Synthesis method of chalcogen-doped bowl-shaped molecule graphene

Abstract

The application discloses a synthesis method of a chalcogen hetero-bowl-shaped molecule graphene, which comprises the following steps: taking cheap and easily obtained 2-bromo-5-chloroacetophenone as raw material, obtaining a trimer product thereof under the catalysis of trifluoromethanesulfonic acid, then introducing sulfur or selenium atoms through Suzuki coupling, Friedel-Crafts acylation and Scholl reaction, and finally obtaining the chalcogen hetero-bowl-shaped molecule graphene. The method has the advantages of short synthesis steps, mild reaction conditions, simple operation and the like, and most importantly, the sulfur or selenium atoms are introduced without the previous palladium catalysis, but in the case of metal-free catalysis, and the yield is high. The compound shows excellent electrical properties and has great application value in organic light-emitting diodes and semiconductor materials.

Description

Technical Field

[0001] This invention belongs to the field of polycyclic aromatic hydrocarbon synthesis technology, specifically relating to a method for synthesizing chalcogenide heterobowl-shaped graphene molecules. Background Technology

[0002] Polycyclic aromatic hydrocarbons (PAHs), also known as nanographene molecules, are closely related to fundamental theoretical research and organic optoelectronic functional materials due to their clear molecular structure, excellent optoelectronic properties, and precise self-assembly characteristics. Research on PAHs has become an important interdisciplinary field at the intersection of chemistry, physics, materials science, and biology. Since the discovery of graphene, PAHs have attracted increasing attention and are hailed as "miracle" materials of the 21st century.

[0003] Hexabenzocoronen (HBC) and its derivatives, as an important class of organic molecules in polycyclic aromatic hydrocarbons (PAHs), have a long synthetic history and a comprehensive research background. Based on the position of their outer benzene rings, hexabenzocoronen can be further divided into two categories: planar hexa-peri-hexabenzocoronen (p-HBC), which shares two carbon-carbon bonds with the benzene ring, and biconcave hexa-cata-hexabenzocoronen (c-HBC), which shares one carbon-carbon bond with the benzene ring. Using these two types of molecules as parent molecules has greatly expanded the variety of PAHs and also provided an opportunity for the synthesis of cup-shaped PAHs.

[0004] Currently, only one mainstream method has been reported for introducing sulfur atoms into the Gulf region. In 2015, Feng Xinliang's research group used unsubstituted hexaphenylbenzene as a starting material and obtained unsubstituted p-HBC through oxidative cyclization with ferric chloride. Then, using iodine chloride as a chlorinating agent, they obtained perchlorinated p-HBC (PCHBC) under aluminum trichloride catalysis. Finally, they reacted with excess sodium thiophene to obtain p-HBC (tri-sulfurannulated HBC, TSHBC) with three sulfur rings and twelve phenylthiol groups on the periphery. The synthesis of bowl-shaped molecules often requires overcoming significant stress. Therefore, most reported literature involves introducing sulfur atoms from the corresponding sulfur source under palladium catalysis, using the attraction force of palladium to synthesize the above molecules. However, palladium metal has a certain influence on the bonding of sulfur atoms, resulting in generally low yields of the target molecules. Therefore, developing a metal-free catalytic reaction system has significant theoretical and practical value. Summary of the Invention

[0005] The purpose of this invention is to provide a method for synthesizing chalcogenide hetero-bowl-shaped graphene molecules without metal catalysis.

[0006] To achieve the above objectives, the synthetic route and method adopted in this invention are as follows:

[0007]

[0008] (1) Compound 1 was synthesized from 2-bromo-5-chloroacetophenone under the catalysis of trifluoromethanesulfonic acid;

[0009] (2) Compound 1 was coupled with methyl 4-fluoro-2-carboxylate phenylboronic acid via Suzuki coupling to obtain compound 2;

[0010] (3) Compound 2 was subjected to Friedel-Crafts acylation under the catalysis of methanesulfonic acid to obtain compound 3;

[0011] (4) Compound 3 was reduced with hydroiodic acid in the presence of red phosphorus to obtain compound 4;

[0012] (5) Compound 4 was reacted with bromobutane in the presence of potassium tert-butoxide to produce compound 5;

[0013] (6) Compound 5 was synthesized into compound 6 by using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone as an oxidant in the presence of trifluoromethanesulfonic acid as a catalyst;

[0014] (7) When M represents S, compound 6 is reacted with tert-butyl mercaptan, potassium carbonate and tetrabutylammonium tetrafluoroborate to obtain chalcogenide hetero-bottle-shaped molecular graphene; when M represents Se, compound 6 is reacted with tert-butyllithium selenide to obtain chalcogenide hetero-bottle-shaped molecular graphene.

[0015] In step (1) above, it is preferable to react 2-bromo-5-chloroacetophenone at 140-150°C for 8-9 hours under the catalysis of trifluoromethanesulfonic acid; the molar ratio of 2-bromo-5-chloroacetophenone to trifluoromethanesulfonic acid is 1:0.10-0.15.

[0016] In step (2) above, toluene is preferably used as a solvent, and under the protection of an inert gas, compound 1 is refluxed with methyl 4-fluoro-2-carboxylate phenylboronic acid, tris(dibenzylacetone)dipalladium, 2-dicyclohexylphosphine-2,6-dimethoxybiphenyl, and potassium phosphate at 100-110°C for 20-24 hours to perform Suzuki coupling; the molar ratio of compound 1 to methyl 4-fluoro-2-carboxylate phenylboronic acid, tris(dibenzylacetone)dipalladium, 2-dicyclohexylphosphine-2,6-dimethoxybiphenyl, and potassium phosphate is 1:4.50-5.00:0.15-0.20:0.45-0.50:9.00-9.10.

[0017] In step (3) above, it is preferable to heat compound 2 under reflux at 110-180°C for 8-10 hours under the catalysis of methanesulfonic acid to carry out Friedel-Crafts acylation; the molar ratio of compound 2 to methanesulfonic acid is 1:200-250.

[0018] In step (4) above, propionic acid is preferably used as a solvent to reflux compound 3, red phosphorus, and hydroiodic acid at 145-155°C for 48-50 hours to carry out a reduction reaction. The molar ratio of compound 3 to red phosphorus and hydroiodic acid is 1:35-40:178-200.

[0019] In step (5) above, dry tetrahydrofuran is preferably used as a solvent, and compound 4 is reacted with potassium tert-butoxide and bromobutane at 75-85°C for 3-5 hours under inert gas protection; the molar ratio of compound 4 to potassium tert-butoxide and bromobutane is 1:14-16:14-15.

[0020] In step (6) above, dry dichloromethane is preferably used as a solvent, and compound 5, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, and trifluoromethanesulfonic acid are heated and reacted at 35°C for 2 hours under inert gas protection; the molar ratio of compound 5 and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone is 1:8, and the amount of trifluoromethanesulfonic acid is 3% of the solvent volume.

[0021] In step (7) above, when M represents S, dry N,N-dimethylformamide is preferably used as a solvent, and compound 6, tert-butyl mercaptan, potassium carbonate, and tetrabutylammonium tetrafluoroborate are heated and reacted at 120-130°C for 48-50 hours under inert gas protection; the molar ratio of compound 6 to tert-butyl mercaptan, potassium carbonate, and tetrabutylammonium tetrafluoroborate is 1:23-25:14-16:2-4. When M represents Se, dry N,N-dimethylformamide is preferably used as a solvent, and compound 6 and tert-butyllithium selenide are heated and reacted at 120-130°C for 48-50 hours under inert gas protection; the molar ratio of compound 6 to tert-butyllithium selenide is 1:60-80.

[0022] The beneficial effects of this invention are as follows:

[0023] This invention uses readily available and inexpensive 2-bromo-5-chloroacetophenone as a starting material. A trimer is obtained via acid catalysis, followed by Suzuki coupling, Friedel-Crafts acylation, and a Shore reaction. Finally, a heteroatom is introduced into the bay region to obtain chalcogenide-based heterobowl-shaped graphene molecules. Besides its advantages of short synthesis steps, mild reaction conditions, and simple operation, the most significant advantage is that the introduction of sulfur atoms does not employ the conventional palladium catalysis. Instead, sulfur atoms are introduced by intermolecular vibrations overcoming intermolecular tension in the absence of metal catalysis. Furthermore, the reaction is easily purified, leaves no catalyst residue, and achieves a high yield. The chalcogenide-based heterobowl-shaped graphene molecules of this invention exhibit excellent electrical properties and have significant application value in organic light-emitting diodes and semiconductor materials. Attached Figure Description

[0024] Figure 1 Compound 7-1 in dichloromethane (5 × 10⁻⁶) -3 Cyclic voltammograms of mol / L were generated at a scan rate of 0.1 V / s.

[0025] Figure 2 Compound 7-1 in dichloromethane (5 × 10⁻⁶) -3 Differential pulse voltammogram of mol / L.

[0026] Figure 3 This is the thermogravimetric analysis diagram of compound 7-1. Detailed Implementation

[0027] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments, but the scope of protection of the present invention is not limited to these embodiments.

[0028] Example 1

[0029]

[0030] 1. 10.00 g (42.83 mmol) of 2-bromo-5-chloroacetophenone (synthesized according to the method in the literature "Hillenbrand J, Leutzsch M, Yiannakas E, et al. "Canopy Catalysts" for Alkyne Metathesis: Molybdenum Alkylidyne Complexes with a Tripodal Ligand Framework[J]. Journal of the American Chemical Society, 2020, 142(25): 11279–11294.") was placed in a 25 mL sealed tube, and then 0.69 g (4.63 mmol) of trifluoromethanesulfonic acid was added dropwise to the sealed tube. The sealed tube was then placed in a microwave oven, sealed, and reacted at 140 °C for 9 hours. After the reaction was completed, dichloromethane was added to dilute the reaction solution to prevent solidification upon cooling. The solution was then washed with sodium bicarbonate aqueous solution, dried over anhydrous sodium sulfate, and the solvent was concentrated. The solution was then purified by column chromatography with silica gel (using a volume ratio of DCM:PE = 1:4 as the eluent) to obtain pure compound 1 in a yield of 51%.

[0031] The spectral data of compound 1 are as follows: 1 H NMR (600MHz, CDCl3) δ7.59 (s, 3H), 7.43 (s, 3H), 7.40 (d, J = 2.5Hz, 3H), 7.18 (dd, J = 8.5, 2.6Hz, 3H). 13 C NMR (151MHz, CDCl3) δ143.03(s), 139.76(s), 134.34(s), 133.51(s), 131.23(s), 129.71(s), 129.20(s), 120.61(s).

[0032] 2. In a 250 mL round-bottom flask, 5.00 g (7.73 mmol) of compound 1, 6.89 g (34.81 mmol) of methyl 4-fluoro-2-carboxylate phenylboronic acid, 1.06 g (1.16 mmol) of tris(dibenzylacetone)dipalladium, 1.43 g (3.48 mmol) of 2-dicyclohexylphosphine-2,6-dimethoxybiphenyl, and 14.78 g (69.61 mmol) of potassium phosphate were dissolved in 100 mL of degassed toluene. The mixture was refluxed at 100 °C for 24 hours under a nitrogen atmosphere. After the reaction was complete, excess insoluble matter was filtered off through a silica gel bed. The solvent was concentrated, and the mixture was purified by column chromatography with silica gel (using a volume ratio of DCM:PE = 2:1 as the eluent) to obtain pure compound 2 in a yield of 63%.

[0033] The spectral data of the obtained compound 2 are as follows:1 H NMR (600MHz, CDCl3) δ7.47(dd,J=8.6,6.7Hz,3H),7.21(dd,J=8.1,1.9Hz,3H),7.08–6.96(m,6H),6.82–6.45(m,9H),3.44(t,J=28.8Hz,9H). 13 C NMR (151MHz, CDCl3) δ166.34(s), 162.27(s), 141.07(s), 139.38(d, J=21.9Hz), 139.28–138.37(m), 137.33( s), 133.67 (d, J = 14.4Hz), 132.92 (s), 131.00 (s), 129.99 (s), 129.64 (s), 129.42 (s), 127.34 (s), 52.29 (s).

[0034] 3. 5.00 g (5.77 mmol) of compound 2 was placed in a 150 mL round-bottom flask, and 80 mL (1.24 mol) of methanesulfonic acid was added. The mixture was heated under reflux at 110 °C for 8 hours. After the reaction was completed, the mixture was quenched with sodium bicarbonate, extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was concentrated. The mixture was then purified by column chromatography with silica gel (using a volume ratio of DCM:PE = 1:1 as the eluent) to obtain pure compound 3 in a yield of 41%.

[0035] The spectral data of the obtained compound 3 are as follows: 1 H NMR (600MHz, CDCl3) δ7.70 (s, 3H), 7.63 (d, J = 2.0Hz, 3H), 7.38 (d, J = 1.9Hz, 3H), 7.33 (dd, J = 6.9, 2.3Hz, 5H), 7.25–7.19 (m, 4H).

[0036] 4. 3 g (3.90 mmol) of compound 3 was placed in a 150 mL round-bottom flask, and 4.34 g (140.26 mmol) of red phosphorus and 89.71 g (701.32 mmol) of hydroiodic acid were added. Then, 50 mL of propionic acid was added as solvent, and the mixture was refluxed at 150 °C for 48 hours. After the reaction was completed, the reaction solution was diluted with dichloromethane, the organic phase was washed with saturated sodium bicarbonate aqueous solution, and finally anhydrous sodium sulfate was added for drying. After concentrating the solvent, the mixture was purified by column chromatography with silica gel (using a volume ratio of DCM:PE = 1:6 as the eluent) to obtain pure compound 4 with a yield of 72%.

[0037] The spectral data of the obtained compound 4 are as follows: 1H NMR (600MHz, CDCl3) δ7.61 (s, 3H), 7.42 (s, 3H), 7.25 (s, 3H), 7.11 (t, J = 18.7Hz, 6H), 6.66 (t, J = 122.4Hz, 3H), 3.84 (s, 6H). 13 CNMR(151MHz, CDCl3)δ144.71(d,J=42.2Hz),144.55–144.11(m),139.81(s),135.70(d,J=80.5Hz),130.9 0(s),128.65–128.37(m),128.22(d,J=30.8Hz),127.78(d,J=28.2Hz),123.53(s),122.17(s),35.83(s).

[0038] 5. Add 2 g (2.75 mmol) of compound 4 and 4.62 g (41.21 mmol) of potassium tert-butoxide to a sealed tube, and add 10 mL of dry THF as solvent. Under nitrogen protection, add 5.65 g (41.21 mmol) of bromobutane using a syringe. After sealing, react in an oil bath at 80 °C for 3 hours. After the reaction is complete, dilute the reaction solution with dichloromethane, wash the organic phase with aqueous solution, dry with anhydrous sodium sulfate, concentrate the solvent, and purify by column chromatography with silica gel (using pure petroleum ether as eluent) to obtain pure compound 5 with a yield of 83%.

[0039] The spectral data of compound 5 are as follows: 1 H NMR (600MHz, CDCl3) δ7.60 (s, 3H), 7.23 (d, J = 5.0Hz, 6H), 7.09 (dd, J = 6.9, 5.1Hz, 2H), 6.93 (d, J = 8. 0Hz, 4H), 6.85–6.24 (m, 3H), 1.95–1.77 (m, 12H), 1.00 (dd, J=14.4, 7.2Hz, 12H), 0.63–0.43 (m, 30H). 13 CNMR(151MHz, CDCl3)δ154.63–152.98(m),140.76(s),137.01(s),136.00(s),135.78(s),132.30(d,J=12.7Hz) ,129.27(s),128.85(s),123.32(d,J=8.5Hz),122.48(s),55.02(s),40.37(s),25.82(s),22.97(s),13.76(s).

[0040] 6. Add 0.20 g (187.85 μmol) of compound 5 and 0.34 g (1.50 mmol) of DDQ to a 100 mL sealed tube. After purging with argon, use 30 mL of dry dichloromethane as solvent. Add 0.9 mL of trifluoromethanesulfonic acid as catalyst under ice bath conditions. Seal the tube and heat at 35 °C for 2 hours. After the reaction is complete, dilute the reaction solution with dichloromethane. Filter the solution through a silica gel bed to remove insoluble impurities. After concentrating the solvent, purify the solution by column chromatography with silica gel (using pure petroleum ether as eluent) to obtain pure compound 6 in a yield of 34%.

[0041] 7. 0.10 g (95.00 μmol) of compound 6, 205.63 mg (2.28 mmol) of tert-butyl mercaptan, 196.95 mg (1.43 mmol) of potassium carbonate, and 93.85 mg (285.01 μmol) of tetrabutylammonium tetrafluoroborate were added to a 10 mL sealed tube. After purging with argon, 2 mL of dry N,N-dimethylformamide was added as a solvent. The tube was sealed and heated at 120 °C for 48 hours. After the reaction was completed, the organic phase was washed with hydrochloric acid, extracted with dichloromethane, dried over anhydrous sodium sulfate, and purified by column chromatography with silica gel (using pure petroleum ether as eluent) to obtain pure compound 7-1 in a yield of 26%.

[0042] The spectral data of the obtained compound 7-1 are as follows: 1 H NMR(600MHz, CDCl3)δ8.06(s,6H),2.70-2.66(m,6H),2.13-2.09(m,6H),2.05-2.00(m,6H),1.58-1.56( m,6H),1.05(t,J=7.4Hz,9H),0.59(dd,J=14.7,7.4Hz,6H),-0.02(t,J=7.3Hz,9H),-1.01--1.07(m,6H). 13 C NMR(151MHz, CDCl3)δ153.00(s),142.88(s),139.79(s),134.76(s),130.82(s),128.59(s),119.60(s),77.26(s),7 7.04(s),76.83(s),64.38(s),42.14(s),35.83(s),28.65(s),26.06(s),23.62(s),22.46(s),14.30(s),13.16(s).

[0043] Example 2

[0044]

[0045] Steps 1 to 6 of this Example 1 are the same as in Example 1. In step 7, 0.01 g (9.50 μmol) of compound 6, 81.52 mg (570.03 μmol) of lithium tert-butylselenide (according to the literature "Guschlbauer J, Vollgraff T, Sundermeyer J. Systematic study on anion-cation interactions via doublyionic H-bonds in 1,3-dimethylimidazolium salts comprising chalcogenolate anions MMIm[ER](E=S,Se;R=H,tBu,SiMe3)[J]. Dalton") was added to a 10 mL sealed tube. The compound 7-2 was synthesized using the method described in Transactions, 2019, 48(29):10971-10978. After replacing the argon gas, 2.5 mL of dry N,N-dimethylformamide was added as a solvent. The mixture was sealed and heated at 120 °C for 48 hours. After the reaction was completed, dilute hydrochloric acid was added to quench the reaction. The mixture was extracted with dichloromethane, and the organic phase was dried with anhydrous sodium sulfate. The solvent was concentrated and purified by column chromatography with silica gel (using petroleum ether as eluent) to obtain pure compound 7-2 with a yield of 17%.

[0046] The spectral data of the obtained compound 7-1 are as follows: 1 H NMR (600MHz, CDCl3): δ8.21(s,6H),2.71–2.66(m,6H),2.17–2.12(m,6H),2.02–1.98(m,6H),1.57–1.54 (m,6H),1.04(t,J=7.4Hz,9H),0.59(dd,J=14.7,7.4Hz,6H),0.01(t,J=7.3Hz,9H),-0.93–-0.98(m,6H). 13 C NMR (150MHz, CDCl3): δ151.8,141.9,139.0,136.0,129.3,128.2,121.6,64.4,41.5,36.5,28.5,25.8,23.6,22.4,14.3,13.2.

[0047] The electrical properties of compound 7-1 were tested using the following method: First, the working electrode was polished with Al2O3, and then it, along with the counter electrode and reference electrode, was immersed in anhydrous ethanol for 15 minutes. After drying, the electrode, electrolytic cell, tetrabutylammonium hexafluorophosphate, and the sample were placed in a glove box. A solution of tetrabutylammonium hexafluorophosphate and the sample was prepared using ultra-dry dichloromethane for testing. Cyclic voltammetry was then performed... Figure 1As can be seen, this compound exhibits two reversible oxidation peaks and no reduction peak within the solvent measurement range, with half-wave potentials of 0.93 V and 1.37 V, respectively. Figure 2 According to formula E HOMO =-(4.8+E) onset ox eV and E LUMO =(E HOMO +E g opt The HOMO and LUMO orbital energy levels of this compound were found to be -5.65 eV and -3.07 eV, respectively. Figure 1 and 2 As can be seen, due to the presence of two reversible peaks, it is an electrochemically stable compound that can be used as a good electronic device and applied in the semiconductor field.

[0048] Compound 7-1 was subjected to thermogravimetric analysis (TGA) under nitrogen protection using a Q1000-SDT instrument. The heating range was 30–800 °C. The obtained data were processed to obtain the TGA curve of the compound. Figure 3 As can be seen, the thermal decomposition temperature of this compound is around 410℃, similar to the thermal stability of traditional HBC derivatives, indicating that the bowl-shaped structure of this compound has high thermal stability. The compound synthesized in this invention exhibits excellent thermal stability and photoelectric properties, which make it a promising candidate for applications in organic optoelectronic devices, semiconductor materials, and new energy batteries.

Claims

1. A method for synthesizing chalcogenide heterobowl-shaped molecular graphene, wherein the structural formula of the chalcogenide heterobowl-shaped molecular graphene is as follows: In the formula, M represents S, characterized in that, The synthesis method consists of the following steps: (1) Compound 1 was synthesized from 2-bromo-5-chloroacetophenone under the catalysis of trifluoromethanesulfonic acid; 1 (2) Compound 1 was coupled with methyl 4-fluoro-2-carboxylate phenylboronic acid via Suzuki coupling to obtain compound 2; 2 (3) Compound 2 was subjected to Friedel-Crafts acylation under the catalysis of methanesulfonic acid to obtain compound 3; 3 (4) Compound 3 was reduced with hydroiodic acid in the presence of red phosphorus to obtain compound 4; 4 (5) Compound 4 was reacted with bromobutane in the presence of potassium tert-butoxide to produce compound 5; 5 (6) Compound 5 was synthesized into compound 6 by using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone as an oxidant in the presence of trifluoromethanesulfonic acid as a catalyst; 6 (7) Compound 6 was subjected to the action of tert-butylthiol, potassium carbonate and tetrabutylammonium tetrafluoroborate to obtain chalcogenide cup-shaped molecular graphene.

2. The method for synthesizing chalcogenide heterobowl-shaped molecular graphene according to claim 1, characterized in that: In step (1), 2-bromo-5-chloroacetophenone is reacted at 140-150°C for 8-9 hours under the catalysis of trifluoromethanesulfonic acid; the molar ratio of 2-bromo-5-chloroacetophenone to trifluoromethanesulfonic acid is 1:0.10-0.

15.

3. The method for synthesizing chalcogenide heterobowl-shaped molecular graphene according to claim 1, characterized in that: In step (2), using toluene as a solvent, under the protection of an inert gas, compound 1 is refluxed with methyl 4-fluoro-2-carboxylate phenylboronic acid, tris(dibenzylacetone)dipalladium, 2-dicyclohexylphosphine-2,6-dimethoxybiphenyl, and potassium phosphate at 100-110°C for 20-24 hours to perform Suzuki coupling; the molar ratio of compound 1 to methyl 4-fluoro-2-carboxylate phenylboronic acid, tris(dibenzylacetone)dipalladium, 2-dicyclohexylphosphine-2,6-dimethoxybiphenyl, and potassium phosphate is 1:4.50-5.00:0.15-0.20:0.45-0.50:9.00-9.

10.

4. The method for synthesizing chalcogenide heterobowl-shaped molecular graphene according to claim 1, characterized in that: In step (3), compound 2 is heated under reflux at 110-180°C for 8-10 hours under the catalysis of methanesulfonic acid to carry out Friedel-Crafts acylation; the molar ratio of compound 2 to methanesulfonic acid is 1:200-250.

5. The method for synthesizing chalcogenide heterobowl-shaped molecular graphene according to claim 1, characterized in that: In step (4), propionic acid is used as a solvent to reflux compound 3, red phosphorus, and hydroiodic acid at 145-155°C for 48-50 hours to carry out a reduction reaction. The molar ratio of compound 3 to red phosphorus and hydroiodic acid is 1:35-40:178-200.

6. The method for synthesizing chalcogenide heterobowl-shaped molecular graphene according to claim 1, characterized in that: In step (5), dry tetrahydrofuran is used as solvent, and under inert gas protection, compound 4 is reacted with potassium tert-butoxide and bromobutane at 75-85°C for 3-5 hours; the molar ratio of compound 4 to potassium tert-butoxide and bromobutane is 1:14-16:14-15.

7. The method for synthesizing chalcogenide heterobowl-shaped molecular graphene according to claim 1, characterized in that: In step (6), dry dichloromethane is used as a solvent, and under inert gas protection, compound 5, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, and trifluoromethanesulfonic acid are heated at 35°C for 2 hours; the molar ratio of compound 5 and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone is 1:8, and the amount of trifluoromethanesulfonic acid is 3% of the solvent volume.

8. The method for synthesizing chalcogenide heterobowl-shaped molecular graphene according to claim 1, characterized in that: In step (7), dry N,N-dimethylformamide is used as a solvent, and under inert gas protection, compound 6, tert-butyl mercaptan, potassium carbonate, and tetrabutyltetrafluoroborate are heated and reacted at 120-130°C for 48-50 hours; the molar ratio of compound 6 to tert-butyl mercaptan, potassium carbonate, and tetrabutyltetrafluoroborate is 1:23-25:14-16:2-4.

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