CN114656646A - Synthetic method of diarylene COFs material and application of diarylene COFs material in light-operated adsorption - Google Patents
Synthetic method of diarylene COFs material and application of diarylene COFs material in light-operated adsorption Download PDFInfo
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Abstract
The invention belongs to the field of light-operated stimulus response functional materials, and particularly relates to a synthesis method of diarylene COFs materials and application of the diarylene COFs materials in light-operated adsorption. The invention firstly prepares the covalent organic framework material by Schiff base reaction based on structural units containing alkynyl diaryl alkene and pyrene, and confirms the photochromic property and the light-operated adsorbability to nitrogen and alkyne through follow-up experimental investigation, thereby filling the blank of the photochromic diaryl alkene covalent organic framework material constructed by the rigid plane pyrene structural units and diaryl alkene structural units.
Description
Technical Field
The invention belongs to the field of light-operated stimulus response functional materials, and particularly relates to a synthesis method of diarylene COFs materials and application of the diarylene COFs materials in light-operated adsorption.
Background
Covalent Organic Framework (COFs) is a crystalline porous polymer, mainly composed of C, H, O, N, B and other light elements, and rigid organic structural units (usually benzene, pyrene, biphenyl and the like) are connected together through covalent bonds, so that a two-dimensional or three-dimensional novel topological polymer with regular and ordered pore channels is obtained. Compared with inorganic nano materials, graphite phase carbon nitride materials, disordered organic porous materials and metal organic framework materials, the COF material has the following advantages: 1) good chemical stability, which lays a foundation for the application of the compound in various fields; 2) the regular crystal structure can reduce the number of charge recombination sites and increase the possibility of generating electrons and holes; 3) the uniform pore channel distribution can enhance the mass transfer capacity of reactants and products, thereby improving the reaction efficiency; 4) the high specific surface area can provide more active sites, and some COF materials can selectively adsorb CO2Is favorable for adsorbing, storing and separating CO2(ii) a 5) The energy band structure can be regulated and controlled through chemical modification so as to meet the requirement of photocatalysis on the energy band; 6) COFs have large pi conjugated structures, which make them excellent in light absorption and conductivity. Currently, COF research is rapidly spreading and developing worldwide, and shows a good development situation in the fields of gas adsorption storage, sensing, catalysis, photoelectricity and the like, and thus COF research is a new heat for research in the fields of international chemistry and materials science.
With the development of organic framework compounds, higher requirements are placed on the type and properties of the framework compounds. However, the reported COFs are all fixed rigid structures, and after synthesis, only active sites on the rigid structures can be used for catalysis, filtration and separation, and the like, and particularly, the COFs have great advantages in gas adsorption and storage.
The diarylethene photochromic molecules have the advantages of good chemical stability, excellent thermal stability, obvious fatigue resistance, high sensitivity and the like. Meanwhile, in the photo-induced isomerization process, the molecular structure of the diarylethene is remarkably changed in space structure, and the expressed absorption spectrum, fluorescence emission spectrum, conductivity and the like are remarkably changed. The change of the properties can be applied to encrypted information storage, light-operated molecular switches and the like. Photochromic diarylenes are applied to framework structure materials, but, so far, no photochromic diarylene covalent organic framework material constructed by rigid plane pyrene structure units and diarylene structure units is reported.
Disclosure of Invention
Aiming at the technical problem of the photochromic diaryl alkene covalent organic framework material constructed by the rigid plane pyrene structural unit and the diaryl alkene structural unit, the invention provides a synthetic method of diaryl alkene COFs material which has reasonable formula and simple method and realizes the synthesis of the diaryl alkene organic covalent framework material by the alkynyl diaryl alkene structural unit and the large plane pyrene structural unit through Schiff base reaction and the application of the diaryl alkene COFs material in light-operated adsorption.
In order to achieve the above object, the present invention adopts a technical scheme that the present invention provides a method for synthesizing diarylene COFs materials, comprising the following steps:
a. under the argon atmosphere, 3, 5-dibromo-2-methylthiophene is dissolved in triethylamine, and then cuprous iodide and trimethylsilyl acetylene are sequentially added into tetratriphenylphosphine palladium for later use;
b. b, stirring and mixing the substance obtained in the step a at 45 ℃ for 7 hours, evaporating the solvent under reduced pressure, and purifying a crude product by column chromatography to obtain ((4-bromo-5-methylthiophene-2-yl) ethynyl) trimethylsilane;
c. then, cooling the solution of ((4-bromo-5-methylthiophen-2-yl) ethynyl) trimethylsilane obtained in step b in anhydrous acetone to-78 ℃ under an argon atmosphere, adding n-butyllithium to the resulting solution, and maintaining the temperature at-78 ℃ for 2 h;
d. then the solution obtained in step c was rapidly added with perfluorocyclopentene by syringe and the mixture was stirred at-78 ℃ for another 2h, then the solution was warmed to room temperature and the mixture was stirred for 2h, then diluted with ether, the mixture was washed with diluted hydrochloric acid solution, extracted with ether and dried with anhydrous Na2SO4, the filtrate was evaporated under reduced pressure, and the crude product was purified by column chromatography to obtain ((4,4' - (perfluorocyclopent-1-en-1, 2-diyl) bis (5-methylthiophene-4, 2-diyl)) bis (acetylene-2, 1-diyl)) bis (trimethylsilane);
e. dissolving ((4,4'- (perfluorocyclopent-1-ene-1, 2-diyl) bis (5-methylthiophene-4, 2-diyl)) bis (acetylene-2, 1-diyl)) bis (trimethylsilane) obtained in the step d in methanol or tetrahydrofuran to obtain a solution, adding sodium hydroxide to the solution, stirring at room temperature for 45 minutes, extracting the obtained solution with dichloromethane, washing the organic layer with water, drying the organic layer with anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and purifying the crude product by chromatography to obtain 3,3' - (perfluorocyclopent-1-ene-1, 2-diyl) bis (5-ethynyl-2-methylthiophene);
f. dissolving the 3,3'- (perfluorocyclopent-1-en-1, 2-diyl) bis (5-ethynyl-2-methylthiophene) obtained in the step e in triethylamine under an argon atmosphere, then adding copper iodide and p-iodobenzaldehyde in this order to tetratriphenylphosphine palladium, mixing with triethylamine in which 3,3' - (perfluorocyclopent-1-en-1, 2-diyl) bis (5-ethynyl-2-methylthiophene) is dissolved, stirring at 45 ℃ for 7 hours, evaporating the solvent under reduced pressure, purifying the crude product by column chromatography to obtain 4,4'- ((4,4' - (perfluorocyclopent-1-en-1, 2-diyl) bis (5-methylthiophene-4), 2-diyl)) bis (acetylene-2, 1-diyl)) benzaldehyde;
g. adding a reaction solvent into a pressure-resistant pipe by a disposable injector through 1,3,6, 8-tetra- (p-aminophenyl) -pyrene and 4,4'- ((4,4' - (perfluorocyclopent-1-ene-1, 2-diyl) bis (5-methylthiophene-4, 2-diyl)) bis (acetylene-2, 1-diyl)) benzaldehyde obtained in the step f, freezing the pressure-resistant pipe by a 77K liquid nitrogen bath, performing three freezing-degassing-thawing cycles on the pressure-resistant pipe, pumping negative pressure, sealing the pressure-resistant pipe in a negative pressure state, placing the pressure-resistant pipe in a program control box at 120 ℃ for 3 days, wherein the heating rate is 0.5 ℃/min, obtaining a dark green blocky solid after the reaction is finished, taking out the solid to pass through N, soxhlet extraction and washing with N-dimethylformamide and acetone, then exchanging with methanol, and finally drying the product at 80 ℃ under reduced pressure for 12 hours to obtain the diarylene COFs material.
The diaryl alkene COFs material is applied as a photochromic material.
The diaryl alkene COFs material is applied as a light-operated adsorption material.
Compared with the prior art, the invention has the advantages and positive effects that,
1. the synthesis method of the diaryl alkene COFs material and the application of the diaryl alkene COFs material in light-operated adsorption prove that the photochromic property and the light-operated adsorbability to nitrogen and alkyne are verified by preparing the covalent organic framework material based on structural units containing alkynyl diaryl alkene and pyrene through Schiff base reaction for the first time and researching through subsequent experiments, thereby filling the blank of the photochromic diaryl alkene covalent organic framework material constructed by the rigid plane pyrene structural unit and the diaryl alkene structural unit.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive labor.
FIG. 1 is a structural formula of a diarylene COF provided in example 1;
FIG. 2 is a scheme for the synthesis of 1,3,6, 8-tetrakis- (p-aminophenyl) -pyrene provided in example 1;
FIG. 3 is a schematic diagram of the synthesis of 4,4'- ((4,4' - (perfluorocyclopent-1-en-1, 2-diyl) bis (5-methylthiophene-4, 2-diyl)) bis (acetylene-2, 1-diyl)) benzaldehyde provided in example 1;
FIG. 4 is a synthesis scheme of diarylene COFs materials provided in example 1;
FIG. 5 is a powder diffraction pattern of a diarylene COF provided in example 1;
FIG. 6 is an IR plot of diarylene COFs provided in example 1 in comparison to the feed stock;
FIG. 7 is a thermogram of diarylene COFs provided in example 1;
FIG. 8 is a photochromic absorbance plot of a diarylene COF provided in example 1;
FIG. 9 is a diagram of a photochromic entity of a diarylene COF provided in example 1;
FIG. 10A is a plot of the light-controlled nitrogen specific surface area of a diarylene COF provided in example 1;
fig. 10B is a plot of the light-controlled nitrogen specific surface area of a diarylene COF provided in example 1;
FIG. 11A is a plot of the photo-controlled acetylene specific surface area of a diarylene COF provided in example 1;
fig. 11B is a plot of the photo-controlled acetylene specific surface area of a diarylene COF provided in example 1;
fig. 12 is a photochromic mechanism diagram of diarylene COFs provided in example 1.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be further described with reference to the accompanying drawings and examples. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and thus the present invention is not limited to the specific embodiments of the present disclosure.
Example 1 this example provides a process for the preparation of diarylene COFs, as shown in figures 1-4.
First, 1,3,6, 8-tetra- (p-aminophenyl) -pyrene, was also commercially available, and in this example, a method for preparing 1,3,6, 8-tetra- (p-aminophenyl) -pyrene was provided specifically.
Adding 1,3,6, 8-tetrabromopyrene (1.48g,2.86mmol) into a 100mL three-necked flask under an argon atmosphere, adding 50mL tetrahydrofuran for dissolving and stirring, adding tetrakistriphenylphosphine palladium (58.0mg, 0.05mmol), stirring at room temperature for 30min, adding pinacol 4-aminophenylborate (3.01g,13.7mmol) into the reaction flask for reaction for 10min, adding 60mL (2.0mol L-1) of Na2CO3 aqueous solution into the reaction system, heating to 80 ℃ for 12 h, detecting and tracking the reaction through a thin-layer chromatography dot plate, stopping stirring after the reaction is completed, cooling the reaction system to room temperature, extracting through decompression rotary evaporation of the solvent and adding 120mL dichloromethane for three times, combining organic phases, washing through supersaturated common salt water, drying through anhydrous sodium sulfate, decompressing rotary evaporation, drying in an oven, recrystallizing the crude product through petroleum ether to obtain 1.14g of a light yellow solid product, the yield is 70%. 1HNMR (400MHz, DMSO-d6) δ 8.01(s,3H),7.67(s,1H)7.23(d, J ═ 8.0Hz,8H),6.66(d, J ═ 8.0Hz,8H),5.20(s,8H),3.46(s, 4H). For convenience of the subsequent description, the ligand 1 will be hereinafter referred to in short in view of its presence as a ligand.
Preparation of 4,4'- ((4,4' - (perfluorocyclopent-1-en-1, 2-diyl) bis (5-methylthiophene-4, 2-diyl)) bis (acetylene-2, 1-diyl)) benzaldehyde, which is referred to below as ligand 2, in view of its also presence as ligand.
Preparation of ((4-bromo-5-methylthiophen-2-yl) ethynyl) trimethylsilane
3, 5-dibromo-2-methylthiophene (0.76g, 3.0mmol) was dissolved in triethylamine (100mL) under an argon atmosphere, and then cuprous iodide (26.6mg, 0.14mmol) and Trimethylsilylacetylene (TMSA) (0.4mL, 2.8mmol) were added to tetratriphenylphosphine palladium (93.0mg, 0.08mmol) in this order.
The two were then mixed and the mixture was stirred at 45 ℃ for 7 hours. The solvent was evaporated under reduced pressure. The crude product was purified by column chromatography to give a yellow solid (350mg, yield: 45.5%). 1HNMR (400MHz, CDCl 3): δ 7.02(s,1H), 2.36(s,3H), 0.23(s,9H), i.e., ((4-bromo-5-methylthiophen-2-yl) ethynyl) trimethylsilane.
Preparation of ((4,4' - (perfluorocyclopent-1-en-1, 2-diyl) bis (5-methylthiophene-4, 2-diyl)) bis (acetylene-2, 1-diyl)) bis (trimethylsilane)
A solution of ((4-bromo-5-methylthiophen-2-yl) ethynyl) trimethylsilane (479mg, 1.76mmol) in dry acetone (25mL) was cooled to-78 ℃ under Ar gas atmosphere. N-butyllithium (1.6mol/L in hexane, 2.2mL, 3.5mmol) was added to the resulting solution, and the temperature was held at-78 ℃ for 2 h. Then quickly using a syringePerfluorocyclopentene (0.1mL, 0.8mmol) was added and the mixture was stirred at-78 deg.C for an additional 2 hours. The solution was then warmed to room temperature and the mixture was stirred for 2 hours and then diluted with ether. The mixture was washed with dilute hydrochloric acid solution (1%, 3X 30mL), extracted with diethyl ether (3X 50mL), and washed with anhydrous Na2SO4And (5) drying. The filtrate was evaporated under reduced pressure, and the crude product was purified by column chromatography (silica gel, petroleum ether as eluent) to give a blue-white solid (250mg, yield: 30.0%). 1HNMR (400MHz, CDCl 3): δ 7.19(s,2H), 1.88(s,6H), 0.24(s,18H), i.e., ((4,4' - (perfluorocyclopent-1-en-1, 2-diyl) bis (5-methylthiophene-4, 2-diyl)) bis (acetylene-2, 1-diyl)) bis (trimethylsilane).
Preparation of 3,3' - (perfluorocyclopent-1-ene-1, 2-diyl) bis (5-ethynyl-2-methylthiophene)
To a solution of ((4,4'- (perfluorocyclopent-1-en-1, 2-diyl) bis (5-methylthiophene-4, 2-diyl)) bis (acetylene-2, 1-diyl)) bis (trimethylsilane (250mg, 0.45mmol) in methanol/tetrahydrofuran (4:1, v: v) was added sodium hydroxide (180mg, 4.5mmol), and the mixture was stirred at room temperature for 45 minutes, the resulting solution was extracted with dichloromethane, the organic layer was washed with water, and dried with anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, the crude product was purified by chromatography to give a bluish white solid (130mg, yield: 70.0%). melting point 95-96 ℃ C., 1HNMR (400MHz, CDCl 3): delta 7.24(s,2H), 3.36(s,2H), 1.89(s,6H), i.e. 3,3' - (perfluorocyclopent-1-en-1, 2-diyl) bis (5-ethynyl-2-methylthiophene).
Preparation of 4,4'- ((4,4' - (perfluorocyclopent-1-ene-1, 2-diyl) bis (5-methylthiophene-4, 2-diyl)) bis (acetylene-2, 1-diyl)) benzaldehyde (ligand 2)
3,3' - (perfluorocyclopent-1-ene-1, 2-diyl) bis (5-ethynyl-2-methylthiophene) (1.248g, 3.0mmol) was dissolved in triethylamine (100mL) under an argon atmosphere, and then copper iodide (26.6mg, 0.14mmol) and p-iodobenzaldehyde (1.299g, 5.6mmol) were added to tetratriphenylphosphine palladium (93.0mg, 0.08mmol) in this order.
The two were then mixed and the mixture was stirred at 45 ℃ for 7 hours. The solvent was evaporated under reduced pressure. The crude product was purified by column chromatography to give a blue solid (1.49g, 80%). 1HNMR (400MHz, DMSO-d6) δ 10.04(s,2H),7.96(d, J ═ 7.9Hz,4H),7.78(d, J ═ 8.0Hz,4H),7.54(s,2H),2.02(s,6H), i.e. 4,4'- ((4,4' - (perfluorocyclopent-1-ene-1, 2-diyl) bis (5-methylthiophene-4, 2-diyl)) bis (acetylene-2, 1-diyl)) benzaldehyde.
An analytical balance accurately weighed 128.4mg (0.05mmol) of ligand and 262.4mg (0.1mmol) of ligand in a pressure-resistant tube, and the reaction solvent was added to the pressure-resistant tube by a one-time syringe. The pressure-resistant pipe is frozen through a liquid nitrogen bath at 77K, and three freezing-degassing-unfreezing cycles are carried out on the pressure-resistant pipe. And pumping negative pressure by a pump, sealing the pressure-resistant pipe in a negative pressure state, placing the pressure-resistant pipe in a program temperature control box for 3 days at 120 ℃, and heating at a rate of 0.5 ℃/min. After the reaction was completed, a dark green block-shaped solid was obtained, and the solid was taken out, washed by soxhlet extraction with N, N-dimethylformamide, acetone, and then exchanged with methanol. The product was finally dried at 80 ℃ under reduced pressure for 12 hours to give 39.4mg of a pale yellow solid substance with a yield of 45%.
The obtained pale yellow solid matter was analyzed:
its crystallinity was tested by XRD: shimadzu LabXXRD-6000 is adopted, and an X light source is a copper target (
Rigaku, D/max2500PC) measured angles from 2o to 40o, and the resulting data was imported into FIG. 5 from Origin.
The method is characterized in that a Shimadzuriaffity-1 infrared spectrometer is used, data obtained by KBr tabletting is introduced into an Origin mapping comparison to obtain a graph 6, based on infrared characterization of a diarylene covalent organic framework material, the purpose of infrared is to compare characteristic peaks of the material and reactants to prove that reaction occurs and COF is synthesized, A and B in the graph are respectively ligand 1 and ligand 2, and the graph can clearly show that an N-H stretching vibration peak near 3344cm-1 and a C-O stretching vibration peak near 1700 ═ 1690cm-1 are obviously changed, so that the aldehyde-amine condensation reaction occurs in the reaction, and a product can be COF.
A ceramic crucible is adopted, the heating rate is 10 ℃/min, the temperature is increased from room temperature to 800 ℃, and a thermal decomposition performance test is carried out under the condition, as can be seen from the figure, COF diaryl alkene has guest molecule loss in the temperature range of 100-430 ℃, when the temperature is increased to 500 ℃, the thermogravimetric curve rapidly becomes very steep, the weight loss is obvious, the material begins to collapse, and the skeleton is completely decomposed after 600 ℃. The measured data were imported into Origin mapping to obtain FIG. 7. Thermogravimetric analysis was performed to test the thermal stability of the synthesized framework material.
The diarylene COF solid is placed in a sample cell, the sample cell is placed on a lambda750 ultraviolet visible near-infrared spectrophotometer with an integrating sphere for testing, after the testing, data are converted from reflection to absorption on the instrument, then the data are derived and are plotted by Origin to obtain a graph 8, and a graph 9 is a photo graph before and after ultraviolet illumination is adopted. The photochromic properties of the material obtained in example 1 were confirmed.
In fig. 10A and 10B, an AutosorbiQ ratio meter was used to test the specific surface area, the material was first soaked in 10mL of methanol solvent, methanol was changed every 12 days for 5 times, the filter material was dried in an oven for 6 days, and after activation treatment, the material was used for gas adsorption testing, COF was used for nitrogen gas adsorption-desorption testing, and during the testing, the material was in an open loop state. And then testing nitrogen adsorption-desorption test of closed loops before and after illumination of the diarylene COF material, wherein the gas adsorption quantity is changed due to the change of material pores and structure caused by open and closed loops of diarylene, and the specific surface area is 285.1796m2Change in/g to 140.2729m2The amount of change is about 1/2, and the amount of adsorption changes from 166.64m3Change in/g to 121.39m3A reduction of 45.25 m/g3And g, the open-close ring of the photoinduced material can obviously cause the change of the nitrogen adsorption amount and the specific surface.
In fig. 11A and 12B, the specific surface area of acetylene was measured in the same manner as in nitrogen adsorption. The specific surface area of the open ring state of the diaryl alkene to the acetylene is 86.24m2(g) the specific surface area of the closed diarylene ring to acetylene is 47.66m2(ii) in terms of/g. It is demonstrated that the open-close ring of the light-inducing material can also significantly cause the change of the acetylene gas adsorption amount and the specific surface. The material was confirmed to have significant adsorption to nitrogen and acetylene in light control.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention in other forms, and any person skilled in the art may apply the above modifications or changes to the equivalent embodiments with equivalent changes, without departing from the technical spirit of the present invention, and any simple modification, equivalent change and change made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the technical spirit of the present invention.
Claims (3)
1. A method for synthesizing diarylene COFs materials is characterized by comprising the following steps:
a. under the argon environment, dissolving 3, 5-dibromo-2-methylthiophene in triethylamine, and then sequentially adding cuprous iodide and trimethylsilyl acetylene to tetratriphenylphosphine palladium for later use;
b. b, stirring and mixing the substance obtained in the step a at 45 ℃ for 7 hours, evaporating the solvent under reduced pressure, and purifying a crude product by using column chromatography to obtain ((4-bromo-5-methylthiophene-2-yl) ethynyl) trimethylsilane;
c. then, placing ((4-bromo-5-methylthiophene-2-yl) ethynyl) trimethylsilane obtained in step b in a three-necked flask and cooling to-78 ℃ in an anhydrous acetone solution under an argon atmosphere, adding n-butyllithium to the resulting solution, and maintaining the temperature at-78 ℃ for 2 hours;
d. then the solution obtained in step c is rapidly added with perfluorocyclopentene by syringe and the mixture is stirred at-78 ℃ for a further 2h, then the solution is warmed to room temperature and the mixture is stirred for 2h, then diluted with ether, the mixture is washed with dilute hydrochloric acid solution, extracted with ether and extracted with anhydrous Na2SO4Drying, evaporating the filtrate under reduced pressure, and purifying the crude product by column chromatography to give ((4,4' - (perfluorocyclopent-1-en-1, 2-diyl) bis (5-methylthiophene-4, 2-diyl)) bis (acetylene-2, 1-diyl)) bis (trimethylsilane);
e. dissolving ((4,4'- (perfluorocyclopent-1-ene-1, 2-diyl) bis (5-methylthiophene-4, 2-diyl)) bis (acetylene-2, 1-diyl)) bis (trimethylsilane) obtained in the step d in methanol or tetrahydrofuran to obtain a solution, adding sodium hydroxide to the solution, stirring at room temperature for 45 minutes, extracting the obtained solution with dichloromethane, washing an organic layer with water, drying the organic layer with anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and purifying the crude product by chromatography to obtain 3,3' - (perfluorocyclopent-1-ene-1, 2-diyl) bis (5-ethynyl-2-methylthiophene);
f. dissolving the 3,3'- (perfluorocyclopent-1-en-1, 2-diyl) bis (5-ethynyl-2-methylthiophene) obtained in the step e in triethylamine under an argon atmosphere, then adding copper iodide and p-iodobenzaldehyde in this order to tetratriphenylphosphine palladium, mixing with triethylamine in which 3,3' - (perfluorocyclopent-1-en-1, 2-diyl) bis (5-ethynyl-2-methylthiophene) is dissolved, stirring at 45 ℃ for 7 hours, evaporating the solvent under reduced pressure, purifying the crude product by column chromatography to obtain 4,4'- ((4,4' - (perfluorocyclopent-1-en-1, 2-diyl) bis (5-methylthiophene-4), 2-diyl)) bis (acetylene-2, 1-diyl)) benzaldehyde;
g. adding a reaction solvent into a pressure-resistant pipe by a disposable injector through 1,3,6, 8-tetra- (p-aminophenyl) -pyrene and 4,4'- ((4,4' - (perfluorocyclopent-1-ene-1, 2-diyl) bis (5-methylthiophene-4, 2-diyl)) bis (acetylene-2, 1-diyl)) benzaldehyde obtained in the step f, freezing the pressure-resistant pipe by a 77K liquid nitrogen bath, performing three freezing-degassing-thawing cycles on the pressure-resistant pipe, pumping negative pressure, sealing the pressure-resistant pipe in a negative pressure state, placing the pressure-resistant pipe in a program control box at 120 ℃ for 3 days, wherein the heating rate is 0.5 ℃/min, obtaining a dark green blocky solid after the reaction is finished, taking out the solid to pass through N, sequentially carrying out Soxhlet extraction and washing on N-dimethylformamide and acetone, then exchanging by using methanol, and finally drying the product at 80 ℃ under reduced pressure for 12 hours to obtain the diaryl ene COFs material.
2. Use of diarylene COFs materials according to claim 1 as photochromic materials.
3. The diarylene COFs material of claim 1, which is used as a light-operated adsorbent material.
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