is 0.414 - 0.6:6.3, and the mass ratio of anhydrous potassium carbonate to benzo[b]thiophene-2-boronic acid is 10.2:6.3.

[0015] In a preferred embodiment of the present invention, when synthesizing Compound 2, the heating reaction temperature is 80 °C, and the heating reaction time is 12 h - 15 h.

[0016] In a preferred embodiment of the present invention, the dosage ratio of Compound 2 to n-butyllithium and trimethyl borate is 11.5 g:16 mL:20 g - 30 g.

[0017] In a preferred embodiment of the present invention, when preparing Compound 3, the reaction temperature is raised from -78 °C to room temperature.

[0018] In a preferred embodiment of the present invention, the mass ratio of Compound 3 to 1-bromo-3,6-diiodocarbazole is 5.24:4, the mass ratio of the palladium catalyst to Compound 3 is 0.426 - 0.6:5.24, the mass ratio of anhydrous sodium carbonate to Compound 3 is 2.78:5.24, and the heating reaction temperature for preparing Compound 4 is 100 °C.

[0019] In a preferred embodiment of the present invention, the dosage ratio of Compound 4 to the anhydrous ferric chloride solution dissolved in nitromethane is 500 mg:10 mL, and the dosage ratio of the nitromethane solution to anhydrous ferric chloride is 10 mL - 1 g - 1.5 g.

[0020] In a preferred embodiment of the present invention, the mass ratio of Compound 5 to sodium tert-butoxide is 2:1, the mass ratio of the palladium catalyst to Compound 5 is 1:4, and the mass ratio of the phosphine ligand to Compound 5 is 8:25.

[0021] The second object of the present invention is to provide a red-light nitrogen-sulfur heterobisnonaspiroacene, with the structural formula: .

[0022] The planar structures after rotating at different angles are as follows: .

[0023] The third object of the present invention is to provide an application of the above-mentioned red-light nitrogen-sulfur heterobisnonaspiroacene in organic optoelectronic materials.

[0024] Compared with the prior art, the beneficial effects of the present invention are: The synthesis method of the red-light nitrogen-sulfur heterobinaphthylene provided by the present invention uses benzothiophene-2-boronic acid as a raw material. Under a protective atmosphere, 2-bromo-4-(tert-butyl)-1-iodobenzene, a catalyst, and anhydrous potassium carbonate are added thereto, and heated to carry out a Suzuki-Miyaura catalytic coupling reaction to obtain Compound 2. Then, using Compound 2 as a raw material, under a protective atmosphere, n-butyllithium is added thereto for reaction, and then trimethyl borate is added. The n-butyllithium removes the halogen atom in Compound 2, and then the carbanion attacks trimethyl borate, and Compound 3 is obtained through acidification. Then, using Compound 3 as a raw material, under a protective atmosphere, 1-bromo-3,6-diiodocarbazole, a catalyst, and anhydrous potassium carbonate are added thereto, and heated to carry out a Suzuki-Miyaura catalytic coupling reaction to obtain Compound 4. Using Compound 4 as a raw material, under a protective atmosphere, an anhydrous ferric chloride solution dissolved in nitromethane is added thereto to carry out an oxidative dehydrogenation cyclization reaction to obtain Compound 5. Finally, using Compound 5 as a raw material, under a protective atmosphere, sodium tert-butoxide, a catalyst, and a phosphine ligand are added thereto, and heated to carry out a Buchwald-Hartwig carbon-nitrogen metal catalytic coupling reaction to obtain Compound 6, red-light nitrogen-sulfur heterobinaphthylene. The present invention embeds an anti-aromatic module into the binaphthylene system. The synthesized binaphthylene compound has strong stability, good luminescence performance, and the solid has strong orange-red light emission. Description of the Drawings

[0025] Figure 1 1H NMR spectrum of Compound 6 prepared in Example 1 of the present invention.

[0026] Figure 2 Mass spectrum of Compound 6 prepared in Example 1 of the present invention.

[0027] Figure 3 Absorption and emission spectra of Compound 6 prepared in Example 1 of the present invention in toluene and dichloromethane and the emission spectrum in the solid state. Detailed Embodiments

[0028] The following combines the embodiments of the present invention to describe the technical solutions in the embodiments of the present invention clearly and completely with the preferred embodiments and the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.

[0029] It should be noted that all the professional terms used in the present invention are only for the purpose of describing specific embodiments, and are not intended to limit the protection scope of the present invention. Unless otherwise specifically stated, various raw materials, reagents, instruments and equipment used in the following embodiments of the present invention can be obtained through market purchase or prepared by existing methods.

[0030] Example 1 A method for synthesizing a red-light nitrogen-sulfur heterobisnonaspiroacene, comprising the following steps: The synthesis route is as follows: 。

[0031] (1) Place 6.3 g of compound 1, benzothiophene-2-boronic acid, 10 g of 2-bromo-4-(tert-butyl)-1-iodobenzene, 414 mg of Pd(PPh3)2Cl2 catalyst, and 10.2 g of anhydrous potassium carbonate in a reaction flask, add 160 mL of the solvent ethylene glycol dimethyl ether and 22 mL of water, perform freeze deoxygenation three times under nitrogen protection, heat and stir the reaction at 80 °C for 12 h, cool the reaction to room temperature after completion, extract with ethyl acetate, combine the organic phases, and purify by column chromatography to obtain compound 2 with a yield of 40%.

[0032] (2) Weigh 11.5 g of compound 2 into a reaction flask, evacuate and replace with nitrogen 3 times, add anhydrous tetrahydrofuran from the purification system, place the reaction flask in a cryostat at -78 °C after replenishing nitrogen, slowly dropwise add 16 mL of 2.5 M n-butyllithium, and stir at -78 °C for 1 hour. After 1 hour, slowly dropwise add 30 g of trimethyl borate. After the addition is complete, turn off the refrigeration, let it stir overnight and slowly return to room temperature. After the reaction is complete, add dilute hydrochloric acid to the reaction flask, extract with ethyl acetate, combine the organic phases, dry and recrystallize with n-hexane to obtain compound 3 with a yield of 84%.

[0033] (3) Place 5.24 g of compound 3, 4 g of 1-bromo-3,6-diiodocarbazole, 426 mg of Pd(PPh3)4 catalyst, and 2.78 g of anhydrous potassium carbonate in a reaction flask, add a mixed solvent of toluene, ethanol and water with a volume ratio of 40:20:20, perform freeze deoxygenation three times under nitrogen protection, heat and stir the reaction under reflux overnight for 12 h, cool the reaction to room temperature after completion, extract with ethyl acetate, combine the organic phases, and purify by column chromatography to obtain compound 4 with a yield of 70%.

[0034] (4) Weigh 500 mg of Compound 4 and place it in a reaction flask. Purge with nitrogen three times and fill the reaction flask with nitrogen. Add anhydrous dichloromethane and cool the reaction flask to 0 °C. Take another small flask, add 1.1 g of anhydrous ferric chloride, add nitromethane solution to the small flask, and ultrasonically dissolve the ferric chloride solid in the nitromethane solution. Slowly drip the nitromethane solution of ferric chloride into the reaction flask, stir at 0 °C for one hour. After the reaction is completed, quench the reaction with saturated sodium bicarbonate aqueous solution, extract with dichloromethane solution, combine the organic layers, and purify by column chromatography to obtain Compound 5 with a yield of 50%.

[0035] (5) Place 100 mg of Compound 5, 50 mg of sodium tert-butoxide, 25 mg of Pd2dba3 catalyst, and 32 mg of P( t -Bu)3HBF4 phosphine ligand in a reaction flask, add anhydrous toluene as the solvent, perform freeze-deoxygenation three times under nitrogen protection, heat and stir the reaction under reflux overnight for 15 h. After the reaction is completed, cool to room temperature, extract with ethyl acetate, combine the organic phases, and purify by column chromatography and recrystallization to obtain Compound 6 with a yield of 20%.

[0036] The 1H NMR data of Compound 6 are as follows: 1 H NMR (400 MHz, chloroform) δ 9.57 (s, 2H), 9.28 (d, J = 8 Hz, 2H), 9.03 (d, J = 8 Hz, 2H), 8.93 (d, J = 8 Hz, 4H), 7.93 (m,,4H), 7.79 - 7.74 (m, 4H), 7.67 (d, J = 8 Hz, 4H), 6.80 – 6.73 (m, 4H), 6.53 (d,J = 8 Hz, 2H), 6.34 (d, J = 8 Hz, 2H), 5.86 – 5.79 (m, 4H), 1.56 (s, 36H).

[0037] Example 2 A method for synthesizing a red-light nitrogen-sulfur heterobinaphthylene, comprising the following steps: The synthesis route is as follows: .

[0038] (1) Place 6.3 g of compound 1, benzothiophene-2-boronic acid, 10 g of 2-bromo-4-(tert-butyl)-1-iodobenzene, 500 mg of Pd(PPh3)2Cl2 catalyst, and 10.2 g of anhydrous potassium carbonate in a reaction flask. Add 160 mL of the solvent ethylene glycol dimethyl ether and 22 mL of water. Conduct freeze deoxygenation three times under nitrogen protection. Heat and stir the reaction at 80 °C for 13 h. After the reaction is completed, cool to room temperature, extract with ethyl acetate, combine the organic phases, and purify by column chromatography to obtain compound 2.

[0039] (2) Weigh 11.5 g of compound 2 and place it in a reaction flask. Purge with nitrogen three times. Add anhydrous tetrahydrofuran from the purification system. After replenishing nitrogen, place the reaction flask in a cryostat at -78 °C. Slowly add 16 mL of 2.5 M n-butyllithium dropwise and stir at -78 °C for 1 h. After 1 h, slowly add 20 g of trimethyl borate dropwise. After the addition is complete, turn off the refrigeration and let it stir overnight and slowly return to room temperature. After the reaction is completed, add dilute hydrochloric acid to the reaction flask and extract with ethyl acetate. Combine the organic phases, dry, and recrystallize with n-hexane to obtain compound 3.

[0040] (3) Place 5.24 g of compound 3, 4 g of 1-bromo-3,6-diiodocarbazole, 500 mg of Pd(PPh3)4 catalyst, and 2.78 g of anhydrous potassium carbonate in a reaction flask. Add a mixed solvent of toluene, ethanol, and water with a volume ratio of 40:20:20. Conduct freeze deoxygenation three times under nitrogen protection. Heat and stir the reaction under reflux overnight for 12 h. After the reaction is completed, cool to room temperature, extract with ethyl acetate, combine the organic phases, and purify by column chromatography to obtain compound 4.

[0041] (4) Weigh 500 mg of compound 4 and place it in a reaction flask. Purge with nitrogen three times and fill the reaction flask with nitrogen. Add anhydrous dichloromethane and cool the reaction flask to 0 °C. Take another small flask, add 1.0 g of anhydrous ferric chloride, and add nitromethane solution to the small flask. Ultrasonically dissolve the ferric chloride solid in the nitromethane solution. Slowly add the ferric chloride nitromethane solution dropwise to the reaction flask and stir at 0 °C for 1 h. After the reaction is completed, quench the reaction with saturated aqueous sodium bicarbonate, extract with dichloromethane solution, combine the organic layers, and purify by column chromatography to obtain compound 5.

[0042] (5) Place 100 mg of compound 5, 50 mg of sodium tert-butoxide, 25 mg of Pd2dba3 catalyst, and 32 mg of P( t -Bu)3HBF4 phosphine ligand in a reaction flask. Add the solvent anhydrous toluene. Conduct freeze deoxygenation three times under nitrogen protection. Heat and stir the reaction under reflux overnight for 12 h. After the reaction is completed, cool to room temperature, extract with ethyl acetate, combine the organic phases, and purify by column chromatography and recrystallization to obtain compound 6.

[0043] Example 3 A method for synthesizing a red-light nitrogen-sulfur heterobinaphthylene includes the following steps: The synthesis route is as follows: 。

[0044] (1) Place 6.3 g of compound 1, benzothiophene-2-boronic acid, 10 g of 2-bromo-4-(tert-butyl)-1-iodobenzene, 600 mg of Pd(PPh3)2Cl2 catalyst, and 10.2 g of anhydrous potassium carbonate in a reaction flask. Add 160 mL of the solvent ethylene glycol dimethyl ether and 22 mL of water. Conduct freeze deoxygenation three times under nitrogen protection. Heat and stir the reaction at 80 °C for 15 h. After the reaction ends, cool to room temperature, extract with ethyl acetate, combine the organic phases, and purify by column chromatography to obtain compound 2.

[0045] (2) Weigh 11.5 g of compound 2 and place it in a reaction flask. Purge with nitrogen 3 times. Add anhydrous tetrahydrofuran from the purification system. After replenishing nitrogen, place the reaction flask in a cryostat at -78 °C. Slowly add 16 mL of 2.5 M n-butyllithium dropwise and stir at -78 °C for 1 h. After 1 h, slowly add 25 g of trimethyl borate dropwise. After the addition is complete, turn off the refrigeration and let it stir overnight and slowly return to room temperature. After the reaction ends, add dilute hydrochloric acid to the reaction flask and extract with ethyl acetate. Combine the organic phases, dry, and recrystallize with n-hexane to obtain compound 3.

[0046] (3) Place 5.24 g of compound 3, 4 g of 1-bromo-3,6-diiodocarbazole, 600 mg of Pd(PPh3)4 catalyst, and 2.78 g of anhydrous potassium carbonate in a reaction flask. Add a mixed solvent of toluene, ethanol, and water with a volume ratio of 40:20:20. Conduct freeze deoxygenation three times under nitrogen protection. Heat and stir the reaction under reflux overnight for 12 h. After the reaction ends, cool to room temperature, extract with ethyl acetate, combine the organic phases, and purify by column chromatography to obtain compound 4.

[0047] (4) Weigh 500 mg of compound 4 and place it in a reaction flask. Purge with nitrogen 3 times and fill the reaction flask with nitrogen. Add anhydrous dichloromethane and cool the reaction flask to 0 °C. Take another small flask, add 1.5 g of anhydrous ferric chloride, add nitromethane solution to the small flask, and ultrasonically dissolve the ferric chloride solid in the nitromethane solution. Slowly add the nitromethane solution of ferric chloride to the reaction flask and stir at 0 °C for 1 h. After the reaction ends, quench the reaction with saturated aqueous sodium bicarbonate, extract with dichloromethane solution, combine the organic layers, and purify by column chromatography to obtain compound 5.

[0048] (5) Place 100 mg of Compound 5, 50 mg of sodium tert-butoxide, 25 mg of Pd2dba3 catalyst, and 32 mg of P( t -Bu)3HBF4 phosphine ligand in a reaction flask, add anhydrous toluene as the solvent, and perform freeze-deoxygenation three times under nitrogen protection. Heat and stir the reaction under reflux overnight for 14 h. After the reaction is completed and cooled to room temperature, extract with ethyl acetate, combine the organic phases, and obtain Compound 6 after purification by column chromatography and recrystallization.

[0049] The synthesis methods of Example 2 and Example 3 are the same as that of Example 1, except that the amounts of some raw materials and reaction conditions are changed. Red-light nitrogen-sulfur hetero-bisnonahelicene can also be synthesized by the methods of Example 2 and Example 3, and it has strong orange-red light emission.

[0050] Result Analysis From Figure 1 it can be seen that according to the characteristic peaks and integrals of NMR, the product can be confirmed to be the designed product, red-light nitrogen-sulfur hetero-bisnonahelicene. Figure 2 The molecular weight of the mass spectrometry peak is consistent with that of the designed molecule, which verifies the correctness of the product again. According to Figure 3 it can be known that its maximum fluorescence emission peak of fluorescence is at 510 nm, and there is also one at 560 nm. Its liquid emits green fluorescence; its solid-state emission peaks are at 580 nm and 620 nm, and its solid emits orange-red fluorescence. In the present invention, an anti-aromatic module is embedded in the bishelicene system, and finally a nitrogen-sulfur hetero-bisnonahelicene compound with orange-red light fluorescence emission is obtained.

[0051] It should be noted that when the present invention involves a numerical range, it should be understood that both endpoints of each numerical range and any value between the two endpoints can be selected. Since the adopted step methods are the same as those of the examples, in order to prevent repetition, the present invention describes the preferred examples. Although the preferred embodiments of the present invention have been described, those skilled in the art can make additional changes and modifications to these embodiments once they know the basic creative concept. Therefore, the scope of the appended protection is intended to be interpreted as including the preferred embodiments and all changes and modifications falling within the scope of the present invention.

[0052] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the present invention and its equivalent technologies, the present invention also intends to include these modifications and variations.

Claims

1. A synthetic method of red-light nitrogen-sulfur heterobisnonacene, characterized in that, It includes the following steps: In a mixed solvent of an organic solvent and water, using benzo[b]thiophene-2-boronic acid as a raw material, under a protective atmosphere, add 2-bromo-4-(tert-butyl)-1-iodobenzene, a palladium catalyst, and anhydrous potassium carbonate thereto, heat, and carry out a Suzuki-Miyaura catalytic coupling reaction to obtain Compound 2; In an organic solvent, using Compound 2 as a raw material, under a protective atmosphere, add n-butyllithium thereto for reaction, and then add trimethyl borate. The n-butyllithium removes the halogen atom in Compound 2, and then the carbanion attacks trimethyl borate, and Compound 3 is obtained through acidification; In a mixed solvent of an organic solvent and water, using Compound 3 as a raw material, under a protective atmosphere, add 1-bromo-3,6-diiodocarbazole, a palladium catalyst, and anhydrous potassium carbonate thereto, heat, and carry out a Suzuki-Miyaura catalytic coupling reaction to obtain Compound 4; In an organic solvent, using Compound 4 as a raw material, under a protective atmosphere, add an anhydrous ferric chloride solution dissolved in nitromethane thereto, and carry out an oxidative dehydrogenation cyclization reaction to obtain Compound 5; In an organic solvent, using Compound 5 as a raw material, under a protective atmosphere, add sodium tert-butoxide, a palladium catalyst, and a phosphine ligand thereto, heat, and carry out a Buchwald-Hartwig carbon-nitrogen metal catalytic coupling reaction to obtain Compound 6, a red-light nitrogen-sulfur heterobisnonahelicene; The synthetic route is: 。 2. The synthesis method of the red-light nitrogen-sulfur heterobisnonacenequinone according to claim 1, wherein The mass ratio of benzo[b]thiophene-2-boronic acid to 2-bromo-4-(tert-butyl)-1-iodobenzene is 6.3:10, the mass ratio of the palladium catalyst to benzo[b]thiophene-2-boronic acid is 0.414 - 0.6:6.3, and the mass ratio of anhydrous potassium carbonate to benzo[b]thiophene-2-boronic acid is 10.2:6.

3.

3. The synthesis method of the red-light nitrogen-sulfur heterobisnonacenequinone according to claim 1, wherein When synthesizing Compound 2, the heating reaction temperature is 80 °C, and the heating reaction time is 12 h - 15 h.

4. The synthesis method of the red-light nitrogen-sulfur heterobisnonacene according to claim 1, wherein The dosage ratio of Compound 2 to n-butyllithium and trimethyl borate is 11.5 g:16 mL:20 g - 30 g.

5. The synthesis method of the red-light nitrogen-sulfur heterobisnonacene according to claim 1, characterized in that, The reaction temperature for preparing Compound 3 is from -78 °C to room temperature.

6. The synthesis method of the red-light nitrogen-sulfur heterobisnonacenequinone according to claim 1, wherein The mass ratio of Compound 3 to 1-bromo-3,6-diiodocarbazole is 5.24:4, the mass ratio of the palladium catalyst to Compound 3 is 0.426 - 0.6:5.24, the mass ratio of anhydrous sodium carbonate to Compound 3 is 2.78:5.24, and the heating reaction temperature for preparing Compound 4 is 100 °C.

7. The synthesis method of the red-light nitrogen-sulfur heterobisnonacenequinone according to claim 1, characterized in that, The dosage ratio of Compound 4 to the anhydrous ferric chloride solution dissolved in nitromethane is 500 mg:10 mL, and the dosage ratio of the nitromethane solution to anhydrous ferric chloride is 10 mL:1 g - 1.5 g.

8. The synthesis method of the red-light nitrogen-sulfur heterobisnonahelicene according to claim 1, wherein The mass ratio of Compound 5 to sodium tert-butoxide is 2:1, the mass ratio of the palladium catalyst to Compound 5 is 1:4, and the mass ratio of the phosphine ligand to Compound 5 is 8:

25.

9. A red-light nitrogen-sulfur heterobisnonacene prepared by the preparation method according to any one of claims 1 to 8, characterized in that, The structural formula of the red-light nitrogen-sulfur heterobisnonahelicene is: 。 10. Application of the red-light nitrogen-sulfur heterobisnonahelicene according to Claim 9 in organic optoelectronic materials.

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