Hydrogen bond organic framework material based on electron donor-receptor type organic element and preparation method and application thereof

Abstract

The invention belongs to the field of porous organic materials, and particularly relates to a hydrogen bond organic framework material based on electron donor-receptor type organic elements and a preparation method and application thereof. The hydrogen bond organic framework material comprises a plurality of electron donor-acceptor type organic elements, the electron donor-acceptor type organic elements are constructed through the synergistic effect of pi-pi interaction force, and an electron donor-acceptor type organic element monomer comprises an electron donor and an electron acceptor connected to the electron donor. The hydrogen bond organic framework material provided by the invention has excellent chemical and thermal stability by utilizing the synergistic effect of multiple hydrogen bonds between electron donor-receptor type organic elements and pi-pi interaction force, and can preserve permanent pore channels.

Description

Technical Field

[0001] The present invention belongs to the field of porous organic materials, and particularly relates to a hydrogen-bonded organic framework material based on electron donor-acceptor type organic building blocks, and a preparation method and application thereof. Background Art

[0002] Hydrogen-bonded organic framework materials (abbreviated as HOFs) are a kind of emerging and attractive highly crystalline porous materials. Due to their excellent biocompatibility, large specific surface area, metal-free and mild synthesis conditions, they show excellent application prospects in the fields of biomedicine, proton conduction, photocatalysis, etc. Since hydrogen bonds are a kind of weak non-covalent interactions, the obtained hydrogen-bonded organic frameworks have poor stability. Under the influence of external environments such as high temperature or chemical reagents, hydrogen bonds are easily broken, resulting in changes in the structure of the hydrogen-bonded organic frameworks, pore collapse, etc. Therefore, preparing a stable hydrogen-bonded organic framework material is still a challenge.

[0003] Currently, there have been reports on methods such as introducing π-π stacking or interpenetrating structures to improve the stability of hydrogen-bonded organic frameworks. However, the reaction conditions of these methods are relatively harsh and the reaction costs are relatively high. Summary of the Invention

[0004] To improve the deficiencies of the existing technology, the present invention provides a hydrogen-bonded organic framework material based on electron donor-acceptor type organic building blocks, and a preparation method and application thereof. The material utilizes the synergistic effect of multiple hydrogen bonds and π-π interactions between electron donor-acceptor type organic building blocks. The material includes at least one of the following characteristics: having excellent chemical and thermal stability and being able to preserve permanent pores.

[0005] As described above, the present invention provides a hydrogen-bonded organic framework material based on electron donor-acceptor type organic building blocks, including a number of electron donor-acceptor type organic building blocks. The hydrogen-bonded organic framework material is formed by the synergistic effect of hydrogen bonds and π-π interactions between the electron donor-acceptor type organic building blocks. The electron donor-acceptor type organic building blocks include an electron donor and an electron acceptor connected to the electron donor. The electron donor is selected from at least one of the structures shown in Formula A:

[0006]

[0007]

[0008] The electron acceptor is selected from at least one of the structures shown in Formula B:

[0009]

[0010] In Formula B, X is selected from O, S or Se;

[0011] R is selected from benzene, thiadiazole, selenadiazole, oxadiazole, methyl, fluorine, chlorine, bromine, iodine, methoxy or amino.

[0012] According to an embodiment of the present invention, the electron donor is The electron acceptor is The electron donor-acceptor type organic moiety is pyrene tetracarboxylic acid functionalized with benzothiadiazole.

[0013] According to an embodiment of the present invention, the pyrene tetracarboxylic acid functionalized with benzothiadiazole has the structural formula shown in Formula C:

[0014]

[0015] According to an embodiment of the present invention, the electron donor is The electron acceptor is The electron donor-acceptor type has the structural formula shown in Formula D:

[0016]

[0017] According to an embodiment of the present invention, the electron donor is The electron acceptor is The electron donor-acceptor type has the structural formula shown in Formula E:

[0018]

[0019] According to an embodiment of the present invention, the hydrogen-bonded organic framework material is a hydrogen-bonded organic framework material constructed by the synergistic action of multiple hydrogen bonds and π-π interactions between organic moieties.

[0020] As an example, the hydrogen-bonded organic framework material is a hydrogen-bonded organic framework material constructed by the synergistic action of multiple hydrogen bonds and π-π interactions between organic moieties using 4,4',4'',4''-(pyrene-1,3,6,8-tetrayltetrakis(benzo[c][1,2,5]thiadiazole-7,4-diyl))tetrabenzoic acid monomer as the organic moiety.

[0021] According to an embodiment of the present invention, the hydrogen-bonded organic framework material is in a powder structure, and preferably the particle size of the hydrogen-bonded organic framework material is 200 nm to 1 μm, for example, 300 nm.

[0022] According to an embodiment of the present invention, the hydrogen-bonded organic framework material has a permanent pore structure, and preferably the pore structure is supported by the framework structure formed by the organic moieties.

[0023] According to an embodiment of the present invention, the hydrogen-bonded organic framework material is a mesoporous material.

[0024] According to an embodiment of the present invention, when the hydrogen-bonded organic framework material is at a temperature less than or equal to 180 °C, the crystal structure of the hydrogen-bonded organic framework material does not change, and it can still maintain a good framework structure.

[0025] According to an embodiment of the present invention, after the hydrogen-bonded organic framework material is soaked in different solvents, the crystal structure of the hydrogen-bonded organic framework material does not change, and it can still maintain a good framework structure.

[0026] According to an embodiment of the present invention, the hydrogen-bonded organic framework material has a porous structure, and the average pore diameter of the porous structure is 23.8 nm to 28.09 nm, for example, 2.51 nm.

[0027] According to an embodiment of the present invention, the specific surface area of the hydrogen-bonded organic framework material is 1000 - 1400 m² / g, for example, 1177 m² / g.

[0028] According to an embodiment of the present invention, the hydrogen-bonded organic framework material has a structure schematic diagram substantially as Figure 4 shown.

[0029] According to an embodiment of the present invention, the hydrogen-bonded organic framework material has an X-ray diffraction pattern substantially as Figure 5 shown.

[0030] According to an embodiment of the present invention, after the hydrogen-bonded organic framework material is activated, at 77 K, it has an N₂ adsorption diagram substantially as Figure 7 shown.

[0031] According to an embodiment of the present invention, the hydrogen-bonded organic framework material has an X-ray diffraction comparison diagram substantially as Figure 8 shown at different temperatures.

[0032] According to an embodiment of the present invention, after the hydrogen-bonded organic framework material is soaked in different solvents, it has an X-ray diffraction comparison diagram substantially as Figure 9 shown.

[0033] According to an embodiment of the present invention, the hydrogen-bonded organic framework material can generate singlet oxygen under visible light and ultraviolet light irradiation. Preferably, the singlet oxygen generation rate of the hydrogen-bonded organic framework material is greater than 0.9. For example, the singlet oxygen generation rate of the hydrogen-bonded organic framework material is close to 1.0.

[0034] According to an embodiment of the present invention, the hydrogen-bonded organic framework material has a DPBF degradation curve substantially as Figure 12 shown.

[0035] As described above, the present invention also provides a method for preparing the above hydrogen-bonded organic framework material, which includes the following steps: preparing the hydrogen-bonded organic framework material by the "recrystallization method" or the "solvent evaporation method" using the electron donor-acceptor type organic building block as described above.

[0036] According to an embodiment of the present invention, the synthesis method of the electron donor-acceptor type organic building block includes the following steps: coupling a compound containing the electron donor and a compound containing the electron acceptor through Suzuki coupling to obtain a precursor ester of the electron donor-acceptor type organic building block, and then hydrolyzing and acidifying to obtain the electron donor-acceptor type organic building block.

[0037] According to an embodiment of the present invention, the molar ratio of the compound containing the electron donor to the compound containing the electron acceptor is (1:4) to (1:6).

[0038] As an example, when the electron donor is and the electron acceptor is the molar ratio of the compound containing the electron donor to the compound containing the electron acceptor is 1:3.

[0039] As an example, when the electron donor is and the electron acceptor is the molar ratio of the compound containing the electron donor to the compound containing the electron acceptor is 1:6.

[0040] According to an embodiment of the present invention, the compound containing the electron donor is selected from at least one of 1,3,5-benzenetriboronic acid tris(pinacol) ester, 1,3,6,8-tetrakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene, 2,3,6,7,10,11-hexakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)triphenylene, 1,3,5-tris(4-phenylboronic acid pinacol ester)benzene, tris(4-boronic acid pinacol ester phenyl)amine, 3,3',6,6'-tetrakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9'-bicarbazole, hexakis(4-pinacolborane phenyl)benzene, for example, 1,3,6,8-tetrakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene.

[0041] According to an embodiment of the present invention, the compound containing an electron acceptor is selected from at least one of dimethyl 6-bromo-1,3,5-triazine-2,4-dicarboxylate, R-substituted derivatives of methyl 4-(4-bromobenzo[c][1,2,5]thiadiazol-7-yl)benzoate, R-substituted derivatives of methyl 4-(4-bromobenzo[c][1,2,5]selenadiazol-7-yl)benzoate, R-substituted derivatives of methyl 4-(4-bromobenzo[c][1,2,5]oxadiazol-7-yl)benzoate, methyl 5-bromo-2,5-dihydrothiazolo[5,4-d]thiazole-2-carboxylate, and methyl 5'-bromo-[2,2'-bipyridine]-5-carboxylate. For example, it is methyl 4-(4-bromobenzo[c][1,2,5]thiadiazol-7-yl)benzoate.

[0042] According to an embodiment of the present invention, the Suzuki coupling is carried out in a catalyst selected from at least one of tetrakis(triphenylphosphine)palladium, [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium, and bis(triphenylphosphine)dichloropalladium. For example, it is tetrakis(triphenylphosphine)palladium.

[0043] According to an embodiment of the present invention, the molar ratio of the compound containing an electron donor to the catalyst is 4:(2 - 5), for example, 4:3.

[0044] According to an embodiment of the present invention, the Suzuki coupling is carried out in an inert atmosphere, which refers to an atmosphere of inert gases N2, argon, or helium.

[0045] According to an embodiment of the present invention, the reaction is carried out in a solvent selected from dioxane and / or DMF. For example, it is DMF.

[0046] According to an embodiment of the present invention, the temperature of the Suzuki coupling reaction is 100 - 150 °C, for example, 120 °C.

[0047] According to an embodiment of the present invention, the time of the Suzuki coupling reaction is 10 - 30 h, for example, 12 h.

[0048] According to an embodiment of the present invention, the hydrolysis includes the following steps: recrystallizing and filtering the coupling product, collecting the organic phase, adding an alkaline solution after removing the solvent, and reacting at a temperature of 70 - 100 °C for 10 - 20 h.

[0049] According to an embodiment of the present invention, the temperature of the hydrolysis reaction is 80 - 90 °C, and the reaction time is 12 - 15 h.

[0050] According to an embodiment of the present invention, after hydrolysis and before acidification, the following steps are further included: removing the solvent from the acidification product and dissolving it in water.

[0051] According to an embodiment of the present invention, the acidification includes the following steps: adding a hydrolysis product into an acid solution for acidification, washing and drying to obtain an electron donor-acceptor type organic motif.

[0052] According to an embodiment of the present invention, after the hydrolysis product is mixed with the acid solution, the pH of the solution is 1-3.

[0053] As an example, the synthesis method of the electron donor-acceptor type organic motif includes the following steps: adding methyl 4-(4-bromobenzo[c][1,2,5]thiadiazol-7-yl)benzoate and 1,3,6,8-tetrakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene into a DMF solvent under N2 protection, using tetrakis(triphenylphosphine)palladium or [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium as a catalyst to carry out Suzuki coupling, and then hydrolyzing and acidifying to obtain a benzothiadiazole-functionalized tetracarboxylic acid pyrene organic motif.

[0054] According to an embodiment of the present invention, the "recrystallization method" includes the following steps: adding a poor solvent to a dilute solution of an organic motif, and obtaining a hydrogen-bonded organic framework material through stirring, standing, centrifuging, and washing.

[0055] According to an embodiment of the present invention, the "recrystallization method" includes the following steps: dissolving the electron donor-acceptor type organic motif in a good solvent to obtain a dilute solution, adding a poor solution to the dilute solution and stirring, standing, centrifuging, and washing at room temperature to obtain a hydrogen-bonded organic framework material based on the electron donor-acceptor type organic motif.

[0056] According to an embodiment of the present invention, in the "recrystallization method", the standing time is 3-18 h, for example, 12 h.

[0057] According to an embodiment of the present invention, in the "recrystallization method", the good solvent is a solution that can dissolve the organic motif well. Preferably, the good solvent can be at least one of N,N-dimethylacetamide and N,N-dimethylformamide.

[0058] According to an embodiment of the present invention, in the "recrystallization method", the concentration of the dilute solution is lower than the saturation concentration. For example, when the good solvent is N,N-dimethylacetamide, the concentration of the dilute solution is 10 mg / mL.

[0059] According to an embodiment of the present invention, in the "recrystallization method", the poor solvent can be at least one of methanol, ethanol, acetone, dichloromethane, chloroform, and acetic acid; preferably, the poor solvent is methanol.

[0060] According to an embodiment of the present invention, in the "recrystallization method", the volume ratio of the poor solvent to the dilute solution is greater than 3:1, and preferably the volume ratio of the poor solvent to the dilute solution is greater than 5:1.

[0061] As an example, when DMF is used as the good solvent, the volume ratio of the poor solvent to the dilute solution is greater than 3:1.

[0062] As another example, when DMA is used as the good solvent, the volume ratio of the poor solvent to the dilute solution is greater than 5:1.

[0063] According to an embodiment of the present invention, the "solvent evaporation method" includes the following steps: adding a high-boiling poor solvent to a dilute solution of an organic building block, followed by high-temperature evaporation, centrifugation, and washing to obtain a hydrogen-bonded organic framework.

[0064] According to an embodiment of the present invention, the "solvent evaporation method" includes the following steps: dissolving the electron donor-acceptor type organic building block in a good solvent to obtain a dilute solution, adding a poor solution to the dilute solution, allowing it to stand and evaporate, followed by centrifugation and washing to obtain a hydrogen-bonded organic framework material based on the electron donor-acceptor type organic building block.

[0065] According to an embodiment of the present invention, in the "solvent evaporation method", the good solvent is a solution that can dissolve the organic building block well. Preferably, the good solvent can be at least one of N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide.

[0066] According to an embodiment of the present invention, the concentration of the dilute solution is lower than the saturation concentration. For example, when the good solvent is N,N-dimethylacetamide, the concentration of the dilute solution is 3 mg / mL.

[0067] According to an embodiment of the present invention, in the "solvent evaporation method", the poor solvent can be at least one of trichlorobenzene and methyl benzoate; preferably, the poor solvent is trichlorobenzene.

[0068] According to an embodiment of the present invention, the volume ratio of the poor solvent to the dilute solution is less than 1:1, and preferably the volume ratio of the poor solvent to the dilute solution is less than 1:3.

[0069] As an example, when DMF is used as the good solvent, the volume ratio of the poor solvent to the dilute solution is less than 1:3.

[0070] As another example, when DMA is used as the good solvent, the volume ratio of the poor solvent to the dilute solution is less than 1:1.

[0071] As another example, the temperature for standing and evaporation is 80°C - 120°C, for example, 100°C.

[0072] According to an embodiment of the present invention, the centrifugation is high-speed centrifugation; preferably, the rotation speed of the centrifugation is between 6000 and 12000 revolutions per minute; for example, centrifuging at a speed of 12000 revolutions per minute for 3 minutes.

[0073] In a third aspect, the present invention also provides an application of the above hydrogen-bonded organic framework material in the fields of catalytic oxidation and biology.

[0074] Beneficial effects

[0075] 1) Based on the synergistic effect of multiple hydrogen bonds and π-π interactions of electron donor-acceptor type organic building blocks, the present invention obtains a hydrogen-bonded organic framework material based on electron donor-acceptor type organic building blocks. This organic framework material has a high specific surface area, permanent pores, high chemical and thermal stability, and solves the problems of poor stability and inability to maintain permanent pores of existing hydrogen-bonded organic framework materials; moreover, the present invention can prepare the hydrogen-bonded organic framework material by the "recrystallization method" or "solvent evaporation method" at room temperature.

[0076] 2) The donor-acceptor structure adopted by the present invention can regulate the energy level of the material and broaden the light absorption range. Therefore, the organic framework material of the present invention has a good light absorption range and a narrow band gap, can be excited under visible light, and has potential photocatalytic and electrocatalytic value.

[0077] 3) The hydrogen-bonded organic framework material of the present invention has excellent chemical and thermal stability and the ability to generate singlet oxygen, and has potential application value in the fields of photocatalytic heterogeneous catalysis and biological applications. Description of the drawings

[0078] Figure 1 It is the molecular formula of the benzothiadiazole-functionalized pyrene organic building block 4,4',4'',4''-(pyrene-1,3,6,8-tetrayltetrakis(benzo[c][1,2,5]thiadiazole-7,4-diyl))tetrabenzoic acid of the present invention.

[0079] Figure 2 It is the 1H NMR spectrum of the benzothiadiazole-functionalized pyrene organic building block 4,4',4'',4''-(pyrene-1,3,6,8-tetrayltetrakis(benzo[c][1,2,5]thiadiazole-7,4-diyl))tetrabenzoic acid of the present invention.

[0080] Figure 3 It is the high-resolution mass spectrum of the benzothiadiazole-functionalized pyrene organic building block 4,4',4'',4''-(pyrene-1,3,6,8-tetrayltetrakis(benzo[c][1,2,5]thiadiazole-7,4-diyl))tetrabenzoic acid of the present invention.

[0081] Figure 4Schematic diagram of the hydrogen-bonded organic framework constructed from benzothiadiazole-functionalized pyrene tetracarboxylic acid organic units of the present invention.

[0082] Figure 5 Comparison diagram of the powder X-ray diffraction of the hydrogen-bonded organic framework constructed from benzothiadiazole-functionalized pyrene tetracarboxylic acid organic units prepared by the recrystallization method in Example 2 and the theoretically simulated one.

[0083] Figure 6 Comparison diagram of the X-ray diffraction of the powders of the hydrogen-bonded organic frameworks constructed from benzothiadiazole-functionalized pyrene tetracarboxylic acid organic units prepared by the recrystallization method and the solvent evaporation method in Example 2.

[0084] Figure 7 N₂ adsorption at 77K of the hydrogen-bonded organic framework constructed from benzothiadiazole-functionalized pyrene tetracarboxylic acid organic units prepared in Example 2 after acetone exchange and activation treatment at 150°C.

[0085] Figure 8 Comparison diagram of the in-situ variable-temperature powder X-ray diffraction of the hydrogen-bonded organic framework constructed from benzothiadiazole-functionalized pyrene tetracarboxylic acid organic units prepared by the recrystallization method in Example 2.

[0086] Figure 9 Comparison diagram of the powder X-ray diffraction of the hydrogen-bonded organic framework constructed from benzothiadiazole-functionalized pyrene tetracarboxylic acid organic units prepared by the recrystallization method in Example 2 after being soaked in different solvents for 48h.

[0087] Figure 10 UV-Vis diffuse reflectance spectrum of the hydrogen-bonded organic framework constructed from benzothiadiazole-functionalized pyrene tetracarboxylic acid organic units prepared by the recrystallization method in Example 2.

[0088] Figure 11 Diagram of the UV-Vis diffuse reflectance spectrum of the hydrogen-bonded organic framework constructed from benzothiadiazole-functionalized pyrene tetracarboxylic acid organic units prepared by the recrystallization method in Example 2 after Kubelka-Munk transformation.

[0089] Figure 12 DPBF degradation curve of the hydrogen-bonded organic framework constructed from benzothiadiazole-functionalized pyrene tetracarboxylic acid organic units prepared by the recrystallization method in Example 2. Detailed implementation manners

[0090] The following will further elaborate on the hydrogen-bonded organic framework materials of the present invention, their preparation methods and applications in combination with specific examples. It should be understood that the following examples are only for illustrative and explanatory purposes of the present invention and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0091] Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

[0092] The information of some instruments used in the following examples is as follows:

[0093] Centrifuge: Jintai Test TG-16;

[0094] X-ray powder diffractometer: Rigaku SmartLab SE of Japan;

[0095] Full-automatic specific surface and porosity analyzer: ASAP 2460 of Micromeritics;

[0096] Nuclear magnetic resonance spectrometer: AVANCE III 400 of Bruker;

[0097] High-resolution mass spectrometer: Impact IIQ-TOF of Bruker;

[0098] Ultraviolet-visible spectrometer: UV-2550 produced by Shimadzu.

[0099] Example 1

[0100] Synthesis method of benzothiadiazole-functionalized pyrene organic unit of tetracarboxylic acid 4,4',4'',4''-(pyrene-1,3,6,8-tetrayltetrakis(benzo[c][1,2,5]thiadiazole-7,4-diyl))tetrabenzoic acid:

[0101] Add 630 mg of methyl 4-(4-bromobenzo[c][1,2,5]thiadiazol-7-yl)benzoate, 255 mg of 1,3,6,8-tetrakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene, 253 mg of K2CO3 and 87 mg of tetrakis(triphenylphosphine)palladium into a three-necked flask. Then transfer 30 mL of N,N-dimethylformamide and 5 mL of pure water to the three-necked flask with a double-headed needle under N2 atmosphere, evacuate, and purge with N2 three times. React at 120 °C for 24 hours under N2 atmosphere. After the reaction is completed, recrystallize the reaction product with ethanol and then perform hot filtration with chloroform. Collect the organic phase. After drying the solvent of the obtained organic phase by rotary evaporation, add 1.5 g of KOH, 30 mL of tetrahydrofuran, 6 mL of methanol and 6 mL of water. React at 85 °C for 12 hours and then filter. Rotary evaporate to remove the low-boiling solvents and then add water until completely dissolved. Acidify with hydrochloric acid to a solution pH = 1 - 3. Wash the product with water and ethanol and then dry to obtain benzothiadiazole-functionalized pyrene organic unit of tetracarboxylic acid 4,4',4'',4''-(pyrene-1,3,6,8-tetrayltetrakis(benzo[c][1,2,5]thiadiazole-7,4-diyl))tetrabenzoic acid. See Figure 1As shown, it is the molecular formula of the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit 4,4',4'',4''-(pyrene-1,3,6,8-tetrayltetrakis(benzo[c][1,2,5]thiadiazole-7,4-diyl))tetrabenzoic acid prepared in this example.

[0102] Dissolve 4,4',4'',4''-(pyrene-1,3,6,8-tetrayltetrakis(benzo[c][1,2,5]thiadiazole-7,4-diyl))tetrabenzoic acid prepared in this example in deuterated DMSO (dimethyl sulfoxide), filter it with a filter head, and add it to an AVANCE III 400 nuclear magnetic resonance spectrometer for testing. See Figure 2 As shown, it is the 1H NMR spectrum of the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit 4,4',4'',4''-(pyrene-1,3,6,8-tetrayltetrakis(benzo[c][1,2,5]thiadiazole-7,4-diyl))tetrabenzoic acid prepared in this example. It can be seen from the figure that according to the peak shifts and the ratio of peak areas of δ = 8.43 (s, 2H), δ = 8.23–8.03 (m, 24H), and δ = 7.93 (s, 4H), it indicates the successful synthesis of the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit.

[0103] Dissolve 4,4',4'',4''-(pyrene-1,3,6,8-tetrayltetrakis(benzo[c][1,2,5]thiadiazole-7,4-diyl))tetrabenzoic acid prepared in this example in DMF (N,N-dimethylformamide), filter it with a filter head, and add it to an Impact II Q-TOF high-resolution mass spectrometer for detection using the EIS mode. Figure 3 It is the high-resolution mass spectrum of the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit 4,4',4'',4''-(pyrene-1,3,6,8-tetrayltetrakis(benzo[c][1,2,5]thiadiazole-7,4-diyl))tetrabenzoic acid prepared in this example. It can be seen from the figure that the mass-to-charge ratio of 4,4',4'',4''-(pyrene-1,3,6,8-tetrayltetrakis(benzo[c][1,2,5]thiadiazole-7,4-diyl))tetrabenzoic acid in the negative ion mode is 608.0611, which is close to the mass-to-charge ratio of 608.0618 simulated by the ChemDraw software, indicating the successful synthesis of the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit.

[0104] From Figure 2 and Figure 3 The test results can prove that the material synthesized in this example is the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit 4,4',4'',4''-(pyrene-1,3,6,8-tetrayltetrakis(benzo[c][1,2,5]thiadiazole-7,4-diyl))tetrabenzoic acid.

[0105] Preparation method of hydrogen-bonded organic framework constructed by benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit:

[0106] Recrystallization method: Dissolve 15 mg of the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit prepared in Example 1 in 5 mL of DMF (N,N-dimethylformamide), pour it into 20 mL of methanol, and leave it standing open for 12 hours. After the reaction is completed, let it stand for 12 hours, centrifuge the product at a speed of 12,000 rpm for 3 minutes, and wash it continuously with acetone 3 times to obtain the hydrogen-bonded organic framework material constructed by the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit.

[0107] Solvent evaporation method: Dissolve 3 mg of the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit prepared in Example 1 in 1 mL of DMA, add 500 μL of trichlorobenzene, and evaporate it at 100 °C for 12 hours. After the reaction is completed, centrifuge the product at a speed of 12,000 rpm for 3 minutes, and wash it continuously with acetone 3 times to obtain the hydrogen-bonded organic framework material constructed by the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit.

[0108] See Figure 4 As shown, it is a schematic structural diagram of the hydrogen-bonded organic framework material constructed by the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit prepared by the recrystallization method and the solvent evaporation method in this example. It can be seen from the figure that the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit constructs a two-dimensional (2D) layer through hydrogen bonds; then, by stacking AA in the (100) direction, a one-dimensional rhombic channel is obtained, indicating that the organic unit has successfully constructed a hydrogen-bonded organic framework under the synergistic action of multiple hydrogen bonds and π-π interactions.

[0109] Both of the above methods can obtain the hydrogen-bonded organic framework material constructed by the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit. Among them, the recrystallization method is more convenient to operate. According to the Brunauuer-Emmett-Teller formula, the specific surface area of the hydrogen-bonded organic framework material constructed by the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit prepared by the recrystallization method in this example is 1177 m² / g, and according to the non-local density functional theory (NLDFT), the average pore size is 2.51 nm.

[0110] Example 3 After expanding the above material ratios equally, the material can still be obtained.

[0111] Recrystallization method: 30 mg of the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit prepared in Example 1 was dissolved in 10 mL of DMF (N,N-dimethylformamide), poured into 40 mL of methanol, and left standing open for 12 hours. After the reaction was completed, it was left standing for another 12 hours. The product was centrifuged at 12,000 rpm for 3 minutes and washed continuously with acetone three times to obtain a hydrogen-bonded organic framework material constructed from the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit.

[0112] Solvent evaporation method: 6 mg of the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit prepared in Example 1 was dissolved in 2 mL of DMA, 100 μL of trichlorobenzene was added, and it was left to evaporate at 100 °C for 24 hours. After the reaction was completed, the product was centrifuged at 12,000 rpm for 3 minutes and washed continuously with acetone three times to obtain a hydrogen-bonded organic framework material constructed from the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit.

[0113] After measurement, the hydrogen-bonded organic framework material constructed from the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit prepared in this example has the same structure as the hydrogen-bonded organic framework material prepared in Example 2.

[0114] Performance testing of the hydrogen-bonded organic framework material constructed from the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit prepared by the recrystallization method and the solvent evaporation method in Example 4 (the hydrogen-bonded organic framework materials prepared by the recrystallization method were selected in both Example 5 and Example 6)

[0115] The hydrogen-bonded organic framework material constructed from the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit prepared by the recrystallization method in Example 2 was dried in an oven at 80 °C, and the powder X-ray diffraction pattern was tested using a Rigaku SmartLab SE at room temperature, and the result was compared with the powder X-ray diffraction pattern obtained by computational simulation.

[0116] See Figure 5 As shown, it is the comparison diagram of the powder X-ray diffraction of the hydrogen-bonded organic framework material constructed from the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic unit prepared in Example 2 and the computational simulation. It can be seen from the figure that the prepared hydrogen-bonded organic framework material is consistent with the simulated structure, and the powder X-ray diffraction peaks of the sample prepared in Example 2 are highly fitted with the results obtained by computational simulation, indicating that the surface structure is consistent with the simulated structure.

[0117] See Figure 6 As shown, it is the powder X-ray diffraction pattern of the hydrogen-bonded organic framework material prepared by the recrystallization method and the solvent evaporation method in Example 3. It can be seen from the figure that the hydrogen-bonded organic framework materials prepared by both methods are consistent with the simulated structure.

[0118] The hydrogen-bonded organic framework material constructed from the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic building blocks prepared in Example 2 was exchanged four times in acetone. After vacuum activation at 150 °C for 10 hours, the 77K nitrogen adsorption characterization was carried out using the ASAP2460 sorptometer of Micromeritics. See Figure 7 As shown in 2 Figure 7 , the N2 adsorption graph at 77K of the hydrogen-bonded organic framework material constructed from the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic building blocks prepared in Example 2 after acetone exchange and activation at 150 °C. It can be seen from the figure that the hydrogen-bonded organic framework material constructed from the organic building blocks has permanent pores. The type-IV adsorption isotherm indicates that the sample of Example 2 is a mesoporous material. The BET of the hydrogen-bonded organic framework material constructed from the organic building blocks is 1177 m

[0119] The hydrogen-bonded organic framework material constructed from the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic building blocks prepared in Example 2 was treated at different temperatures of 25 °C, 60 °C, 90 °C, 120 °C, 150 °C, 180 °C, and 210 °C respectively, and then the X-ray diffraction pattern was tested. See Figure 8 As shown in

[0120] Figure 8 , the X-ray diffraction pattern of the hydrogen-bonded organic framework material constructed from the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic building blocks after treatment at different temperatures is consistent with the simulated powder X-ray diffraction pattern, indicating that the hydrogen-bonded organic framework material prepared in Example 2 still maintains a good framework structure at 180 °C, the crystal structure does not undergo an obvious phase change, and it has excellent thermal stability. The hydrogen-bonded organic framework material constructed from the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic building blocks prepared in Example 2 was soaked in water, acetic acid, and methanol solution for 2 days respectively, and then the X-ray diffraction pattern was tested. See Figure 9 As shown in

[0121] Figure 9 , the X-ray diffraction pattern of the soaked hydrogen-bonded organic framework material is consistent with the simulated powder X-ray diffraction pattern, indicating that the hydrogen-bonded organic framework material prepared in Example 2 still maintains a good framework structure after soaking in methanol, acetic acid, and water, the crystal structure does not undergo an obvious phase change, and it has excellent chemical stability. Example 5 tested the light absorption range and band gap of the hydrogen-bonded organic framework constructed from the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic building blocks prepared in Example 2

[0122] Test conditions: 5 mg of the hydrogen-bonded organic framework powder constructed from the benzothiadiazole-functionalized pyrene tetracarboxylic acid organic building blocks prepared in Example 2 was subjected to ultraviolet-visible diffuse reflectance spectroscopy on a UV-2550 instrument, and the ultraviolet-visible diffuse reflectance spectrum was subjected to Kubelka-Munk transformation to obtain the band gap of the sample.

[0123] Reference Figure 10It can be seen that the absorption band edge of the sample in Example 2 is at 690 nm, indicating that it has a wide absorption range. Refer to Figure 11 As shown, it can be seen that the band gap of the sample in Example 2 is 1.8 eV, indicating that it has a relatively narrow band gap.

[0124] Example 6 Singlet oxygen generation performance of a hydrogen-bonded organic framework constructed from benzothiadiazole-functionalized pyrene tetracarboxylic acid organic units prepared in Example 2

[0125] Test conditions: Add 300 μL of an ethyl acetate solution of 1,3-diphenylisobenzofuran at 0.5 mg / mL to 3 mL of an ethyl acetate solution of the sample in Example 2 at 0.0625 mg / mL, and under the irradiation of a xenon lamp (wavelength greater than 500 nm), measure the ultraviolet-visible absorption spectrum of the singlet oxygen probe 1,3-diphenylisobenzofuran (DPBF).

[0126] Refer to Figure 12 It can be seen that the singlet oxygen generation rate of the sample in Example 2 is close to 1.0, showing excellent singlet oxygen generation rate.

[0127] The specific embodiments of the present invention have been exemplarily described above through examples. However, the protection scope of the present invention is not limited to the above exemplary embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.

Claims

1. A hydrogen-bonded organic framework material based on electron donor-acceptor type organic building blocks, characterized in that, The hydrogen-bonded organic framework material includes a number of electron donor-acceptor type organic building blocks, and the hydrogen-bonded organic framework material is formed by the synergistic action of hydrogen bonds and π-π interactions between the electron donor-acceptor type organic building blocks. The electron donor is selected from at least one of the structures shown in Formula A: The electron acceptor is selected from at least one of the structures shown in Formula B: In Formula B, X is selected from O, S or Se; R is selected from benzene, thiadiazole, selenadiazole, oxadiazole, methyl, fluorine, chlorine, bromine, iodine, methoxy or amino.

2. The hydrogen-bonded organic framework material based on electron donor-acceptor type organic building blocks according to claim 1, characterized in that, The electron donor is The electron acceptor is The organic building block is pyrene tetracarboxylic acid functionalized with benzothiadiazole; Preferably, the benzothiadiazole-functionalized pyrene tetracarboxylic acid has the structural formula shown in Formula C: Preferably, the organic framework is a hydrogen-bonded organic framework material formed by using 4,4',4”,4”-(pyrene-1,3,6,8-tetrayltetrakis(benzo[c][1,2,5]thiadiazole-7,4-diyl))tetrabenzoic acid monomer as an organic building block and through the synergistic action of multiple hydrogen bonds and π-π interactions between organic building blocks.

3. The hydrogen-bonded organic framework material based on electron donor-acceptor type organic building blocks according to claim 1 or 2, characterized in that, The hydrogen-bonded organic framework material is in a powder structure, and the particle size of the organic framework material is 200 nm to 1 μm. Preferably, the organic framework material has a permanent pore structure inside, forming a porous structure, and the pore structure is supported by the framework structure formed by the organic building blocks. Preferably, the average pore diameter of the porous structure is 23.8 nm - 28.09 nm.

4. A method for preparing the hydrogen-bonded organic framework material according to any one of claims 1 to 3, characterized in that, It includes the following steps: preparing the hydrogen-bonded organic framework material from the electron donor-acceptor type organic building blocks by the "recrystallization method" or the "solvent evaporation method". Preferably, the synthesis method of the electron donor-acceptor type organic building blocks includes the following steps: coupling a compound containing the electron donor and a compound containing the electron acceptor through suzuki coupling to obtain a precursor ester of the electron donor-acceptor type organic building block, and then obtaining the electron donor-acceptor type organic building block after hydrolysis and acidification.

5. The preparation method according to claim 4, wherein The compound containing the electron donor is selected from at least one of 1,3,5-benzenetriboronic acid tri-pinacol ester, 1,3,6,8-tetrakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene, 2,3,6,7,10,11-hexakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)triphenylene, 1,3,5-tris(4-phenylboronic acid pinacol ester)benzene, tris(4-boronic acid pinacol ester phenyl)amine, 3,3',6,6'-tetrakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9'-bicarbazole, hexakis(4-pinacol borane phenyl)benzene; The compound containing an electron acceptor is selected from at least one of dimethyl 6-bromo-1,3,5-triazine-2,4-dicarboxylate, R-substituted derivatives of methyl 4-(4-bromobenzo[c][1,2,5]thiadiazol-7-yl)benzoate, R-substituted derivatives of methyl 4-(4-bromobenzo[c][1,2,5]selenadiazol-7-yl)benzoate, R-substituted derivatives of methyl 4-(4-bromobenzo[c][1,2,5]oxadiazol-7-yl)benzoate, methyl 5-bromo-2,5-dihydrothiazolo[5,4-d]thiazole-2-carboxylate, and methyl 5'-bromo-[2,2'-bipyridine]-5-carboxylate. Preferably, the Suzuki coupling is carried out in a catalyst selected from at least one of tetrakis(triphenylphosphine)palladium, dichloride [1,1-bis(diphenylphosphino)ferrocene]palladium, and dichloride bis(triphenylphosphine)palladium. According to an embodiment of the present invention, the "recrystallization method" includes the following steps: adding a poor solvent to a dilute solution of an organic building block, and obtaining a hydrogen-bonded organic framework material through stirring, standing, centrifuging, and washing.

6. The preparation method according to claim 4 or 5, characterized in that, The "recrystallization method" includes the following steps: dissolving the electron donor-acceptor type organic building block in a good solvent to obtain a dilute solution, adding a poor solution to the dilute solution and stirring, standing, centrifuging, and washing at room temperature to obtain a hydrogen-bonded organic framework material based on the electron donor-acceptor type organic building block.

7. The preparation method according to claim 6, wherein, In the "recrystallization method", the standing time is 3 to 18 h. Preferably, in the "recrystallization method", the concentration of the dilute solution is lower than the saturation concentration. Preferably, in the "recrystallization method", the volume ratio of the poor solvent to the dilute solution is greater than 3:

1.

8. The preparation method according to claim 4 or 5, characterized in that, The "solvent evaporation method" includes the following steps: adding a high-boiling poor solvent to a dilute solution of an organic building block, and obtaining a hydrogen-bonded organic framework through high-temperature evaporation, centrifuging, and washing. Preferably, the "solvent evaporation method" includes the following steps: dissolving the electron donor-acceptor type organic building block in a good solvent to obtain a dilute solution, adding a poor solution to the dilute solution, standing and evaporating, and then centrifuging and washing to obtain a hydrogen-bonded organic framework material based on the electron donor-acceptor type organic building block.

9. The preparation method according to claim 8, characterized in that, In the "solvent evaporation method", the concentration of the dilute solution is lower than the saturation concentration. Preferably, in the "solvent evaporation method", the volume ratio of the poor solvent to the dilute solution is less than 1:

1. Preferably, in the "solvent evaporation method", the temperature for standing and evaporating is 80°C - 120°C.

10. Use of the hydrogen-bonded organic framework material according to any one of claims 1-3 or the hydrogen-bonded organic framework material prepared by the method according to any one of claims 4-9 in the fields of catalytic oxidation and biology.

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