Preparation method of bionic parallel vein-shaped two-dimensional supramolecular layer

Abstract

The invention relates to a preparation method of a bionic parallel vein-like two-dimensional supramolecular layer, which comprises the following steps: forming a two-dimensional supramolecular layer through hierarchical self-assembly among multi-arm rigid monomers, and further stacking layer by layer to construct a parallel vein-like structure. Different from a traditional two-dimensional layered structure which forms a vertical channel in a three-dimensional structure through layer-by-layer stacking, the bionic two-dimensional supramolecular layer provided by the invention contains a one-dimensional channel parallel to a plane. The channels effectively promote a multi-electron transfer pathway and significantly increase the number of active sites, and long-range cation-pi accumulation enhances electron coupling, so that the charge transport efficiency is improved, and the bionic structure shows excellent photocatalytic hydrogen evolution activity. The research result of the invention not only provides a new design thought for designing the two-dimensional supramolecular layer embedded into the one-dimensional channel, but also provides a theoretical basis for developing molecular engineering of a future high-performance organic photocatalyst.

Description

Technical Field

[0001] The invention belongs to the field of two-dimensional materials and preparation methods, and relates to a bionic parallel leaf vein-shaped two-dimensional supramolecular layer and a preparation method thereof. Background Art

[0002] Inspired by nature, chemists have successfully constructed a large number of supramolecular structures through self-assembly strategies. Among the many assemblies, two-dimensional supramolecular assemblies (2DSAs) constructed by organic units have attracted much attention due to their high controllability in composition, structure and function, showing a wide range of application prospects, covering multiple fields such as biology and biomedicine, chemical separation and catalysis (especially photocatalysis). Although two-dimensional supramolecular assemblies (including frontal and side assemblies) have made significant progress, under the current structure-function research framework, there are still many challenges to achieve efficient charge transfer and sufficient active sites at the same time. This is crucial for improving photocatalytic performance because it facilitates the effective separation of electrons and holes and effective interaction with substrates. Therefore, developing a new 2DSA structure with continuous π stacking and abundant interaction sites, which can achieve efficient charge transfer and provide multiple active sites, will be the key to improving photocatalytic efficiency.

[0003] Document 1 "Luka Hiroaki Sai, Yang Yang, Nicholas A. Sather, Liam C. Palmer, Samuel I. Stupp. Heterocyclic Chromophore Amphiphiles and their Supramolecular Polymerization. Angewandte Chemie International Edition, 2023, 62, e202214997. "A strategy for constructing a functional edge-up assembled nanobelt structure by supramolecular polymerization of π-conjugated amphiphiles was disclosed, which successfully improved the conductivity of crystalline nanobelts. However, this construction method usually has hydrophobic flexible chains on the surface, which hinder the effective binding of the substrate and the photoelectrically active chromophore. Therefore, when used as a photocatalytic material, it often exhibits fewer active sites. This structural characteristic is not conducive to the improvement of photocatalytic performance.

[0004] Document 2 "Martin Pfeffermann, Renhao Dong, Robert Graf, Wojciech Zajaczkowski, Tatiana Gorelik, Wojciech Pisula, Akimitsu Narita, Klaus Müllen, Xinliang Feng. Free-Standing Monolayer Two-Dimensional Supramolecular Organic Framework with Good Internal Order. Journal of the American Chemical Society, 2015, 137, 14525-14532." discloses a strategy of constructing a face-up two-dimensional supramolecular organic framework using host-guest interactions, which usually provides multiple active sites. However, charge transport is usually hindered by insufficient electronic coupling, which is caused by the reduced orbital overlap in these non-covalent interactions, and ultimately affects its catalytic activity. Summary of the invention

[0005] Technical issues to be solved

[0006] In order to avoid the shortcomings of the prior art, the present invention proposes a biomimetic parallel vein-shaped two-dimensional supramolecular layer and a preparation method thereof, and overcomes the shortcomings of the prior art. The present invention proposes a hierarchical self-assembly strategy based on cation-modified rigid multi-arm monomers to construct a series of biomimetic parallel vein-shaped two-dimensional supramolecular layers (PV-2DSL). This strategy effectively solves the problems in the prior art, and can achieve efficient charge transfer and sufficient active sites, thereby significantly improving the hydrogen production rate.

[0007] Technical Solution

[0008] A biomimetic parallel leaf vein-shaped two-dimensional supramolecular layer, characterized in that: by utilizing the synergistic effect of aromatic cation-π action and hydrogen bond, three rigid monomers EG containing pyridinium salt are self-assembled into a two-dimensional supramolecular layer with biomimetic parallel leaf vein shape; the three rigid monomers EG containing pyridinium salt all have C3 symmetry, and the cores of the three monomers are triphenylamine TPA, triphenylbenzene TPB and triphenylamine TBA, respectively; then, the precursor BD is synthesized by connecting the pyridine group through enaminoketone, and then the rigid monomers EG containing pyridinium salt are synthesized respectively through acidification reaction; a two-dimensional supramolecular layer is formed by hierarchical self-assembly between multi-arm rigid monomers, and then layer by layer is stacked to construct a parallel leaf vein-like structure;

[0009] The structural formulas of the three rigid monomers EG containing pyridinium salts are:

[0010]

[0011] The C3 symmetrical monomers triphenylamine TPA, triphenylbenzene TPB and triphenylamine TBA are obtained by a synthetic method.

[0012] A method for preparing the biomimetic parallel vein-shaped two-dimensional supramolecular layer is characterized by the following steps:

[0013] Step 1: dissolving 4-acetylpyridine in N,N-dimethylformamide-dimethylacetal, stirring and reacting at 100-105° C. for 2-3 hours; after the reaction solution is cooled to room temperature, removing the solvent by distillation under reduced pressure, followed by extraction with dichloromethane, and then separation and purification by column chromatography to obtain A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one;

[0014] Step 2: A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and tri(4-aminophenyl)amine are dissolved in acetic acid, and the mixture is stirred at room temperature for 46 to 50 hours; after the reaction solution is cooled to room temperature, water is added to quench the reaction, followed by filtration, washing with water 3 to 4 times, and then dissolved in dichloromethane, and then dried over anhydrous magnesium sulfate and rotary evaporated to remove the solvent, and then separated and purified by column chromatography to obtain B dark red solid (2Z,2'Z,2"Z)-3,3',3"-((triazinebiphenyl-4,1-diyl))tri(amino group))tri(1-(pyridin-4-yl)prop-2-ene-1-one);

[0015] Step 3: A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and 1,3,5-tri(4-aminophenyl)benzene are dissolved in acetic acid, and the reaction is stirred at room temperature for 46 to 59 hours; after the reaction solution is cooled to room temperature, water is added to quench the reaction, followed by filtration, washing with water 3 to 4 times, and then dissolved in dichloromethane, and then dried over anhydrous magnesium sulfate and rotary evaporated to remove the solvent, and then separated and purified by column chromatography to obtain C bright yellow solid 1,3,5-tri(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enaminoketone)benzene);

[0016] Step 4: A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and N4,N4-bis(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine are dissolved in acetic acid, and the mixture is stirred at room temperature for 46 to 50 hours; after the reaction solution is cooled to room temperature, water is added to quench the reaction, followed by filtration, washing with water 3 to 4 times, and then dissolved in dichloromethane, and then dried over anhydrous magnesium sulfate and rotary evaporated to remove the solvent, and then separated and purified by column chromatography to obtain D orange solid (2Z,2'Z,2"Z)-3,3',3"-((triazine([1,1'-biphenyl]-4',4-diyl))tri(amino group))tri(1-(pyridin-4-yl)prop-2-en-1-one);

[0017] Step 5: Place the dark red solid (2Z,2'Z,2"Z)-3,3',3"-((triazinebiphenyl-4,1-diyl))tri(amino group))tri(1-(pyridin-4-yl)prop-2-en-1-one) powder of B in container A, and then place the container in container B containing concentrated hydrochloric acid, seal the mouth of container B, and react for 1 to 2 hours to obtain the first monomer EG black solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((triphenylaziridine)triazine)tri(acryloyl))tri(pyridin-1-ammonium)) chloride salt;

[0018] Step 6: Place the bright yellow solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enaminoketone)benzene powder of C in container C, then place container C in container D containing concentrated hydrochloric acid, seal the mouth of container D, and react for 1 to 2 hours to obtain the second monomer EG red solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enaminoketone)benzene-1-ammonium chloride;

[0019] Step 7: Place D orange solid (2Z,2'Z,2"Z)-3,3',3"-((triazine([1,1'-biphenyl]-4',4-diyl))tri(amino group))tri(1-(pyridin-4-yl)prop-2-en-1-one) powder in container E, then place container E in container F containing concentrated hydrochloric acid, seal the mouth of container F, and react for 1 to 2 hours to obtain the third monomer EG dark red solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((tri(4,4'-diphenyl)nitride)tri(nitrogen))tri(acryloyl))tri(pyridin-1-ammonium)) chloride salt;

[0020] Step 8: Place the powders of the three monomers EG in step 5, step 6 and step 7 in container G, then add methanol to completely dissolve them, then slowly add THF while stirring, then let stand overnight, filter, and the filter cakes are the prepared different bionic two-dimensional supramolecular layers.

[0021] The step 1 is to dissolve 0.2 to 0.4 mole of 4-acetylpyridine in N,N-dimethylformamide-dimethylacetal.

[0022] The steps 2, 3 and 4 are as follows: A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and tri(4-aminophenyl)amine in a molar ratio of 4:1 to 6:1 are dissolved in acetic acid.

[0023] The step 5 is to place 0.2-0.4 mmol of dark red solid (2Z,2'Z,2"Z)-3,3',3"-((triazinebiphenyl-4,1-diyl)tris(amino group))tris(1-(pyridin-4-yl)prop-2-en-1-one) powder of B in container A.

[0024] The step 6 is to place 0.2 to 0.4 mmol of C bright yellow solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene powder in C container.

[0025] 0.2-0.4 mmol of D orange solid (2Z,2'Z,2"Z)-3,3',3"-((triazine([1,1'-biphenyl]-4',4-diyl))tris(amino))tris(1-(pyridin-4-yl)prop-2-en-1-one) powder is placed in the E container.

[0026] The solution heating is carried out in a constant temperature oil bath; the room temperature stirring reaction is carried out in a constant temperature 25° C. oil bath.

[0027] Beneficial Effects

[0028] The present invention proposes a biomimetic parallel vein-shaped two-dimensional supramolecular layer and a preparation method thereof. The method forms a two-dimensional supramolecular layer through hierarchical self-assembly between multi-arm rigid monomers, and then stacks layers to construct a parallel vein-like structure. First, monomers (M1-M3) with three pyridine groups on the periphery and C3 symmetric monomers triphenylamine (TPA), triphenylbenzene (TPB) and triphenylamine (TBA) as the core are synthesized. The corresponding tripyridinium salt monomers are obtained through a simple acidification reaction. Subsequently, these monomers form a parallel vein-shaped two-dimensional supramolecular layer through the synergistic drive of the self-assembled aromatic cation-π action and hydrogen bonds. Different from the traditional two-dimensional layered structure that forms a vertical channel in a three-dimensional structure by stacking layers, the biomimetic two-dimensional supramolecular layer of the present invention contains a one-dimensional channel parallel to the plane. These channels effectively promote the multi-electron transfer pathway, significantly increase the number of active sites, and the long-range cation-π stacking enhances the electron coupling, thereby improving the charge transport efficiency, so that the biomimetic structure exhibits excellent photocatalytic hydrogen evolution activity. The research results of the present invention not only provide a new design idea for designing two-dimensional supramolecular layers embedded in one-dimensional channels, but also provide a theoretical basis for the molecular engineering of developing future high-performance organic photocatalysts. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 Schematic diagram of the molecular structure of the supramolecular two-dimensional layer prepared by the method of the present invention

[0030] Figure 2 This is a representative H NMR spectrum of the EG monomer prepared by the method of the present invention.

[0031] a: H NMR spectrum of E molecule;

[0032] b: H NMR spectrum of F molecule

[0033] c: H NMR spectrum of G molecule

[0034] Figure 3 The representative single crystal X-ray diffraction structure of the E molecule prepared in Example 1 of the method of the present invention is

[0035] Figure 4 This is an atomic force microscope image of the two-dimensional supramolecular layer prepared by the E molecule in Example 2 of the method of the present invention.

[0036] Figure 5 The photocatalytic hydrogen production effect of the two-dimensional supramolecular layer prepared by the E molecule in Example 3 of the method of the present invention is DETAILED DESCRIPTION

[0037] The present invention will now be further described with reference to the embodiments and the accompanying drawings:

[0038] In the preparation of the biomimetic parallel vein-shaped two-dimensional supramolecular layer, the structural formula of the monomer is:

[0039] The structural formulas of three rigid monomers EG containing pyridinium salts are:

[0040]

[0041] The example of preparing the biomimetic parallel vein-shaped two-dimensional supramolecular layer is as follows:

[0042] Embodiment 1:

[0043] [Step 1] Dissolve 25 g of 4-acetylpyridine in 40 ml of N,N-dimethylformamide-dimethylacetal, and stir at 105° C. for 2 h. After the reaction solution is cooled to room temperature, remove the solvent by distillation under reduced pressure, then extract with dichloromethane 100 mL×2 times, and then separate and purify by column chromatography (eluent is n-hexane:ethyl acetate=10:1) to obtain a yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one;

[0044] [Step 2] Dissolve 2.4 g of 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and 1 g of tris(4-aminophenyl)amine in 100 mL of acetic acid, and stir at room temperature for 48 h. After the reaction solution is cooled to room temperature, add 200 mL of water to quench the reaction, then filter, wash with 100 mL of water three times, and then dissolve in 500 mL of dichloromethane. Then, dry over anhydrous magnesium sulfate and remove the solvent by rotary evaporation. Then, separate and purify by column chromatography (eluent is methanol: ethyl acetate = 1:10) to obtain a dark red solid (2Z,2'Z,2"Z)-3,3',3"-((triazinebiphenyl-4,1-diyl))tris(amino group))tris(1-(pyridin-4-yl)prop-2-ene-1-one);

[0045] [Step 3] Dissolve 2.0 g of 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and 1 g of 1,3,5-tri(4-aminophenyl)benzene in 100 mL of acetic acid, and stir at room temperature for 48 h. After the reaction solution is cooled to room temperature, add 200 mL of water to quench the reaction, then filter, wash with 100 mL of water three times, and then dissolve in 500 mL of dichloromethane. Then, dry over anhydrous magnesium sulfate and remove the solvent by rotary evaporation. Then, separate and purify by column chromatography (eluent is methanol: ethyl acetate = 1:20) to obtain a bright yellow solid 1,3,5-tri(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enaminoketone)benzene.

[0046] [Step 4] Dissolve 1.4 g of 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and 1 g of N4,N4-bis(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine in 100 mL of acetic acid and stir at room temperature for 48 h. After the reaction solution is cooled to room temperature, add 200 mL of water to quench the reaction, then filter and wash with 100 mL of water for 3 hours. The mixture was then dissolved in 500 mL of dichloromethane, dried over anhydrous magnesium sulfate, and then rotary evaporated to remove the solvent. The mixture was then separated and purified by column chromatography (eluent: methanol:ethyl acetate = 1:15) to obtain an orange solid (2Z,2'Z,2"Z)-3,3',3"-((triazine([1,1'-biphenyl]-4',4-diyl))tris(amino group))tris(1-(pyridin-4-yl)prop-2-en-1-one);

[0047] [Step 5] Place 100 mg of (2Z,2'Z,2"Z)-3,3',3"-((triazinebiphenyl-4,1-diyl))tri(amino))tri(1-(pyridin-4-yl)prop-2-en-1-one) powder in a 25 mL small beaker, then place the 25 mL small beaker in a 100 mL large beaker containing 20 mL of concentrated hydrochloric acid, seal the mouth of the large beaker with plastic wrap, and react for 1 hour to obtain a black solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((triphenylazino)triazine)tri(acryloyl))tri(pyridin-1-ammonium)) chloride salt;

[0048] [Step 6] Place 100 mg of 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene powder in a 25 mL small beaker, then place the 25 mL small beaker in a 100 mL large beaker containing 20 mL of concentrated hydrochloric acid, seal the mouth of the large beaker with plastic wrap, and react for 1 hour to obtain a red solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene-1-ammonium chloride;

[0049] [Step 7] Place 100 mg of (2Z,2'Z,2"Z)-3,3',3"-((triazine([1,1'-biphenyl]-4',4-diyl))tri(amino))tri(1-(pyridin-4-yl)prop-2-en-1-one) powder in a 25 mL small beaker, then place the 25 mL small beaker in a 100 mL large beaker containing 20 mL of concentrated hydrochloric acid, seal the mouth of the large beaker with plastic wrap, and react for 1 hour to obtain a dark red solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((tri(4,4'-diphenyl)nitride)tri(nitro))tri(acryloyl))tri(pyridin-1-ammonium)) chloride salt;

[0050] [Step 8] The powders of the three monomers EG in steps 5, 6 and 7 are placed in a G container, and then methanol is added to completely dissolve them. Then, THF is slowly added thereto while stirring, and then allowed to stand overnight and filtered. The filter cakes are the different biomimetic two-dimensional supramolecular layers prepared.

[0051] Embodiment 2:

[0052] [Step 1] Dissolve 30 g of 4-acetylpyridine in 48 ml of N,N-dimethylformamide-dimethylacetal, and stir at 105° C. for 2 h. After the reaction solution is cooled to room temperature, remove the solvent by distillation under reduced pressure, then extract with dichloromethane 100 mL × 3 times, and then separate and purify by column chromatography (eluent is n-hexane:ethyl acetate=10:1) to obtain a yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one;

[0053] [Step 2] Dissolve 3.6 g of 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and 1.5 g of tris(4-aminophenyl)amine in 120 mL of acetic acid, and stir at room temperature for 48 h. After the reaction solution is cooled to room temperature, add 250 mL of water to quench the reaction, then filter, wash with 100 mL of water 4 times, and then dissolve in 700 mL of dichloromethane. Then, dry over anhydrous magnesium sulfate and remove the solvent by rotary evaporation. Then, separate and purify by column chromatography (eluent is methanol: ethyl acetate = 1:10) to obtain a dark red solid (2Z,2'Z,2"Z)-3,3',3"-((triazinebiphenyl-4,1-diyl))tris(amino group))tris(1-(pyridin-4-yl)prop-2-ene-1-one);

[0054] [Step 3] Dissolve 3.0 g of 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and 1.5 g of 1,3,5-tri(4-aminophenyl)benzene in 120 mL of acetic acid, and stir at room temperature for 48 h. After the reaction solution is cooled to room temperature, add 250 mL of water to quench the reaction, then filter, wash 4 times with 100 mL of water, and then dissolve in 700 mL of dichloromethane. Then, dry over anhydrous magnesium sulfate and remove the solvent by rotary evaporation. Then, separate and purify by column chromatography (eluent is methanol: ethyl acetate = 1:20) to obtain a bright yellow solid 1,3,5-tri(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enaminoketone)benzene.

[0055] [Step 4] Dissolve 1.8 g of 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and 1.5 g of N4,N4-bis(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine in 120 mL of acetic acid and stir at room temperature for 48 h. After the reaction solution is cooled to room temperature, add 250 mL of water to quench the reaction, then filter and wash with 100 mL of water. 4 times, then dissolved in 700 mL of dichloromethane, then dried over anhydrous magnesium sulfate and rotary evaporated to remove the solvent, and then separated and purified by column chromatography (eluent: methanol: ethyl acetate = 1:15) to obtain an orange solid (2Z,2'Z,2"Z)-3,3',3"-((triazine([1,1'-biphenyl]-4',4-diyl))tris(amino group))tris(1-(pyridin-4-yl)prop-2-en-1-one);

[0056] [Step 5] Place 150 mg of (2Z,2'Z,2"Z)-3,3',3"-((triazinebiphenyl-4,1-diyl))tri(amino))tri(1-(pyridin-4-yl)prop-2-en-1-one) powder in a 25 mL small beaker, then place the 25 mL small beaker in a 100 mL large beaker containing 20 mL of concentrated hydrochloric acid, seal the mouth of the large beaker with plastic wrap, and react for 1.2 hours to obtain a black solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((triphenylazino)triazine)tri(acryloyl))tri(pyridin-1-ammonium)) chloride salt;

[0057] [Step 6] Place 150 mg of 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene powder in a 25 mL small beaker, then place the 25 mL small beaker in a 100 mL large beaker containing 20 mL of concentrated hydrochloric acid, seal the mouth of the large beaker with plastic wrap, and react for 1.2 hours to obtain a red solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene-1-ammonium chloride;

[0058] [Step 7] Place 150 mg of (2Z,2'Z,2"Z)-3,3',3"-((triazine([1,1'-biphenyl]-4',4-diyl))tri(amino))tri(1-(pyridin-4-yl)prop-2-en-1-one) powder in a 25 mL small beaker, then place the 25 mL small beaker in a 100 mL large beaker containing 20 mL of concentrated hydrochloric acid, seal the mouth of the large beaker with plastic wrap, and react for 1.2 hours to obtain a dark red solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((tri(4,4'-diphenyl)nitride)tri(nitro))tri(acryloyl))tri(pyridin-1-ammonium)) chloride salt;

[0059] [Step 8] The powders of the three monomers EG in steps 5, 6 and 7 are placed in a G container, and then methanol is added to completely dissolve them. Then, THF is slowly added thereto while stirring, and then allowed to stand overnight and filtered. The filter cakes are the different biomimetic two-dimensional supramolecular layers prepared.

[0060] Embodiment three:

[0061] [Step 1] Dissolve 35 g of 4-acetylpyridine in 56 ml of N,N-dimethylformamide-dimethylacetal, and stir at 105° C. for 2 h. After the reaction solution is cooled to room temperature, remove the solvent by distillation under reduced pressure, then extract with dichloromethane 100 mL×4 times, and then separate and purify by column chromatography (eluent is n-hexane:ethyl acetate=10:1) to obtain a yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one;

[0062] [Step 2] Dissolve 4.8 g of 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and 2 g of tris(4-aminophenyl)amine in 150 mL of acetic acid, and stir at room temperature for 48 h. After the reaction solution is cooled to room temperature, add 300 mL of water to quench the reaction, then filter, wash with 100 mL of water 5 times, and then dissolve in 1000 mL of dichloromethane. Then, dry over anhydrous magnesium sulfate and remove the solvent by rotary evaporation. Then, separate and purify by column chromatography (eluent is methanol: ethyl acetate = 1:10) to obtain a dark red solid (2Z,2'Z,2"Z)-3,3',3"-((triazinebiphenyl-4,1-diyl))tris(amino group))tris(1-(pyridin-4-yl)prop-2-ene-1-one);

[0063] [Step 3] Dissolve 4.0 g of 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and 2 g of 1,3,5-tri(4-aminophenyl)benzene in 150 mL of acetic acid, and stir at room temperature for 48 h. After the reaction solution is cooled to room temperature, add 300 mL of water to quench the reaction, then filter, wash with 100 mL of water 5 times, and then dissolve in 1000 mL of dichloromethane. Then, dry over anhydrous magnesium sulfate and remove the solvent by rotary evaporation. Then, separate and purify by column chromatography (eluent is methanol: ethyl acetate = 1:20) to obtain a bright yellow solid 1,3,5-tri(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enaminoketone)benzene.

[0064] [Step 4] Dissolve 2.4 g of 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and 2 g of N4,N4-bis(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine in 150 mL of acetic acid and stir at room temperature for 48 h. After the reaction solution is cooled to room temperature, add 300 mL of water to quench the reaction, then filter and wash with 100 mL of water 5 times. , then dissolved in 1000 mL of dichloromethane, then dried over anhydrous magnesium sulfate and rotary evaporated to remove the solvent, and then separated and purified by column chromatography (eluent: methanol: ethyl acetate = 1:15) to obtain an orange solid (2Z,2'Z,2"Z)-3,3',3"-((triazine([1,1'-biphenyl]-4',4-diyl))tri(amino group))tri(1-(pyridin-4-yl)prop-2-en-1-one);

[0065] [Step 5] Place 200 mg of (2Z,2'Z,2"Z)-3,3',3"-((triazinebiphenyl-4,1-diyl))tri(amino))tri(1-(pyridin-4-yl)prop-2-en-1-one) powder in a 25 mL small beaker, then place the 25 mL small beaker in a 100 mL large beaker containing 20 mL of concentrated hydrochloric acid, seal the mouth of the large beaker with plastic wrap, and react for 1.5 hours to obtain a black solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((triphenylazino)triazine)tri(acryloyl))tri(pyridin-1-ammonium)) chloride salt;

[0066] [Step 6] Place 200 mg of 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene powder in a 25 mL small beaker, then place the 25 mL small beaker in a 100 mL large beaker containing 20 mL of concentrated hydrochloric acid, seal the mouth of the large beaker with plastic wrap, and react for 1.5 hours to obtain a red solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene-1-ammonium chloride;

[0067] [Step 7] Place 200 mg of (2Z,2'Z,2"Z)-3,3',3"-((triazine([1,1'-biphenyl]-4',4-diyl))tri(amino))tri(1-(pyridin-4-yl)prop-2-en-1-one) powder in a 25 mL small beaker, then place the 25 mL small beaker in a 100 mL large beaker containing 20 mL of concentrated hydrochloric acid, seal the mouth of the large beaker with plastic wrap, and react for 1.5 hours to obtain a dark red solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((tri(4,4'-diphenyl)nitride)tri(nitro))tri(acryloyl))tri(pyridin-1-ammonium)) chloride salt;

[0068] [Step 8] The powders of the three monomers EG in steps 5, 6 and 7 are placed in a G container, and then methanol is added to completely dissolve them. Then, THF is slowly added thereto while stirring, and then allowed to stand overnight and filtered. The filter cakes are the different biomimetic two-dimensional supramolecular layers prepared.

[0069] from Figure 2 It can be seen from the H NMR spectra that the three molecules prepared in Example 1 have been successfully synthesized;

[0070] from Figure 3 It can be seen from the single crystal X-ray diffraction structure diagram that the E molecule prepared in Example 1 presents an ordered two-dimensional layered stacking structure containing one-dimensional channels;

[0071] from Figure 4 It can be seen from the atomic force microscopy image that the two-dimensional supramolecular layer prepared by the E molecule in this Example 2 presents a 4 nm sheet structure;

[0072] from Figure 5 It can be seen from the photocatalytic hydrogen production rate that the two-dimensional supramolecular layer prepared by the E molecule in this Example 3 exhibits a higher hydrogen production activity.

Claims

1. A biomimetic parallel vein-shaped two-dimensional supramolecular layer, characterized in that: By utilizing the synergistic effect of aromatic cation-π interaction and hydrogen bonding, three rigid monomers EG containing pyridinium salts are self-assembled into a two-dimensional supramolecular layer with a biomimetic parallel leaf vein shape; the three rigid monomers EG containing pyridinium salts all have C3 symmetry, and the cores of the three monomers are triphenylamine TPA, triphenylbenzene TPB and triphenylamine TBA, respectively. Then, the pyridine group is connected by enaminone to synthesize the precursor BD, and then the rigid monomers EG containing pyridinium salts are synthesized respectively through acidification reaction; a two-dimensional supramolecular layer is formed through hierarchical self-assembly between multi-arm rigid monomers, and then layer by layer is stacked to construct a parallel leaf vein structure.

2. The biomimetic parallel vein-shaped two-dimensional supramolecular layer according to claim 1, characterized in that: The structural formulas of the three rigid monomers EG containing pyridinium salts are:

3. The biomimetic parallel vein-shaped two-dimensional supramolecular layer according to claim 1, characterized in that: The C3 symmetrical monomers triphenylamine TPA, triphenylbenzene TPB and triphenylamine TBA are obtained by a synthetic method.

4. A method for preparing the biomimetic parallel vein-shaped two-dimensional supramolecular layer according to claim 1, 2 or 3, characterized in that Here are the steps: Step 1: dissolving 4-acetylpyridine in N,N-dimethylformamide-dimethylacetal, stirring and reacting at 100-105° C. for 2-3 hours; after the reaction solution is cooled to room temperature, removing the solvent by distillation under reduced pressure, followed by extraction with dichloromethane, and then separation and purification by column chromatography to obtain A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one; Step 2: A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and tri(4-aminophenyl)amine are dissolved in acetic acid, and the mixture is stirred at room temperature for 46 to 50 hours; after the reaction solution is cooled to room temperature, water is added to quench the reaction, followed by filtration, washing with water 3 to 4 times, and then dissolved in dichloromethane, and then dried over anhydrous magnesium sulfate and rotary evaporated to remove the solvent, and then separated and purified by column chromatography to obtain B dark red solid (2Z,2'Z,2"Z)-3,3',3"-((triazinebiphenyl-4,1-diyl))tri(amino group))tri(1-(pyridin-4-yl)prop-2-ene-1-one); Step 3: A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and 1,3,5-tri(4-aminophenyl)benzene are dissolved in acetic acid, and the reaction is stirred at room temperature for 46 to 59 hours; after the reaction solution is cooled to room temperature, water is added to quench the reaction, followed by filtration, washing with water 3 to 4 times, and then dissolved in dichloromethane, and then dried over anhydrous magnesium sulfate and rotary evaporated to remove the solvent, and then separated and purified by column chromatography to obtain C bright yellow solid 1,3,5-tri(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enaminoketone)benzene); Step 4: A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and N4,N4-bis(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine are dissolved in acetic acid, and the mixture is stirred at room temperature for 46 to 50 hours; after the reaction solution is cooled to room temperature, water is added to quench the reaction, followed by filtration, washing with water 3 to 4 times, and then dissolved in dichloromethane, and then dried over anhydrous magnesium sulfate and rotary evaporated to remove the solvent, and then separated and purified by column chromatography to obtain D orange solid (2Z,2'Z,2"Z)-3,3',3"-((triazine([1,1'-biphenyl]-4',4-diyl))tri(amino group))tri(1-(pyridin-4-yl)prop-2-en-1-one); Step 5: Place the dark red solid (2Z,2'Z,2"Z)-3,3',3"-((triazinebiphenyl-4,1-diyl))tri(amino group))tri(1-(pyridin-4-yl)prop-2-en-1-one) powder of B in container A, and then place the container in container B containing concentrated hydrochloric acid, seal the mouth of container B, and react for 1 to 2 hours to obtain the first monomer EG black solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((triphenylaziridine)triazine)tri(acryloyl))tri(pyridin-1-ammonium)) chloride salt; Step 6: Place the bright yellow solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enaminoketone)benzene powder of C in container C, then place container C in container D containing concentrated hydrochloric acid, seal the mouth of container D, and react for 1 to 2 hours to obtain the second monomer EG red solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enaminoketone)benzene-1-ammonium chloride; Step 7: Place D orange solid (2Z,2'Z,2"Z)-3,3',3"-((triazine([1,1'-biphenyl]-4',4-diyl))tri(amino group))tri(1-(pyridin-4-yl)prop-2-en-1-one) powder in container E, then place container E in container F containing concentrated hydrochloric acid, seal the mouth of container F, and react for 1 to 2 hours to obtain the third monomer EG dark red solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((tri(4,4'-diphenyl)nitride)tri(nitrogen))tri(acryloyl))tri(pyridin-1-ammonium)) chloride salt; Step 8: Place the powders of the three monomers EG in step 5, step 6 and step 7 in container G, then add methanol to completely dissolve them, then slowly add THF while stirring, then let stand overnight, filter, and the filter cakes are the prepared different bionic two-dimensional supramolecular layers.

5. The method according to claim 4, characterized in that: The step 1 is to dissolve 0.2 to 0.4 mole of 4-acetylpyridine in N,N-dimethylformamide-dimethylacetal.

6. The method according to claim 4, characterized in that: The steps 2, 3 and 4 are as follows: A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and tri(4-aminophenyl)amine in a molar ratio of 4:1 to 6:1 are dissolved in acetic acid.

7. The method according to claim 4, characterized in that: The step 5 is to place 0.2-0.4 mmol of dark red solid (2Z,2'Z,2"Z)-3,3',3"-((triazinebiphenyl-4,1-diyl)tris(amino group))tris(1-(pyridin-4-yl)prop-2-en-1-one) powder of B in container A.

8. The method according to claim 4, characterized in that: The step 6 is to place 0.2 to 0.4 mmol of C bright yellow solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene powder in C container.

9. The method according to claim 4, characterized in that: 0.2-0.4 mmol of D orange solid (2Z,2'Z,2"Z)-3,3',3"-((triazine([1,1'-biphenyl]-4',4-diyl))tris(amino))tris(1-(pyridin-4-yl)prop-2-en-1-one) powder is placed in the E container.

10. The method according to claim 4, characterized in that: The solution heating is carried out in a constant temperature oil bath; the room temperature stirring reaction is carried out in a constant temperature 25° C. oil bath.

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