Preparation method of a bionic parallel venation two-dimensional supramolecular layer

Abstract

The application relates to a preparation method of a bionic parallel leaf vein two-dimensional supramolecular layer, which is formed through hierarchical self-assembly of multi-arm rigid monomers, and then is stacked layer by layer to construct a bionic parallel leaf vein structure. Unlike 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 of the application contains one-dimensional channels parallel to the plane. The channels effectively promote a multi-electron transfer pathway, significantly increase the number of active sites, and long-range cation-pi stacking enhances electron coupling, thereby improving the charge transport efficiency, so that the bionic structure exhibits excellent photocatalytic hydrogen evolution activity. The research result of the application not only provides a new design idea for designing a two-dimensional supramolecular layer embedded with one-dimensional channels, but also provides a theoretical basis for developing future molecular engineering of high-performance organic photocatalysts.

Description

Technical Field

[0001] The present 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 from 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, achieving efficient charge transport and sufficient active sites at the same time still faces many challenges. 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 that can achieve efficient charge transport 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 functional edge-up nanoribbon structures through supramolecular polymerization of π-conjugated amphiphiles was disclosed. This method successfully improved the electrical conductivity of crystalline nanoribbons. However, this construction method usually hinders the effective binding of substrates and photoelectrically active chromophores due to the presence of hydrophobic flexible chains on the surface. Therefore, when used as a photocatalytic material, it often exhibits fewer active sites. This structural characteristic is not conducive to improving photocatalytic performance.

[0004] Reference 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 for constructing face-up two-dimensional supramolecular organic frameworks using host-guest interactions. Such structures typically provide multiple active sites. However, charge transport is often hindered by insufficient electronic coupling, which is due to reduced orbital overlap in these non-covalent interactions, and ultimately affects their catalytic activity. Summary of the Invention

[0005] Technical problems to be solved

[0006] To address the shortcomings of the prior art, the present invention proposes a biomimetic parallel vein-shaped two-dimensional supramolecular layer and its preparation method. This overcomes the shortcomings of the prior art by proposing 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 addresses the challenges of the prior art, enabling efficient charge transfer and sufficient active sites to coexist, significantly improving the hydrogen production rate.

[0007] Technical Solution

[0008] A biomimetic parallel leaf vein-shaped two-dimensional supramolecular layer, characterized by utilizing the synergistic effect of aromatic cation-π interaction and hydrogen bonding to self-assemble three rigid monomers (EG) containing pyridinium salts into a biomimetic parallel leaf vein-shaped two-dimensional supramolecular layer; 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 terphenylamine TBA, respectively; then, a precursor (BD) is synthesized by linking pyridine groups via enaminone, and then, the rigid monomers (EG) containing pyridinium salts are synthesized separately through an acidification reaction; a two-dimensional supramolecular layer is formed through hierarchical self-assembly between the multi-arm rigid monomers, and then stacked layer by layer 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 terphenylamine 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: Dissolve 4-acetylpyridine in N,N-dimethylformamide-dimethyl acetal and react with stirring at 100-105°C for 2-3 hours. After the reaction solution is cooled to room temperature, the solvent is removed by distillation under reduced pressure, followed by extraction with dichloromethane and purification by column chromatography to obtain 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one A as a yellow solid.

[0014] Step 2: A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one and tris(4-aminophenyl)amine were dissolved in acetic acid and stirred at room temperature for 46 to 50 hours; after the reaction solution was cooled to room temperature, water was added to quench the reaction, followed by filtration and washing with water 3 to 4 times, and then dissolved in dichloromethane, and then dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation. The solution was 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))tris(amino group))tris(1-(pyridin-4-yl)prop-2-en-1-one);

[0015] Step 3: Dissolve A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one and 1,3,5-tris(4-aminophenyl)benzene in acetic acid and stir at room temperature for 46 to 59 hours; after the reaction solution is cooled to room temperature, add water to quench the reaction, then filter and wash with water 3 to 4 times, then dissolve in dichloromethane, and then dry over anhydrous magnesium sulfate and remove the solvent by rotary evaporation. Then, separate and purify by column chromatography to obtain C bright yellow solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enaminobenzene);

[0016] Step 4: A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one and N4,N4-bis(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine were dissolved in acetic acid and stirred at room temperature for 46 to 50 hours; after the reaction solution was cooled to room temperature, water was added to quench the reaction, followed by filtration and washing with water 3 to 4 times, and then dissolved in dichloromethane, and then dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation, and then separated and purified by column chromatography to obtain D orange solid (2Z,2'Z,2"Z)-3,3',3"-((triazabi([1,1'-biphenyl]-4',4-diyl))tris(amino group))tris(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"-((triazabiphenyl-4,1-diyl))tris(amino group))tris(1-(pyridin-4-yl)prop-2-en-1-one) powder of B in container A, 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"-((triphenylazaolefin)triazayl)tris(acryloyl))tris(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(enamino)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(enamino)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))tris(amino group))tris(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"-((tris(4,4'-diphenyl)nitride)tris(amino))tris(acryloyl))tris(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 it stand overnight, filter, and the filter cake is the prepared different biomimetic two-dimensional supramolecular layers.

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

[0022] In step 2, step 3 and step 4, yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and tris(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 to 0.4 mmol of dark red solid (2Z,2'Z,2"Z)-3,3',3"-((triazabiphenyl-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"-((triazabiphenyl([1,1'-biphenyl]-4',4-diyl))tris(amino))tris(1-(pyridin-4-yl)prop-2-en-1-one) powder was placed in 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 oil bath at 25°C.

[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 them layer by layer to construct a parallel vein-like structure. First, monomers (M1-M3) with C3 symmetrical monomers triphenylamine (TPA), triphenylbenzene (TPB) and terphenylamine (TBA) as the core and three pyridine groups on the periphery are synthesized. The corresponding tripyridinium salt monomers are prepared by a simple acidification reaction. Subsequently, these monomers form a parallel vein-shaped two-dimensional supramolecular layer through the synergistic drive of self-assembled aromatic cation-π interaction and hydrogen bonding. Unlike traditional two-dimensional layered structures that form vertical channels in a three-dimensional structure by stacking layers, the biomimetic two-dimensional supramolecular layer of the present invention contains one-dimensional channels parallel to the plane. These channels effectively promote multiple electron transfer pathways, significantly increase the number of active sites, and long-range cation-π stacking enhances electron coupling, thereby improving charge transport efficiency, so that the biomimetic structure exhibits excellent photocatalytic hydrogen evolution activity. The research results of this invention not only provide new design ideas for the design of 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 This is a 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 This is a representative single crystal X-ray diffraction structure of the E molecule prepared in Example 1 of the present invention.

[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 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 examples of preparing biomimetic parallel vein-shaped two-dimensional supramolecular layers are as follows:

[0042] Example 1:

[0043] [Step 1] Dissolve 25 g of 4-acetylpyridine in 40 ml of N,N-dimethylformamide-dimethyl acetal, and stir at 105° C. for 2 h. After the reaction solution is cooled to room temperature, the solvent is removed by distillation under reduced pressure. The mixture is then extracted with dichloromethane (100 mL x 2) and purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one as a yellow solid.

[0044] [Step 2] Dissolve 2.4 g of 3-(dimethylamino)-1-(2-phenyl)-2-propen-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, filter, wash three times with 100 mL of water, and then dissolve in 500 mL of dichloromethane. After drying over anhydrous magnesium sulfate, remove the solvent by rotary evaporation, and separate and purify by column chromatography (eluent: methanol:ethyl acetate = 1:10) to obtain a dark red solid (2Z,2'Z,2"Z)-3,3',3"-((triazinobiphenyl-4,1-diyl))tris(amino group))tris(1-(pyridin-4-yl)prop-2-en-1-one);

[0045] [Step 3] Dissolve 2.0 g of 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one and 1 g of 1,3,5-tris(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 and wash three times with 100 mL of water, then dissolve in 500 mL of dichloromethane, and then dry over anhydrous magnesium sulfate and remove the solvent by rotary evaporation. Then, separate and purify by column chromatography (eluent: methanol:ethyl acetate = 1:20) to obtain 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene as a bright yellow solid.

[0046] [Step 4] 1.4 g of 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one and 1 g of N4,N4-bis(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine were dissolved in 100 mL of acetic acid and stirred at room temperature for 48 h. After the reaction solution was cooled to room temperature, 200 mL of water was added to quench the reaction, and then the mixture was filtered and washed with 100 mL of water for 3 hours. The mixture was dissolved in 500 mL of dichloromethane, dried over anhydrous magnesium sulfate, and then the solvent was removed by rotary evaporation. 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"-((triazabiphenyl([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"-((triazabi(phenyl-4,1-diyl))tris(amino))tris(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. After reacting for 1 hour, a black solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((triphenylazaolefin)triazolo)tris(acryloyl))tris(pyridin-1-ammonium)) chloride salt is obtained;

[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 beaker with plastic wrap. After reacting for 1 hour, a red solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene-1-ammonium chloride is obtained.

[0049] [Step 7] Place 100 mg of (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 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 beaker with plastic wrap. After reacting for 1 hour, a deep red solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((tris(4,4'-diphenyl)nitride)tris(amino))tris(acryloyl))tris(pyridin-1-ammonium)) chloride salt is obtained;

[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 the mixture is allowed to stand overnight and filtered. The filter cakes are the different biomimetic two-dimensional supramolecular layers prepared.

[0051] Example 2:

[0052] [Step 1] Dissolve 30 g of 4-acetylpyridine in 48 ml of N,N-dimethylformamide-dimethyl acetal, and stir at 105° C. for 2 h. After the reaction solution is cooled to room temperature, the solvent is removed by distillation under reduced pressure. The mixture is then extracted with 100 mL of dichloromethane three times, and then purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one as a yellow solid.

[0053] [Step 2] 3.6 g of 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one and 1.5 g of tris(4-aminophenyl)amine were dissolved in 120 mL of acetic acid and stirred at room temperature for 48 h. After the reaction solution was cooled to room temperature, 250 mL of water was added to quench the reaction, followed by filtration and washing with 100 mL of water four times. The solution was then dissolved in 700 mL of dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The solution was then separated and purified by column chromatography (eluent: methanol:ethyl acetate = 1:10) to obtain a dark red solid (2Z,2'Z,2"Z)-3,3',3"-((triazinobiphenyl-4,1-diyl))tris(amino group))tris(1-(pyridin-4-yl)prop-2-en-1-one);

[0054] [Step 3] 3.0 g of 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one and 1.5 g of 1,3,5-tris(4-aminophenyl)benzene were dissolved in 120 mL of acetic acid and stirred at room temperature for 48 h. After the reaction solution was cooled to room temperature, 250 mL of water was added to quench the reaction, followed by filtration and washing with 100 mL of water four times. The mixture was then dissolved in 700 mL of dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The mixture was then separated and purified by column chromatography (eluent: methanol:ethyl acetate = 1:20) to obtain 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene as a bright yellow solid.

[0055] [Step 4] Dissolve 1.8 g of 3-(dimethylamino)-1-(2-phenyl)-2-propen-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, dried over anhydrous magnesium sulfate, and then rotary evaporated to remove the solvent. Then, it was 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"-((triazabiphenyl([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"-((triazabi(phenyl-4,1-diyl))tris(amino))tris(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 beaker with plastic wrap and react for 1.2 h to obtain a black solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((triphenylazaolefin)triazolo)tris(acryloyl))tris(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 beaker with plastic wrap. After reacting for 1.2 h, a red solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene-1-ammonium chloride is obtained.

[0058] [Step 7] Place 150 mg of (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 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 beaker with plastic wrap. After reacting for 1.2 h, a deep red solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((tris(4,4'-diphenyl)nitride)tris(amino))tris(acryloyl))tris(pyridin-1-ammonium)) chloride is obtained;

[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 the mixture is allowed to stand overnight and filtered. The filter cakes are the different biomimetic two-dimensional supramolecular layers prepared.

[0060] Example 3:

[0061] [Step 1] 35 g of 4-acetylpyridine was dissolved in 56 ml of N,N-dimethylformamide-dimethylacetal, and the mixture was stirred at 105° C. for 2 h. After the reaction solution was cooled to room temperature, the solvent was distilled off under reduced pressure, and then extracted with dichloromethane (100 mL) x 4 times. The mixture was then separated and purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one.

[0062] [Step 2] 4.8 g of 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one and 2 g of tris(4-aminophenyl)amine were dissolved in 150 mL of acetic acid and stirred at room temperature for 48 h. After the reaction solution was cooled to room temperature, 300 mL of water was added to quench the reaction, followed by filtration and washing with 100 mL of water five times. The solution was then dissolved in 1000 mL of dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The solution was then separated and purified by column chromatography (eluent: methanol:ethyl acetate = 1:10) to obtain a dark red solid (2Z,2'Z,2"Z)-3,3',3"-((triazinobiphenyl-4,1-diyl))tris(amino group))tris(1-(pyridin-4-yl)prop-2-en-1-one);

[0063] [Step 3] 4.0 g of 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one and 2 g of 1,3,5-tris(4-aminophenyl)benzene were dissolved in 150 mL of acetic acid and stirred at room temperature for 48 h. After the reaction solution was cooled to room temperature, 300 mL of water was added to quench the reaction, followed by filtration and washing with 100 mL of water five times. The mixture was then dissolved in 1000 mL of dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The mixture was then separated and purified by column chromatography (eluent: methanol:ethyl acetate = 1:20) to obtain 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene as a bright yellow solid.

[0064] [Step 4] Dissolve 2.4 g of 3-(dimethylamino)-1-(2-phenyl)-2-propen-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, dried over anhydrous magnesium sulfate, and then rotary evaporated to remove the solvent. Then, it was 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"-((triazabiphenyl([1,1'-biphenyl]-4',4-diyl))tris(amino group))tris(1-(pyridin-4-yl)prop-2-en-1-one);

[0065] [Step 5] Place 200 mg of (2Z,2'Z,2"Z)-3,3',3"-((triazabi(phenyl-4,1-diyl))tris(amino))tris(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. After reacting for 1.5 hours, a black solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((triphenylazaolefin)triazine)tris(acryloyl))tris(pyridin-1-ammonium)) chloride salt is obtained;

[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 beaker with plastic wrap. After reacting for 1.5 hours, a red solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene-1-ammonium chloride is obtained.

[0067] [Step 7] Place 200 mg of (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 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 beaker with plastic wrap. After reacting for 1.5 hours, a deep red solid 4,4',4"-((2Z,2'Z,2"Z)-3,3',3"-((tris(4,4'-diphenyl)nitride)tris(amino))tris(acryloyl))tris(pyridin-1-ammonium)) chloride is obtained;

[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 the mixture is 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 exhibits a 4 nm lamellar 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 molecules in Example 3 exhibits high hydrogen production activity.

Claims

1. A biomimetic parallel vein-shaped two-dimensional supramolecular layer, characterized by: Utilizing the synergistic effect of aromatic cation-π interactions and hydrogen bonds, three rigid monomers containing pyridinium salts, EG, were self-assembled into a two-dimensional supramolecular layer with a biomimetic parallel vein shape. The three rigid monomers containing pyridinium salts all had C3 symmetry, and the cores of the three monomers were triphenylamine TPA, triphenylbenzene TPB, and triphenylamine TBA, respectively. The precursor BD was then synthesized by linking the pyridine groups via enaminone. Subsequently, the rigid monomers containing pyridinium salts, EG, were synthesized separately through an acidification reaction. A two-dimensional supramolecular layer was formed through hierarchical self-assembly between the multi-arm rigid monomers, and then layered stacking was performed to construct a parallel vein-mimicking structure. The structural formulas of the three rigid monomers EG containing pyridinium salts are: 。 2. 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 terphenylamine TBA are obtained by a synthetic method.

3. A method for preparing the biomimetic parallel vein-shaped two-dimensional supramolecular layer according to claim 1 or 2, characterized in that Here are the steps: Step 1: Dissolve 4-acetylpyridine in N,N-dimethylformamide-dimethyl acetal and react with stirring at 100-105°C for 2-3 hours. After the reaction solution is cooled to room temperature, the solvent is removed by distillation under reduced pressure, followed by extraction with dichloromethane and purification by column chromatography to obtain 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one A as a yellow solid. Step 2: A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one and tris(4-aminophenyl)amine were dissolved in acetic acid and stirred at room temperature for 46 to 50 hours; after the reaction solution was cooled to room temperature, water was added to quench the reaction, followed by filtration and washing with water 3 to 4 times, and then dissolved in dichloromethane, and then dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation, 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))tris(amino group))tris(1-(pyridin-4-yl)prop-2-en-1-one); Step 3: Dissolve A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one and 1,3,5-tris(4-aminophenyl)benzene in acetic acid and stir at room temperature for 46 to 59 hours; after the reaction solution is cooled to room temperature, add water to quench the reaction, then filter and wash with water 3 to 4 times, then dissolve in dichloromethane, and then dry over anhydrous magnesium sulfate and remove the solvent by rotary evaporation. Then, separate and purify by column chromatography to obtain C bright yellow solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enaminobenzene); Step 4: A yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propen-1-one and N4,N4-bis(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine were dissolved in acetic acid and stirred at room temperature for 46 to 50 hours; after the reaction solution was cooled to room temperature, water was added to quench the reaction, followed by filtration and washing with water 3 to 4 times, and then dissolved in dichloromethane, and then dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation, and then separated and purified by column chromatography to obtain D orange solid (2Z,2'Z,2''Z)-3,3',3''-((triazabi([1,1'-biphenyl]-4',4-diyl))tris(amino group))tris(1-(pyridin-4-yl)prop-2-en-1-one); Step 5: Place the dark red solid B (2Z,2'Z,2''Z)-3,3',3''-((triazinobiphenyl-4,1-diyl))tris(amino group))tris(1-(pyridin-4-yl)prop-2-en-1-one) powder in container A, 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''-((triphenylazaolefin)triazine)tris(acryloyl))tris(pyridin-1-ammonium)) chloride; Step 6: Place the bright yellow solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene powder (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, a red solid 1,3,5-tris(4-[pyridine-2-carboxamido]phenyl)-2,4,6-tri(enamino)benzene-1-ammonium chloride; Step 7: Place the 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) powder of D in container E, then place the E container 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''-((tris(4,4'-diphenyl)nitride)tris(amino))tris(acryloyl))tris(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 it stand overnight, filter, and the filter cake is the prepared different biomimetic two-dimensional supramolecular layers.

4. The method according to claim 3, wherein: The step 1 is to dissolve 0.2 to 0.4 moles of 4-acetylpyridine in N,N-dimethylformamide-dimethyl acetal.

5. The method according to claim 3, wherein: In step 2, step 3 and step 4, yellow solid 3-(dimethylamino)-1-(2-phenyl)-2-propene-1-one and tris(4-aminophenyl)amine in a molar ratio of 4:1 to 6:1 are dissolved in acetic acid.

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

7. The method according to claim 3, wherein: 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(enaminoketone)benzene powder in C container.

8. The method according to claim 3, wherein: Place 0.2-0.4 mmol of D orange solid (2Z,2'Z,2''Z)-3,3',3''-((triazabiphenyl([1,1'-biphenyl]-4',4-diyl))tris(amino))tris(1-(pyridin-4-yl)prop-2-en-1-one) powder in E container.

9. The method according to claim 3, wherein: The solution heating is carried out in a constant temperature oil bath; the room temperature stirring reaction is carried out in a constant temperature oil bath at 25°C.

Images