Supramolecular nanotubes based on cation-pi interactions and applications

Abstract

The application discloses a supramolecular nanotube based on cation-pi interaction and application, and belongs to the technical field of supramolecular functional materials. The supramolecular nanotube based on cation-pi interaction is a hexagonal columnar structure formed by self-assembly of cations of V-type pyridine, and the V-type pyridine is 4,4'-((1E,1'E)-(5'-(undecan-11-yloxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethene-2,1-diyl))bis(1-methylpyridinium-1-iodide) or 4,4'-((1E,1'E)-(5'-(undecan-11-yloxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethene-2,1-diyl))bis(1-methylpyridinium-1-chloride), and structural formulae are as follows: or.

Description

Technical Field

[0001] This invention relates to the field of supramolecular functional materials technology, and more specifically, to a supramolecular nanotube based on cation-π interaction and its application. Background Technology

[0002] Supramolecular nanotubes, as a class of one-dimensional hollow structures formed through self-assembly based on non-covalent interactions, have shown broad application prospects in fields such as catalysis. The regulatory role of non-covalent interactions, especially hydrogen bonding and electrostatic interactions, in supramolecular assembly has gradually attracted attention. Cation-π interactions, as a strong and directional intermolecular force existing between cations and aromatic systems, have received increasing attention in recent years for their regulatory role in supramolecular assembly. By precisely introducing or regulating cation-π interactions, it is possible to guide the stacking pattern and control the assembly path at the molecular level. Therefore, systematically studying the influence of cation-π interactions on molecular stacking behavior, assembly kinetics, and the final nanostructure, and establishing a simple and efficient supramolecular nanotube regulation strategy based on cation-π interactions, has significant scientific and application value.

[0003] In a 2025 paper titled "Homochiral Single Crystals of Helical Polymer Nanotubes: Synthesis and Application" published in the Journal of the American Chemical Society, Yinghua Yu et al. disclosed a method for hierarchical self-assembly from linear chains to helical nanotubes, driven by the synergistic effect of dynamic covalent bonds (BO and BN) and non-covalent interactions. However, although this crystallization-induced helical nanotube structure achieves precise chiral arrangement at the atomic scale, the helical ordering of its polymer backbone still depends on the driving force of the crystallization process, and sufficient helical ordering in solution has not yet been achieved, thus limiting the programmability of its structure to some extent.

[0004] In their 2025 paper "Rigid Supramolecular Aramid Nanotubes as Catalyst Supports" published in *Advanced Materials*, Yukio Cho et al. disclosed a supramolecular nanotube constructed by the self-assembly of aromatic amide amphiphilic molecules. By precisely designing molecular head groups to regulate the surface chemistry of the nanotubes, they achieved the controllable construction of rigid one-dimensional nanotube structures with high aspect ratio, high endurance length, and high mechanical stiffness. Furthermore, they successfully constructed a highly active, easily recyclable, and reusable nanocatalyst system by achieving covalent anchoring of gold nanoparticles through surface functionalization. However, its catalytic activity is highly dependent on the loading density and uniformity of gold nanoparticles on the nanotube surface. The loading process is limited by the efficiency of the covalent interaction between thiol groups and gold, making it difficult to achieve dynamic and reconfigurable control of catalytic activity in complex catalytic systems, thus limiting its further application.

[0005] In summary, existing technologies all rely on molecular self-assembly to form a structural framework, after which the geometry and surface chemistry of nanotubes tend to be fixed. However, this method has the following drawbacks: First, to obtain different nanotubes, it is usually necessary to redesign and synthesize molecular assembly units; second, catalytic performance requires loading, and although this fixed assembly configuration can form stable nanotubes, its surface functionalization mode is singular, and catalytic activity depends on exogenous loading. It has not yet achieved precise spatial arrangement of multi-level catalytic centers and universal control of non-covalent anchoring modes, thus limiting its application in complex catalytic systems; third, the helical ordering of the polymer backbone has not yet been achieved. Summary of the Invention

[0006] To address the shortcomings of the existing technologies, this invention provides a supramolecular nanotube based on cation-π interactions and its applications. The supramolecular nanotube based on cation-π interactions of this invention is a hexagonal columnar structure formed by the self-assembly of V-type pyridine cations. The V-type pyridine is 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) or 4 ,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-chloro), 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4' '-Diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-chloro) is prepared from 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) as a raw material; In addition, supramolecular nanotubes based on cation-π interactions can precisely control the structure of supramolecular nanotubes through non-covalent interactions. It is a V-type pyridine cation derivative based on cation-π interactions, which can achieve ordered and controllable self-assembly of the structure and form stable supramolecular nanotubes; At the same time, the nanotube framework itself contains catalytically active sites (C on the C=C bond is the active site), avoiding the efficiency and uniformity problems caused by additional catalyst loading. Therefore, this invention overcomes the shortcomings of existing technologies, such as catalytic performance depending on exogenous loading, limited structural order after self-assembly, and the need to redesign and synthesize molecular assembly units to obtain new nanotubes.

[0007] Based on the above technical objectives, the present invention adopts the following technical solution: This invention protects a supramolecular nanotube based on cation-π interaction. The supramolecular nanotube based on cation-π interaction is a hexagonal columnar structure formed by the self-assembly of V-type pyridine cations. The V-type pyridine is 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) or 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-chloro).

[0008] The structural formula of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) is: .

[0009] The structural formula of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-chloro) is: .

[0010] Preferably, 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) is prepared according to the following steps: S1. Using a halogenated hydrocarbon organic solvent as a solvent, 11-neco-co-ol and 4-toluenesulfonyl chloride as raw materials, and triethylamine and trimethylamine hydrochloride as catalysts, an amidation reaction is carried out to obtain 11-neco-co-co-toluenesulfonate.

[0011] S2. Using amide-based organic solvents as solvents, 11-neocenealkyl-p-toluenesulfonate and 3,5-dibromophenol were subjected to a Williamson ether synthesis reaction under alkaline conditions to obtain 1,3-dibromo-5-(undecaprinylundecyloxy)benzene.

[0012] S3. In an inert atmosphere, using an ether-based organic solvent as a solvent, 1,3-dibromo-5-(undecenylundecyloxy)benzene and 4-formylphenylboronic acid undergo a Suzuki coupling reaction under alkaline and catalytic conditions to obtain 5'-(undecane-11-oxy)-[1,1':3',1''-terphenyl]-4,4''-dicarboxaldehyde.

[0013] S4. In an inert atmosphere, using furan organic solvent as solvent, 4-((chlorotriphenyl-λ5-phosphino)methyl)pyridine, NaH, and 5'-(undecane-11-oxy)-[1,1':3',1''-terphenyl]-4,4''-dicarboxaldehyde undergo a Wittig reaction to yield 4,4'-[(1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dimethylene)bis(ethylene-2,1-diyl)]dipyridine.

[0014] S5. Using a halocarbon organic solvent as a solvent, 4,4'-[(1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dimethylene)bis(ethylene-2,1-diyl)]dipyridine and iodomethane undergo a methylation reaction to obtain 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide).

[0015] Preferably, in step S1, the molar ratio of 11-co-dodecyl alcohol, 4-toluenesulfonyl chloride, triethylamine and trimethylamine hydrochloride is 1:1.00-1.25:1.8-2:0.8-1.

[0016] Preferably, in step S2, the molar ratio of 11-tetradecyl p-toluenesulfonate, base and 3,5-dibromophenol is 1:1.0-1.2:4.8-5.

[0017] Preferably, in step S3, the molar ratio of 1,3-dibromo-5-(undecaprinylundecyloxy)benzene, 4-formylphenylboronic acid, catalyst and base is 1:3.7-4:0.04-0.05:4.8-5.

[0018] Preferably, in step S4, the molar ratio of 4-((chlorotriphenyl-λ5-phosphino)methyl)pyridine, NaH and 5'-(undecane-11-oxy)-[1,1':3',1''-terphenyl]-4,4''-dicarboxaldehyde is 2.7-3:1.8-2:1.

[0019] Preferably, in step S5, the molar ratio of 4,4'-[(1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dimethylene)bis(ethylene-2,1-diyl)]dipyridine to iodomethane is 1:3.8-4.

[0020] Preferably, in step S1, the conditions for the amidation reaction are: stirring at room temperature for 11-12 hours.

[0021] Preferably, in step S2, the conditions for the Williamson ether synthesis reaction are: stirring at 100℃-110℃ under reflux for 11-12 hours.

[0022] Preferably, in step S3, the conditions for the Suzuki coupling reaction are: stirring at 80℃-90℃ for 11-12 hours.

[0023] Preferably, in step S4, the conditions for the Wittig reaction are: stirring at room temperature for 11-12 hours.

[0024] Preferably, in step S5, the methylation reaction is carried out under reflux conditions of 50℃-53℃ for 11-12 hours.

[0025] Preferably, 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-chloro) is prepared according to the following steps: 1) Using alcohol as a solvent, 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) and ammonium hexafluorophosphate were subjected to an ion exchange reaction to obtain 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-hexafluorophosphate).

[0026] 2) Using acetonitrile as a solvent, 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-hexafluorophosphate) and tetraethylammonium chloride were subjected to an ion exchange reaction in acetonitrile to obtain 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-chlorophosphate).

[0027] Preferably, in step 1), the molar ratio of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) to ammonium hexafluorophosphate is 1:4.8-5.

[0028] Preferably, in step 2), the molar ratio of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-hexafluorophosphate) to tetraethylammonium chloride is 1:4.8-5.

[0029] Preferably, the conditions for the ion exchange reaction in steps 1) and 2) are the same, which is stirring at room temperature for 11-12 hours.

[0030] This invention also protects the application of supramolecular nanotubes based on cation-π interactions in the preparation of photocatalytic catalysts for the production of hydrogen peroxide.

[0031] Compared with the prior art, the present invention has the following beneficial effects: 1. This invention provides supramolecular nanotubes based on cation-π interactions. These supramolecular nanotubes are hexagonal columnar structures formed by the self-assembly of V-type pyridine cations. V-type pyridine is... or This invention uses cation-π interaction as the core assembly driving force to complete the hexagonal columnar structure formed by the self-assembly of V-type pyridine cations, which is different from the existing technology that relies on crystal induction or rigid covalent framework.

[0032] 2. The catalytic activity of supramolecular nanotubes based on cation-π interactions in this invention originates from the supramolecular framework constructed by cation-π interactions, resulting in hexagonal columnar nanotubes with uniform mesoporous pore size and high specific surface area. Compared to existing technologies where catalytic activity is highly dependent on the covalent loading of gold nanoparticles, this invention achieves a "structure-function" catalytic mode, avoiding efficiency loss, poor uniformity, and instability issues associated with exogenous loading.

[0033] 3. The present invention use The nanotubes were prepared by first undergoing an ion exchange reaction with ammonium hexafluorophosphate, followed by an ion exchange reaction with tetraethylammonium chloride, resulting in two types of supramolecular nanotubes based on cation-π interactions. Studies have shown that... compared to, It has superior photocatalytic performance in the production of hydrogen peroxide. Attached Figure Description

[0034] Figure 1 The 1H NMR spectrum of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) prepared in Example 1 of this invention.

[0035] Figure 2 In the middle, the left figure is a two-dimensional small-angle X-ray scattering pattern of the supramolecular nanotubes prepared in Example 1 of the present invention; the right figure is a columnar stacking model of the supramolecular nanotubes prepared in Example 1 and a size diagram.

[0036] Figure 3 This is a pore size distribution diagram of the supramolecular nanotubes prepared in Example 1 of the present invention.

[0037] Figure 4 This is a transmission electron microscope image of the supramolecular nanotubes prepared in Example 1 of the present invention.

[0038] Figure 5 The graph shows the photocatalytic H2O2 production performance of the supramolecular nanotubes prepared in Examples 1 and 2 of this invention.

[0039] Figure 6 This is a schematic diagram illustrating the preparation principle of supramolecular nanotubes based on cation-π interactions according to the present invention.

[0040] Figure 7 The diagram shows the preparation equations for 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) and 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-chloro) of the present invention. Detailed Implementation

[0041] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0042] Considering the technical shortcomings of existing technologies, which require "redesigning and synthesizing molecular assembly units to obtain different nanotubes," the supramolecular nanotubes of this invention can be prepared using only ion exchange reactions to achieve the preparation of two types of supramolecular nanotubes. Considering the technical shortcomings of existing technologies, which require loading for catalytic performance and, although such fixed assembly configurations can form stable nanotubes, their surface functionalization methods are limited, the supramolecular nanotubes of this invention contain catalytically active sites (C on the C=C bond serves as the active site) in their own framework, thus avoiding the problems caused by additional catalyst loading. Considering that the helical ordering of the polymer backbone in existing technologies still depends on the driving force of the crystallization process, the V-type pyridine cations of this invention can undergo self-assembly to form a hexagonal columnar structure. That is, after obtaining V-type pyridine, V-type pyridine spontaneously self-assembles to obtain supramolecular nanotubes based on cation-π interactions.

[0043] This invention enables the application of supramolecular nanotubes in catalytic systems through the precise spatial arrangement of multi-level catalytic centers and the universal control of non-covalent anchoring modes. This invention assembles molecules into nanotubes through non-covalent interactions; the non-covalent anchoring mode is a strategy that achieves functional site construction and dynamic reconstruction through the synergistic and regulatory effects of weak interactions.

[0044] To overcome the shortcomings of existing technologies, this invention proposes supramolecular nanotubes based on cation-π, and the preparation process is expressed by the following equation: Figure 7 As shown, the preparation principle is as follows: Step 1: Using a halogenated hydrocarbon organic solvent as the solvent, 11-eicosyl alcohol and 4-toluenesulfonyl chloride as reactants, and triethylamine and trimethylamine hydrochloride as catalysts, an amidation reaction is carried out using 11-eicosyl alcohol, 4-toluenesulfonyl chloride, triethylamine and trimethylamine hydrochloride. In the presence of an organic base (triethylamine) and a nucleophilic catalyst (trimethylamine hydrochloride), the hydroxyl group of 11-eicosyl alcohol undergoes a nucleophilic substitution reaction with 4-toluenesulfonyl chloride, removing one molecule of HCl to generate 11-eicosyl p-toluenesulfonate.

[0045] Step 2: Using amide-based organic solvents as solvents, 11-neocenealkyl-p-toluenesulfonate and 3,5-dibromophenol undergo a Williamson ether synthesis reaction in an alkaline environment provided by K2CO3. The reaction mechanism is as follows: Under alkaline conditions, the phenolic hydroxyl group is deprotonated to form a more nucleophilic phenoxy anion. This anion undergoes nucleophilic substitution of the saturated carbon atom in the alkylating reagent to generate an ether bond, yielding 1,3-dibromo-5-(undecaprinylundecyloxy)benzene.

[0046] Step 3: Under an inert gas atmosphere, using an ether-based organic solvent as a solvent, 1,3-dibromo-5-(undecenylundecyloxy)benzene, 4-formylphenylboronic acid, and tetra(triphenylphosphine)palladium undergo a Suzuki coupling reaction in an alkaline environment provided by K2CO3. Under the action of the palladium catalyst, arylboronic acid and aryl halides undergo cross-coupling to form new C–C bonds, generating biaryl compounds, yielding 5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dicarboxaldehyde.

[0047] Step 4: Under an inert gas atmosphere, using furan organic solvent as solvent, 4-((chlorotriphenyl-λ5-phosphino)methyl)pyridine, NaH, and 5'-(undecane-11-oxy)-[1,1':3',1''-terphenyl]-4,4''-dicarboxaldehyde undergo a Wittig reaction. Phosphorus ylide (the carbanion intermediate generated by the alkaline action of phosphorus salt) undergoes nucleophilic addition with the aldehyde group to form a four-membered epoxy phosphorus heterocyclic intermediate, which then undergoes elimination to generate an olefin and triphenylphosphine oxide, achieving carbon chain growth to obtain 4,4'-[(1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dimethylene)bis(ethylene-2,1-diyl)]dipyridine.

[0048] Step 5: Using a halogenated hydrocarbon organic solvent as the solvent, a methylation reaction is carried out between 4,4'-[(1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dimethylene)bis(ethylene-2,1-diyl)]dipyridine and iodomethane. The nitrogen atom on the pyridine ring acts as a nucleophile, undergoing nucleophilic substitution with the halogenated alkane (iodomethane) to generate a pyridine cation. At the same time, the iodide ion acts as an anti-anion and pairs with it to form a pyridine salt, yielding 4,4'-[(1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dimethylene)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide).

[0049] The technical solution of the present invention will be studied using the following embodiments, as detailed below: Example 1 The preparation method of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) includes the following steps: Step 1: 5g of 11-hexaenoic alcohol, 3.8g of 4-toluenesulfonyl chloride, 3.23g of triethylamine, and 1.52g of trimethylamine hydrochloride were added sequentially to a reaction flask. Then, 150mL of dichloromethane solvent was added, and the mixture was stirred at room temperature for 12h. After the reaction was completed, the reaction mixture was poured into water and extracted with dichloromethane. The extract was dried over anhydrous MgSO4, filtered, and concentrated under reduced pressure to obtain 7.46g of 11-hexaenoic acid p-toluenesulfonate.

[0050] Step 2: Add 5g of 11-tetradecyl p-toluenesulfonate to a round-bottom flask, then add 150mL of N,N-dimethylformamide to dissolve it, followed by 3.23g of 3,5-dibromophenol and 7.40g of K2CO3. Stir the mixture under reflux at 110℃ for 12h. After the reaction is complete, cool to room temperature, concentrate under reduced pressure, pour into water, and extract with dichloromethane. The crude product is purified by silica gel column chromatography using petroleum ether as the eluent to obtain 4.09g of 1,3-dibromo-5-(undecenylundecyloxy)benzene.

[0051] Step 3: Add 4g of 1,3-dibromo-5-(undecenylundecyloxy)benzene to a round-bottom flask, dissolve it in 150mL of ethylene glycol dimethyl ether, then add 4.39g of 4-formylphenylboronic acid, 0.42g of tetrakis(triphenylphosphine)palladium and 5.05g of K2CO3, and stir the reaction mixture at 90℃ under a nitrogen atmosphere for 12h. After the reaction is completed, cool the reaction mixture to room temperature, pour it into water, extract with dichloromethane, and purify the crude product by silica gel column chromatography using a petroleum ether / ethyl acetate mixed solvent (100:5, v / v) as the eluent to obtain 2.18g of 5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dicarboxaldehyde.

[0052] Step 4: Add 4g of 4-((chlorotriphenyl-λ5-phosphino)methyl)pyridine and 0.16g of NaH to a round-bottom flask and dissolve in 120mL of ultra-dry tetrahydrofuran. Stir at 0℃ for 1h under nitrogen. Then add 2g of 5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dicarboxaldehyde and stir at room temperature for 12h. After the reaction is complete, quench the reaction with water. Extract the resulting mixture with ethyl acetate. Purify the crude product by silica gel chromatography using a petroleum ether / ethyl acetate mixed solvent (3:2, v / v) as the eluent to obtain 1.16g of 4,4'-[(1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dimethylene)bis(ethylene-2,1-diyl)]dipyridine.

[0053] Step 5: Add 70 mg of 4,4'-[(1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dimethyl)bis(ethylene-2,1-diyl)]dipyridine and 3 mL of iodomethane to 80 mL of dichloromethane solvent. Reflux at 53 °C for 12 h. After the reaction, filter, wash three times with dichloromethane, and then vacuum dry in a 60 °C oven for 3 h to obtain 79.5 mg of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide). Its structural formula is as follows:

[0054] .

[0055] Example 2 The preparation method of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-chloro) salt includes the following steps: Step 1: 5g of 11-hexaenoic alcohol, 3.8g of 4-toluenesulfonyl chloride, 3.23g of triethylamine, and 1.52g of trimethylamine hydrochloride were added sequentially to a reaction flask. Then, 150mL of dichloromethane solvent was added, and the mixture was stirred at room temperature for 12h. After the reaction was completed, the reaction mixture was poured into water and extracted with dichloromethane. The extract was dried over anhydrous MgSO4, filtered, and concentrated under reduced pressure to obtain 7.46g of 11-hexaenoic acid p-toluenesulfonate.

[0056] Step 2: Add 5g of 11-tetradecyl p-toluenesulfonate to a round-bottom flask, then add 150mL of N,N-dimethylformamide to dissolve it, followed by 3.23g of 3,5-dibromophenol and 7.40g of K2CO3. Stir the mixture under reflux at 110℃ for 12h. After the reaction is complete, cool to room temperature, concentrate under reduced pressure, pour into water, and extract with dichloromethane. The crude product is purified by silica gel column chromatography using petroleum ether as the eluent to obtain 4.09g of 1,3-dibromo-5-(undecenylundecyloxy)benzene.

[0057] Step 3: Add 4g of 1,3-dibromo-5-(undecenylundecyloxy)benzene to a round-bottom flask, dissolve it in 150mL of ethylene glycol dimethyl ether, then add 4.39g of 4-formylphenylboronic acid, 0.42g of tetrakis(triphenylphosphine)palladium and 5.05g of K2CO3, and stir the reaction mixture at 90℃ under a nitrogen atmosphere for 12h. After the reaction is completed, cool the reaction mixture to room temperature, pour it into water, extract with dichloromethane, and purify the crude product by silica gel column chromatography using a petroleum ether / ethyl acetate mixed solvent (100:5, v / v) as the eluent to obtain 2.18g of 5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dicarboxaldehyde.

[0058] Step 4: Add 4g of 4-((chlorotriphenyl-λ5-phosphino)methyl)pyridine and 0.16g of NaH to a round-bottom flask and dissolve in 120mL of ultra-dry tetrahydrofuran. Stir at 0℃ for 1h under nitrogen. Then add 2g of 5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dicarboxaldehyde and stir at room temperature for 12h. After the reaction is complete, quench the reaction with water. Extract the resulting mixture with ethyl acetate. Purify the crude product by silica gel chromatography using a petroleum ether / ethyl acetate mixed solvent (3:2, v / v) as the eluent to obtain 1.16g of 4,4'-[(1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dimethylene)bis(ethylene-2,1-diyl)]dipyridine.

[0059] Step 5: Add 70 mg of 4,4'-[(1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dimethyl)bis(ethylene-2,1-diyl)]dipyridine and 3 mL of iodomethane to 80 mL of dichloromethane solvent. Reflux at 53 °C for 12 h. After the reaction is complete, filter and wash three times with dichloromethane. Then place in a 60 °C oven and vacuum dry for 3 h to obtain 79.5 mg of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide).

[0060] Step 6: Add 500 mg of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) and a saturated solution of ammonium hexafluorophosphate to 80 mL of anhydrous methanol. The reaction solution is reacted at 25 °C for 12 h. After the reaction is completed, filter the solution and wash it three times with anhydrous methanol. Then, dry it in a vacuum oven at 60 °C for 3 h to obtain 410 mg of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-hexafluorophosphate).

[0061] Step 7: Add 300 mg of a saturated solution of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-hexafluorophosphate) and tetraethylammonium chloride to 80 mL of acetonitrile. React the solution at 25°C for 12 h. After the reaction, filter the solution, wash three times with acetonitrile, and then vacuum dry it in a 60°C oven for 3 h to obtain 190 mg of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-chlorophosphate). Its structure is as follows:

[0062] .

[0063] The proton NMR spectrum of the supramolecular nanotubes prepared in Example 1 of this invention is shown below. Figure 1 The graph shows the positions of the corresponding peaks and the proportions of different peaks, indicating that the target molecule has been successfully synthesized. 1 H NMR (400 MHz, DMSO): δ (ppm)=8.87(d, 4H), 8.24(d, 4H),8.10 (s, 1H),8.05(s, 1H), 7.93(d, 4H), 7.86(d, 4H),7.61(m, 2H), 7.57(s, 1H), 7.27(s, 2H), 4.68-4.55(m, 1H), 4.26(s, 6H), 1.71-1.56(m, 4H), 1.42-1.06(m, 32H), 0.98-0.71(m, 6H).

[0064] Two-dimensional small-angle X-ray scattering (SAXS) pattern of the supramolecular nanotubes prepared in Example 1 of this invention is shown in Figure 1. Figure 2 ,from Figure 2 As can be seen, V-type pyridine cations self-assemble to form a hexagonal columnar structure. The left figure is a small-angle X-ray scattering pattern, in which a set of scattering peaks with a q-value ratio of 1:√3 were observed at 20℃, which matches the hexagonal columnar phase (Colh, p6mm) in the liquid crystal phase. The two sets of peaks correspond to the diffraction signals of the (10) and (11) crystal planes, respectively. The right figure shows the columnar packing model and size. Hexagonal packing is the densest packing mode in a two-dimensional plane. The molecules are closely arranged in the direction perpendicular to the tube axis, forming a highly ordered columnar liquid crystal phase.

[0065] The pore size distribution diagram of the supramolecular nanotubes prepared in Example 1 of this invention is shown in the figure. Figure 3 The pore size distribution is 1.4 nm, indicating the formation of a nanotube-like structure; furthermore, from Figure 3 It can be seen that the hexagonal columnar structure formed by self-assembly has a regular internal channel structure.

[0066] The scanning electron microscope image of the supramolecular nanotubes prepared in Example 1 of this invention is shown below. Figure 4 ,from Figure 4 The tubular structure of supramolecular nanotubes can be observed, when the anti-anion is I. - or Cl - At this time, the positively charged pyridine cation generates a strong electrostatic –π interaction with the adjacent aromatic π system, driving the formation of a hexagonal nanotube structure.

[0067] 10 mg of supramolecular nanotube catalyst was placed in a 50 mL glass bottle, and 50 mL of ultrapure water was added. The mixture was sonicated for 20 min in the dark until the catalyst powder was completely dispersed. Subsequently, O2 was continuously injected into the solution in the dark until O2 saturation was achieved, and the photoreaction experiment was initiated. The liquid was continuously stirred during the reaction, and 1 mL of sample was taken every half hour. The sample was filtered through a 0.22 μM polyethersulfone needle filter, and the filtrate was collected. The concentration of generated H2O2 was detected using iodometric titration-UV-Vis spectrophotometry. The photocatalytic H2O2 production performance of the supramolecular nanotubes prepared in Examples 1 and 2 of this invention is shown in the figure. Figure 5 ,from Figure 5 As can be seen from this, the liquid crystal polymer has the ability to produce H2O2 through photocatalysis.

[0068] The preparation principle of supramolecular nanotubes based on cation-π interactions in this invention is as follows: Figure 6 As shown, when the anti-anion is I - or Cl - At this time, the positively charged pyridine cations generate strong electrostatic –π interactions with the adjacent aromatic π system, driving the formation of hexagonal nanotube structures.

[0069] Example 3 The preparation method of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) includes the following steps: Step 1: 5g of 11-hexaenoic alcohol, 3.04g of 4-toluenesulfonyl chloride, 2.907g of triethylamine, and 1.216g of trimethylamine hydrochloride were added sequentially to a reaction flask. Then, 150mL of dichloromethane solvent was added, and the mixture was stirred at room temperature for 11h. After the reaction was completed, the reaction mixture was poured into water and extracted with dichloromethane. The extract was dried over anhydrous MgSO4, filtered, and concentrated under reduced pressure to obtain 11-hexaenoic p-toluenesulfonate.

[0070] Step 2: Add 5g of 11-tetradecyl p-toluenesulfonate to a round-bottom flask, then add 150mL of N,N-dimethylformamide to dissolve it, followed by 3.1g of 3,5-dibromophenol and 8.88g of K2CO3. Stir the mixture under reflux at 110℃ for 11h. After the reaction is complete, cool to room temperature, concentrate under reduced pressure, pour into water, and extract with dichloromethane. The crude product is purified by silica gel column chromatography using petroleum ether as the eluent to obtain 1,3-dibromo-5-(undecenylundecyloxy)benzene.

[0071] Step 3: Add 4g of 1,3-dibromo-5-(undecenylundecyloxy)benzene to a round-bottom flask, dissolve it in 150mL of ethylene glycol dimethyl ether, then add 4.06g of 4-formylphenylboronic acid, 0.525g of tetrakis(triphenylphosphine)palladium and 4.848g of K2CO3, and stir the reaction at 80℃ under a nitrogen atmosphere for 11h. After the reaction is completed, cool the reaction mixture to room temperature, pour it into water, extract with dichloromethane, and purify the crude product by silica gel column chromatography using a petroleum ether / ethyl acetate mixed solvent (100:5, v / v) as the eluent to obtain 5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dicarboxaldehyde.

[0072] Step 4: Add 3.6 g of 4-((chlorotriphenyl-λ5-phosphino)methyl)pyridine and 0.144 g of NaH to a round-bottom flask and dissolve in 120 mL of ultra-dry tetrahydrofuran. Stir at 0 °C for 1 h under nitrogen. Then add 2 g of 5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dicarboxaldehyde and stir at room temperature for 11 h. After the reaction is complete, quench the reaction with water. Extract the resulting mixture with ethyl acetate. Purify the crude product by silica gel chromatography using a petroleum ether / ethyl acetate mixed solvent (3:2, v / v) as the eluent to obtain 4,4'-[(1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dimethylene)bis(ethylene-2,1-diyl)]dipyridine.

[0073] Step 5: Add 70 mg of 4,4'-[(1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dimethyl)bis(ethylene-2,1-diyl)]dipyridine and 3 mL of iodomethane to 80 mL of dichloromethane solvent. Reflux at 50 °C for 11 h. After the reaction is complete, filter, wash three times with dichloromethane, and then place in a 60 °C oven for vacuum drying for 3 h to obtain 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide).

[0074] Although preferred embodiments of the invention have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including both the preferred embodiments and all changes and modifications falling within the scope of the invention.

[0075] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A supramolecular nanotube based on cation-π interaction, characterized in that, The supramolecular nanotubes based on cation-π interaction are hexagonal columnar structures formed by the self-assembly of V-type pyridine cations. The V-type pyridine is 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) or 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-chloro). The structural formula of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) is: ; The structural formula of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-chloro) is: .

2. A supramolecular nanotube based on cation-π interaction as described in any one of claims 1, characterized in that, 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) is prepared according to the following steps: Using halogenated hydrocarbon organic solvents as solvents, 11-neco-co-ol and 4-toluenesulfonyl chloride as raw materials, and triethylamine and trimethylamine hydrochloride as catalysts, an amidation reaction is carried out to obtain 11-neco-co-co-toluenesulfonate. Using amide-based organic solvents as solvents, 1,3-dibromo-5-(undecaprinylundecyloxy)benzene was synthesized by reacting 11-neocenealkyl-p-toluenesulfonate and 3,5-dibromophenol under alkaline conditions via a Williamson ether synthesis reaction. In an inert atmosphere, using ether-based organic solvents as solvents, 1,3-dibromo-5-(undecenylundecyloxy)benzene and 4-formylphenylboronic acid undergo a Suzuki coupling reaction under alkaline and catalytic conditions to yield 5'-(undecane-11-oxy)-[1,1':3',1''-terphenyl]-4,4''-dicarboxaldehyde; In an inert atmosphere, using furan organic solvent as solvent, 4-((chlorotriphenyl-λ5-phosphino)methyl)pyridine, NaH, and 5'-(undecane-11-oxy)-[1,1':3',1''-terphenyl]-4,4''-dicarboxaldehyde undergo a Wittig reaction to yield 4,4'-[(1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dimethylene)bis(ethylene-2,1-diyl)]dipyridine; Using a haloalkanes as a solvent, 4,4'-[(1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dimethylene)bis(ethylene-2,1-diyl)]dipyridine and iodomethane were subjected to a methylation reaction to obtain 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide).

3. The supramolecular nanotube based on cation-π interaction according to claim 2, characterized in that, The molar ratio of 11-hexaenoic acid, 4-toluenesulfonyl chloride, triethylamine and trimethylamine hydrochloride is 1:1.00-1.25:1.8-2:0.8-1.

4. The supramolecular nanotube based on cation-π interaction according to claim 2, characterized in that, The molar ratio of 11-tetradecyl p-toluenesulfonate, base and 3,5-dibromophenol is 1:1.0-1.2:4.8-5.

5. The supramolecular nanotube based on cation-π interaction according to claim 2, characterized in that, The molar ratio of 1,3-dibromo-5-(undecenylundecyloxy)benzene, 4-formylphenylboronic acid, catalyst and base is 1:3.7-4:0.04-0.05:4.8-5.

6. A supramolecular nanotube based on cation-π according to claim 2, characterized in that, The molar ratio of 4-((chlorotriphenyl-λ5-phosphino)methyl)pyridine, NaH and 5'-(undecane-11-oxy)-[1,1':3',1''-terphenyl]-4,4''-dicarboxaldehyde is 2.7-3:1.8-2:

1.

7. A supramolecular nanotube based on cation-π according to claim 2, characterized in that, The molar ratio of 4,4'-[(1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-dimethylene)bis(ethylene-2,1-diyl)]dipyridine to iodomethane is 1:3.8-4.

8. A supramolecular nanotube based on cation-π interaction as described in claim 1, characterized in that, 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-chloro) is prepared according to the following steps: Using an alcohol as a solvent, 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) and ammonium hexafluorophosphate were subjected to an ion exchange reaction to obtain 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-hexafluorophosphate); Using acetonitrile as a solvent, 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-hexafluorophosphate) and tetraethylammonium chloride were subjected to an ion exchange reaction in acetonitrile to obtain 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-chlorophosphate).

9. The supramolecular nanotube based on cation-π interaction according to claim 8, characterized in that, The molar ratio of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-iodide) to ammonium hexafluorophosphate is 1:4.8-5; The molar ratio of 4,4'-((1E,1'E)-(5'-(undecane-11-oxy)-[1,1':3',1''-triphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridine-1-hexafluorophosphate) to tetraethylammonium chloride is 1:4.8-5.

10. The application of the supramolecular nanotube based on cation-π interaction as described in claim 1 in the preparation of a photocatalytic catalyst for the production of hydrogen peroxide.

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