CN113388127A - Triphenylene group-containing hydrogen bond organic framework compound and preparation method thereof - Google Patents
Triphenylene group-containing hydrogen bond organic framework compound and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrogen bond organic framework compound containing triphenylene groups and a preparation method thereof. The method comprises the steps of taking 2,3,6,7,10, 11-hexabromotriphenylene and 4-acetylenic ethyl benzoate as raw materials, obtaining hexa (4-ethyl benzoate alkynyl) triphenylene through a coupling reaction, further hydrolyzing to obtain hexa (4-carboxyl phenyl ethynyl) triphenylene, and finally obtaining the hydrogen bond organic framework compound containing triphenylene groups through steam diffusion. The preparation method has the advantages of simple route and process, mild reaction conditions, high yield and good repeatability. The hydrogen bond organic framework compound containing triphenylene groups has multiple hydrogen bonds and aromatic ring pi-pi stacking effect in the structure, has the property of constant pores, and the BET specific surface area can reach 1560m2/g。
Description
Technical Field
The invention relates to a hydrogen bond organic framework compound and a preparation method thereof, in particular to a hydrogen bond organic framework compound containing triphenylene groups and a preparation method thereof, which are applied to the technical field of porous materials and preparation processes thereof.
Background
The hydrogen bond organic framework compound is becoming a hot point of porous material research as a novel porous framework material appearing in the last decade, and meanwhile, the regulation and control effect of the hydrogen bond on the porous material structure is more and more paid attention by people. Compared with other porous frame materials, the hydrogen bond organic frame compound is simpler and more convenient in preparation method and milder in preparation conditions, avoids the harsh hydrothermal or solvothermal conditions required by the preparation of other frame compounds, uses the crystallization conditions which are easy to control such as evaporation, cooling or solvent diffusion and the like, and can effectively regulate and control the frame structure; the recyclability and repeatability of the hydrogen bond organic framework compound are also superior to other framework compounds; furthermore, hydrogen-bonded organic framework compounds may also exhibit unique advantages in gas storage and separation. By comprehensively regulating pore characteristics such as pores, pore diameters, active sites and the like, the hydrogen bond organic framework compound can realize the property of constant pores, has the functions of storing and separating specific gas, and further shows potential application prospects in the fields of catalysis, luminescence, energy sources and the like.
Hydrogen-bonded organic framework compounds generally have the disadvantage of low stability and easy collapse of the framework structure due to the weak strength of the hydrogen bonds. Therefore, the development of highly stable hydrogen bonding organic framework compounds with permanent porosity is a challenge in current research. In the face of these problems, on one hand, the symmetry of the framework compound can be regulated and controlled through the geometric configuration of the organic ligand, and the pore characteristics of the framework compound can be further reasonably regulated; on the other hand, the stability of the framework can be improved by increasing the number of hydrogen bonding bonds and enhancing the interaction among groups.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects of the prior art and provide a hydrogen bond organic framework compound containing triphenylene groups and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hydrogen bond organic framework compound containing triphenylene groups has a structural element of hexa (4-carboxyphenylethynyl) triphenylene, multiple hydrogen bonding effects and pi-pi stacking effects of aromatic ring planes exist in the compound, the compound has high structural stability, and high BET specific surface area and hydrogen adsorption capacity can be shown after guest solvent molecules are removed. The invention adopts a characteristic rigid plane structure of triphenylene groups, and strong pi-pi stacking effect exists between the groups. Triphenylene is used as a parent, a plurality of carboxyl groups are introduced through the connection of acetylene bonds, and the structural stability of the hydrogen bond organic framework compound is realized by utilizing the hydrogen bond linkage action of the carboxyl groups and the pi-pi accumulation action of an aromatic ring plane, so that the framework compound has wide application prospect.
Preferably, the compound has better structural stability, the framework of the compound shows a constant pore property after removing guest solvent molecules, and the BET specific surface area is not less than 1560m2G, Langmiur specific surface area not less than 1642m2A hydrogen adsorption amount of not less than 112cm at 77K and 100kPa3/g。
Preferably, the compound is crystallized in an orthorhombic system Pnc2 space group, six (4-carboxyphenylethynyl) triphenylene structural elements are connected through multiple hydrogen bonds to form a three-dimensional framework structure with a double-insertion characteristic, and the pi-pi stacking effect of an aromatic ring plane exists between two sets of frameworks in a double-insertion relationship.
Preferably, the compound structure has one-dimensional pore channels with two sizes respectively
And
the invention relates to a preparation method of a hydrogen bond organic framework compound containing triphenylene groups, which adopts the following synthetic steps:
preparation of ethyl 4-trimethylsilyl alkynyl benzoate:
dissolving ethyl p-iodobenzoate in triethylamine, and deoxidizing the solution by bubbling nitrogen for at least 30 minutes; then sequentially adding bis (triphenylphosphine) palladium dichloride, cuprous iodide and triphenylphosphine, and then carrying out nitrogen bubbling to remove oxygen for at least 30 minutes; adding trimethylsilylacetylene through an injector, and stirring and reacting for at least 24 hours at normal temperature; after the reaction is finished, performing post-treatment to obtain 4-trimethylsilyl propargyl ethyl benzoate;
b, preparation of ethyl 4-alkynylbenzoate:
firstly, adding the 4-trimethylsilyl alkynyl ethyl benzoate prepared in the step a into absolute ethyl alcohol, then adding potassium carbonate, and reacting at room temperature for at least 12 hours; after post-treatment, 4-alkynyl ethyl benzoate is obtained;
c. hexa (4-ethylcarbamoylalkynyl) triphenylene preparation:
adding the ethyl 4-alkynylbenzoate prepared in the step b and 2,3,6,7,10, 11-hexabromotriphenylene into a Schlenk bottle, then adding tetrahydrofuran and diisopropylamine, and carrying out nitrogen bubbling for deoxygenation for at least 30 minutes; then adding bis (triphenylphosphine) palladium dichloride, cuprous iodide and triphenylphosphine, and continuing nitrogen bubbling for deoxygenation for at least 30 minutes; heating and reacting at a temperature of not less than 85 ℃ for at least 48 hours; then the reaction mixture was cooled to room temperature, and tetrahydrofuran and dichloromethane were added to the mixture to completely dissolve the solid; vacuum filtering with diatomite, concentrating the filtrate, and separating by silica gel column chromatography to obtain yellow solid; adding ethanol into the yellow solid, stirring and washing the mixture at room temperature for at least 12 hours, centrifuging and collecting the solid, and drying to obtain hexa (4-ethyl benzoate alkynyl) triphenylene;
d. preparation of hexa (4-carboxyphenylethynyl) triphenylene:
dissolving the hexa (4-ethylcarbamoylalkynyl) triphenylene prepared in the step c in tetrahydrofuran, and then adding a potassium hydroxide solution; heating reflux reaction at 65 deg.c for at least 48 hr; cooling to room temperature, and performing post-treatment to obtain hexa (4-carboxyphenylethynyl) triphenylene;
e. preparation of triphenylene group-containing hydrogen bonding organic framework compound:
and (3) carrying out solvent vapor diffusion crystallization, dissolving the hexa (4-carboxyphenylethynyl) triphenylene prepared in the step (d) in DMSO to obtain a mixed solution, placing an open container containing the mixed solution in a closed bottle filled with an acetone atmosphere, standing, and diffusing through acetone vapor to obtain the target framework compound in a yellow needle shape.
Preferably, the post-treatment operation is at least one of vacuum filtration of diatomite, solvent extraction, washing with saturated sodium chloride, vacuum concentration and silica gel column chromatography.
Preferably, in said step a, the total oxygen removal time is not less than 1 hour.
Preferably, in the step a, the feeding molar ratio of the ethyl p-iodobenzoate, the trimethylsilylacetylene, the bis (triphenylphosphine) palladium dichloride, the cuprous iodide and the triphenylphosphine is 1:1.5:0.04:0.024: 0.016.
Preferably, in said step c, the total oxygen removal time is not less than 1 hour.
Preferably, in the step c, the volume ratio of tetrahydrofuran to diisopropylamine is 1:1.
Preferably, in the step c, the feeding molar ratio of the 2,3,6,7,10, 11-hexabromotriphenylene, the ethyl 4-alkynylbenzoate, the bis (triphenylphosphine) palladium dichloride, the cuprous iodide and the triphenylphosphine is 1:18:0.25:0.5: 0.5.
Preferably, in the step c, 0.57-1.17mmol of 2,3,6,7,10, 11-hexabromotriphenylene and 10.35-21.14mmol of ethyl 4-alkynylbenzoate are weighed in a 150-mL Schlenk bottle, 40-65mL of each of tetrahydrofuran and diisopropylamine is weighed and dissolved, nitrogen is bubbled for deoxygenation for at least 30 minutes, then 0.15-0.30mmol of bis (triphenylphosphine) palladium dichloride, 0.30-0.60mmol of cuprous iodide and 0.29-0.59mmol of triphenylphosphine are sequentially added, and nitrogen is bubbled for deoxygenation for at least 30 minutes; then reacting at a temperature of not less than 85 ℃ for at least 48 hours to obtain brown yellow oily liquid and earthy yellow precipitate; tetrahydrofuran and dichloromethane were then added to the reaction mixture and the solids were almost completely dissolved; filtering with diatomite, and removing solvent from the filtrate under reduced pressure to obtain a brownish red solid; separating and purifying the crude product by silica gel column chromatography, and obtaining a yellow solid by using a mixed reagent of ethyl acetate and dichloromethane in a mass ratio of 5:1 as an eluent; and soaking the obtained yellow solid in ethanol, stirring for at least 12 hours, centrifuging, carrying out vacuum filtration, and drying in vacuum to obtain hexa (4-ethyl benzoate alkynyl) triphenylene.
Preferably, in the step d, the feeding molar ratio of the hexa (4-ethyl-benzoate alkynyl) triphenylene to the potassium hydroxide is 1: 76.
Preferably, in the step d, the volume ratio of water to tetrahydrofuran is 1: 2.
Preferably, in the step e, solvent vapor is used for diffusion crystallization, and the volume ratio of dimethyl sulfoxide to acetone is 1: 6.
Preferably, in the step e, 8.20mg of hexa (4-carboxyphenylethynyl) triphenylene is weighed into a sample bottle, 2-4mL of dimethyl sulfoxide is added, and a clear brown yellow solution is obtained after ultrasonic treatment for at least 20 min; then filtering through a filter membrane, putting at least 0.5mL of filtrate into a 3mL small sample bottle, adding 3mL of acetone into a large sample bottle in advance, putting the small sample bottle into a 25mL large sample bottle, and sealing; standing at normal temperature, and separating out light yellow needle crystals on the bottle wall and the bottle bottom after steam is diffused for at least 4 days, namely the target framework compound.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the triphenylene group-containing hydrogen bond organic framework compound has the advantages of novel structure, high stability, large specific surface area, high adsorption capacity to hydrogen and micropore property;
2. the synthesis route has simple and convenient process, mild reaction conditions, high yield and good repeatability, and provides reference for synthesizing the hydrogen bond organic framework compound with higher structural stability and larger specific surface area;
3. the preparation method has the advantages of simple route and process, mild reaction conditions, high yield and good repeatability.
Drawings
FIG. 1 is a schematic diagram of the structural elements employed in the present invention.
FIG. 2 is a flow diagram of a process for the synthesis of triphenylene group-containing hydrogen bonding organic framework compounds of the present invention.
FIG. 3 is a schematic diagram of the structure of a triphenylene group-containing hydrogen bonding organic framework compound of the present invention.
FIG. 4 is a graph showing the isothermal adsorption of nitrogen for hydrogen bonding organic framework compounds containing triphenylene groups in example one of the present invention.
FIG. 5 is a graph showing isothermal adsorption of hydrogen for hydrogen bonding organic framework compounds containing triphenylene groups in example one of the present invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
the first embodiment is as follows:
in this example, referring to fig. 1 to 3, a hydrogen bonding organic framework compound containing triphenylene group, the structural element of which is hexa (4-carboxyphenylethynyl) triphenylene, has multiple hydrogen bonding effects and pi-pi stacking effect of aromatic ring plane in the compound, has higher structural stability, and can show high BET specific surface area and hydrogen adsorption amount after removing guest solvent molecules.
In the embodiment, the compound has better structural stability, the framework of the compound shows constant pore property after the guest solvent molecules are removed, and the BET specific surface area reaches 1560m2The specific surface area of Langmiur reaches 1642m2The amount of hydrogen adsorbed reaches 112cm at 77K and 100kPa3/g。
In this example, the compound crystallizes in the orthorhombic Pnc2 space group, the six (4-carboxyphenylethynyl) triphenylene structural elements are connected through multiple hydrogen bonds to form a three-dimensional framework structure with a double-insertion characteristic, and the pi-pi stacking effect of the aromatic ring plane exists between two sets of frameworks in the double-insertion relationship.
In this embodiment, there are two sizes of one-dimensional pores in the compound structure, and the sizes are respectively
And
in this example, a method of making a hydrogen bonding organic framework compound containing triphenylene groups according to this example employs the following synthetic steps:
preparation of ethyl 4-trimethylsilyl alkynyl benzoate:
weighing ethyl p-iodobenzoate (5.00g,18.11mmol) into a 250mL round-bottom flask, measuring 60mL triethylamine to dissolve the ethyl p-iodobenzoate, bubbling nitrogen to remove oxygen for 30 minutes, then sequentially adding bis (triphenylphosphine) palladium dichloride (60.0mg,0.085mmol), cuprous iodide (85.0mg,0.44mmol) and triphenylphosphine (80.0mg,0.31mmol), and further bubbling to remove oxygen for 30 minutes; stirring for 20 minutes at normal temperature, adding 3.8mL of trimethylsilylacetylene by using an injector, gradually generating milky white solid in the stirring process, and stopping the reaction after 24 hours; carrying out vacuum filtration to obtain yellow filtrate, and removing the solvent to obtain orange oily liquid; separating and purifying the crude product by silica gel column chromatography, and finally obtaining light yellow oily liquid by using a mixed reagent of petroleum ether and ethyl acetate with the mass ratio of 10:1 as an eluent;1H NMR:(400MHz,CDCl3ppm) δ 8.00-7.94(m),7.54-7.48(m),4.37(q, J ═ 7.1Hz),1.39(t, J ═ 7.1Hz), 0.26(s); obtaining 4-trimethylsilyl alkynyl ethyl benzoate;
b, preparation of ethyl 4-alkynylbenzoate:
weighing the 4-trimethylsilylacetylbenzoic acid ethyl ester (3.60g,14.57mmol) prepared in the step a into a 100mL round-bottom flask, adding 35mL of absolute ethyl alcohol to dissolve the ethyl ester, adding potassium carbonate (170.0mg,1.23mmol) continuously, and stirring at normal temperature for 12 hours under the protection of nitrogen; filtering the reaction solution by diatomite, concentrating the filtrate, adding a small amount of water, extracting with diethyl ether for three times, combining the extracts, washing with saturated saline water for three times, drying the drying agent, and removing the solvent under reduced pressure to obtain yellow oily liquid;1HNMR:(400MHz,CDCl3ppm) δ 8.03-7.97(m),7.57-7.52(m),4.38(q, J ═ 7.1Hz),3.23(s),1.40(t, J ═ 7.1 Hz); obtaining 4-alkynyl ethyl benzoate;
c. hexa (4-ethylcarbamoylalkynyl) triphenylene preparation:
weighing 2,3,6,7,10, 11-hexabromotriphenylene (820.0mg,1.17mmol), ethyl 4-alkynylbenzoate (3.68g,21.14mmol) in a 200mL Schlenk bottle, measuring and dissolving tetrahydrofuran and diisopropylamine in 65mL each, bubbling nitrogen for deoxygenation for 30 minutes, then adding bis (triphenylphosphine) palladium dichloride (209.6mg,0.30mmol), cuprous iodide (113.60mg,0.60mmol), triphenylphosphine (155.20mg,0.59mmol), and bubbling again for deoxygenation for 30 minutes; reacting at 85 ℃ for 48 hours to obtain brown yellow oily liquid and earthy yellow precipitate; the reaction mixture was then cooled to room temperature and tetrahydrofuran and dichloromethane were added to the mixture and the solids were almost completely dissolved; suction filtration through celite and removal of the solvent from the filtrate under reduced pressure gave a reddish-brown solid. Separating and purifying the crude product by silica gel column chromatography, and obtaining a yellow solid by using a mixed reagent of ethyl acetate and dichloromethane in a mass ratio of 5:1 as an eluent; soaking the obtained yellow solid in ethanol, stirring for 12 hours, centrifuging, carrying out vacuum filtration, and drying in vacuum to finally obtain a light yellow solid, wherein the yield is as follows: 75 percent;1HNMR:(400MHz,CDCl3,ppm)δ:7.45(d,J＝6.9Hz),7.20(s),6.99(d,J＝6.8Hz),4.28(dd,J＝12.1,7.0Hz),1.38(t,J＝7.3Hz).13C NMR:(101MHz,CDCl3ppm) delta 165.37,131.14,129.55,128.95,126.93,126.52,125.74,123.63,93.73,90.74,77.48,77.16,76.84,61.05, 14.33; thus, hexa (4-ethylcarbamoylalkynyl) triphenylene was obtained;
d. preparation of hexa (4-carboxyphenylethynyl) triphenylene:
six (4-benzoic acid ethyl ester alkynyl) triphenylene (240.0mg,0.19mmol) is weighed into a 100mL round-bottom flask, and 40mL tetrahydrofuran is added; weighing potassium hydroxide (809mg,14.42mmol) solid in a 50mL beaker, and weighing 20mL distilled water to dissolve the solid to obtain a potassium hydroxide aqueous solution; adding a potassium hydroxide aqueous solution into the 100mL reaction bottle, and carrying out reflux reaction for 48 hours under the protection of nitrogen; after the reaction is finished, removing tetrahydrofuran under reduced pressure, adding 400mL of distilled water to dissolve the solid, filtering through kieselguhr under reduced pressure, dropwise adding hydrochloric acid into the filtrate to adjust the pH value to 1, and separating out yellow precipitateStanding, centrifuging, washing the precipitate with water until the pH of the supernatant is 7, performing vacuum filtration and vacuum drying to obtain a yellow solid; yield: 85 percent;1H NMR(400MHz,DMSO-d6,ppm)δ:12.98(s),8.08(s),7.67(d,J＝6.1Hz),7.34(d,J＝5.7Hz)；13C NMR(101MHz,DMSO-d6ppm) delta 166.45,131.25,130.26,128.98,127.01,126.52,123.41,93.34,90.85,40.15,39.94,39.73,39.52,39.31,39.10, 38.89; thus, hexa (4-carboxyphenylethynyl) triphenylene was obtained;
e. preparation of triphenylene group-containing hydrogen bonding organic framework compound:
weighing 8.20mg of hexa (4-carboxyphenylethynyl) triphenylene into a sample bottle, adding 4mL of dimethyl sulfoxide, and performing ultrasonic treatment for 20min to obtain a clear brown yellow solution; filtering with a filter membrane, putting 0.5mL of filtrate into a 3mL small sample bottle, adding 3mL of acetone into a large sample bottle in advance, putting the small sample bottle into a 25mL large sample bottle, and sealing; standing at normal temperature, and observing that faint yellow needle crystals are separated from the bottle wall and the bottle bottom after steam is diffused for four days; yield: 30 percent. The target compound can be obtained by analyzing the X-ray single crystal diffraction structure.
In this example, the prepared triphenylene group-containing hydrogen bonding organic framework compound was crystallized in the orthorhombic Pnc2 space group, unit cell parameters:
α＝β＝γ＝90°，
Z＝2，Dc＝0.832g/cm3f (000) ═ 2244. The hexa (4-carboxyphenylethynyl) triphenylene is connected with six surrounding hexa (4-carboxyphenylethynyl) triphenylenes through hydrogen bonds to form a set of three-dimensional framework structures; there are two such sets of frameworks in the overall compound, the relative displacement between the two sets being
The two sets of frames form a three-dimensional frame structure with two-dimensional penetration characteristics through the pi-pi accumulation effect of the aromatic ring plane of triphenylene; two sizes of holes present in the structure, respectively, can be observed along the a-axis direction
And
see fig. 3.
In this example, after the prepared hydrogen bond organic framework compound containing triphenylene group is soaked in acetone and activated by supercritical carbon dioxide, a type I nitrogen adsorption curve can be obtained under 77K condition, referring to fig. 4, the hydrogen bond organic framework compound shows microporous characteristics, shows constant pore property, and has BET specific surface area up to 1560m2The specific surface area of Langmiur can reach 1642m2(ii) in terms of/g. Under the conditions of 77K and 100kPa, the adsorption capacity of the hydrogen can reach 112cm3See FIG. 5 for,/g.
Experimental test analysis:
1. single crystal structure determination of compounds:
the appropriate single crystal was selected under an Olympus SZX-10 microscope, quickly wrapped with Paratone-N, and quickly transferred to an angle measuring head using a crystal carrier for testing. Single crystal X-ray diffraction data for the compound prepared in this example was collected from a Shanghai light source BL17B1 line station Bruker/ARINAX MD2 diffractometer with MarCCD-300 as the detector. Collection temperature 100K, diffraction wavelength
The distance between the detectors is 90mm, diffraction data are collected in an omega scanning mode, the scanning range is 0-360 degrees, and the swing angle is 1 degree. Absorption correction and data reduction were performed using HKL 3000. Refinement was performed using SHELXTL. The final refinement parameter is R1＝0.1164，wR2＝0.2790，S＝1.021。
2. Activation, specific surface area and hydrogen adsorption of the compound:
polycrystalline samples of the compound prepared in this example were immersed in anhydrous acetone for 3 days, then transferred to a drying chamber of a supercritical drying apparatus together with a solvent, subjected to supercritical drying for 8 hours or more, 160mg of the activated sample was weighed, subjected to vacuum evacuation at room temperature, and then subjected to specific surface analysis and hydrogen adsorption test.
This example uses a triphenylene group having a characteristic rigid planar structure with strong pi-pi stacking between groups. Triphenylene is used as a parent, a plurality of carboxyl groups are introduced through the connection of acetylene bonds, and the structural stability of the hydrogen bond organic framework compound is realized by utilizing the hydrogen bond linkage action of the carboxyl groups and the pi-pi accumulation action of an aromatic ring plane, so that the framework compound has wide application prospect.
Example two:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
in this example, in step c, 2,3,6,7,10, 11-hexabromotriphenylene (399.90mg,0.57mmol), ethyl 4-alkynylbenzoate (1.8g,10.35mmol) were weighed into a 150mL Schlenk bottle, and tetrahydrofuran and diisopropylamine were dissolved by measuring 40mL each, and oxygen was removed by bubbling nitrogen for 30 minutes, followed by adding bis (triphenylphosphine) palladium dichloride (103.00mg,0.15mmol), cuprous iodide (57.50mg,0.30mmol), triphenylphosphine (76.40mg,0.29mmol), and oxygen was removed by bubbling nitrogen again for 30 min. The reaction was carried out at 85 ℃ for 48 hours to give a brown-yellow oily liquid and a yellowish-brown precipitate. Tetrahydrofuran and dichloromethane were added to the reaction mixture and the solid was almost completely dissolved. Suction filtration through celite and removal of the solvent from the filtrate under reduced pressure gave a reddish-brown solid. And separating and purifying the crude product by silica gel column chromatography, and using a mixed reagent of ethyl acetate and dichloromethane in a mass ratio of 5:1 as an eluent to obtain a yellow solid. Soaking the obtained yellow solid in ethanol, stirring for 12 hours, centrifuging, carrying out vacuum filtration, and drying in vacuum to finally obtain hexa (4-ethyl benzoate alkynyl) triphenylene; yield: 70 percent.
Example three:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, in step e, 8.20mg of hexa (4-carboxyphenylethynyl) triphenylene was weighed into a sample vial, 2mL of dimethyl sulfoxide was added, and a clear brown-yellow solution was obtained after sonication for 20 min. After filtration through a filter membrane, 0.5mL of the filtrate was taken out into a 3mL small sample bottle, 3mL of acetone was previously added to the large sample bottle, and the small sample bottle was put into a 25mL large sample bottle and sealed. Standing at normal temperature, and observing that faint yellow needle crystals are separated from the bottle wall and the bottle bottom after steam is diffused for four days; yield: 72 percent.
In summary, the coupling of 2,3,6,7,10, 11-hexabromotriphenylene and ethyl 4-alkynylbenzoate in the above examples gave hexa (4-ethylbenzoates alkynyls) triphenylene, which was further hydrolyzed to give hexa (4-carboxyphenylethynyl) triphenylene, and finally, the hydrogen bonding organic framework compound containing triphenylene group was obtained by vapor diffusion. The preparation method has the advantages of simple route and process, mild reaction conditions, high yield and good repeatability. The hydrogen bond organic framework compound containing triphenylene groups has multiple hydrogen bonds and aromatic ring pi-pi stacking effect in the structure, has the property of constant pores, and the BET specific surface area can reach 1560m2The specific surface area of Langmiur can reach 1642m2(ii) in terms of/g. Under the conditions of 77K and 100kPa, the adsorption capacity of the hydrogen can reach 112cm3/g。
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention should be replaced with equivalents as long as the object of the present invention is met, and the technical principle and the inventive concept of the present invention are not departed from the scope of the present invention.
Claims (10)
1. A hydrogen bonding organic framework compound comprising triphenylene groups, characterized in that: the structural element is hexa (4-carboxyphenylethynyl) triphenylene, multiple hydrogen bonding effects and pi-pi stacking effects of aromatic ring planes exist in the compound, and after guest solvent molecules are removed, the compound can show high BET specific surface area and hydrogen adsorption quantity.
2. The triphenylene group-containing hydrogen-bonding organic framework compound of claim 1, wherein: the framework shows a constant pore property after removing guest solvent molecules, and the BET specific surface area is not less than 1560m2G, Langmiur specific surface area not less than 1642m2A hydrogen adsorption amount of not less than 112cm at 77K and 100kPa3/g。
3. The triphenylene group-containing hydrogen-bonding organic framework compound of claim 1, wherein: the compound is crystallized in an orthorhombic system Pnc2 space group, six (4-carboxyphenylethynyl) triphenylene structural elements are connected through multiple hydrogen bonds to form a three-dimensional framework structure with a double-insertion characteristic, and the pi-pi accumulation effect of an aromatic ring plane exists between two sets of frameworks in a double-insertion relationship.
4. The triphenylene group-containing hydrogen-bonding organic framework compound of claim 1, wherein: the compound structure has one-dimensional pore canals with two sizes respectively
And
5. a process for the preparation of triphenylene group-containing hydrogen bonding organic framework compound of claim 1, wherein the following synthetic steps are employed:
preparation of ethyl 4-trimethylsilyl alkynyl benzoate:
dissolving ethyl p-iodobenzoate in triethylamine, and deoxidizing the solution by bubbling nitrogen for at least 30 minutes; then sequentially adding bis (triphenylphosphine) palladium dichloride, cuprous iodide and triphenylphosphine, and then carrying out nitrogen bubbling to remove oxygen for at least 30 minutes; adding trimethylsilylacetylene through an injector, and stirring and reacting for at least 24 hours at normal temperature; after the reaction is finished, performing post-treatment to obtain 4-trimethylsilyl propargyl ethyl benzoate;
b, preparation of ethyl 4-alkynylbenzoate:
firstly, adding the 4-trimethylsilyl alkynyl ethyl benzoate prepared in the step a into absolute ethyl alcohol, then adding potassium carbonate, and reacting at room temperature for at least 12 hours; after post-treatment, 4-alkynyl ethyl benzoate is obtained;
c. hexa (4-ethylcarbamoylalkynyl) triphenylene preparation:
adding the ethyl 4-alkynylbenzoate prepared in the step b and 2,3,6,7,10, 11-hexabromotriphenylene into a Schlenk bottle, then adding tetrahydrofuran and diisopropylamine, and carrying out nitrogen bubbling for deoxygenation for at least 30 minutes; then adding bis (triphenylphosphine) palladium dichloride, cuprous iodide and triphenylphosphine, and continuing nitrogen bubbling for deoxygenation for at least 30 minutes; heating and reacting at a temperature of not less than 85 ℃ for at least 48 hours; then the reaction mixture was cooled to room temperature, and tetrahydrofuran and dichloromethane were added to the mixture to completely dissolve the solid; vacuum filtering with diatomite, concentrating the filtrate, and separating by silica gel column chromatography to obtain yellow solid; adding ethanol into the yellow solid, stirring and washing the mixture at room temperature for at least 12 hours, centrifuging and collecting the solid, and drying to obtain hexa (4-ethyl benzoate alkynyl) triphenylene;
d. preparation of hexa (4-carboxyphenylethynyl) triphenylene:
dissolving the hexa (4-ethylcarbamoylalkynyl) triphenylene prepared in the step c in tetrahydrofuran, and then adding a potassium hydroxide solution; heating reflux reaction at 65 deg.c for at least 48 hr; cooling to room temperature, and performing post-treatment to obtain hexa (4-carboxyphenylethynyl) triphenylene;
e. preparation of triphenylene group-containing hydrogen bonding organic framework compound:
and (3) carrying out solvent vapor diffusion crystallization, dissolving the hexa (4-carboxyphenylethynyl) triphenylene prepared in the step (d) in DMSO to obtain a mixed solution, placing an open container containing the mixed solution in a closed bottle filled with an acetone atmosphere, standing, and diffusing through acetone vapor to obtain the target framework compound in a yellow needle shape.
6. The method of preparing a triphenylene group-containing hydrogen bonding organic framework compound according to claim 5, wherein: the post-treatment operation adopts at least one of kieselguhr reduced pressure suction filtration, solvent extraction, saturated sodium chloride washing, reduced pressure concentration and silica gel column chromatography.
7. The method of preparing a triphenylene group-containing hydrogen bonding organic framework compound according to claim 5, wherein: in the step a, the total oxygen removal time is not less than 1 hour;
alternatively, in the step a, the feeding molar ratio of the ethyl p-iodobenzoate, the trimethylsilylacetylene, the bis (triphenylphosphine) palladium dichloride, the cuprous iodide and the triphenylphosphine is 1:1.5:0.04:0.024: 0.016.
8. The method of preparing a triphenylene group-containing hydrogen bonding organic framework compound according to claim 5, wherein: in the step c, the total oxygen removal time is not less than 1 hour;
or, in the step c, the volume ratio of tetrahydrofuran to diisopropylamine is 1: 1;
alternatively, in step c, the feed molar ratio of 2,3,6,7,10, 11-hexabromotriphenylene, ethyl 4-alkynylbenzoate, bis (triphenylphosphine) palladium dichloride, cuprous iodide and triphenylphosphine was 1:18:0.25:0.5: 0.5.
9. The method of preparing a triphenylene group-containing hydrogen bonding organic framework compound according to claim 5, wherein: in the step d, the feeding molar ratio of hexa (4-ethyl benzoate alkynyl) triphenylene to potassium hydroxide is 1: 76;
alternatively, in step d, the volume ratio of water to tetrahydrofuran is 1: 2.
10. The method of preparing a triphenylene group-containing hydrogen bonding organic framework compound according to claim 5, wherein: in the step e, solvent vapor is used for diffusion crystallization, and the volume ratio of dimethyl sulfoxide to acetone is 1: 6.
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