Preparation method of two-dimensional supramolecular materials based on arene-perfluoroarene interaction

Abstract

The present invention relates to a preparation method of a two-dimensional supramolecular material based on the interaction of aromatic hydrocarbons and perfluoroaromatic hydrocarbons. First, a monomer molecule tetra-tert-butyl ((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrakis(oxygen))tetrakis(ethane-2,1-diyl))tetracarbamate is synthesized, and the monomer molecule is co-assembled with octafluoronaphthalene to form a two-dimensional supramolecular material based on the interaction of aromatic hydrocarbons and perfluoroaromatic hydrocarbons. The monomer molecule is effectively co-assembled with octafluoronaphthalene in an aqueous solution by alternating stacking and the assembly of peripheral alkyl chains in an aqueous phase, forming a two-dimensional sheet structure, which has fluorescent color change characteristics and good photocatalytic hydrogen evolution performance compared to the self-assembly of the monomer, further broadens the scope of the force of the two-dimensional supramolecular material, and makes the supramolecular material have potential application prospects in the fields of fluorescence sensing, fluorescence anti-counterfeiting, and photocatalytic hydrogen evolution.

Description

Technical Field

[0001] The present invention belongs to the technical field of supramolecular materials, and in particular relates to a method for preparing a two-dimensional supramolecular material based on arene-perfluoroarene interaction. Background Art

[0002] The research on two-dimensional supramolecular materials can be traced back to the discovery of graphene in 2004. Due to its dynamic reversible characteristics and good physical and chemical properties, it has been widely used in fields such as green energy (Sol.RRL, 2021, 5(3), 13), new catalysts (Coord.Chem.Rev.2020, 415, 27), and biomedical technology (Adv.Mater.2020, 32(51), 15). Although two-dimensional supramolecular materials are constantly developing, the driving force for supramolecular assembly is often weak in the molecular design stage, making it difficult to establish a precise assembly mechanism. The constructed two-dimensional supramolecular materials still lack strength and stability. Therefore, current research mainly focuses on the design of monomer molecules, the exploration of new driving forces, the control of assembly paths, and the separation of supramolecular products (Nat.Nanotechnol.2015, 10(2), 111-119; Chem.Mater.2014, 26(1), 576-586). The key challenge in the research of the new generation of two-dimensional supramolecular materials lies in understanding the non-covalent bond constraints required for monomers to assemble into highly ordered supramolecular polymers during the construction process, avoiding competing assembly pathways, and maintaining adaptive stimulus-responsive behavior.

[0003] The interaction between aromatic hydrocarbons and perfluoroaromatic hydrocarbons, referred to as AP interaction, is an interaction caused by the deflection of the dipole moment between aromatic hydrocarbons and perfluoroaromatic hydrocarbons, which often results in a change in the color of the fluorescence. This interaction is very strong and often leads to alternating stacking of aromatic hydrocarbons and perfluoroaromatic hydrocarbons. This stacking characteristic has good directionality, thus promoting the formation of regular arrangement at the microscopic scale and often showing a good long-range ordered morphology at the macroscopic scale. (J.Org.Chem.2021,86(12),8425-8436)

[0004] Therefore, forming two-dimensional supramolecular materials by introducing AP interactions with strong and excellent directionality is an effective way to solve the above scientific problems. Summary of the Invention

[0005] The purpose of the present invention is to avoid the deficiencies of the prior art and provide a method for preparing a two-dimensional supramolecular material based on arene-perfluoroarene interaction.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is: a method for preparing a two-dimensional supramolecular material based on the interaction of aromatic hydrocarbons and perfluoroaromatic hydrocarbons, characterized in that: first, a monomer molecule tetra-tert-butyl ((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate is synthesized, and the synthesis route is as follows:

[0007]

[0008] Secondly, the monomer molecule tetra-tert-butyl ((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate was co-assembled with octafluoronaphthalene to form a two-dimensional supramolecular material based on the interaction of aromatic hydrocarbons and perfluoroaromatic hydrocarbons; the structural formula of octafluoronaphthalene is as follows:

[0009]

[0010] The specific steps of the synthesis method of the monomer molecule tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate are as follows:

[0011] Step 1: 5-bromoresorcinol, potassium carbonate, and potassium iodide are added to a container in proportion, and the solvent N,N-dimethylformamide is added under a nitrogen environment. After stirring and dissolving, 2-(BOC-amino) bromoethane is added dropwise to the reaction mixture, and stirred at 50-70°C for 12-24 hours. The reaction progress is monitored in real time by thin layer chromatography. After the reaction is completed and cooled to room temperature, the solvent N,N-dimethylformamide is evaporated at low pressure, and the reaction mixture is extracted 2-3 times with water and dichloromethane. The combined organic extracts are dried, and the solvent is removed by rotary evaporation to obtain a crude product, which is then purified to obtain product 3, which is specifically di-tert-butyl (((5-bromo-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate;

[0012] Step 2: The product 3, bistriphenylphosphine palladium dichloride, cuprous iodide and triphenylphosphine are added to a container in proportion, and the solvent triethylamine is added under a nitrogen atmosphere and stirred evenly. After the mixture is fully dissolved, the triethylamine solution of trimethylethynylsilane is slowly added dropwise to the reaction mixture, and stirred at 45-55° C. for 12-24 hours. The reaction progress is monitored in real time by thin layer chromatography. After the reaction is completed and cooled to room temperature, the solvent triethylamine is removed by low pressure evaporation, and the reaction mixture is extracted with water and dichloromethane 2-3 times, and the combined organic extracts are dried, and the solvent is removed by rotary evaporation to obtain a crude product. The crude product is purified to obtain product 2, which is specifically di-tert-butyl (((5-((trimethylsilyl)ethynyl)-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl))dicarbamate;

[0013] Step 3: Product 2, potassium carbonate, and potassium hydroxide are added to a container in proportion, and then a mixed solvent, i.e., a mixture of tetrahydrofuran, methanol, and water, is added. The mixture is reacted in an oil bath at a constant temperature of 25° C. for 6-8 hours, and the reaction progress is monitored in real time by thin layer chromatography. After the reaction is completed and cooled to room temperature, the mixed solvent is removed by low-pressure evaporation, and the reaction mixture is extracted 2-3 times with water and dichloromethane. The combined organic extracts are dried, and the solvent is removed by a rotary evaporator to obtain a crude product. After purifying the crude product, product 1 is obtained, and the product 1 is specifically di-tert-butyl (((5-ethynyl-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate;

[0014] Step 4: 9,10-diiodoanthracene, product 1, bistriphenylphosphine palladium dichloride and cuprous iodide are added to a container in proportion, and the solvent triethylamine is added to fully dissolve under a nitrogen atmosphere, and stirred at a constant temperature of 75°C for 12-24 hours. The reaction progress is monitored in real time by thin layer chromatography. After the reaction is completed and cooled to room temperature, the solvent triethylamine is removed by low pressure evaporation, and then the reaction mixture is extracted with water and dichloromethane 2-3 times. The combined organic extracts are dried and the solvent is removed by rotary evaporation to obtain a crude product. The crude product is washed three times with triethylamine and then placed in a vacuum environment at 50-60°C for 12-24 hours. The obtained solid is cooled to room temperature to obtain the target product M1, wherein M1 is specifically a monomer molecule tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate.

[0015] Furthermore, in step 1, 5-bromoresorcinol, potassium carbonate, and potassium iodide are added in a molar ratio of 1:4:1; the amount of 2-(BOC-amino)bromoethane added dropwise is twice the molar ratio of 5-bromoresorcinol, and the addition time is controlled within 30 minutes; the crude product is purified by column chromatography filled with silica gel, and the eluent is petroleum ether / ethyl acetate in a volume ratio of 20:1.

[0016] In step 2, product 3, bistriphenylphosphine palladium dichloride, cuprous iodide and triphenylphosphine are added in a molar ratio of 5:2:2:2; preparing the triethylamine solution of trimethylethynyl silicon is specifically as follows: trimethylethynyl silicon is added to triethylamine and fully dissolved, and the amount of trimethylethynyl silicon added is 25 times the molar ratio equivalent of di-tert-butyl (((5-bromo-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate; the time for adding the triethylamine solution of trimethylethynyl silicon dropwise to the reaction mixture is controlled to be more than 30 minutes; the crude product is purified by column chromatography filled with silica gel, and the eluent is petroleum ether / ethyl acetate in a volume ratio of 1:1 to 10:1.

[0017] In step 3, product 2, potassium carbonate, and potassium hydroxide are added in a molar ratio of 1:6:6; a mixed solvent of tetrahydrofuran, methanol, and water is prepared in a volume ratio of 2:1:1; the crude product is purified by column chromatography filled with silica gel, and the eluent is petroleum ether / ethyl acetate in a volume ratio of 10:1.

[0018] In step 4, 9,10-diiodoanthracene, product 1, bistriphenylphosphine palladium dichloride and cuprous iodide are added in a molar ratio of 2:5:1:3.

[0019] Furthermore, in steps 1-4, the drying of the combined organic extracts is carried out by adding anhydrous sodium sulfate to the combined organic extracts for drying.

[0020] In steps 1-4, the solvents are all solvents dried with 5A molecular sieves, and the solutions are heated in a constant temperature oil bath.

[0021] The specific steps of co-assembling the monomer molecule tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate with octafluoronaphthalene to form a two-dimensional supramolecular material based on arene-perfluoroarene interaction are:

[0022] The monomer molecules tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate and octafluoronaphthalene were dissolved in a small amount of a common good solvent, chloroform, and ultrasonically premixed to ensure full contact between the two components at the molecular level. After removing the good solvent, the two components were added to a quantitative assembly solution and ultrasonically premixed. The mixture was then assembled at 20-25°C for a certain period of time to obtain a co-assembly of the monomer molecules tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate and octafluoronaphthalene.

[0023] Furthermore, the concentration ratio of the monomer molecule tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate to octafluoronaphthalene is 1:1 to 1:20; the removal of the good solvent is carried out by nitrogen drying or oven drying; the assembly liquid is a mixed solvent of cyclohexane and good chloroform in a volume ratio of 95:5; and the assembly time is controlled to be more than 2 hours.

[0024] The beneficial effects of the present invention are as follows: the desired monomer molecule tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate, abbreviated as M1, is obtained through a series of organic synthesis methods. Octafluoronaphthalene, abbreviated as OFN, is introduced, and the non-covalent bond interaction between the monomer molecule M1 and anthracene allows the monomer molecule M1 to effectively undergo supramolecular co-assembly in an aqueous solution through alternating stacking with octafluoronaphthalene and assembly of peripheral alkyl chains in the aqueous phase, forming a two-dimensional sheet structure. Compared to the self-assembled structure of the monomer, this sheet material has fluorescent color-changing properties and good photocatalytic hydrogen evolution performance, further broadening the scope of the interaction force of the two-dimensional supramolecular material, giving the supramolecular material potential application prospects in the fields of fluorescent sensing, fluorescent anti-counterfeiting, and photocatalytic hydrogen evolution, and providing a new strategy for the preparation of two-dimensional supramolecular materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is a fluorescence spectrum diagram of M1 self-assembly and M1 and OFN co-assembly involved in the present invention;

[0026] Figure 2 is the hydrogen nuclear magnetic resonance spectrum of the monomer molecule M1 involved in the present invention;

[0027] Figure 3 This is a TEM electron microscope image of the M1 self-assembly involved in the present invention;

[0028] Figure 4This is a TEM electron microscope image of the two-dimensional supramolecular material based on the interaction of aromatic hydrocarbons and perfluoroaromatic hydrocarbons of the present invention. DETAILED DESCRIPTION

[0029] The principles and features of the present invention are described below in conjunction with the accompanying drawings. The examples given are only used to illustrate the present invention and are not intended to limit the scope of the present invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention pertains. The terms used in this specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0030] Example 1

[0031] A method for preparing a two-dimensional supramolecular material based on arene-perfluoroarene interaction, the specific steps are as follows:

[0032] Step 1: 1.0 g of 5-bromoresorcinol, 2.93 g of potassium carbonate, and 0.9 g of potassium iodide were added sequentially to a 100 mL eggplant-shaped flask. Under a nitrogen atmosphere, 20 mL of N,N-dimethylformamide was added and stirred thoroughly. Then, 3.0 g of 2-(BOC-amino)ethyl bromide was added dropwise to the reaction mixture over 30 minutes. After stirring at 60°C for 12 hours, the reaction progress was monitored in real time by thin-layer chromatography (TLC). After the reaction was completed and cooled to room temperature, the solvent was evaporated under low pressure. The reaction mixture was then extracted three times with water and dichloromethane. The combined organic extracts were dried over anhydrous sodium sulfate and the solvent was removed using a rotary evaporator to obtain a crude product. The crude product was purified by silica gel-packed column chromatography using petroleum ether / ethyl acetate in a volume ratio of 20:1 as the eluent to obtain 2.3 g of di-tert-butyl (((5-bromo-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate as a light yellow oily liquid in a yield of 93.0%.

[0033] Step 2: Add 250.2 mg of di-tert-butyl (((5-bromo-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate, 134.5 mg of bistriphenylphosphine palladium dichloride, 36.2 mg of cuprous iodide, and 50.1 mg of triphenylphosphine to a 100 mL eggplant-shaped flask. Under a nitrogen atmosphere, add 20 mL of triethylamine and stir until the mixture is fully dissolved. After the mixture is fully dissolved, slowly add a solution of 257.7 mg of trimethylethynylsilane in 5 mL of triethylamine dropwise to the reaction mixture, controlling the addition time to at least 30 minutes. Stir at 55°C for 12 hours, and monitor the reaction progress in real time by thin-layer chromatography. After the reaction is completed and cooled to room temperature, the solvent is evaporated under low pressure, and the reaction mixture is extracted three times with water and dichloromethane. The combined organic extracts are dried over anhydrous sodium sulfate, and the solvent is removed using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel-packed column chromatography with a volume ratio of 10:1 petroleum ether to ethyl acetate as the eluent to obtain 209.9 mg of di-tert-butyl (((5-((trimethylsilyl)ethynyl)-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate as a light yellow solid in a yield of 80.5%.

[0034] Step 3: Transfer 209.9 mg of di-tert-butyl (((5-((trimethylsilyl)ethynyl)-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate, 327.6 mg of potassium carbonate, and 133.0 mg of potassium hydroxide to a 100 mL eggplant-shaped flask. Add 22 mL of a mixed solvent consisting of tetrahydrofuran, methanol, and water in a 2:1:1 volume ratio. The mixture is then reacted in an oil bath at a constant temperature of 25°C for 6 h. The reaction progress is monitored in real time by thin-layer chromatography (TLC). After the reaction is completed and cooled to room temperature, the solvent is evaporated off at low pressure, and the reaction mixture is extracted three times with water and dichloromethane. Anhydrous sodium sulfate was added to the combined organic extracts and dried, and the solvent was removed by rotary evaporation to obtain a crude product. The crude product was purified by column chromatography packed with silica gel, wherein the eluent was petroleum ether / ethyl acetate in a volume ratio of 10:1, to obtain 151.7 mg of di-tert-butyl (((5-ethynyl-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate as a white solid in a yield of 68%.

[0035] Step 4: Add 50.3 mg of 9,10-diiodoanthracene, 122.2 mg of di-tert-butyl (((5-ethynyl-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate, 31.8 mg of bistriphenylphosphine palladium dichloride, and 30.9 mg of cuprous iodide to a 100 mL eggplant-shaped flask and dissolve in 15 mL of triethylamine under a nitrogen atmosphere. Stir at 75°C for 12 hours, and monitor the reaction progress in real time by thin-layer chromatography. After the reaction is completed and cooled to room temperature, the solvent is evaporated under low pressure, and the reaction mixture is then extracted three times with water and dichloromethane. The combined organic extracts are dried over anhydrous sodium sulfate, and the solvent is removed on a rotary evaporator to obtain a crude product. The crude product was washed three times with triethylamine and then placed in a vacuum environment at 50°C for 12 hours. The obtained solid was cooled to room temperature to obtain 83.7 mg of the target product monomer molecule M1, which is specifically tetra-tert-butyl ((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate, which is a light yellow solid with a yield of 68.7%.

[0036] The H NMR spectrum of monomer molecule M1 is shown in Figure 2 , it can be seen that the monomer molecule M1 was successfully synthesized.

[0037] Step 5: According to the concentration ratio [M1]: [octafluoronaphthalene] = 1:5, appropriate amounts of monomer molecules M1 and octafluoronaphthalene are placed in a 5 mL sample bottle, dissolved in a small amount of the common good solvent chloroform, and ultrasonically premixed to ensure that the two components are fully in contact at the molecular level. The good solvent is removed by nitrogen drying and then added to the quantitative assembly solution and ultrasonicated. The assembly solution is a mixed solvent of the poor solvent hexane and the good solvent chloroform. The volume ratio of the mixed solvent is cyclohexane / chloroform 95:5. The mixture is assembled at room temperature for more than 2 hours to obtain a co-assembly of M1 and OFN, that is, a two-dimensional supramolecular material based on aromatic hydrocarbon-perfluoroaromatic hydrocarbon interaction.

[0038] The solid fluorescence of the co-assembly of M1 and OFN was tested and the test result was green. Figure 1 .

[0039] TEM electron microscope image of the co-assembly of M1 and OFN is shown in Figure 4 , it can be seen that the co-assembly of M1 and OFN presents a two-dimensional lamellar structure.

[0040] Comparative Example 1

[0041] Preparation of M1 self-assembly, the specific steps are:

[0042] An appropriate amount of monomer molecules M1 were weighed into a 5 mL sample vial, dissolved in a quantitative assembly solution and sonicated. The assembly solution was a mixed solvent of a poor solvent cyclohexane and a good solvent chloroform. The volume ratio of the mixed solvent was cyclohexane / chloroform of 95:1. The mixture was assembled at 20-25 ° C for more than 2 hours to obtain an M1 self-assembly.

[0043] The fluorescence test of M1 self-assembly was carried out in dichloromethane and solid state. Figure 1 , it can be seen that the M1 self-assembly is green when tested in dichloromethane and orange when tested in solid state.

[0044] TEM electron microscope image of M1 self-assembly Figure 3 , it can be seen that the M1 self-assembly presents a nanowire structure.

[0045] Example 2

[0046] Step 1: 2.0 g of 5-bromoresorcinol, 5.85 g of potassium carbonate, and 1.8 g of potassium iodide were added sequentially to a 100 mL eggplant-shaped flask. Under a nitrogen atmosphere, 30 mL of N,N-dimethylformamide was added and stirred thoroughly. Then, 5.92 g of 2-(BOC-amino)ethyl bromide was added dropwise to the reaction mixture over 30 minutes. After stirring at 60°C for 12 hours, the reaction progress was monitored in real time by thin-layer chromatography (TLC). After the reaction was completed and cooled to room temperature, the solvent was removed by low-pressure evaporation. The reaction mixture was then extracted three times with water and dichloromethane. The combined organic extracts were dried over anhydrous sodium sulfate and the solvent was removed by rotary evaporation to obtain a crude product. The crude product was purified by silica gel-packed column chromatography using a petroleum ether / ethyl acetate volume ratio of 20:1 as the eluent to obtain 3.6 g of di-tert-butyl (((5-bromo-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate as a light yellow oily liquid in a yield of 71.0%.

[0047] Step 2: Add 3.6 g of di-tert-butyl (((5-bromo-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate, 263.3 mg of bistriphenylphosphine palladium dichloride, 76.2 mg of cuprous iodide and 105.0 mg of triphenylphosphine into a 100 mL eggplant-shaped flask, add 30 mL of triethylamine under a nitrogen atmosphere, and after the mixture is fully dissolved, slowly add a solution prepared by dissolving 1.5 g of trimethylethynyl silicon in 5 mL of triethylamine to the reaction mixture dropwise, controlling the addition time to be more than 30 minutes, stirring at a constant temperature of 55°C for 12 hours, and monitoring the reaction progress by thin layer chromatography. After the reaction was completed, the solvent was removed by low-pressure distillation after cooling to room temperature, and the mixture was extracted three times with water and dichloromethane. The organic phase was dried over anhydrous sodium sulfate and then removed by rotary evaporator to obtain a crude product. Finally, the crude product was purified by column chromatography filled with silica gel, wherein the eluent ratio was petroleum ether / ethyl acetate in a volume ratio of 10:1, and 3.2 g of di-tert-butyl (((5-((trimethylsilyl)ethynyl)-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate was obtained as a light yellow solid in a yield of 87.1%.

[0048] Step 3: 3.2 g of di-tert-butyl (((5-((trimethylsilyl)ethynyl)-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate, 1.8 g of potassium carbonate, 728 mg of potassium hydroxide and 30 mL of a mixed solvent were transferred to a 100 mL eggplant-shaped flask. The mixed solvent was prepared by tetrahydrofuran, methanol and water in a volume ratio of 2:1:1. The mixture was then reacted under a constant temperature of 25°C in an oil bath for 6 h. The progress of the deprotection reaction was monitored by thin layer chromatography. After the reaction was completed, the mixture was evaporated under low pressure. The mixed solvent was removed by distillation, and the mixture was extracted repeatedly with water and dichloromethane several times. After the organic phase was dried over anhydrous sodium sulfate, the organic solvent was removed by a rotary evaporator to obtain a white crude product. The crude product was purified by column chromatography filled with silica gel, wherein the eluent ratio was petroleum ether / ethyl acetate in a volume ratio of 10:1, and 1.7 g of di-tert-butyl (((5-ethynyl-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate was obtained as a white solid in a yield of 61.3%.

[0049] Step 4: 48.1 mg of 9,10-diiodoanthracene, 120.5 mg of di-tert-butyl (((5-ethynyl-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate, 21.1 mg of bistriphenylphosphine palladium dichloride, and 12.9 mg of cuprous iodide were added to a 100 mL eggplant-shaped flask and dissolved in 15 mL of triethylamine under a nitrogen atmosphere. Stir at 75°C for 24 hours, and the reaction progress was monitored in real time by thin-layer chromatography. After the reaction was completed and cooled to room temperature, the solvent was evaporated under low pressure, and the reaction mixture was then extracted three times with water and dichloromethane. Anhydrous sodium sulfate was added to the combined organic extracts for drying, and the solvent was removed using a rotary evaporator to obtain a crude product. The crude product was washed three times with triethylamine and then placed in a vacuum environment at 50°C for 12 hours. The obtained solid was cooled to room temperature to obtain 70 mg of the target product monomer molecule M1, which is specifically tetra-tert-butyl ((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate, which is a light yellow solid with a yield of 60.7%.

[0050] Step 5: The method for preparing the monomer molecule tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate and co-assembling it with octafluoronaphthalene to form a two-dimensional supramolecular material based on aromatic hydrocarbon-perfluoroaromatic hydrocarbon interaction is the same as in Example 1.

[0051] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a two-dimensional supramolecular material based on arene-perfluoroarene interaction, characterized in that: First, the monomer molecule tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate was synthesized using the following synthesis route: Secondly, the monomer molecule tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate was co-assembled with octafluoronaphthalene to form a two-dimensional supramolecular material based on aromatic hydrocarbon-perfluoroaromatic hydrocarbon interaction.

2. The method for preparing a two-dimensional supramolecular material based on arene-perfluoroarene interaction according to claim 1, characterized in that: The specific steps of the synthesis method of the monomer molecule tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate are as follows: Step 1: 5-bromoresorcinol, potassium carbonate, and potassium iodide are added to a container in proportion, and the solvent N,N-dimethylformamide is added under a nitrogen environment. After stirring and dissolving, 2-(BOC-amino) bromoethane is added dropwise to the reaction mixture, and stirred at 50-70°C for 12-24 hours. The reaction progress is monitored in real time by thin layer chromatography. After the reaction is completed and cooled to room temperature, the solvent N,N-dimethylformamide is evaporated at low pressure, and the reaction mixture is extracted 2-3 times with water and dichloromethane. The combined organic extracts are dried, and the solvent is removed by rotary evaporation to obtain a crude product, which is then purified to obtain product 3, which is specifically di-tert-butyl (((5-bromo-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate; Step 2: The product 3, bistriphenylphosphine palladium dichloride, cuprous iodide and triphenylphosphine are added to a container in proportion, and the solvent triethylamine is added under a nitrogen atmosphere and stirred evenly. After the mixture is fully dissolved, the triethylamine solution of trimethylethynylsilane is slowly added dropwise to the reaction mixture, and stirred at 45-55° C. for 12-24 hours. The reaction progress is monitored in real time by thin layer chromatography. After the reaction is completed and cooled to room temperature, the solvent triethylamine is removed by low pressure evaporation, and the reaction mixture is extracted with water and dichloromethane 2-3 times, and the combined organic extracts are dried, and the solvent is removed by rotary evaporation to obtain a crude product. The crude product is purified to obtain product 2, which is specifically di-tert-butyl (((5-((trimethylsilyl)ethynyl)-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl))dicarbamate; Step 3: Product 2, potassium carbonate, and potassium hydroxide are added to a container in proportion, and then a mixed solvent, i.e., a mixture of tetrahydrofuran, methanol, and water, is added. The mixture is reacted in an oil bath at a constant temperature of 25° C. for 6-8 hours, and the reaction progress is monitored in real time by thin layer chromatography. After the reaction is completed and cooled to room temperature, the mixed solvent is removed by low-pressure evaporation, and the reaction mixture is extracted 2-3 times with water and dichloromethane. The combined organic extracts are dried, and the solvent is removed by a rotary evaporator to obtain a crude product. After purifying the crude product, product 1 is obtained, and the product 1 is specifically di-tert-butyl (((5-ethynyl-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl)) dicarbamate; Step 4: 9,10-diiodoanthracene, product 1, bistriphenylphosphine palladium dichloride and cuprous iodide are added to a container in proportion, and the solvent triethylamine is added to fully dissolve under a nitrogen atmosphere, and stirred at a constant temperature of 75°C for 12-24 hours. The reaction progress is monitored in real time by thin layer chromatography. After the reaction is completed and cooled to room temperature, the solvent triethylamine is removed by low pressure evaporation, and then the reaction mixture is extracted with water and dichloromethane 2-3 times. The combined organic extracts are dried and the solvent is removed by rotary evaporation to obtain a crude product. The crude product is washed three times with triethylamine and then placed in a vacuum environment at 50-60°C for 12-24 hours. The obtained solid is cooled to room temperature to obtain the target product M1, wherein M1 is specifically a monomer molecule tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate.

3. The method for preparing a two-dimensional supramolecular material based on arene-perfluoroarene interaction according to claim 2, characterized in that: In the step 1, 5-bromoresorcinol, potassium carbonate, and potassium iodide are added in a molar ratio of 1:4:1; the amount of 2-(BOC-amino)bromoethane added dropwise is calculated as 2 times the molar ratio of 5-bromoresorcinol, and the addition time is controlled within 30 minutes; the crude product is purified by column chromatography filled with silica gel, and the eluent is petroleum ether / ethyl acetate in a volume ratio of 20:

1.

4. The method for preparing a two-dimensional supramolecular material based on arene-perfluoroarene interaction according to claim 2, characterized in that: In the step 2, product 3, bistriphenylphosphine palladium dichloride, cuprous iodide and triphenylphosphine are added in a molar ratio of 5:2:2:2; preparing the triethylamine solution of trimethylethynylsilicon specifically comprises: adding trimethylethynylsilicon to triethylamine to fully dissolve it, and the amount of trimethylethynylsilicon added is calculated as 25 times the molar equivalent of di-tert-butyl(((5-bromo-1,3-phenylene)bis(oxy))bis(ethane-2,1-diyl))dicarbamate; the time for adding the triethylamine solution of trimethylethynylsilicon dropwise to the reaction mixture is controlled to be more than 30 minutes; the crude product is purified by column chromatography filled with silica gel, and the eluent is petroleum ether / ethyl acetate in a volume ratio of 1:1 to 10:

1.

5. The method for preparing a two-dimensional supramolecular material based on arene-perfluoroarene interaction according to claim 2, characterized in that: In the step 3, the product 2, potassium carbonate, and potassium hydroxide are added in a molar ratio of 1:6:6; a mixed solvent of tetrahydrofuran, methanol, and water is prepared in a volume ratio of 2:1:1; and the crude product is purified by column chromatography filled with silica gel, and the eluent is petroleum ether / ethyl acetate in a volume ratio of 10:

1.

6. The method for preparing a two-dimensional supramolecular material based on arene-perfluoroarene interaction according to claim 2, characterized in that: In step 4, 9,10-diiodoanthracene, product 1, bistriphenylphosphine palladium dichloride and cuprous iodide are added in a molar ratio of 2:5:1:

3.

7. The method for preparing a two-dimensional supramolecular material based on arene-perfluoroarene interaction according to claim 2, characterized in that: In steps 1-4, the combined organic extracts are dried by adding anhydrous sodium sulfate to the combined organic extracts for drying.

8. The method for preparing a two-dimensional supramolecular material based on arene-perfluoroarene interaction according to claim 2, characterized in that: In steps 1-4, the solvents are all solvents dried with 5A molecular sieves, and the solutions are heated in a constant temperature oil bath.

9. The method for preparing a two-dimensional supramolecular material based on arene-perfluoroarene interaction according to claim 1, characterized in that: The specific steps of co-assembling the monomer molecule tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate with octafluoronaphthalene to form a two-dimensional supramolecular material based on arene-perfluoroarene interaction are: The monomer molecules tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate and octafluoronaphthalene were dissolved in a small amount of a common good solvent, chloroform, and ultrasonically premixed to ensure full contact between the two components at the molecular level. After removing the good solvent, the two components were added to a quantitative assembly solution and ultrasonically premixed. The mixture was then assembled at 20-25°C for a certain period of time to obtain a co-assembly of the monomer molecules tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate and octafluoronaphthalene.

10. The method for preparing a two-dimensional supramolecular material based on arene-perfluoroarene interaction according to claim 9, characterized in that: The concentration ratio of the monomer molecule tetra-tert-butyl((((anthracene-9,10-diylbis(acetylene-2,1-diyl))bis(benzene-5,1,3-triyl))tetrayl(oxy))tetrayl(ethane-2,1-diyl))tetracarbamate to octafluoronaphthalene is 1:1 to 1:20; the good solvent is removed by nitrogen drying or oven drying; the assembly liquid is a mixed solvent of cyclohexane and good chloroform in a volume ratio of 95:5; and the assembly time is controlled to be more than 2 hours.

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