A preparation method of a two-dimensional supramolecular polymer based on cation-π interaction co-assembly

Abstract

The application discloses a preparation method of a two-dimensional supramolecular polymer based on cation-pi interaction co-assembly, and relates to the technical field of supramolecular polymer materials. + As a cationic unit, a monomer molecule 4,4',4''-(3,7,11-trimethyltriphenylene-2,6,10-triyl)tris(N-dodecylbenzamide) is synthesized as a pi unit, and then the cationic unit and the pi unit are co-assembled to form a two-dimensional supramolecular polymer based on cation-pi interaction co-assembly. The prepared two-dimensional supramolecular polymer has fluorescence color change characteristics and photocatalytic hydrogen evolution performance, further widens the force category of two-dimensional supramolecular materials, and provides a new strategy for the preparation of two-dimensional supramolecular materials and the application of the two-dimensional supramolecular materials in the fields of fluorescence sensing, fluorescence anti-counterfeiting and photocatalytic hydrogen evolution.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of supramolecular materials, and particularly relates to a preparation method of a two-dimensional supramolecular polymer based on cation-π interaction co-assembly. BACKGROUND

[0002] In the field of chemistry and material science, it is crucial to precisely control the arrangement of structural units to form size- and morphology-controllable nanomaterials. Two-dimensional (2D) organic polymers have attracted extensive attention due to their unique optoelectronic properties, large specific surface area, and broad application prospects in catalysis (Coord. Chem. Rev. 2020, 415, 27), porous membranes (Sol. RRL, 2021, 5(3), 13), and semiconductor devices (Adv. Mater. 2020, 32(51)). Compared with traditional solid-state polymers, two-dimensional supramolecular polymers (2DSPs) can achieve highly ordered structures in both solid state and solution through non-covalent interactions, becoming an important strategy for constructing periodic two-dimensional materials. At present, the driving forces for constructing 2DSPs mainly include host-guest interactions, hydrogen bonds, aromatic stacking, and hydrophobic effects. However, the driving force for supramolecular assembly is usually weak during the molecular design stage, leading to the challenge of precisely controlling the assembly mechanism, which further affects the mechanical strength and stability of the obtained materials. Current research mainly focuses on the rational design of monomer molecules, exploration of new driving forces, regulation of assembly pathways, and separation of supramolecular products (Nat. Nanotechnol. 2015, 10(2), 111-119; Chem. Mater. 2014, 26(1), 576-586). However, the construction of a new generation of two-dimensional supramolecular materials still faces the following key problems: how to utilize non-covalent bond constraints to promote the assembly of monomers into highly ordered two-dimensional polymers, how to avoid structural heterogeneity caused by competitive assembly pathways, and how to endow the material with self-adaptive stimulus response behavior while maintaining its stability. In-depth understanding of these problems is crucial for the rational design and application of high-performance two-dimensional supramolecular materials.

[0003] Cation-π interactions are electrostatic in nature because positively charged cations interact with the electron cloud of negatively charged π systems, which induce dipoles in the aromatic systems and generate electrostatic attractive forces between the induced dipoles of the ionic species and the aromatic moieties. Therefore, it can be said that it is the strongest among the non-covalent interactions. Obviously, this strong interaction is expected to have a profound impact on controlling the structural environment of the neighborhood. The molecular stacking properties caused by cation-π have good directionality, thus promoting the generation of regular arrangement at the microscale, and often showing good morphology of long-range order at the macroscale. In today's nanotechnology era, understanding the nature, scope and relevance of cation-π interactions is crucial for the design of molecules and materials. Relevance and role of cation-π interactions in chemistry, biology, materials science and nanosystems. Special attention is paid to understanding the factors that modulate cation-π interactions and their structural and functional significance.

[0004] Therefore, it is an effective way to solve the above scientific problems by introducing cation-π interactions with strong action force and excellent directionality to form two-dimensional supramolecular materials. SUMMARY

[0005] In order to overcome the above-mentioned deficiencies of the prior art, the purpose of the present application is to provide a preparation method of two-dimensional supramolecular polymer based on cation-π interactions.

[0006] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0007] The present application provides a preparation method of two-dimensional supramolecular polymer based on cation-π interaction co-assembly, which comprises the following steps:

[0008] S1: Synthesis of monomer molecule trioxatricyclohexa-2,4-diene ion TOTA + As a cationic unit, the synthesis route is as follows:

[0009]

[0010] S2: Synthesis of monomer molecule 4,4',4"-(3,7,11-trimethyltriphenyl-2,6,10-triyl) tri(N-dodecylbenzamide) as π unit, the synthesis route is as follows:

[0011]

[0012] S3: The cationic unit trioxatricyclohexa-2,4-diene ion TOTA obtained in step S1 is co-assembled with the π unit 4,4',4"-(3,7,11-trimethyltriphenyl-2,6,10-triyl) tri(N-dodecylbenzamide) to form a two-dimensional supramolecular polymer based on cation-π interaction co-assembly. +co-assembled with the π motif 4,4',4"-(3,7,11-trimethyltriphenylen-2,6,10- triyl)tris(N-dodecylbenzamide) obtained in step S2 to form a two-dimensional supramolecular polymer based on co-assembly of cation-π interactions.

[0013] 3. A method for preparing a two-dimensional supramolecular polymer based on cation-π interactions according to claim 1, characterized in that the monomer molecule is trioxatriphenalenium ion TOTA + The synthesis method of the monomer molecule TOTA

[0014] Step 1 : Under a nitrogen atmosphere, dimethoxybenzene was dissolved in anhydrous diethyl ether in a vessel, n-butyllithium was added, the reaction mixture was stirred at room temperature for 3 hours, then diethyl carbonate was added, and the stirring reaction was continued at 45°C, after the reaction was completed, it was cooled to room temperature, water was added; after the layers were separated, the reaction mixture was extracted with water and diethyl ether, the combined organic phase was dried with anhydrous magnesium sulfate and filtered; 50% aqueous tetrafluoroboric acid was added to the filtrate, stirred for 10 minutes, the generated precipitate was removed by filtration and dried to obtain product 1, tris(2,6-dimethoxyphenyl)methyl tetrafluoroborate, as a dark green solid;

[0015] Step 2: Product 1 obtained in step 1 was mixed with pyridine hydrochloride under vigorous stirring, a small amount of pure pyridine was added, the dark purple reaction mixture was heated to 220°C and reacted for 6 hours, the color gradually turned brick red; after the reaction was completed, the reaction system was cooled to room temperature, the resulting mixture was poured into water, and the resulting solution was filtered to remove the resulting precipitate; then the filtrate was basified, the resulting precipitate was collected and added to diethyl ether, chloroform and HBF4, and a yellow precipitate immediately appeared; the precipitate was washed thoroughly with diethyl ether, and finally recovered by dissolving in CH3CN and evaporating and vacuum drying to obtain TOTA + ;

[0016] Step 3: 4-methylcyclohexanone was refluxed with zirconium tetrachloride overnight, water was generated during the reaction, forming a biphasic mixture; after cooling to room temperature, hot chloroform was added, and the viscous solid was filtered off; after the solvent was evaporated, the product was recrystallized with butanol to obtain product 2, 2,6,10-trimethyldodecahydrotriphenylene, which is a 1:1 mixture of C3 symmetric R,R,R / S,S,S and asymmetric R,R,S / S,S,R diastereomers;

[0017] Step 4: Product 2 obtained in step 3 was dissolved in triethylene glycol dimethyl ether with 10% Pd / C, and refluxed under an argon atmosphere for several hours, after the reaction was cooled to room temperature, chloroform was added, and heated to reflux to redissolve part of the precipitated product; the reaction mixture was hot filtered, the chloroform was evaporated, and the product was recrystallized with butanol to obtain product 3, 2,6,10-trimethyltriphenylene.

[0018] Step 5: The product 3 from step 4 and iron powder were dissolved in nitrobenzene, bromine was added, the reaction mixture was refluxed at 100 °C overnight, after cooling to room temperature, diethyl ether was added, the precipitated solid was filtered and washed with dry ether, and finally dried in vacuum, the product 4, 2,6,10-tribromo-3,7,11-trimethyltriphenylene, was obtained by recrystallization from bromobenzene;

[0019] Step 6: The product 4, 4'-(3,7,11-trimethyltriphenylene-2,6,10-triyl)tris(N- dodecylbenzamide), was obtained by purifying the crude product further using column chromatography with silica gel as the packing material. The purified product was a white solid.

[0020] Further, in step 1, dimethoxybenzene, n-butyllithium and diethyl carbonate were added in a molar ratio of 3:3:1; the amount of anhydrous ether added was 10-20 mL; the reaction time of dimethoxybenzene and n-butyllithium was 3 hours, and the reaction time after adding diethyl carbonate was 3 days.

[0021] Further, in step 2, product 1 and pyridine hydrochloride were added in a molar ratio of 1:19; the aqueous phase was alkalinized by stirring with sodium hydroxide solution until the pH value reached 14, the formed off-white precipitate was filtered through filter paper and washed with 0.5 M sodium hydroxide solution; then, the off-white solid was extracted with ether and 1:4 chloroform / ether solution to obtain a clear light yellow solution, and after adding 48 wt% HBF4, a yellow precipitate appeared immediately.

[0022] Further, in step 3, 4-methylcyclohexanone and zirconium tetrachloride were added in a molar ratio of 50:1, and the crude product was purified by recrystallization, i.e., by adding butanol to the crude product solid and heating to 90 °C to completely dissolve the crude product, then slowly cooling to precipitate the solid, and after overnight, the precipitated solid was filtered, and the obtained filter residue was the product 2.

[0023] Further, in step 4, the product 2 was added in an amount of 50:1 molar ratio with 10% Pd / C, the reaction was carried out at a reflux temperature of 220°C, and the crude product was purified by recrystallization. The crude product was completely dissolved by adding butanol to the solid crude product and heating to 90°C, and then the solid was precipitated by slowly cooling. The precipitated solid was filtered after overnight, and the obtained filter residue was the product 3.

[0024] Further, in step 5, the product 3, iron powder, and bromine were added in an amount of 9:1:40 molar ratio, the reaction was carried out at a reflux temperature of 100°C, and the crude product was purified by recrystallization. The crude product was completely dissolved by adding bromobenzene to the solid crude product and heating to 90°C, and then the solid was precipitated by slowly cooling. The precipitated solid was filtered after overnight, and the obtained filter residue was the product 4.

[0025] Further, in step 6, the product 4, 4-(methylcarbamoyl)phenylboronic acid, K2CO3, and tetrakis(triphenylphosphine)palladium were added in an amount of 5:20:20:1 molar ratio, and the crude product was purified by column chromatography with silica gel packing. Petroleum ether:dichloromethane = 1:4 (v / v) was used as the eluent.

[0026] Further, the trioxatricyclohexa-2,4-di-ene ion TOTA + The specific steps of co-assembly of the monomer molecule trioxatricyclohexa-2,4-di-ene ion TOTA

[0027] The monomer molecule trioxatricyclohexa-2,4-di-ene ion TOTA + and 4,4',4”-(3,7,11-trimethyltriphen-2,6,10-triyl)tris(N-dodecylbenzamide) were dissolved in a small amount of common good solvent dichloromethane and ultrasonically premixed to ensure sufficient contact of the two components at the molecular level. After removing the good solvent, a quantitative assembly solution was added and ultrasonically treated, and then assembled at 20-25°C for a certain period of time to obtain the co-assembly body of the monomer molecule trioxatricyclohexa-2,4-di-ene ion TOTA

[0028] Further, the trioxatricyclohexa-2,4-di-ene ion TOTA + The concentration ratio of the trioxatricyclohexa-2,4-di-ene ion TOTA

[0029] Compared with the prior art, the present application has the following beneficial effects:

[0030] The present application obtains the required monomer molecule trioxatricubane ion (TOTA + ) and TOTA + by a series of organic synthesis methods. Non-covalent bond interaction between 4,4', 4''-(3,7,11-trimethyltriphenyl-2,6,10-triyl) tri(N-dodecylbenzamide) (abbreviated as D1) and TOTA + is introduced, and the monomer molecule TOTA + is effectively supermolecularly co-assembled by alternating stacking with 4,4', 4''-(3,7,11-trimethyltriphenyl-2,6,10-triyl) tri(N-dodecylbenzamide) and assembly of peripheral alkyl chains in an organic phase in a 1,2-dichloroethane and methylcyclohexane solution, forming a two-dimensional sheet structure. The sheet material has obvious structural change characteristics, fluorescence color change characteristics and photocatalytic hydrogen evolution performance compared with the 1D rod-like structure formed by self-assembly of the monomer 4,4', 4''-(3,7,11-trimethyltriphenyl-2,6,10-triyl) tri(N-dodecylbenzamide). The force range of the two-dimensional supermolecular material is further widened, and the supermolecular material has potential application prospects in the fields of fluorescence sensing, fluorescence anti-counterfeiting and photocatalytic hydrogen evolution. At the same time, a new strategy is provided for the preparation of two-dimensional supermolecular materials. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 is the fluorescence spectrum of the self-assembly of TOTA + and D1 provided by the embodiment of the present application; + is the fluorescence spectrum of the co-assembly of TOTA + and D1 provided by the embodiment of the present application;

[0032] Figure 2 is the nuclear magnetic resonance hydrogen spectrum of the monomer molecule D1 provided by the embodiment of the present application;

[0033] Figure 3 is the nuclear magnetic resonance hydrogen spectrum of the monomer molecule TOTA + provided by the embodiment of the present application;

[0034] Figure 4 is the SEM electron microscope graph of the self-assembly of D1 provided by the embodiment of the present application;

[0035] Figure 5 is the SEM electron microscope graph of the two-dimensional supermolecular material based on cation-π interaction based on the co-assembly of TOTA + and D1 provided by the embodiment of the present application. DETAILED DESCRIPTION

[0036] The principles and features of the present application are described below in conjunction with the accompanying drawings, in which the examples are presented only to explain the present application and are not intended to limit the scope of the present application. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terms used in the specification of the present application herein are only for the purpose of describing the specific examples and are not intended to limit the present application.

[0037] Example 1

[0038] A method for preparing a two-dimensional supramolecular polymer based on cation-π interaction, the specific steps are as follows:

[0039] Step 1: Dissolve 2.4 mL of dimethoxybenzene (18.11 mmol) in anhydrous ether (12 mL) in a Schlenk flask under a nitrogen atmosphere, add 2M n-butyllithium (n-BuLi) (9 mL, 18 mmol), and stir the reaction mixture at room temperature for 3 hours. Then, add diethyl carbonate (0.65 mL, 5.4 mmol) and continue stirring at 45°C for 3 days. After the reaction is completed, cool to room temperature, and add water (15 mL). After layering, extract the reaction mixture with water and ether 2-3 times. Dry the combined organic phase with anhydrous magnesium sulfate (MgSO4) and filter. Add 50% aqueous tetrafluoroboric acid (HBF4) (1.3 mL) to the filtrate, stir for 10 minutes, remove the resulting precipitate by filtration and dry to obtain the target product 1 (1.02 g, 33%) in the form of a dark green solid;

[0040] Step 2: Mix product 1 (1.53 g, 3 mmol, 1.0 equivalent) with pyridine hydrochloride (6.49 g, 56.2 mmol, 19 equivalents) with vigorous stirring, and add a small amount of pure pyridine (5 mL). Heat the dark purple reaction mixture to 220°C and react for 6 hours, and the color gradually changes to brick red. After the reaction is completed, cool the reaction system to room temperature, pour the resulting mixture into water, and filter the resulting solution to remove the resulting precipitate. Then, basify the filtrate (1M NaOH), collect the resulting precipitate and add ether, chloroform and HBF4 (48wt%, 3 mL, 7.6 mmol, 7 equivalents), and a yellow precipitate immediately appears. The precipitate is washed thoroughly with ether, and finally recovered by dissolving in CH3CN and evaporating and vacuum drying, to obtain dark yellow needle-shaped crystals of TOTA+, with a yield of 67%;

[0041] Step 3: 4-methylcyclohexanone (40 g, 0.35 mol) was refluxed with zirconium tetrachloride (4 g, 17 mmol) overnight. Water was generated during the reaction, forming a biphasic mixture. After cooling to room temperature, hot chloroform (100 mL) was added and the viscous solid was filtered off. After evaporation of the solvent, the product was recrystallized from butanol. The final product was a 1:1 mixture of C3 symmetric (R,R,R / S,S,S) and asymmetric (R,R,S / S,S,R) diastereomers 2, yield 23.3 g (82 mmol, 69%).

[0042] Step 4: Product 2 (15 g, 53 mmol) was dissolved in 50 mL of triethylene glycol dimethyl ether with 10% Pd / C (1.5 g, 1.4 mmol) and refluxed under argon atmosphere for several hours. After cooling the reaction to room temperature, chloroform (250 mL) was added and heated to reflux to redissolve the partially precipitated product. The reaction mixture was hot filtered and after evaporation of the chloroform, the product was recrystallized from butanol. The yield of the final product 3 was 11.0 g (41 mmol, 77%).

[0043] Step 5: Product 3 (2.7 g, 9.99 mmol) and iron powder (0.1 g, 1.8 mmol) were dissolved in 50 mL of nitrobenzene and bromine (2.1 mL, 6.4 g, 40.0 mmol) was added. The reaction mixture was refluxed at 100 °C overnight. After cooling to room temperature, diethyl ether (150 mL) was added, the precipitated solid was filtered off and washed with dry diethyl ether and finally dried in vacuum. The product 4 was obtained by recrystallization from bromobenzene (3.9 g, 7.69 mmol, 77%).

[0044] Step 6: Product 4 (510 mg, 1.01 mmol), 4-(methylcarbamoyl)phenylboronic acid (715 mg, 4 mmol), K2CO3(550 mg, 3.98 mmol), tetrakis(triphenylphosphine)palladium (250 mg, 0.21 mmol) were taken in a 100 mL Schlenk flask under nitrogen atmosphere, 10 mL of water and 40 mL of tetrahydrofuran were added and the reaction mixture was refluxed at 80 °C under constant temperature condition for 48 h. The progress of the reaction was monitored in real time by thin layer chromatography after overnight reaction. The reaction mixture was rotary evaporated when the reaction mixture was cooled to room temperature. The reaction mixture was extracted with water / dichloromethane three to four times. The organic layer was dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure to obtain the crude product. The crude product was further purified by column chromatography using silica gel packed column to obtain the target molecule 4,4',4”-(3,7,11-trimethyltriphenylen-2,6,10-triyl)tris(N-dodecylbenzamide) as a white solid (380 mg, yield 50%).

[0045] Monomeric molecule TOTA+ The D1 nuclear magnetic resonance hydrogen spectrum is shown in Figure 1. Figure 2 , Figure 3 It can be seen that the monomer molecule TOTA + is successfully synthesized with D1.

[0046] Step 7: A certain amount of monomer molecule D1 is placed in a 5 mL sample bottle in a proportion of [D1]: [TOTA + ] = 1:2, dissolved in a small amount of good solvent dichloromethane, and after removing the good solvent by nitrogen blowing, a quantitative assembly solution is added and ultrasonic is performed. The assembly solution is selected as a mixture of poor solvent methylcyclohexane and good solvent 1,2-dichloroethane, and the mixture solvent ratio is methylcyclohexane / 1,2-dichloroethane 3:2 by volume. Assemble for more than 2h at room temperature to obtain D1 and self-assembly.

[0047] Step 8: A certain amount of monomer molecule D1 and TOTA+ are placed in a 5 mL sample bottle in a proportion of [D1]: [TOTA + ] = 1:2, dissolved in a small amount of common good solvent dichloromethane, and ultrasonic premixing is performed to ensure that the two components are fully contacted at the molecular level. After removing the good solvent by nitrogen blowing, a quantitative assembly solution is added and ultrasonic is performed. The assembly solution is selected as a mixture of poor solvent methylcyclohexane and good solvent 1,2-dichloroethane, and the mixture solvent ratio is methylcyclohexane / 1,2-dichloroethane 3:2 by volume. Assemble for more than 2h at room temperature to obtain D1 and TOTA + co-assembly, i.e. two-dimensional supramolecular material based on cation-π interaction co-assembly.

[0048] The fluorescence spectrum of TOTA + , D1 self-assembly and TOTA + and D1 co-assembly is tested, and the solid fluorescence test results are shown in Figure 3. Figure 1 When the cation TOTA + and D1 two-component assembly, the characteristic emission peak of the cation TOTA + at 500 to 600 nm is quenched with the addition of D1, and then a new peak is generated at 600 to 700 nm, indicating that typical cation-π interaction is generated here. This fluorescence quenching and red shift and charge transfer effect provides a good premise for subsequent photocatalytic hydrogen production application.

[0049] The SEM electron microscope image of the two-dimensional supramolecular material based on cation-π interaction of D1 self-assembly and TOTA + and D1 co-assembly is shown in Figure 4. Figure 4 , Figure 5 . From Figure 4It can be seen that D1 self-assembles into one-dimensional rods through π-π stacking and hydrogen bonding. The addition of cationic TOTA + Afterwards, the cationic TOTA + Because of the cation-π interaction of D1 binding, the change of force (the addition of cation-π interaction and the change of hydrogen bonding mode) uses structural transformation to become regular two-dimensional sheet, as Figure 5 shown. This sheet material has obvious structural change characteristics, fluorescence color change characteristics and photocatalytic hydrogen evolution performance compared with the one-dimensional rod structure formed by the self-assembly of monomer 4,4',4"-(3,7,11-trimethyltriphenylene-2,6,10-triyl) tri(N-dodecylbenzamide). This further broadens the force range of two-dimensional supramolecular materials, and the supramolecular materials have potential application prospects in the fields of fluorescence sensing, fluorescence anti-counterfeiting and photocatalytic hydrogen evolution. At the same time, it provides a new strategy for the preparation of two-dimensional supramolecular materials.

[0050] It should be noted that the above-described embodiments are only preferred embodiments of the present application. Those skilled in the art can make several modifications, improvements and equivalent replacements to the present application without departing from the principles of the present application, and these modifications, improvements and equivalent replacements are also considered to fall within the protection scope of the claims of the present application.

Claims

1. A method for preparing a two-dimensional supramolecular polymer based on cation-π interaction co-assembly, characterized in that, Includes the following steps: S1: Synthetic monomer molecule trioxatrigonene ion TOTA + As a cationic building block, the synthetic route is as follows: ； S2: The synthetic route for synthesizing the monomer 4,4',4''-(3,7,11-trimethyltrimethylene-2,6,10-triyl)tris(N-dodecylbenzamide) as the π-unit is as follows: ； S3: To make the cationic trioxatrigonene ion TOTA obtained in step S1 + The π-unit 4,4',4''-(3,7,11-trimethyltrimethylene-2,6,10-triyl)tris(N-dodecylbenzamide) obtained in step S2 is co-assembled to form a two-dimensional supramolecular polymer based on cation-π interaction co-assembly.

2. The method for preparing two-dimensional supramolecular polymers based on cation-π interaction co-assembly according to claim 1, characterized in that, The specific steps are as follows: Step 1: Under a nitrogen atmosphere, dimethoxybenzene was dissolved in anhydrous diethyl ether and added to a container. Butyllithium was added, and the reaction mixture was stirred at room temperature for 3 hours. Diethyl carbonate was then added, and the reaction was continued at 45°C. After the reaction was complete, the mixture was cooled to room temperature, and water was added. After separation, the reaction mixture was extracted with water and diethyl ether. The combined organic phases were dried with anhydrous magnesium sulfate and filtered. A 50% tetrafluoroborate aqueous solution was added to the filtrate, and the mixture was stirred for 10 minutes. The resulting precipitate was removed by filtration and dried to obtain product 1, tris(2,6-dimethoxyphenyl)methyltetrafluoroborate, as a dark green solid. Step 2: Product 1 obtained in Step 1 was mixed with pyridine hydrochloride under vigorous stirring. A small amount of pure pyridine was added. The deep purple reaction mixture was heated to 220°C and reacted for 6 hours, gradually turning brick red. After the reaction was complete, the reaction system was cooled to room temperature. The resulting mixture was poured into water, and the solution was filtered to remove the precipitate. The filtrate was then alkalized, the precipitate was collected, and after adding diethyl ether, chloroform, and HBF4, a yellow precipitate immediately appeared. The precipitate was thoroughly washed with diethyl ether and finally recovered by dissolving in CH3CN, evaporation, and vacuum drying to obtain deep yellow needle-like crystals of TOTA. + ; Step 3: 4-Methylcyclohexanone and zirconium tetrachloride were refluxed together overnight. Water was generated during the reaction, forming a two-phase mixture. After cooling to room temperature, hot chloroform was added, and the viscous solid was filtered off. After evaporating the solvent, the product was recrystallized from butanol to obtain product 2, namely 2,6,10-trimethyldodecyltriphenylene, which is a 1:1 mixture of C3 symmetrical R,R,R / S,S,S and asymmetric R,R,S / S,S,R enantiomeric derivatives. Step 4: Dissolve product 2 obtained in step 3 with 10% Pd / C in triethylene glycol dimethyl ether and reflux the reaction under argon atmosphere for several hours. After the reaction is cooled to room temperature, chloroform is added and the mixture is heated under reflux to redissolve part of the precipitated product. The reaction mixture is hot filtered, and after evaporating the chloroform, the product is recrystallized with butanol to obtain product 3, namely 2,6,10-trimethyltriphenylene. Step 5: Dissolve product 3 obtained in step 4 and iron powder in nitrobenzene, add bromine, reflux the reaction mixture at 100°C overnight, cool to room temperature, add diethyl ether, filter out the precipitated solid, wash with anhydrous diethyl ether, and finally dry in vacuum. Recrystallize from bromobenzene to obtain product 4, namely 2,6,10-tribromo-3,7,11-trimethyltriphenylene. Step 6: Under nitrogen protection, the product 4,4-(dodecylcarbamoyl)phenylboronic acid, K2CO3, and tetra(triphenylphosphine)palladium obtained in step 5 were added to a container, along with water and tetrahydrofuran. The mixture was refluxed at 80 °C and stirred until homogeneous for 48 h. After reacting overnight, the reaction progress was monitored in real time by thin-layer chromatography. When the reaction was completed and the reaction mixture was cooled to room temperature, the reaction mixture was evaporated by rotary evaporation. The reaction mixture was extracted with water / dichloromethane, and the organic layer was dried with anhydrous sodium sulfate. The solvent was then removed under reduced pressure to obtain the crude product. The crude product was further purified by silica gel-packed column chromatography to obtain the target molecule 4,4',4''-(3,7,11-trimethyltrimethylene-2,6,10-triyl)tris(N-dodecylbenzamide) as a white solid.

3. The method for preparing two-dimensional supramolecular polymers based on cation-π interaction co-assembly according to claim 2, characterized in that, In step 1, dimethoxybenzene, n-butyllithium, and diethyl carbonate are added in a molar ratio of 3:3:1; the amount of anhydrous diethyl ether added is 10-20 mL; the reaction time of dimethoxybenzene and n-butyllithium is 3 hours, and the reaction time after adding diethyl carbonate is 3 days.

4. The method for preparing two-dimensional supramolecular polymers based on cation-π interaction co-assembly according to claim 2, characterized in that, In step 2, product 1 and pyridine hydrochloride are added in a molar ratio of 1:19; the aqueous phase is alkalized by adding sodium hydroxide solution and stirring until the pH value is 14, and the resulting grayish-white precipitate is filtered through filter paper and washed with 0.5 M sodium hydroxide solution. The grayish-white solid was then extracted with diethyl ether and a 1:4 chloroform / diethyl ether solution to obtain a clear, pale yellow solution. Upon addition of 48 wt% HBF4, a yellow precipitate immediately appeared.

5. The method for preparing two-dimensional supramolecular polymers based on cation-π interaction co-assembly according to claim 2, characterized in that, In step 3, 4-methylcyclohexanone and zirconium tetrachloride are added in a molar ratio of 50:

1. The crude product is purified by recrystallization. Butanol is added to the crude product solid and heated to 90°C to completely dissolve the crude product. Then, the solid is slowly cooled to precipitate. After overnight, the precipitated solid is filtered, and the resulting filter residue is product 2.

6. The method for preparing two-dimensional supramolecular polymers based on cation-π interaction co-assembly according to claim 2, characterized in that, In step 4, product 2 and 10% Pd / C were added at a molar ratio of 50:

1. The reaction reflux temperature was 220℃. The crude product was purified by recrystallization. Butanol was added to the crude product solid and heated to 90℃ to completely dissolve the crude product. Then the solid was slowly cooled to precipitate. After overnight, the precipitated solid was filtered, and the resulting filter residue was product 3.

7. The method for preparing two-dimensional supramolecular polymers based on cation-π interaction co-assembly according to claim 2, characterized in that, In step 5, product 3, iron powder, and bromine are added in a molar ratio of 9:1:

40. The reaction reflux temperature is 100°C. The crude product is purified by recrystallization. Bromobenzene is added to the crude product solid and heated to 90°C to completely dissolve the crude product. Then, the solid is slowly cooled to precipitate. After overnight, the precipitated solid is filtered, and the resulting filter residue is product 4.

8. The method for preparing two-dimensional supramolecular polymers based on cation-π interaction co-assembly according to claim 2, characterized in that, In step 6, product 4, 4-(dodecylcarbamoyl)phenylboronic acid, K2CO3, and tetra(triphenylphosphine)palladium in a molar ratio of 5:20:20:1 are added to purify the crude product using silica gel-packed column chromatography with petroleum ether:dichloromethane = 1:4 (v / v) as the eluent.

9. The method for preparing a two-dimensional supramolecular polymer based on cation-π interaction co-assembly according to any one of claims 1 to 8, characterized in that, The trioxatrigonene ion TOTA + The specific steps for co-assembling with 4,4',4''-(3,7,11-trimethyltrimethylene-2,6,10-triyl)tris(N-dodecylbenzamide) to form a two-dimensional supramolecular polymer based on cation-π interaction co-assembly are as follows: The monomeric molecule trioxatrigonene ion TOTA+ and 4,4',4''-(3,7,11-trimethyltrimethylene-2,6,10-triyl)tris(N-dodecylbenzamide) were dissolved in a small amount of a common good solvent, dichloromethane, and ultrasonically premixed to ensure sufficient contact between the two components at the molecular level. After removing the good solvent, the mixture was added to a quantitative assembly solution and ultrasonically sonicated. Assembly was then performed at 20-25℃ for a certain period of time to obtain the monomeric molecule trioxatrigonene ion TOTA+. + Co-assemblies with 4,4',4''-(3,7,11-trimethyltriphenyl-2,6,10-triyl)tris(N-dodecylbenzamide).

10. The method for preparing the two-dimensional supramolecular polymer based on cation-π interaction co-assembly according to claim 9, characterized in that, The trioxatrigonene ion TOTA + The concentration ratio of 4,4',4''-(3,7,11-trimethyltriphenyl-2,6,10-triyl)tris(N-dodecylbenzamide) is 2:1; the removal of the good solvent is carried out by nitrogen blowing or oven drying; the assembly solution is a mixed solvent of methylcyclohexane and 1,2-dichloroethane in a volume ratio of 3:2; the assembly time is controlled to be more than 2 hours.

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