A photocatalytic oxidation material based on cation-pi interaction and host-guest interaction cooperative construction and a preparation method and application thereof

Abstract

The application discloses a kind of photocatalytic oxidation materials based on cation-π interaction and host-guest interaction cooperative construction and preparation method and application thereof, it is related to photocatalytic material technical field.The photocatalytic oxidation material is assembled by host molecule and guest molecule;The host molecule is 1 5 ,12 5 -Di (benzyloxy) -2,5,8,11,13,16,19,22-octaoxa-1,12 (1,3) -diphenylcyclo-docosane, the guest molecule is 1,1 '-bis [4- ((E) -2- (1-methylpyridine-1-azonium-4-yl) vinyl) phenyl] -[4,4 '-bipyridine] -1,1 '-diazonium tetra (hexafluorophosphate).The guest molecule is sequentially assembled by the cation-π interaction between head-to-tail alternating benzene ring and pyridine onium cation, and forms one-dimensional ordered supramolecular material.The material can be used for photocatalytic oxidation reaction, especially can be used for o-phenylenediamine and benzaldehyde oxidation coupling preparation 2-phenylbenzimidazole, has the advantages of assembly mode clear, preparation condition mild, structural stability is good and recycling performance good.

Description

Technical Field

[0001] This invention relates to the field of photocatalytic materials technology, specifically to a photocatalytic oxidation material based on the synergistic construction of cation-π interactions and host-guest interactions, its preparation method, and its application. Background Technology

[0002] Photocatalytic oxidation materials, as a class of functional catalytic materials capable of utilizing light energy to achieve oxidation conversion, have promising applications in fields such as organic synthesis, environmental remediation, water purification, and pollutant degradation. Among them, ordered photocatalytic oxidation materials constructed through supramolecular interactions can achieve spatial organization and functional synergy of catalytic units under mild conditions, providing a new pathway for the structural design of photocatalytic materials.

[0003] Existing photocatalytic oxidation materials often improve photogenerated charge separation and substrate activation capabilities through covalent framework regulation, modification with strong electron-withdrawing groups, metal coordination, or host-guest complexation. However, these methods typically require the introduction of specific covalent linking units, metal coordination sites, or strong recognition groups, which can limit the scalability of the molecular structure and may affect the ordered stacking of catalytic units and material stability.

[0004] Furthermore, supramolecular photocatalytic systems constructed using single non-covalent interactions still have room for improvement in terms of assembly stability, synergistic interaction sites, and catalytic cycle retention. Therefore, developing a photocatalytic oxidation material capable of achieving ordered assembly through both cation-π interactions and host-guest interactions is of great significance for broadening the range of forces involved in supramolecular photocatalytic materials and enhancing their catalytic application stability.

[0005] Existing technologies disclose two-dimensional covalent organic framework photocatalytic materials constructed by regulating tautomerism balance through donor-acceptor electronic effects, achieving efficient separation of photogenerated carriers and visible light organic oxidation catalysis. However, this regulation method usually requires the introduction of strong electron-withdrawing substituents, which limits the diversity of covalent organic framework construction molecules. Moreover, the additionally introduced polar electron-withdrawing groups may interfere with the orderly stacking of framework molecules. These factors will be detrimental to the stability of supramolecular framework materials and the expression and optimization of their photocatalytic functions. Existing technologies also disclose the construction of supramolecular photocatalytic systems using a host-guest assembly strategy of cucurbita[8]urea and viologen derivatives, and the high-selectivity aerobic oxidation of benzyl alcohol to benzaldehyde was achieved through visible light excitation. However, this construction method also relies on the introduction of cucurbita macrocycle and electron-deficient viologen recognition groups, which limits the expansion range of substrate molecules. The efficiency of the charge transfer complex formed by host-guest combination directly determines the catalytic activity and product selectivity. Summary of the Invention

[0006] To address the shortcomings of the aforementioned background technologies, this invention provides a photocatalytic oxidation material based on the synergistic construction of cation-π interactions and host-guest interactions, along with its preparation method and applications. It aims to solve the problems of single assembly interaction, insufficient structural stability, and the need to improve catalytic cycle performance in existing supramolecular photocatalytic oxidation materials, further broadening the range of interaction forces in supramolecular photocatalytic oxidation materials and providing a new strategy for their preparation.

[0007] The first objective of this invention is to provide a photocatalytic oxidation material based on the synergistic construction of cation-π interactions and host-guest interactions, wherein the photocatalytic oxidation material is assembled from host molecules and guest molecules; The main molecular structure is as follows: ; The molecular structure of the guest is: ; Wherein, the main molecule is 1 5 ,12 5 -Di(benzyloxy)-2,5,8,11,13,16,19,22-octaoxa-1,12(1,3)-diphenylcyclododecane, wherein the guest molecule is 1,1'-bis[4-((E)-2-(1-methylpyridin-1-onthiol-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionthiol tetra(hexafluorophosphate).

[0008] Preferably, during assembly, multiple guest molecules are arranged in an alternating head-to-tail manner through cation-π interactions between the benzene ring and the pyridinium cation, and the cyclic cavity of the host molecule is bonded to the pyridinium cation site in the guest molecule through host-guest interactions.

[0009] Preferably, the molar ratio of the host molecule to the guest molecule is 1:(0.8~1.2).

[0010] The second objective of this invention is to provide a method for preparing a photocatalytic oxidation material based on the synergistic construction of cation-π interactions and host-guest interactions, comprising the following steps: The host molecule and the guest molecule were prepared separately; The host molecule and the guest molecule are dissolved in acetonitrile, and the acetonitrile is volatilized and assembled at room temperature to obtain the photocatalytic oxidation material.

[0011] Preferably, the molar ratio of the host molecule to the guest molecule dissolved in acetonitrile is 1:(0.8~1.2); the room temperature is 20~30℃.

[0012] Preferably, the host molecule is prepared according to the following steps: 4-Methylbenzenesulfonyl chloride, triethylene glycol and triethylamine were reacted in dichloromethane to give 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate. Phloroglucinol, benzyl bromide and anhydrous potassium carbonate were reacted in N,N-dimethylformamide to give 5-(benzyloxy)benzene-1,3-diol; The 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate, the 5-(benzyloxy)benzene-1,3-diol, anhydrous potassium carbonate and lithium bromide were reacted in N,N-dimethylformamide to give 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoct-1-yl)oxy]benzene; The 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoct-1-yl)oxy]benzene, 4-methylbenzenesulfonyl chloride and triethylamine were reacted in dichloromethane to give 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoct-1-yl)oxy]benzene; The main molecule is obtained by reacting the 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoctyl-1-yl)oxy]benzene, the 5-(benzyloxy)benzene-1,3-diphenol, cesium carbonate, and lithium bromide in N,N-dimethylformamide.

[0013] Preferably, the molar ratio of 4-methylbenzenesulfonyl chloride, triethylene glycol, and triethylamine is 1:4:4.5; The molar ratio of phloroglucinol, benzyl bromide and anhydrous potassium carbonate is 1:0.6:4; The molar ratio of 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate, 5-(benzyloxy)benzene-1,3-diol, anhydrous potassium carbonate, and lithium bromide is 1:2.2:5:0.3. The molar ratio of 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoctyl-1-yl)oxy]benzene, 4-methylbenzenesulfonyl chloride, and triethylamine is 1:2.2:0.17; The molar ratio of 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoctyl-1-yl)oxy]benzene, 5-(benzyloxy)benzene-1,3-diphenol, cesium carbonate and lithium bromide is 1:1:20:0.2.

[0014] Preferably, the guest molecule is prepared according to the following steps: p-Iodoaniline, 4-vinylpyridine, palladium acetate, trimethylphenylphosphine and triethylamine were reacted in acetonitrile under light-shielded reflux to give (E)-4-[2-(pyridin-4-yl)vinyl]aniline; The (E)-4-[2-(pyridin-4-yl)vinyl]aniline and iodomethane were reacted in acetonitrile in the dark to give (E)-4-(4-aminostyryl)-1-methylpyridin-1-onium iodide; 4,4'-bipyridine and 1-chloro-2,4-dinitrobenzene were reacted in acetonitrile to give 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-diamium dichloride; The 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-dionium dichloride was reacted with the (E)-4-(4-aminostyryl)-1-methylpyridine-1-onium iodide to give 1,1'-bis[4-((E)-2-(1-methylpyridine-1-onium-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionium dichlorodiiodide; The dichlorodiiodide was anion-exchanged with ammonium hexafluorophosphate to obtain the guest molecule.

[0015] Preferably, the molar ratio of p-iodoaniline, 4-vinylpyridine, palladium acetate, trimethylphenylphosphine, and triethylamine is 1:1.37:0.0025:0.005:2.75; The molar ratio of (E)-4-[2-(pyridin-4-yl)vinyl]aniline to iodomethane is 1:5; The molar ratio of 4,4'-bipyridine to 1-chloro-2,4-dinitrobenzene is 1:4; The molar ratio of 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-dionium dichloride and (E)-4-(4-aminostyryl)-1-methylpyridine-1-onium iodide is 1:6; The molar ratio of dichlorodiiodide to ammonium hexafluorophosphate is 1:5.

[0016] The third objective of this invention is to provide an application of a photocatalytic oxidation material constructed based on the synergistic interaction of cation-π interaction and host-guest interaction in photocatalytic oxidation reactions.

[0017] Compared with existing technologies, the photocatalytic oxidation material, its preparation method, and its application, constructed based on the synergistic interaction of cation-π interactions and host-guest interactions, provided by this invention, have the following significant beneficial effects: This invention constructs photocatalytic oxidation materials through the synergistic construction of cation-π interactions and host-guest interactions, avoiding the insufficient assembly stability caused by relying solely on single non-covalent interactions, and facilitating the formation of a spatially defined one-dimensional supramolecular structure. The guest molecule simultaneously contains styrylpyridinium cation-π interaction sites and bipyridinium host-guest recognition sites, enabling the guest molecule to both stack orderly through alternating head-tail arrangements and recognize and bind to the ring cavity of the host molecule, thereby improving the orderly assembly capability between catalytic units. The assembly is carried out by slowly evaporating the host and guest molecules after dissolving them in acetonitrile, resulting in mild preparation conditions, simple operation, and no need to introduce additional metal anchoring sites or complex covalent frameworks. The photocatalytic oxidation material obtained by this invention can be used in the oxidative coupling reaction of o-phenylenediamine and benzaldehyde to prepare 2-phenylbenzimidazole, and the yield remains stable after recycling, indicating that it has good potential for photocatalytic oxidation applications and good cycling stability. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of the main molecular structure of a photocatalytic oxidation material constructed based on the synergistic interaction of cation-π interaction and host-guest interaction according to the present invention; Figure 2 This is a schematic diagram of the guest molecular structure of a photocatalytic oxidation material constructed based on the synergistic interaction of cation-π interaction and host-guest interaction according to the present invention; Figure 3 This is a schematic diagram of the host molecule, guest molecule, and their cooperative assembly in the photocatalytic oxidation material of the present invention; Figure 4 The 1H NMR spectrum of the host molecule prepared in Example 1 of this invention; Figure 5 This is a high-resolution mass spectrum of the host molecule prepared in Example 1 of the present invention; Figure 6 The hydrogen NMR spectrum of the guest molecule prepared in Example 1 of this invention; Figure 7 This is a high-resolution mass spectrum of the guest molecule prepared in Example 1 of the present invention; Figure 8 This is a microscopic single-crystal structure diagram of the host molecule prepared in Example 2 of the present invention; Figure 9 This is a microscopic single-crystal structure diagram of the guest molecule prepared in Example 2 of the present invention; Figure 10 The above is the 1H NMR spectrum of the photocatalytic oxidation reaction product of Example 1 of the present invention; Figure 11 This is a bar chart showing the photocatalytic oxidation reaction yields of various embodiments of the present invention; Figure 12 This is a bar chart comparing the yields of the catalytic reaction of this invention. Detailed Implementation

[0019] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below in conjunction with specific embodiments and accompanying drawings. However, the embodiments described are not intended to limit the present invention.

[0020] The main objective of this invention is to provide a photocatalytic oxidation material based on the synergistic construction of cation-π interactions and host-guest interactions, as well as its preparation method and applications. This invention aims to address the problems of single assembly interaction, insufficient structural stability, and the need to improve catalytic cycle performance in existing supramolecular photocatalytic oxidation materials, further broadening the scope of interaction forces in supramolecular photocatalytic oxidation materials and providing a new strategy for the preparation of supramolecular photocatalytic oxidation materials.

[0021] To achieve the above objectives, the first aspect of the present invention provides a photocatalytic oxidation material based on the synergistic construction of cation-π interaction and host-guest interaction, wherein the photocatalytic oxidation material is assembled from host molecules and guest molecules; The main molecular structure is as follows: ; The molecular structure of the guest is: ; Wherein, the main molecule is 1 5 ,12 5 -Di(benzyloxy)-2,5,8,11,13,16,19,22-octaoxa-1,12(1,3)-diphenylcyclododecane, wherein the guest molecule is 1,1'-bis[4-((E)-2-(1-methylpyridin-1-onthiol-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionthiol tetra(hexafluorophosphate).

[0022] See Figure 1 As shown, the host molecule is a polyether aromatic macrocycle with a cyclic cavity; See Figure 2 As shown, the guest molecule simultaneously possesses dual cation-π interaction sites and host-guest recognition sites.

[0023] See Figure 3 As shown, during the assembly process, multiple guest molecules are arranged in an alternating head-to-tail manner through cation-π interactions between the benzene ring and the pyridinium cation. The ring cavity of the host molecule and the pyridinium cation sites in the guest molecules are bound together through host-guest interactions.

[0024] The molar ratio of the host molecule to the guest molecule is 1:(0.8~1.2).

[0025] This invention arranges multiple guest molecules in an orderly manner with alternating head-to-tail arrangements through cation-π interactions between benzene rings and pyridinium cations; simultaneously, the bipyridinium cation sites in the guest molecules interact with the ring cavities of the host molecules, thereby forming a one-dimensional ordered supramolecular material.

[0026] A second aspect of this invention provides a method for preparing a photocatalytic oxidation material based on the synergistic construction of cation-π interactions and host-guest interactions, comprising the following steps: The host molecule and the guest molecule were prepared separately; The host molecule and the guest molecule are dissolved in acetonitrile, and the acetonitrile is volatilized and assembled at room temperature to obtain the photocatalytic oxidation material.

[0027] Wherein, the molar ratio of the host molecule to the guest molecule dissolved in acetonitrile is 1:(0.8~1.2); and the room temperature is 20~30℃.

[0028] The main molecule is prepared according to the following steps: 4-Methylbenzenesulfonyl chloride, triethylene glycol and triethylamine were reacted in dichloromethane to give 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate. Phloroglucinol, benzyl bromide and anhydrous potassium carbonate were reacted in N,N-dimethylformamide to give 5-(benzyloxy)benzene-1,3-diol; The 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate, the 5-(benzyloxy)benzene-1,3-diol, anhydrous potassium carbonate and lithium bromide were reacted in N,N-dimethylformamide to give 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoct-1-yl)oxy]benzene; The 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoct-1-yl)oxy]benzene, 4-methylbenzenesulfonyl chloride and triethylamine were reacted in dichloromethane to give 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoct-1-yl)oxy]benzene; The main molecule is obtained by reacting the 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoctyl-1-yl)oxy]benzene, the 5-(benzyloxy)benzene-1,3-diphenol, cesium carbonate, and lithium bromide in N,N-dimethylformamide.

[0029] The molar ratio of 4-methylbenzenesulfonyl chloride, triethylene glycol, and triethylamine is 1:4:4.5; The molar ratio of phloroglucinol, benzyl bromide and anhydrous potassium carbonate is 1:0.6:4; The molar ratio of 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate, 5-(benzyloxy)benzene-1,3-diol, anhydrous potassium carbonate, and lithium bromide is 1:2.2:5:0.3. The molar ratio of 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoctyl-1-yl)oxy]benzene, 4-methylbenzenesulfonyl chloride, and triethylamine is 1:2.2:0.17; The molar ratio of 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoctyl-1-yl)oxy]benzene, 5-(benzyloxy)benzene-1,3-diphenol, cesium carbonate and lithium bromide is 1:1:20:0.2.

[0030] The guest molecule is prepared according to the following steps: p-Iodoaniline, 4-vinylpyridine, palladium acetate, trimethylphenylphosphine and triethylamine were reacted in acetonitrile under light-shielded reflux to give (E)-4-[2-(pyridin-4-yl)vinyl]aniline; The (E)-4-[2-(pyridin-4-yl)vinyl]aniline and iodomethane were reacted in acetonitrile in the dark to give (E)-4-(4-aminostyryl)-1-methylpyridin-1-onium iodide; 4,4'-bipyridine and 1-chloro-2,4-dinitrobenzene were reacted in acetonitrile to give 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-diamium dichloride; The 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-dionium dichloride was reacted with the (E)-4-(4-aminostyryl)-1-methylpyridine-1-onium iodide to give 1,1'-bis[4-((E)-2-(1-methylpyridine-1-onium-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionium dichlorodiiodide; The dichlorodiiodide was anion-exchanged with ammonium hexafluorophosphate to obtain the guest molecule.

[0031] The molar ratio of p-iodoaniline, 4-vinylpyridine, palladium acetate, trimethylphenylphosphine, and triethylamine is 1:1.37:0.0025:0.005:2.75; The molar ratio of (E)-4-[2-(pyridin-4-yl)vinyl]aniline to iodomethane is 1:5; The molar ratio of 4,4'-bipyridine to 1-chloro-2,4-dinitrobenzene is 1:4; The molar ratio of 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-dionium dichloride and (E)-4-(4-aminostyryl)-1-methylpyridine-1-onium iodide is 1:6; The molar ratio of dichlorodiiodide to ammonium hexafluorophosphate is 1:5.

[0032] An exemplary method for preparing photocatalytic oxidation materials includes the preparation of host molecules, the preparation of guest molecules, and the co-assembly of host and guest molecules, specifically including the following steps: In step S1, 4-methylbenzenesulfonyl chloride, triethylene glycol, and triethylamine are reacted in dichloromethane as a solvent to obtain 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate. The molar ratio of 4-methylbenzenesulfonyl chloride, triethylene glycol, and triethylamine is 1:4:4.5. The dichloromethane solution of 4-methylbenzenesulfonyl chloride is slowly added dropwise to the dichloromethane solution of triethylene glycol and triethylamine at -5 to 0°C. After the addition is complete, the mixture is moved to room temperature and stirred overnight.

[0033] In step S2, phloroglucinol, benzyl bromide, and anhydrous potassium carbonate are reacted in N,N-dimethylformamide as a solvent to obtain 5-(benzyloxy)benzene-1,3-diol. The molar ratio of phloroglucinol, benzyl bromide, and anhydrous potassium carbonate is 1:0.6:4. A solution of benzyl bromide in N,N-dimethylformamide is slowly added dropwise to a solution of phloroglucinol and anhydrous potassium carbonate in N,N-dimethylformamide at room temperature, and the reaction is carried out at room temperature.

[0034] In step S3, 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate, 5-(benzyloxy)benzene-1,3-diol, anhydrous potassium carbonate, and lithium bromide are dissolved in N,N-dimethylformamide and reacted at 80-85°C under a nitrogen atmosphere to obtain 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoct-1-yl)oxy]benzene. The molar ratio of 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate, 5-(benzyloxy)benzene-1,3-diol, anhydrous potassium carbonate, and lithium bromide is 1:2.2:5:0.3.

[0035] In step S4, 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoct-1-yl)oxy]benzene, 4-methylbenzenesulfonyl chloride, and triethylamine are dissolved in dichloromethane and reacted at room temperature to obtain 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoct-1-yl)oxy]benzene. The molar ratio of 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoct-1-yl)oxy]benzene, 4-methylbenzenesulfonyl chloride, and triethylamine is 1:2.2:0.17.

[0036] In step S5, 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoctyl-1-yl)oxy]benzene, 5-(benzyloxy)benzene-1,3-diol, cesium carbonate, and lithium bromide are reacted with N,N-dimethylformamide as a solvent to obtain the main molecule.

[0037] The molar ratio of 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoct-1-yl)oxy]benzene, 5-(benzyloxy)benzene-1,3-diphenol, cesium carbonate, and lithium bromide was 1:1:20:0.2, the reaction temperature was 80~85℃, and the reaction time was 4 days.

[0038] In step S6, p-iodoaniline, 4-vinylpyridine, palladium acetate, trimethylphenylphosphine, and triethylamine are dissolved in acetonitrile and reacted under nitrogen atmosphere at 85-90°C in the dark to obtain (E)-4-[2-(pyridin-4-yl)vinyl]aniline. The molar ratio of p-iodoaniline, 4-vinylpyridine, palladium acetate, trimethylphenylphosphine, and triethylamine is 1:1.37:0.0025:0.005:2.75, and the reaction time is 2 days.

[0039] In step S7, (E)-4-[2-(pyridin-4-yl)vinyl]aniline and iodomethane are dissolved in acetonitrile and reacted at 50-55°C in the dark to obtain (E)-4-(4-aminostyryl)-1-methylpyridin-1-onium iodide. For example, the molar ratio of the two is 1:5.

[0040] In step S8, 4,4'-bipyridine and 1-chloro-2,4-dinitrobenzene are dissolved in acetonitrile and refluxed at 95-100°C to obtain 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-diamium dichloride. The molar ratio of 4,4'-bipyridine to 1-chloro-2,4-dinitrobenzene is 1:4, and the reaction time is 3 days.

[0041] In step S9, 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-dionium dichloride and (E)-4-(4-aminostyryl)-1-methylpyridine-1-onium iodide are reacted under reflux at 90-95°C in the dark with a mixed solution of ethanol and water in a volume ratio of 1:1 as the solvent to obtain 1,1'-bis[4-((E)-2-(1-methylpyridine-1-onium-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionium dichloride. The molar ratio of 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-diamium dichloride and (E)-4-(4-aminostyryl)-1-methylpyridine-1-diamium iodide was 1:6. The suspension of iodide was added dropwise to the solution of dichloride at 90-95°C for 2 days.

[0042] In step S10, 1,1'-bis[4-((E)-2-(1-methylpyridin-1-onth-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionthium dichlorodiiodide and ammonium hexafluorophosphate are dissolved in methanol and reacted at room temperature in the dark to obtain the guest molecule, wherein the molar ratio of 1,1'-bis[4-((E)-2-(1-methylpyridin-1-onth-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionthium dichlorodiiodide and ammonium hexafluorophosphate is 1:5.

[0043] Step S11: The host molecule and guest molecule are dissolved in acetonitrile at a molar ratio of 1:1, and the acetonitrile is allowed to slowly evaporate at room temperature to obtain a photocatalytic oxidation material based on the synergistic construction of cation-π interaction and host-guest interaction.

[0044] The third aspect of this invention provides the application of a photocatalytic oxidation material constructed based on the synergistic interaction of cation-π interaction and host-guest interaction in photocatalytic oxidation reactions.

[0045] It should be noted that, unless otherwise specified, the experimental methods used in this invention are all conventional methods; and the reagents and materials used, unless otherwise specified, are all commercially available.

[0046] All reagents used in the embodiments of the present invention are commercially available reagents in the art. The room temperature is 20~30℃, preferably 25℃. All solution cooling can be carried out under constant temperature ethanol bath conditions, all solution heating can be carried out under constant temperature oil bath conditions, and all room temperature stirring reactions can be carried out under constant temperature 25℃ conditions.

[0047] Example 1 Step S1: Weigh 1.6 g of 4-methylbenzenesulfonyl chloride, 5 g of triethylene glycol, and 5 mL of triethylamine. Dissolve the 4-methylbenzenesulfonyl chloride in 100 mL of dichloromethane. Mix the triethylene glycol and triethylamine and dissolve them in 100 mL of dichloromethane. At -2°C, slowly add the dichloromethane solution of 4-methylbenzenesulfonyl chloride to the dichloromethane solution of triethylene glycol and triethylamine over 4 h. After the addition is complete, transfer the reaction system to room temperature and stir overnight. After the reaction is complete, add sodium bicarbonate to adjust the pH of the reaction system to neutral. After removing the sodium bicarbonate by filtration, add 100 mL of water to the filtrate, then extract with 50 mL of dichloromethane twice. Purify by column chromatography (eluent: petroleum ether: ethyl acetate = 1:2) to obtain a colorless liquid, 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate.

[0048] Step S2: Weigh 1.12 g of phloroglucinol, 1 g of benzyl bromide, and 4.91 g of anhydrous potassium carbonate. Mix the phloroglucinol and anhydrous potassium carbonate and dissolve them in 100 mL of N,N-dimethylformamide. Dissolve the benzyl bromide in 100 mL of N,N-dimethylformamide. Slowly add the benzyl bromide solution in N,N-dimethylformamide to the phloroglucinol and anhydrous potassium carbonate solution over 3 h. After the addition is complete, continue stirring for 1 h. After the reaction is complete, remove the solid by filtration, then remove the solvent by rotary evaporation. Add 100 mL of water, extract with 50 mL of dichloromethane twice, and then purify by column chromatography (eluent: dichloromethane: anhydrous methanol = 300:1) to obtain a brown liquid, 5-(benzyloxy)benzene-1,3-diol.

[0049] Step S3: Dissolve 1.55 g of 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate, 0.5 g of 5-(benzyloxy)benzene-1,3-diol, 1.6 g of anhydrous potassium carbonate, and 0.05 g of lithium bromide in 100 mL of N,N-dimethylformamide. Vacuum the mixture for 5 minutes using a double-row tube, then purge with nitrogen for 2 minutes. Repeat this process three times. Stir the mixture overnight at 80°C. After the reaction solution cools to room temperature, remove the solids by filtration, then remove the solvent by rotary evaporation. Add 100 mL of water, extract twice with 50 mL of dichloromethane, and then purify by column chromatography (eluent: dichloromethane:anhydrous methanol = 50:1) to obtain a colorless liquid, 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoct-1-yl)oxy]benzene.

[0050] In step S4, 0.5 g of 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoct-1-yl)oxy]benzene, 0.437 g of 4-methylbenzenesulfonyl chloride, and 15 mL of triethylamine were dissolved in 100 mL of dichloromethane and stirred overnight at room temperature. After the reaction was complete, sodium bicarbonate was added to adjust the pH of the reaction system to neutral; after removing the sodium bicarbonate by filtration, 100 mL of water was added to the filtrate, followed by extraction with 50 mL of dichloromethane twice, and then purification by column chromatography (eluent: dichloromethane: anhydrous methanol = 400:1) to obtain a colorless liquid 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoct-1-yl)oxy]benzene.

[0051] Step S5: Weigh 1.34 g of 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoct-1-yl)oxy]benzene, 0.367 g of 5-(benzyloxy)benzene-1,3-diphenol, 11.08 g of cesium carbonate and 0.04 g of lithium bromide. Mix 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoct-1-yl)oxy]benzene and 5-(benzyloxy)benzene-1,3-diphenol and dissolve them in 60 mL of N,N-dimethylformamide. Mix cesium carbonate and lithium bromide and place them in 50 mL of N,N-dimethylformamide. A solution of 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoct-1-yl)oxy]benzene and 5-(benzyloxy)benzene-1,3-diol in N,N-dimethylformamide was slowly and continuously added dropwise to a solution of cesium carbonate and lithium bromide in N,N-dimethylformamide over 24 h. The reaction mixture was stirred at 80 °C for 4 days. After the reaction solution cooled to room temperature, the solid was removed by filtration, followed by solvent removal by rotary evaporation. Then, 100 mL of water was added, and the mixture was extracted twice with 50 mL of dichloromethane. The final product was purified by column chromatography (eluent: dichloromethane:anhydrous methanol = 400:1) to obtain a white solid. 5 ,12 5 -Di(benzyloxy)-2,5,8,11,13,16,19,22-octaoxa-1,12(1,3)-diphenylcyclododecane.

[0052] In step S6, 5.58 g of p-iodoaniline, 3.67 g of 4-vinylpyridine, 0.014 g of palladium acetate, 0.039 g of trimethylphenylphosphine, and 7.08 g of triethylamine were dissolved in 150 mL of acetonitrile. The mixture was evacuated for 5 minutes using a double-row tube and then purged with nitrogen for 2 minutes. This process was repeated three times. The mixture was refluxed at 90°C in the dark with stirring for 2 days. After the reaction solution cooled to room temperature, 100 mL of cold water was added. The precipitated solid was filtered off and washed three times with 20 mL of acetonitrile. The precipitate was then dried to obtain a dark green solid (E)-4-[2-(pyridin-4-yl)vinyl]aniline.

[0053] In step S7, 2 g of (E)-4-[2-(pyridin-4-yl)vinyl]aniline and 8.4 g of iodomethane were dissolved in 100 mL of acetonitrile, and the mixture was stirred overnight at 50 °C in the dark. After the reaction solution cooled to room temperature, the precipitated solid was filtered off, washed three times with 20 mL of acetonitrile, and dried to obtain a red solid (E)-4-(4-aminostyryl)-1-methylpyridin-1-onium iodide.

[0054] In step S8, 2 g of 4,4'-bipyridine and 10.4 g of 1-chloro-2,4-dinitrobenzene were dissolved in 100 mL of acetonitrile, and the mixture was refluxed and stirred at 95 °C for 3 days. After the reaction solution cooled to room temperature, the precipitated solid was filtered off, washed three times with 20 mL of acetonitrile, and dried to obtain a yellow solid 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-dionium dichloride.

[0055] In step S9, 0.5 g of 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-dionium dichloride and 1.81 g of (E)-4-(4-aminostyryl)-1-methylpyridine-1-onium iodide were dissolved in a mixed solution of 50 mL ethanol and 50 mL water, respectively. The iodide suspension was added dropwise to the chloride solution at 90 °C, and the mixture was stirred under reflux in the dark for 2 days. After the reaction solution cooled to room temperature, the precipitated solid was filtered off and washed three times with 20 mL acetonitrile. The precipitate was then dried to obtain a deep red solid, 1,1'-bis[4-((E)-2-(1-methylpyridine-1-onium-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionium dichloride.

[0056] In step S10, 1.2 g of 1,1'-bis[4-((E)-2-(1-methylpyridin-1-onthium-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionthium dichlorodiiodide and 1.12 g of ammonium hexafluorophosphate were dissolved in 100 mL of methanol and reacted overnight at room temperature with stirring. After the reaction was completed, the precipitated solid was filtered, dissolved in 100 mL of methanol, and then purified by column chromatography (eluting agent was acetonitrile: dichloromethane = 1:5 with added ammonium hexafluorophosphate). The purified substance was washed three times with 50 mL of water, three times with 10 mL of anhydrous methanol, and three times with 20 mL of diethyl ether. After drying, a pale yellow solid 1,1'-bis[4-((E)-2-(1-methylpyridin-1-onthium-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionthium tetra(hexafluorophosphate) was obtained.

[0057] Step S11, take 0.33 g of 1 5 ,12 5 -Di(benzyloxy)-2,5,8,11,13,16,19,22-octaoxa-1,12(1,3)-diphenylcyclododecane and 0.563 g of 1,1'-bis[4-((E)-2-(1-methylpyridin-1-onthiol-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionthiol tetra(hexafluorophosphate) were dissolved in acetonitrile, and the acetonitrile was allowed to slowly evaporate at room temperature to finally obtain the photocatalytic oxidation material.

[0058] In step S12, 0.432 g of o-phenylenediamine and 0.212 g of benzaldehyde were dissolved in a mixed solution of 20 mL of anhydrous methanol and 20 mL of tetrahydrofuran. 9 mg of the prepared photocatalytic oxidation material was added, and the mixture was stirred overnight at room temperature. After the reaction was complete, the photocatalytic oxidation material was recovered by filtration, and the filtrate was purified by column chromatography (eluent: petroleum ether: ethyl acetate = 1:1) to obtain a white solid, 2-phenylbenzimidazole. The recovered material was used for a cycle test under constant conditions for a total of 3 cycles, and the yield for each cycle was calculated.

[0059] from Figure 4 The 1H NMR spectrum and Figure 5 The high-resolution mass spectrum shows that the main molecule prepared in this embodiment has been successfully synthesized; from Figure 6 The 1H NMR spectrum and Figure 7 The high-resolution mass spectrum shows that the guest molecule prepared in this embodiment has been successfully synthesized; from Figure 10 As can be seen from the 1H NMR spectrum, the photocatalytic oxidation reaction product of this embodiment has been successfully prepared.

[0060] Example 2 Step S1: Weigh 4.1 g of 4-methylbenzenesulfonyl chloride, 12.8 g of triethylene glycol and 13 mL of triethylamine, react and post-process according to the method described in Example 1 to obtain colorless liquid 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate.

[0061] In step S2, 2.87 g of phloroglucinol, 2.56 g of benzyl bromide and 12.55 g of anhydrous potassium carbonate were weighed and reacted and post-treated according to the method described in Example 1 to obtain a brown liquid 5-(benzyloxy)benzene-1,3-diol.

[0062] In step S3, 3.97 g of 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate, 1.28 g of 5-(benzyloxy)benzene-1,3-diol, 4.1 g of anhydrous potassium carbonate and 0.13 g of lithium bromide were dissolved in 100 mL of N,N-dimethylformamide and reacted and post-treated according to the method described in Example 1 to obtain a colorless liquid 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoct-1-yl)oxy]benzene.

[0063] In step S4, 1.28 g of 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoct-1-yl)oxy]benzene, 1.12 g of 4-methylbenzenesulfonyl chloride, and 38 mL of triethylamine were dissolved in 200 mL of dichloromethane and reacted and post-treated according to the method described in Example 1 to obtain a colorless liquid 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoct-1-yl)oxy]benzene.

[0064] Step S5: Weigh 3.43 g of 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoct-1-yl)oxy]benzene, 0.94 g of 5-(benzyloxy)benzene-1,3-diol, 28.4 g of cesium carbonate, and 0.1 g of lithium bromide. React and post-treat according to the method described in Example 1 to obtain a white solid 1. 5 ,12 5 -Di(benzyloxy)-2,5,8,11,13,16,19,22-octaoxa-1,12(1,3)-diphenylcyclododecane.

[0065] In step S6, 14.3 g of p-iodoaniline, 9.4 g of 4-vinylpyridine, 0.035 g of palladium acetate, 0.1 g of trimethylphenylphosphine and 18.14 g of triethylamine were dissolved in 150 mL of acetonitrile, reacted and post-treated according to the method described in Example 1, to obtain a dark green solid (E)-4-[2-(pyridin-4-yl)vinyl]aniline.

[0066] Step S7: 5.13 g of (E)-4-[2-(pyridin-4-yl)vinyl]aniline and 21.5 g of iodomethane were dissolved in 200 mL of acetonitrile, reacted and post-treated according to the method described in Example 1, to obtain a red solid (E)-4-(4-aminostyryl)-1-methylpyridin-1-onium iodide.

[0067] In step S8, 5.13 g of 4,4'-bipyridine and 26.65 g of 1-chloro-2,4-dinitrobenzene were dissolved in 200 mL of acetonitrile, reacted and post-treated according to the method described in Example 1, to obtain a yellow solid 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-diamium dichloride.

[0068] Step S9: 1.28 g of 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-dionium dichloride and 4.63 g of (E)-4-(4-aminostyryl)-1-methylpyridine-1-onium iodide were dissolved in a mixed solution of 100 mL ethanol and 100 mL water, respectively. The mixture was reacted and post-treated according to the method described in Example 1 to obtain a dark red solid 1,1'-bis[4-((E)-2-(1-methylpyridine-1-onium-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionium dichloride.

[0069] In step S10, 3.07 g of 1,1'-bis[4-((E)-2-(1-methylpyridin-1-onth-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionium dichlorodiiodide and 2.87 g of ammonium hexafluorophosphate were dissolved in 100 mL of methanol and reacted and post-treated according to the method described in Example 1 to obtain a pale yellow solid 1,1'-bis[4-((E)-2-(1-methylpyridin-1-onth-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionium tetra(hexafluorophosphate).

[0070] Step S11, take 0.85 g of 1 5 ,12 5 -Di(benzyloxy)-2,5,8,11,13,16,19,22-octaoxa-1,12(1,3)-diphenylcyclododecane and 1.44 g of 1,1'-bis[4-((E)-2-(1-methylpyridin-1-onthium-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionthium tetra(hexafluorophosphate) were dissolved in acetonitrile, and the acetonitrile was allowed to slowly evaporate at room temperature to finally obtain the photocatalytic oxidation material.

[0071] In step S12, 1.107 g of o-phenylenediamine and 0.543 g of benzaldehyde were dissolved in a mixed solution of 20 mL of anhydrous methanol and 20 mL of tetrahydrofuran. 23 mg of the prepared photocatalytic oxidation material was added, and the mixture was stirred overnight at room temperature. After the reaction was complete, the photocatalytic oxidation material was recovered by filtration, and the filtrate was purified by column chromatography (eluent: petroleum ether: ethyl acetate = 1:1) to obtain a white solid, 2-phenylbenzimidazole. The recovered material was used for a cycle test under constant conditions for a total of 3 cycles, and the yield of each cycle was measured.

[0072] from Figure 8 As can be seen from the microscope single-crystal structure image, the main molecular single crystal prepared in this embodiment is plate-like; from Figure 9 As can be seen from the microscope single-crystal structure image, the guest molecule single crystal prepared in this embodiment is columnar.

[0073] Example 3 Step S1: Weigh 5.7 g of 4-methylbenzenesulfonyl chloride, 17.7 g of triethylene glycol and 18 mL of triethylamine, react and post-process according to the method described in Example 1 to obtain colorless liquid 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate.

[0074] In step S2, 4 g of phloroglucinol, 3.56 g of benzyl bromide and 17.44 g of anhydrous potassium carbonate were weighed and reacted and post-treated according to the method described in Example 1 to obtain a brown liquid 5-(benzyloxy)benzene-1,3-diol.

[0075] In step S3, 5.52 g of 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate, 1.77 g of 5-(benzyloxy)benzene-1,3-diol, 5.7 g of anhydrous potassium carbonate and 0.17 g of lithium bromide were dissolved in 100 mL of N,N-dimethylformamide, reacted and post-treated according to the method described in Example 1, to obtain a colorless liquid 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoct-1-yl)oxy]benzene.

[0076] Step S4: 1.78 g of 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoct-1-yl)oxy]benzene, 1.55 g of 4-methylbenzenesulfonyl chloride, and 50 mL of triethylamine were dissolved in 200 mL of dichloromethane and reacted and post-treated according to the method described in Example 1 to obtain a colorless liquid 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoct-1-yl)oxy]benzene.

[0077] Step S5: Weigh 4.77 g of 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoct-1-yl)oxy]benzene, 1.3 g of 5-(benzyloxy)benzene-1,3-diol, 39 g of cesium carbonate, and 0.13 g of lithium bromide. React and post-treat according to the method described in Example 1 to obtain a white solid 1. 5 ,12 5 -Di(benzyloxy)-2,5,8,11,13,16,19,22-octaoxa-1,12(1,3)-diphenylcyclododecane.

[0078] In step S6, 19.9 g of p-iodoaniline, 13.06 g of 4-vinylpyridine, 0.049 g of palladium acetate, 0.14 g of trimethylphenylphosphine and 25.22 g of triethylamine were dissolved in 200 mL of acetonitrile, reacted and post-treated according to the method described in Example 1, to obtain a dark green solid (E)-4-[2-(pyridin-4-yl)vinyl]aniline.

[0079] In step S7, 7.13 g of (E)-4-[2-(pyridin-4-yl)vinyl]aniline and 29.9 g of iodomethane were dissolved in 250 mL of acetonitrile, reacted and post-treated according to the method described in Example 1, to obtain a red solid (E)-4-(4-aminostyryl)-1-methylpyridin-1-onium iodide.

[0080] In step S8, 7.13 g of 4,4'-bipyridine and 37.05 g of 1-chloro-2,4-dinitrobenzene were dissolved in 250 mL of acetonitrile, reacted and post-treated according to the method described in Example 1, to obtain a yellow solid 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-dionium dichloride.

[0081] Step S9: 1.78 g of 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-dionium dichloride and 6.44 g of (E)-4-(4-aminostyryl)-1-methylpyridine-1-onium iodide were dissolved in a mixed solution of 100 mL ethanol and 100 mL water, respectively. The mixture was reacted and post-treated according to the method described in Example 1 to obtain a dark red solid 1,1'-bis[4-((E)-2-(1-methylpyridine-1-onium-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionium dichloride.

[0082] In step S10, 4.27 g of 1,1'-bis[4-((E)-2-(1-methylpyridin-1-onth-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionthium dichlorodiiodide and 4 g of ammonium hexafluorophosphate were dissolved in 100 mL of methanol and reacted and post-treated according to the method described in Example 1 to obtain a pale yellow solid 1,1'-bis[4-((E)-2-(1-methylpyridin-1-onth-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionthium tetra(hexafluorophosphate).

[0083] Step S11, take 1.18 g of 1 5 ,12 5 -Di(benzyloxy)-2,5,8,11,13,16,19,22-octaoxa-1,12(1,3)-diphenylcyclododecane and 2 g of 1,1'-bis[4-((E)-2-(1-methylpyridin-1-onthium-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionthium tetra(hexafluorophosphate) were dissolved in acetonitrile, and the acetonitrile was allowed to slowly evaporate at room temperature to finally obtain the photocatalytic oxidation material.

[0084] In step S12, 1.539 g of o-phenylenediamine and 0.755 g of benzaldehyde were dissolved in a mixed solution of 20 mL of anhydrous methanol and 20 mL of tetrahydrofuran. 32 mg of the prepared photocatalytic oxidation material was added, and the mixture was stirred overnight at room temperature. After the reaction was complete, the photocatalytic oxidation material was recovered by filtration, and the filtrate was purified by column chromatography (eluent: petroleum ether: ethyl acetate = 1:1) to obtain a white solid, 2-phenylbenzimidazole. The recovered material was used for a cycle test under constant conditions for a total of 3 cycles, and the yield of each cycle was measured.

[0085] from Figure 11 The bar chart of catalytic reaction yields shows that the photocatalytic oxidation materials obtained in Examples 1, 2, and 3, after three cycles ( Figure 11 The yields of each of the three cycles (represented by orange, green, and purple in each example) remained basically stable after each reaction, indicating that the photocatalytic oxidation material prepared by this invention has good stability for repeated use.

[0086] from Figure 12 The bar chart comparing the catalytic reaction yields shows that the assembled photocatalytic oxidation material prepared in Example 1 has better catalytic performance than the individual host and guest molecules.

[0087] In summary, this invention provides a photocatalytic oxidation material based on the synergistic construction of cation-π interactions and host-guest interactions, its preparation method, and its application. This photocatalytic oxidation material comprises a host molecule and a guest molecule, wherein the host molecule is 1...5 ,12 5 -Di(benzyloxy)-2,5,8,11,13,16,19,22-octaoxa-1,12(1,3)-diphenylcyclododecane, with 1,1'-bis[4-((E)-2-(1-methylpyridin-1-onthi-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionthiol tetra(hexafluorophosphate) as the guest molecule. The preparation method includes: synthesizing a host molecule with a cyclic cavity; synthesizing a guest molecule containing dual cation-π interaction sites and host-guest recognition sites; dissolving the host molecule and guest molecule in acetonitrile and allowing the solvent to slowly evaporate to obtain the photocatalytic oxidation material. The guest molecules are orderly assembled through cation-π interactions between the alternating head-tail benzene rings and pyridinium cations, while the bipyridinium cation sites in the guest molecule interact with the cyclic cavity of the host molecule, thus forming a one-dimensional ordered supramolecular material. This material can be used for photocatalytic oxidation reactions, especially for the oxidative coupling of o-phenylenediamine and benzaldehyde to prepare 2-phenylbenzimidazole. It has the advantages of clear assembly method, mild preparation conditions, good structural stability and good recyclability.

[0088] Although embodiments of the present invention have been shown and described above, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A photocatalytic oxidation material constructed based on the synergistic interaction of cation-π interactions and host-guest interactions, characterized in that, This photocatalytic oxidation material is assembled from host molecules and guest molecules; The main molecular structure is as follows: ； The molecular structure of the guest is: ； Wherein, the main molecule is 1 5 ,12 5 -Di(benzyloxy)-2,5,8,11,13,16,19,22-octaoxa-1,12(1,3)-diphenylcyclododecane, wherein the guest molecule is 1,1'-bis[4-((E)-2-(1-methylpyridin-1-onthiol-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionthiol tetra(hexafluorophosphate).

2. The photocatalytic oxidation material based on the synergistic construction of cation-π interactions and host-guest interactions according to claim 1, characterized in that, During assembly, multiple guest molecules are arranged in an alternating head-to-tail manner through cation-π interactions between the benzene ring and the pyridinium cation. The ring cavity of the host molecule and the pyridinium cation sites in the guest molecules are bound together through host-guest interactions.

3. The photocatalytic oxidation material based on the synergistic construction of cation-π interactions and host-guest interactions according to claim 1, characterized in that, The molar ratio of the host molecule to the guest molecule is 1:(0.8~1.2).

4. A method for preparing a photocatalytic oxidation material based on the synergistic construction of cation-π interactions and host-guest interactions as described in any one of claims 1 to 3, characterized in that, Includes the following steps: The host molecule and the guest molecule were prepared separately; The host molecule and the guest molecule are dissolved in acetonitrile, and the acetonitrile is volatilized and assembled at room temperature to obtain the photocatalytic oxidation material.

5. The photocatalytic oxidation material based on the synergistic construction of cation-π interactions and host-guest interactions according to claim 4, characterized in that, The molar ratio of the host molecule to the guest molecule dissolved in acetonitrile is 1:(0.8~1.2); the room temperature is 20~30℃.

6. The photocatalytic oxidation material constructed based on the synergistic interaction of cation-π interaction and host-guest interaction according to claim 4, characterized in that, The main molecule is prepared according to the following steps: 4-Methylbenzenesulfonyl chloride, triethylene glycol and triethylamine were reacted in dichloromethane to give 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate. Phloroglucinol, benzyl bromide and anhydrous potassium carbonate were reacted in N,N-dimethylformamide to give 5-(benzyloxy)benzene-1,3-diol; The 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate, the 5-(benzyloxy)benzene-1,3-diol, anhydrous potassium carbonate and lithium bromide were reacted in N,N-dimethylformamide to give 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoct-1-yl)oxy]benzene; The 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoct-1-yl)oxy]benzene, 4-methylbenzenesulfonyl chloride and triethylamine were reacted in dichloromethane to give 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoct-1-yl)oxy]benzene; The main molecule is obtained by reacting the 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoctyl-1-yl)oxy]benzene, the 5-(benzyloxy)benzene-1,3-diphenol, cesium carbonate, and lithium bromide in N,N-dimethylformamide.

7. The photocatalytic oxidation material based on the synergistic construction of cation-π interactions and host-guest interactions according to claim 6, characterized in that, The molar ratio of 4-methylbenzenesulfonyl chloride, triethylene glycol, and triethylamine is 1:4:4.5; The molar ratio of phloroglucinol, benzyl bromide and anhydrous potassium carbonate is 1:0.6:4; The molar ratio of 8-hydroxy-3,6-dioxaoct-1-yl-4-methylbenzenesulfonate, 5-(benzyloxy)benzene-1,3-diol, anhydrous potassium carbonate, and lithium bromide is 1:2.2:5:0.

3. The molar ratio of 5-(benzyloxy)-1,3-bis[(8-hydroxy-3,6-dioxaoctyl-1-yl)oxy]benzene, 4-methylbenzenesulfonyl chloride, and triethylamine is 1:2.2:0.17; The molar ratio of 5-(benzyloxy)-1,3-bis[(8-(4-methylbenzenesulfonyloxy)-3,6-dioxaoctyl-1-yl)oxy]benzene, 5-(benzyloxy)benzene-1,3-diphenol, cesium carbonate and lithium bromide is 1:1:20:0.

2.

8. The photocatalytic oxidation material based on the synergistic construction of cation-π interactions and host-guest interactions according to claim 4, characterized in that, The guest molecule is prepared according to the following steps: p-Iodoaniline, 4-vinylpyridine, palladium acetate, trimethylphenylphosphine and triethylamine were reacted in acetonitrile under light-shielded reflux to give (E)-4-[2-(pyridin-4-yl)vinyl]aniline; The (E)-4-[2-(pyridin-4-yl)vinyl]aniline and iodomethane were reacted in acetonitrile in the dark to give (E)-4-(4-aminostyryl)-1-methylpyridin-1-onium iodide; 4,4'-bipyridine and 1-chloro-2,4-dinitrobenzene were reacted in acetonitrile to give 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-diamium dichloride; The 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-dionium dichloride was reacted with the (E)-4-(4-aminostyryl)-1-methylpyridine-1-onium iodide to give 1,1'-bis[4-((E)-2-(1-methylpyridine-1-onium-4-yl)vinyl)phenyl]-[4,4'-bipyridine]-1,1'-dionium dichlorodiiodide; The dichlorodiiodide was anion-exchanged with ammonium hexafluorophosphate to obtain the guest molecule.

9. The photocatalytic oxidation material based on the synergistic construction of cation-π interactions and host-guest interactions according to claim 8, characterized in that, The molar ratio of p-iodoaniline, 4-vinylpyridine, palladium acetate, trimethylphenylphosphine, and triethylamine is 1:1.37:0.0025:0.005:2.75; The molar ratio of (E)-4-[2-(pyridin-4-yl)vinyl]aniline to iodomethane is 1:5; The molar ratio of 4,4'-bipyridine to 1-chloro-2,4-dinitrobenzene is 1:4; The molar ratio of 1,1'-bis(2,4-dinitrophenyl)-[4,4'-bipyridine]-1,1'-dionium dichloride and (E)-4-(4-aminostyryl)-1-methylpyridine-1-onium iodide is 1:6; The molar ratio of dichlorodiiodide to ammonium hexafluorophosphate is 1:

5.

10. The application of a photocatalytic oxidation material based on the synergistic construction of cation-π interaction and host-guest interaction as described in any one of claims 1 to 3 in a photocatalytic oxidation reaction.

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