Conductive two-dimensional supramolecular polymer constructed based on aromatic ring cation-pi effect and preparation method of conductive two-dimensional supramolecular polymer

Abstract

The invention discloses a conductive two-dimensional supramolecular polymer constructed based on aromatic ring cation-pi interaction and a preparation method of the conductive two-dimensional supramolecular polymer, and relates to the technical field of supramolecular polymer materials. According to the method, a two-dimensional supramolecular polymer structure is formed by stacking through the head-tail alternating cation-pi action between aromatic ring cationic monomers. The invention provides a preparation method for constructing a conductive two-dimensional supramolecular polymer material through aromatic ring cation-pi action between styryl pyridinium salts, the acting force range of the supramolecular polymer material is further widened, and a new strategy is provided for preparation of the supramolecular polymer material and application of the supramolecular polymer material in the aspect of conductivity.

Description

Technical Field

[0001] The invention relates to the technical field of supramolecular polymer materials, and in particular to a conductive two-dimensional supramolecular polymer constructed based on an aromatic ring cation-π interaction and a preparation method thereof. Background Art

[0002] Two-dimensional supramolecular polymers represent the frontier research at the intersection of polymer science and supramolecular science. They extend monomers in a two-dimensional plane by combining non-covalent forces in two orthogonal dimensions to form periodically arranged polymers. Due to the dynamic reversible nature of non-covalent bonds, supramolecular polymers exhibit many unique properties that traditional covalent polymers do not have. This approach provides an effective way to prepare two-dimensional organic materials and has potential applications in membrane materials and optoelectronics. However, most of the two-dimensional supramolecular polymers developed to date are generally poor conductors, mainly due to insufficient overlap of π orbitals between π-conjugated structural units. Therefore, there is an urgent need to develop effective strategies to design and synthesize two-dimensional supramolecular polymers with good conductivity.

[0003] In the prior art, two-dimensional supramolecular polymers are self-assembled completely by alternating hydrogen bonds through a synergistic mechanism. However, this construction method usually requires the introduction of specific hydrogen bonding groups, which limits the diversity of supramolecular polymer design. In addition, the two-dimensional supramolecular polymer layer constructed by hydrogen bonding lacks strong π electron delocalization and therefore does not have the ability to conduct electricity. Similarly, the strategy of self-assembly driven by host-guest interaction in the prior art is used to construct two-dimensional supramolecular polymers. The adjustable complexation between cucurbituril and bipyridine-containing aromatic guests promotes its self-assembly into a monolayer supramolecular skeleton in solution. However, this method relies on the introduction of specific guests, and the lack of strong π electron delocalization in the layer causes the polymer to have no conductivity. The orderliness of supramolecular polymers directly affects the stability of its materials and the ultimate optoelectronic properties. Summary of the invention

[0004] In order to address the deficiencies in the above-mentioned background technology, the present invention provides a conductive two-dimensional supramolecular polymer constructed based on aromatic ring cation-π interaction and a preparation method thereof, which broadens the scope of the force of supramolecular polymer materials and provides a new strategy for the preparation of supramolecular polymer materials and their application in conductivity.

[0005] In order to achieve the above objectives, the first objective of the present invention is to provide a conductive two-dimensional supramolecular monomer, characterized in that the structural formula of the monomer is: or

[0006] In the formula, X is I - , PF6- or BF4 - .

[0007] A second object of the present invention is to provide a method for preparing the conductive two-dimensional supramolecular monomer according to claim 1, characterized in that it comprises the following steps: Step 1: In a nitrogen atmosphere, 1,3-dibromo-5-(tert-butyl)benzene or 1,4-dibromo-2,5-diethylbenzene, 4-formyl-2-methoxyphenylboronic acid, and tetrakis(triphenylphosphine)palladium are dissolved in ultra-dry 1,2-ethylene glycol dimethyl ether, and stirred at 90° C. for 12 to 24 hours to obtain a white solid 5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarbaldehyde or 2',5'-diethyl-2,2''-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-dicarbaldehyde; Step 2: Dissolve 4-chloromethylpyridine and triphenylphosphine in 1,4-dioxane and reflux to obtain 4-((chlorotriphenylphosphine)-λ 5 -phosphonyl)methyl)pyridine; Step 3: In a nitrogen atmosphere, 5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarbaldehyde or 2',5'-diethyl-2,2''-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-dicarbaldehyde, 4-((chlorotriphenyl)-λ 5 -phosphonyl)methyl)pyridine and sodium hydride are dissolved in ultra-dry THF and cooled to 0°C, and the solution is stirred in an ice bath for 1-2 hours, and then the reactants are moved to room temperature and stirred for 10-15 hours. After the reaction is completed, the product 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine or 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine is obtained; Step 4: Dissolve 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine or 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine and iodomethane in dichloromethane, reflux for 12-24 h in the dark, and react. After the reaction is completed, a yellow solid powder of 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridin-1-ium) or 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridin-1-ium) can be obtained.

[0008] Preferably, the molar ratio of 1,3-dibromo-5-(tert-butyl)benzene or 1,4-dibromo-2,5-diethylbenzene, 4-formyl-2-methoxyphenylboric acid, and tetrakis(triphenylphosphine)palladium is 1:4:0.05:3-6.

[0009] Preferably, the molar ratio of 4-chloromethylpyridine to triphenylphosphine is 1:0.5-1.5. Wherein, the 4-chloromethylpyridine is prepared according to the following steps: Dissolve (chloromethyl)pyridine hydrochloride and sodium bicarbonate in distilled water. After the neutralization reaction is completed, extract with dichloromethane. Dry the extract over anhydrous MgSO4 and concentrate under reduced pressure at 30°C to obtain 4-chloromethylpyridine. The molar ratio of the (chloromethyl)pyridine hydrochloride to sodium bicarbonate is 1:0.5-1.5.

[0010] Preferably, the 5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarbaldehyde or 2',5'-diethyl-2,2''-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-dicarbaldehyde, 4-((chlorotriphenyl-λ 5 -phosphonyl)methyl)pyridine and sodium hydride in a molar ratio of 1:3:1-3; The molar ratio of the 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine or 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine to iodomethane is 1:2~4.

[0011] Preferably, in step 4, after the reaction is completed, the reactant is filtered and then washed with dichloromethane for multiple times; then placed in a 50-60° C. oven and dried for 2-4 hours; In step 3, after the reaction is completed, the mixture is quenched with water, extracted with ethyl acetate, and then separated and purified by column chromatography; In step 2, after reflux reaction for 12 to 24 hours, the mixture is cooled to room temperature, the reactant is filtered, and then the solid is dried under high vacuum at 70 to 80° C. for 2 to 4 hours.

[0012] Preferably, the ultra-dry 1,2-ethylene glycol dimethyl ether is a solvent dried with 5A molecular sieve.

[0013] The third object of the present invention is to provide a conductive two-dimensional supramolecular polymer constructed based on aromatic ring cation-π interaction, wherein the polymer is constructed from the above-mentioned conductive two-dimensional supramolecular monomer based on aromatic ring cation-π interaction.

[0014] The fourth object of the present invention is to provide a method for preparing a conductive two-dimensional supramolecular polymer based on aromatic ring cation-π interaction, comprising the following steps: The conductive two-dimensional supramolecular monomer is dissolved in a DMF solution to prepare a mother solution; The mother solution is added into a mixed solvent of a good solvent and a poor solvent in a volume ratio of 4:4-5, and a conductive two-dimensional supramolecular polymer constructed based on the aromatic ring cation-π interaction is obtained through polymerization reaction; Wherein, the good solvent is DMF and the poor solvent is isopropyl ether.

[0015] The fifth object of the present invention is to provide a conductive two-dimensional supramolecular polymer constructed based on aromatic ring cation-π interaction and its application in transistors or optoelectronic materials.

[0016] Compared with the prior art, the present invention has the following beneficial effects: The present invention provides a conductive two-dimensional supramolecular polymer constructed based on aromatic ring cation-π interaction and a preparation method thereof. The method forms a two-dimensional supramolecular polymer structure by stacking through the head-to-tail alternating cation-π interaction between aromatic ring cation monomers. First, the present invention synthesizes a monomer molecule carrying a two-arm styryl pyridine structure, and obtains the corresponding styryl pyridinium salt through a simple methylation reaction. Then, through the cation-π interaction between the head-to-tail alternating benzene ring and the pyridinium salt cation, an orderly assembly is formed to form a two-dimensional supramolecular structure. The aromatic ring cation-π interaction effectively enhances the π electron interaction between molecular units, thereby giving the two-dimensional supramolecular polymer material good electrical conductivity. This preparation method for constructing supramolecular polymer materials based on aromatic ring cation-π interaction not only broadens the scope of the action force of supramolecular polymer materials, but also provides a new strategy for the preparation of supramolecular polymer materials. The prepared conductive two-dimensional supramolecular polymer material based on aromatic ring cation-π interaction has broad application prospects in the fields of transistors, optoelectronic materials, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a schematic diagram of the structure of the conductive two-dimensional supramolecular polymer material prepared by the method of the present invention; Figure 2 This is the H NMR spectrum of the monomer used to prepare the conductive two-dimensional supramolecular polymer in Example 1; Figure 3 is a representative crystal structure diagram of the conductive two-dimensional supramolecular polymer material prepared in Example 1; Figure 4 is an image of the conductive two-dimensional supramolecular polymer material prepared in Example 1 under an atomic force microscope; Figure 5 is the IV curve of the conductive two-dimensional supramolecular polymer material prepared in Example 1; Figure 6 This is the H NMR spectrum of the monomer used to prepare the conductive two-dimensional supramolecular polymer in Example 2; Figure 7 This is a representative crystal structure diagram of the conductive two-dimensional supramolecular polymer material prepared in Example 2. DETAILED DESCRIPTION

[0018] In order to enable those skilled in the art to better understand and implement the technical solution of the present invention, the present invention is further described below in conjunction with specific embodiments and drawings, but the embodiments are not intended to limit the present invention.

[0019] The first aspect of the present invention provides a conductive two-dimensional supramolecular monomer, the structural formula of the monomer is: or

[0020] In the formula, X is I - , PF6 - or BF4 - .

[0021] It should be noted that the X anion has no specific substitution position because the pyridinium cation plays a role in balancing the charge.

[0022] A second aspect of the present invention provides a method for preparing the conductive two-dimensional supramolecular monomer according to claim 1, comprising the following steps: Step 1: In a nitrogen atmosphere, 1,3-dibromo-5-(tert-butyl)benzene or 1,4-dibromo-2,5-diethylbenzene, 4-formyl-2-methoxyphenylboronic acid, and tetrakis(triphenylphosphine)palladium are dissolved in ultra-dry 1,2-ethylene glycol dimethyl ether, and stirred at 90° C. for 12 to 24 hours to obtain a white solid 5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarbaldehyde or 2',5'-diethyl-2,2''-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-dicarbaldehyde; Step 2: Dissolve 4-chloromethylpyridine and triphenylphosphine in 1,4-dioxane and reflux to obtain 4-((chlorotriphenylphosphine)-λ 5 -phosphonyl)methyl)pyridine; Step 3: In a nitrogen atmosphere, 5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarbaldehyde or 2',5'-diethyl-2,2''-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-dicarbaldehyde, 4-((chlorotriphenyl)-λ 5 -phosphonyl)methyl)pyridine and sodium hydride are dissolved in ultra-dry THF and cooled to 0°C, and the solution is stirred in an ice bath for 1-2 hours, and then the reactants are moved to room temperature and stirred for 10-15 hours. After the reaction is completed, the product 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine or 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine is obtained; Step 4: Dissolve 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine or 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine and iodomethane in dichloromethane, reflux for 12-24 h in the dark, and react. After the reaction is completed, a yellow solid powder of 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridin-1-ium) or 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridin-1-ium) can be obtained.

[0023] Wherein, the molar ratio of the 1,3-dibromo-5-(tert-butyl)benzene or 1,4-dibromo-2,5-diethylbenzene, 4-formyl-2-methoxyphenylboric acid and tetrakis(triphenylphosphine)palladium is 1:4:0.05:3-6.

[0024] The molar ratio of the 4-chloromethylpyridine to triphenylphosphine is 1:0.5-1.5, wherein the 4-chloromethylpyridine is prepared according to the following steps: Dissolve (chloromethyl)pyridine hydrochloride and sodium bicarbonate in distilled water. After the neutralization reaction is completed, extract with dichloromethane. Dry the extract over anhydrous MgSO4 and concentrate under reduced pressure at 30°C to obtain 4-chloromethylpyridine. The molar ratio of the (chloromethyl)pyridine hydrochloride to sodium bicarbonate is 1:0.5-1.5.

[0025] The 5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarboxaldehyde or 2',5'-diethyl-2,2''-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-dicarboxaldehyde, 4-((chlorotriphenyl-λ 5 -phosphonyl)methyl)pyridine and sodium hydride in a molar ratio of 1:3:1-3; The molar ratio of the 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine or 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine to iodomethane is 1:2~4.

[0026] In step 4, after the reaction is completed, the reactant is filtered and washed with dichloromethane for multiple times; then placed in a 50-60°C oven and dried for 2-4 hours; In step 3, after the reaction is completed, the mixture is quenched with water, extracted with ethyl acetate, and then separated and purified by column chromatography; In step 2, after reflux reaction for 12 to 24 hours, the mixture is cooled to room temperature, the reactant is filtered, and then the solid is dried under high vacuum at 70 to 80° C. for 2 to 4 hours.

[0027] The ultra-dry 1,2-ethylene glycol dimethyl ether is a solvent dried with a 5A molecular sieve.

[0028] In one embodiment, a conductive two-dimensional supramolecular polymer material constructed based on aromatic ring cation-π interaction, the structural formula of the monomer molecule is:

[0029] A method for preparing a conductive two-dimensional supramolecular polymer material based on aromatic ring cation-π interaction, the preparation steps of which are as follows: Step 1: In a nitrogen atmosphere, 1,3-dibromo-5-(tert-butyl)benzene / 1,4-dibromo-2,5-diethylbenzene, 4-formyl-2-methoxyphenylboronic acid, and tetrakis(triphenylphosphine)palladium in a molar ratio of 1:4:0.05:5 were dissolved in ultra-dry 1,2-ethylene glycol dimethyl ether (DME), and stirred at 90°C for overnight reaction; after the reaction solution was cooled to room temperature, it was extracted with dichloromethane, and then separated and purified by column chromatography to obtain a white solid 5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diformaldehyde / 2',5'-diethyl-2,2''-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-dicarbaldehyde; super dry 1,2-ethylene glycol dimethyl ether is the solvent after drying with 5A molecular sieve.

[0030] Step 2: Dissolve (chloromethyl) pyridine hydrochloride and sodium bicarbonate in distilled water at a molar ratio of 1:1, and stir the reaction at room temperature for 20 minutes; after neutralization, extract with dichloromethane, dry the extract over anhydrous MgSO4, and concentrate under reduced pressure at 30°C to obtain a light yellow oily product 4-chloromethyl pyridine; then immediately dissolve 4-chloromethyl pyridine and triphenylphosphine in a molar ratio of 1:1 in 1,4-dioxane; heat and reflux for 14 hours, and then cool to room temperature. Filter the solution, and then dry the solid at high vacuum at 75°C for 2 hours to obtain a pink solid powder product 4-((chlorotriphenyl-λ 5 -phosphonyl)methyl)pyridine.

[0031] Step 3: In a nitrogen atmosphere, 5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarbaldehyde / 2',5'-diethyl-2,2''-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-dicarbaldehyde, 4-((chlorotriphenyl)-λ 5 -phosphonyl)methyl)pyridine and sodium hydride were dissolved in ultra-dry THF and cooled to 0 °C, and the solution was stirred in an ice bath for 1 hour. The reactants were then moved to room temperature and stirred for 13 hours. After the reaction was completed, it was quenched with water. It was extracted with ethyl acetate and then separated and purified by column chromatography to obtain the product 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine / 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine, which was a white solid powder.

[0032] Step 4: Dissolve 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine / 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine and iodomethane in a molar ratio of 1:3 in dichloromethane and reflux overnight in the dark. After the reaction is completed, the mixture is filtered and washed with dichloromethane for three times; then, it is placed in a 60°C oven and dried for 3 hours to obtain a yellow solid powder 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridin-1-ium) / 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridin-1-ium).

[0033] All the solutions were heated in a constant temperature oil bath.

[0034] All reactions were carried out in an oil bath at 25°C.

[0035] The third aspect of the present invention provides a conductive two-dimensional supramolecular polymer constructed based on aromatic ring cation-π interaction, wherein the polymer is constructed from the above conductive two-dimensional supramolecular monomer based on aromatic ring cation-π interaction.

[0036] A fourth aspect of the present invention provides a method for preparing a conductive two-dimensional supramolecular polymer constructed based on an aromatic ring cation-π interaction, comprising the following steps: The conductive two-dimensional supramolecular monomer is dissolved in a DMF solution to prepare a mother solution; The mother solution is added into a mixed solvent of a good solvent and a poor solvent in a volume ratio of 4:4-5, and a conductive two-dimensional supramolecular polymer constructed based on the aromatic ring cation-π interaction is obtained through polymerization reaction; Wherein, the good solvent is DMF and the poor solvent is isopropyl ether.

[0037] In one embodiment, see Figure 1 As shown, a method for preparing a conductive two-dimensional supramolecular polymer based on aromatic ring cation-π interaction comprises: Step 1: Take 1.67 mg of the previously prepared powder 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridin-1-ium) or 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridin-1-ium) and dissolve it in DMF solution to prepare 2×10 -3 mol / L of mother solution.

[0038] Step 2: Take 20 μL of the above mother solution into a sample bottle, and then use a pipette to add 800 μL of DMF good solvent and 1000 μL of isopropyl ether poor solvent to prepare a 2×10 -5 mol / L polymer solution, and then after the solvent in the polymer solution evaporates, a conductive two-dimensional supramolecular polymer constructed based on the aromatic ring cation-π interaction is obtained.

[0039] A fifth aspect of the present invention provides an application of a conductive two-dimensional supramolecular polymer constructed based on aromatic ring cation-π interaction in transistors or optoelectronic materials.

[0040] It should be noted that the experimental methods used in the present invention are all conventional methods unless otherwise specified; the reagents and materials used are all commercially available unless otherwise specified. The details are as follows: Example 1 A method for preparing a conductive two-dimensional supramolecular polymer based on aromatic ring cation-π interaction comprises the following steps: A mixture of 4-formyl-2-methoxyphenylboronic acid (3.94 g, 22 mmol), 1,3-dibromo-5-(tert-butyl)benzene (1.6 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium (317 mg, 0.27 mmol) and K2CO3 (3.79 g, 27.4 mmol) in 1,2-ethylene glycol dimethyl ether (DME) (150 mL) was stirred at 90°C for 12 hours under nitrogen; after cooling to room temperature, the mixture was poured into H2O and extracted with dichloromethane. The extract was dried over anhydrous MgSO4; after filtration and concentration under reduced pressure, the product 5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarbaldehyde was obtained by silica gel column chromatography (petroleum ether / ethyl acetate 5 / 1, v / v) as a white solid powder.

[0041] Commercially available (chloromethyl)pyridine hydrochloride (5g, 30.7mmol) was dissolved in water (100mL), sodium bicarbonate (3g, 35.7mmol excess) was added in batches, and the solution was stirred for 20 minutes; after neutralization, the mixture was poured into water and extracted with dichloromethane. The extract was dried over anhydrous MgSO4; after concentration under reduced pressure at 30°C, a pale yellow oily product 4-chloromethylpyridine (3.9g, 100%) was obtained. Immediately thereafter, the obtained crude product was dissolved in 1,4-dioxane (150mL) and triphenylphosphine (8g) was added; the reaction mixture was heated to reflux for 14 hours and then cooled to room temperature. The solution was filtered, and the solid was then dried at high vacuum at 75°C for 2 hours to obtain a pink solid powder product 4-((chlorotriphenyl-λ 5 -phosphonyl)methyl)pyridine.

[0042] 4-((chlorotriphenyl-λ 5 -phosphonyl)methyl)pyridine (0.87g, 2.2mmol) was dissolved in ultra-dry THF (120mL) and cooled to 0 ° C. Sodium hydride (0.072g, 3mmol, 60% dispersed in mineral oil) was quickly added, and the solution was stirred in an ice bath for 1 hour. Then 5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diformaldehyde (0.3g, 0.75mmol) was added, and the reactants were warmed to room temperature and stirred for 13 hours. After the reaction was completed, it was quenched with water. The two-phase system was extracted three times with EtOAc. The extract was dried over anhydrous MgSO4; filtered and concentrated under reduced pressure, and then silica gel column chromatography (petroleum ether / ethyl acetate 1 / 1, v / v) was used to obtain the product 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine as a white solid powder.

[0043] 70 mg of white solid powder of 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine was dissolved in dichloromethane (80 mL), and then distilled iodomethane (3 mL, excess) was added; it was refluxed overnight under light-proof conditions. After the reaction was completed, it was filtered and washed with dichloromethane three times; then it was placed in a 60°C oven and dried for 3 hours to obtain a yellow solid powder 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridin-1-ium).

[0044] Take 1.67 mg of the powder 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridin-1-ium) prepared in the previous step and dissolve it in DMF solution to prepare 2×10 -3 mol / L of mother solution.

[0045] Then, 20 μL of the mother solution was taken into a sample bottle, and then 800 μL of DMF good solvent and 1000 μL of isopropyl ether poor solvent were added using a pipette to prepare a 2×10-60% ethanol solution with a volume ratio of good solvent to poor solvent of 1:1. - 5 mol / L polymer solution, and then after the solvent in the polymer solution evaporates, a conductive two-dimensional supramolecular polymer constructed based on the aromatic ring cation-π interaction is obtained.

[0046] from Figure 2 It can be seen from the H NMR spectrum that the conductive two-dimensional supramolecular polymer molecules prepared in Example 1 have been successfully synthesized; from Figure 3 It can be seen from the crystal structure diagram that the conductive two-dimensional supramolecular polymer material prepared in Example 1 presents a two-dimensional layered structure; from Figure 4 It can be seen from the image under the atomic force microscope that the conductive two-dimensional supramolecular polymer material prepared in this Example 1 presents a typical two-dimensional sheet structure; from Figure 5 It can be seen from the IV curve that the conductive two-dimensional supramolecular polymer prepared in this Example 1 has good electrical conductivity.

[0047] Example 2 A method for preparing a conductive two-dimensional supramolecular polymer based on aromatic ring cation-π interaction comprises the following steps: A mixture of 4-formyl-2-methoxyphenylboronic acid (3.94 g, 22 mmol), 1,4-dibromo-2,5-diethylbenzene (1.6 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (317 mg, 0.27 mmol) and K2CO3 (3.79 g, 27.4 mmol) in 1,2-ethylene glycol dimethyl ether (DME) (150 mL) was stirred at 90°C for 12 hours under nitrogen; after cooling to room temperature, the mixture was poured into H2O and extracted with dichloromethane. The extract was dried over anhydrous MgSO4; after filtration and concentration under reduced pressure, the product 2',5'-diethyl-2,2''-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-dicarbaldehyde was obtained by silica gel column chromatography (petroleum ether / ethyl acetate 5 / 1, v / v) as a white solid powder.

[0048] Commercially available (chloromethyl) pyridine hydrochloride (5 g, 30.7 mmol) was dissolved in water (100 mL), sodium bicarbonate (3 g, 35.7 mmol excess) was added in batches, and the solution was stirred for 20 minutes; after neutralization, the mixture was poured into water and extracted with dichloromethane. The extract was dried over anhydrous MgSO4; after concentration under reduced pressure at 30°C, a pale yellow oily product (3.9 g, 100%) was obtained. Immediately thereafter, the obtained crude product was dissolved in 1,4-dioxane (150 mL) and triphenylphosphine (8 g) was added; the reaction mixture was heated to reflux for 14 hours and then cooled to room temperature. The solution was filtered, and the solid was then dried at high vacuum at 75°C for 2 hours to obtain a pink solid powder product 4-((chlorotriphenyl-λ 5 -phosphonyl)methyl)pyridine.

[0049] 4-((chlorotriphenyl-λ 5 -phosphonyl)methyl)pyridine (0.87g, 2.2mmol) was dissolved in ultra-dry THF (120mL) and cooled to 0 ° C. Sodium hydride (0.072g, 3mmol, 60% dispersed in mineral oil) was quickly added, and the solution was stirred in an ice bath for 1 hour. Then 2', 5'-diethyl-2,2''-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-diformaldehyde (0.3g, 0.75mmol) was added, and the reactant was warmed to room temperature and stirred for 13 hours. After the reaction was completed, it was quenched with water. The two-phase system was extracted three times with EtOAc. The extract was dried over anhydrous MgSO4; filtered and concentrated under reduced pressure, and then silica gel column chromatography (petroleum ether / ethyl acetate 1 / 1, v / v) was used to obtain the product 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine as a white solid powder.

[0050] Take 70 mg of white solid powder of 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine and dissolve it in dichloromethane (80 mL), then add distilled iodomethane (3 mL, excess); reflux it overnight under light-proof conditions. After the reaction is completed, filter it with suction, wash it with dichloromethane three times, and then put it in a 60°C oven to dry for 3 hours to obtain a yellow solid powder 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridin-1-ium).

[0051] Take 1.67 mg of the powder 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridin-1-ium) prepared in the previous step and dissolve it in DMF solution to prepare 2×10 -3 mol / L of mother solution.

[0052] Then, 20 μL of the mother solution was taken into a sample bottle, and then 800 μL of DMF good solvent and 1000 μL of isopropyl ether poor solvent were added using a pipette to prepare a 2×10-60% ethanol solution with a volume ratio of good solvent to poor solvent of 1:1. - 5 mol / L polymer solution, and then after the solvent in the polymer solution evaporates, a conductive two-dimensional supramolecular polymer constructed based on the aromatic ring cation-π interaction is obtained.

[0053] from Figure 6 It can be seen from the H NMR spectrum that the conductive two-dimensional supramolecular polymer molecules prepared in Example 2 have been successfully synthesized; from Figure 7 It can be seen from the crystal structure diagram that the conductive two-dimensional supramolecular polymer material prepared in Example 2 presents a two-dimensional layered structure.

[0054] The present invention mainly designs the polymer monomer structure to make the constructed two-dimensional supramolecular polymer have conductivity, but most of the two-dimensional supramolecular polymers constructed by non-covalent interactions currently do not have conductivity.

Claims

1. A conductive two-dimensional supramolecular monomer, characterized in that: The structural formula of the monomer is: or In the formula, X is I - , PF6 - or BF4 - .

2. A method for preparing the conductive two-dimensional supramolecular monomer according to claim 1, characterized in that: The following steps are involved: Step 1: In a nitrogen atmosphere, 1,3-dibromo-5-(tert-butyl)benzene or 1,4-dibromo-2,5-diethylbenzene, 4-formyl-2-methoxyphenylboronic acid, and tetrakis(triphenylphosphine)palladium are dissolved in ultra-dry 1,2-ethylene glycol dimethyl ether, and stirred at 90° C. for 12 to 24 hours to obtain a white solid 5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarbaldehyde or 2',5'-diethyl-2,2''-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-dicarbaldehyde; Step 2: Dissolve 4-chloromethylpyridine and triphenylphosphine in 1,4-dioxane and reflux to obtain 4-((chlorotriphenylphosphine)-λ 5 -phosphonyl)methyl)pyridine; Step 3: In a nitrogen atmosphere, 5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarbaldehyde or 2',5'-diethyl-2,2''-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-dicarbaldehyde, 4-((chlorotriphenyl)-λ 5 -phosphonyl)methyl)pyridine and sodium hydride are dissolved in ultra-dry THF and cooled to 0°C, and the solution is stirred in an ice bath for 1-2 hours, and then the reactants are moved to room temperature and stirred for 10-15 hours. After the reaction is completed, the product 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine or 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine is obtained; Step 4: Dissolve 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine or 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine and iodomethane in dichloromethane, reflux for 12-24 h in the dark, and react. After the reaction is completed, a yellow solid powder of 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridin-1-ium) or 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bis(1-methylpyridin-1-ium) can be obtained.

3. The method for preparing a conductive two-dimensional supramolecular monomer according to claim 2, characterized in that: The molar ratio of the 1,3-dibromo-5-(tert-butyl)benzene or 1,4-dibromo-2,5-diethylbenzene, 4-formyl-2-methoxyphenylboric acid and tetrakis(triphenylphosphine)palladium is 1:4:0.05:3-6.

4. The method for preparing a conductive two-dimensional supramolecular monomer according to claim 2, characterized in that: The molar ratio of 4-chloromethylpyridine to triphenylphosphine is 1:0.5-1.5, Wherein, the 4-chloromethylpyridine is prepared according to the following steps: Dissolve (chloromethyl)pyridine hydrochloride and sodium bicarbonate in distilled water. After the neutralization reaction is completed, extract with dichloromethane. Dry the extract over anhydrous MgSO4 and concentrate under reduced pressure at 30°C to obtain 4-chloromethylpyridine. The molar ratio of the (chloromethyl)pyridine hydrochloride to sodium bicarbonate is 1:0.5-1.

5.

5. The method for preparing a conductive two-dimensional supramolecular monomer according to claim 2, characterized in that: The 5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarboxaldehyde or 2',5'-diethyl-2,2''-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-dicarboxaldehyde, 4-((chlorotriphenyl-λ 5 -phosphonyl)methyl)pyridine and sodium hydride in a molar ratio of 1:3:1-3; The molar ratio of the 4,4'-((1E,1'E)-(5'-(tert-butyl)-2,2''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine or 4,4'-((1E,1'E)-(2',5'-diethyl-[1,1':4',1''-terphenyl]-4,4''-diyl)bis(ethylene-2,1-diyl))bipyridine to iodomethane is 1:2~4.

6. The method for preparing a conductive two-dimensional supramolecular monomer according to claim 2, characterized in that: In step 4, after the reaction is completed, the reactant is filtered and washed with dichloromethane for multiple times; then placed in a 50-60°C oven and dried for 2-4 hours; In step 3, after the reaction is completed, the mixture is quenched with water, extracted with ethyl acetate, and then separated and purified by column chromatography; In step 2, after reflux reaction for 12 to 24 hours, the mixture is cooled to room temperature, the reactant is filtered, and then the solid is dried under high vacuum at 70 to 80° C. for 2 to 4 hours.

7. The method for preparing a conductive two-dimensional supramolecular monomer according to claim 2, characterized in that: The ultra-dry 1,2-ethylene glycol dimethyl ether is a solvent dried with a 5A molecular sieve.

8. A conductive two-dimensional supramolecular polymer constructed based on aromatic ring cation-π interaction, characterized in that: The polymer is constructed by the conductive two-dimensional supramolecular monomer described in claim 1 based on the aromatic ring cation-π interaction.

9. A method for preparing a conductive two-dimensional supramolecular polymer based on aromatic ring cation-π interaction as claimed in claim 8, characterized in that: The following steps are involved: The conductive two-dimensional supramolecular monomer is dissolved in a DMF solution to prepare a mother solution; The mother solution is added into a mixed solvent of a good solvent and a poor solvent in a volume ratio of 4:4-5, and a conductive two-dimensional supramolecular polymer constructed based on the aromatic ring cation-π interaction is obtained through polymerization reaction; Wherein, the good solvent is DMF and the poor solvent is isopropyl ether.

10. Use of the conductive two-dimensional supramolecular polymer constructed based on aromatic ring cation-π interaction as claimed in claim 8 in transistors or optoelectronic materials.

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