CN112210057A - Fluorescent three-dimensional covalent organic framework material and preparation method and application thereof - Google Patents

Fluorescent three-dimensional covalent organic framework material and preparation method and application thereof Download PDF

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CN112210057A
CN112210057A CN202010626984.XA CN202010626984A CN112210057A CN 112210057 A CN112210057 A CN 112210057A CN 202010626984 A CN202010626984 A CN 202010626984A CN 112210057 A CN112210057 A CN 112210057A
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肖胜雄
方千荣
任军霞
刘耀祖
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ZHUHAI CITY STATE KEY LABORATORY OF INORGANIC SYNTHESIS AND PREPARATIVE CHEMISTRY JILIN UNIVERSITY
Shanghai Normal University
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Abstract

The invention relates to a fluorescent three-dimensional covalent organic framework material and a preparation method and application thereof, TPE fluorescent molecules are used as side chains of COFs precursor units, 3D COFs with a ten-fold penetrating structure are generated through polymerization of the precursor molecules, and the TPE molecules on the skeleton side chains are gathered and fully exposed in three-dimensional pore channels, so that the molecular rotation of the TPE molecules is limited, and the AIE effect is enhanced. Compared with the prior art, when the fluorescent three-dimensional covalent organic framework material is used for molecular fluorescence detection, the three-dimensional pore channel obviously increases the contact area of TPE molecules and detected molecules, and improves the fluorescence detection sensitivity. In particular, the 3D COFs has high sensitivity to nitrobenzene, KSVEight orders of magnitude are achieved.

Description

Fluorescent three-dimensional covalent organic framework material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and relates to a fluorescent three-dimensional covalent organic framework material (3D COFs), and a preparation method and application thereof.
Background
Since the first report of Covalent Organic Framework (COFs) in 2005, it has become a new type of crystalline Organic porous polymer with predictable structure and excellent performance, and in recent years, it has received increasing attention for its potential applications in gas adsorption and separation, chiral separation, chemical sensing, heterogeneous catalysis, photocatalytic hydrogen production, proton conduction, drug delivery, and energy storage. Since the comprehensive properties of COFs are closely related to their molecular structures, the development of novel COFs with various functional groups has become a research hotspot for expanding their applications. On the other hand, in 2001, the subject group of the Thanksonics discovered the phenomenon of "aggregation-induced emission" (AIE), and a molecular rotor having AIE properties plays an important role in fluorescence emission behavior. These AIE luminescent materials (AIEgens) do not generally emit light in solution, but exhibit strong luminescent behavior in the aggregate state, with Tetraphenylethylene (TPE) and its derivatives being one of the most important AIE luminescent materials.
A large number of fluorescence detection methods are gradually applied to the detection of dangerous chemicals or important biomolecules in the environment, and in the process, the fluorescence of a fluorescence detection agent is changed due to the influence of a detected object or a microenvironment, so that the fluorescence detection is realized. Many fluorescence detection methods based on COFs or AIEgens have been reported, but the number of materials taking both characteristics of COFs and AIE into consideration is relatively small. For example, Jiangdong forest project group reported a borate COFs luminescent material containing TPE, which can achieve high sensitivity detection on ammonia (JACS,2016,138, 5797). Wang topic group reports a COFs incorporating TPE rotors with AIE properties in the backbone, which materials emit yellow fluorescence when excited and fluorescence quantum efficiency up to 20% (nat. The Zhaodan task group reports COFs nano-sheets with biomolecule recognition capability and realizes the recognition of amino acid and drug small molecules (Ldopa) (JACS,2019,31, 146).
The prior art has the following characteristics: 1) hitherto, in the reported COFs structure containing TPE, TPE groups are all used for constructing a COFs framework (nat. Commun.,2018,9,1), and although the movement of TPE molecules in the structure is limited to a certain extent, the TPE molecules cannot be fully exposed in a pore channel and cannot be fully contacted with a detected object, so that the detection sensitivity is greatly reduced, and the maximum advantage of AIEgens in the aspect of molecular recognition cannot be exerted. 2) To date, few reports have been made regarding molecular recognition of COFs containing AIEgens (JACS,2016,138, 5797; JACS,2019,31,146), especially its reports on the highly sensitive recognition of dangerous compounds are still blank. 3) The detection sensitivity to dangerous compounds needs to be improved, and particularly the detection sensitivity to nitrobenzene compounds, polycyclic aromatic hydrocarbons and sulfur-containing aromatic hydrocarbons needs to be improved.
Disclosure of Invention
The invention aims to provide a fluorescent three-dimensional covalent organic framework material, a preparation method and application thereof, and particularly provides a 3D COFs structure with TPE as a COFs framework side chain, and the structure is applied to high-sensitivity fluorescence detection of dangerous compounds. The TPE fluorescent molecules are used as the side chains of the COFs precursor unit (compound 4), the 3D COFs with a ten-fold penetrating structure is generated through polymerization of the precursor molecules (compound 4), and the TPE molecules on the skeleton side chains are gathered and fully exposed in three-dimensional channels, so that the molecular rotation of the TPE molecules is limited, and the AIE effect is enhanced.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a fluorescent three-dimensional covalent organic framework material which is a 3D COFs structure consisting of a COFs framework and AIEgens connected to the side chain of the COFs framework.
Further, the AIEgens include, but are not limited to, TPE. Of course, TPE can also be generalized to the rest of the fluorescent molecules with AIE properties.
Furthermore, the COFs framework is also preferably such that the chemical structure of the resulting 3D COFs is as follows:
Figure BDA0002566887780000021
the invention designs a COFs precursor molecule for connecting AIEgens (TPE is taken as an example) on a monomer side chain, and successfully prepares high-crystalline 3D COFs with the pore diameter of 1.3nm by a polymerization method, which is named as JUC-555. The 3D COFs have a ten-fold penetrating structure, a plurality of TPE molecules are concentrated in the ordered pore channels, and the AIE effect is enhanced. When the TPE molecular fluorescent probe is used for molecular fluorescent detection, the three-dimensional pore channel obviously increases the contact area of TPE molecules and detected molecules, and improves the fluorescent detection sensitivity. Especially, the 3D COFs has high sensitivity to nitrobenzene, KSVEight orders of magnitude are achieved.
The second technical scheme of the invention provides a preparation method of a fluorescent three-dimensional covalent organic framework material, taking JUC-555 as an example, comprising the following steps:
(1) taking compound I, Ce (NH)4)2(NO3)6Mixing with hydrogen peroxide, adding acetonitrile for dissolving, adding a compound II, stirring uniformly, heating for reaction, cooling to room temperature, and filtering to obtain a compound III;
(2) taking the compounds of tri, 4-formyl phenylboronic acid and Na2CO3Adding mixed solvent of THF and water, stirring, adding Pd (PPh)3)4Heating for reaction, and filtering to obtain a compound IV;
(3) weighing compounds IV and Tetrakis- (4-aminophenyl) -methane (TAPM) to be suspended in dioxane and mesitylene, taking acetic acid as a catalyst, freezing, vacuumizing, sealing, heating for reaction, filtering, separating and washing the obtained product, immersing the product in anhydrous DMF, taking out the product, drying, and standing overnight in vacuum to obtain a target product;
wherein, the compound I and the compound II are respectively as follows:
Figure BDA0002566887780000031
further, the preparation process of the compound I is as follows:
weighing 2-bromo-1, 1, 2-triphenylethylene, 4-formylphenylboronic acid and Na2CO3Adding mixed solvent of THF and water, stirring, and adding Pd (PPh)3)2Cl2Heating for reaction to obtain a compound I, wherein the volume ratio of THF to water in the mixed solvent is 5: 2; the process conditions of the temperature-rising reaction are as follows: reacting for 24 hours at 80 ℃;
the preparation process of the compound II comprises the following steps:
dissolving compound five in ethanol, cooling, and adding NaBH4Mixing and stirring overnight, evaporating and concentrating the obtained reaction mixture, adding water for dilution, extracting and drying to obtain a compound II;
wherein, the chemical structural formula of the compound five is as follows:
Figure BDA0002566887780000041
the compound 4, 7-dibromo-2, 1, 3-benzothiadiazole, ethanol and NaBH4The ratio of the addition amounts of (A) to (B) is 10mmol:100mL of: 20mmol of the active carbon; the temperature of the mixture was 20 ℃ with stirring overnight.
Further, in the step (1), compound I, Ce (NH)4)2(NO3)6The ratio of the molar amount of hydrogen peroxide to the compound II added was 4mmol:5mmol:5mmol:5 mmol.
Further, in the step (1), the process conditions of the temperature-rising reaction are as follows: the reaction was carried out at 83 ℃ for 3 h.
Further, in the step (2), the compound of tri, 4-formyl phenylboronic acid and Na2CO3And Pd (PPh)3)4The molar ratio of (2) to (3) to (6) is 10mmol to 45mmol to 2mmol to 100 mmol.
Further, in the step (2), the process conditions of the temperature-rising reaction are as follows: the reaction was carried out at 80 ℃ for 24 h.
Further, in the step (2), the volume ratio of THF to water in the mixed solvent is 7: 3.
Further, in the step (3), the molar ratio of the compounds tetra, TAPM, dioxane and mesitylene added was 0.05mmol, 0.0125mmol, 0.8mL, 0.2 mL.
Further, in the step (3), the process conditions of the heating reaction are as follows: the reaction was carried out at 120 ℃ for 72 h.
Further, in the step (3), the immersion time in anhydrous DMF is 24 h.
The preparation process flow of the invention is as follows:
Figure BDA0002566887780000042
Figure BDA0002566887780000051
the reaction mechanism is as follows:
compound 1: pd (II) and 2-bromo-1, 1, 2-triphenylethylene to form Pd (II) complex, and then OH-Nucleophilic substitution is carried out to generate-Pd-OH; OH group-The B of the 4-formylphenylboronic acid is attacked continuously, then the reaction is carried out with-Pd-OH, and the B (OH) is removed-Another complex with respect to pd (ii) is formed, after which pd (ii) is removed to form compound 1. (mechanism is as follows)
Figure BDA0002566887780000052
Compound 2: in ethanol solution, H+Attack a nitrogen atom to cause electron transfer, another nitrogen atom bearing a positive charge, BH4 -The negative hydrogen ion attacks the positive nitrogen ion, the positive hydrogen ion attacks the secondary amine and is converted into the positive ammonia ion, BH4 -The hydrogen negative ions attack the nitrogen positive ions to break S-N into sulfydryl, and then the hydrogen positive ions attack secondary amines to be converted into ammonia positive ions which are converted into primary amines under the action of the hydrogen negative ions to generate hydrogen sulfide. (mechanism is as follows)
Figure BDA0002566887780000061
Compound 3: condensation of compound 1 and compound 2, removal of one molecule of water to form C ═ N, -NH2The carbon-carbon double bond is attacked to form a five-membered ring in a closed loop manner, intramolecular proton transfer occurs under the oxidation action of ceric nitrate and hydrogen peroxide, and the proton is separated to form stable C ═ N under the continuous oxidation.
Figure BDA0002566887780000071
Compound 4: the mechanism is consistent with that of compound 1, and is a Suzuki-Miyaura mechanism.
The third technical scheme of the invention provides application of the fluorescent three-dimensional covalent organic framework material, and the fluorescent three-dimensional covalent organic framework material is used for detecting dangerous compounds. Preferred hazardous compounds are nitrobenzene compounds, polycyclic aromatic hydrocarbons, sulfur-containing aromatic hydrocarbons, and the like, and nitrobenzene is particularly preferred.
Compared with the prior art, the invention has the following advantages:
(1) hitherto, in the reported COFs structure containing TPE, TPE groups are all used for constructing COFs frameworks (JACS,2019,31, 146; nat. Commun.,2018,9,1), TPE fluorescent molecules are used as side chains of COFs precursor units, 3D COFs with a ten-fold penetrating structure are generated through precursor polymerization, TPE molecules on the side chains of the frameworks are aggregated and fully exposed in three-dimensional channels, the molecular rotation of the TPE molecules is limited, and the AIE effect is enhanced.
(2) So far, the COFs containing AIEgens have few reports on molecular recognition (JACS,2016,138,5797; JACS,2019,31,146), especially the reports on high-sensitivity recognition of dangerous compounds are blank, and the 3D COFs can be used for fluorescence detection of nitrobenzene, polycyclic aromatic hydrocarbon and sulfur-containing aromatic hydrocarbon.
(3) The 3D COFs can realize high-sensitivity identification on dangerous compounds, and particularly the detection sensitivity of the p-nitrobenzene compounds is over 100 times higher than the best known detection sensitivity (J.solid State chem.,2017,252,142). The reason is that the fixed size and shape of the pore channels of the ordered 3D COFs have strong molecular recognition capability on small molecules, and when the appropriate detected molecules enter the pore channels, the molecules are subjected to electron transfer with adjacent dense TPE molecules, so that the phenomenon of fluorescence quenching is generated, and the ultrahigh-sensitivity detection of the target molecules is realized.
Drawings
FIG. 1 shows the preparation of Compound 21H NMR chart;
FIG. 2 shows the preparation of Compound 31H NMR chart;
FIG. 3 shows the preparation of Compound 313C NMR chart;
FIG. 4 is a high resolution mass spectrum of the prepared compound 3;
FIG. 5 shows preparation of Compound 41H NMR chart;
FIG. 6 shows preparation of Compound 413C NMR chart;
FIG. 7 is a high resolution mass spectrum of the prepared compound 4;
FIG. 8 is an infrared spectrum of a prepared compound JUC-555;
FIG. 9 shows preparation of compound JUC-55513C NMR chart;
FIG. 10 is a schematic 3D structure of the prepared compound JUC-555;
FIG. 11 is a PXRD pattern of prepared compound JUC-555;
FIG. 12 is a thermogravimetric analysis spectrum of synthetic JUC-555;
FIG. 13 is a graph of nitrogen adsorption and desorption curves for synthetic JUC-555;
FIG. 14 is a graph of the pore size distribution of the synthesized JUC-555;
FIG. 15 is a PXRD pattern of synthetic JUC-555 in different solutions;
FIG. 16 is an ultraviolet absorption spectrum and a photoemission spectrum of monomer and JUC-555;
FIG. 17 is a CIE chromatogram of JUC-555, and a comparison plot under white light illumination with an ultraviolet lamp at 365nm (upper right corner);
FIG. 18 is a graph showing the fluorescence change of nitrobenzene titrated by the JUC-555 solution dispersed in DMF;
FIG. 19 shows Stern-
Figure BDA0002566887780000081
plots and KSV；
FIG. 20 shows K measured for p-nitrobenzene in the prior artSVCompare the figures.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, the specific sources of the raw materials were from the company welfare;
the detection of dangerous compounds such as nitrobenzene by 3D COFs is tested by fluorescence titration (JACS,2018,140: 4035; chem. Mater.,2016,28: 7889).
The rest of the raw material reagents or processing techniques are conventional commercial products or conventional processing techniques in the field unless otherwise specified.
Example 1:
this example provides a fluorescent three-dimensional covalent organic framework material, i.e., 3D COFs, whose chemical structural repeat units are as follows:
Figure BDA0002566887780000091
the specific preparation process of the fluorescent three-dimensional covalent organic framework material 3D COFs is as follows:
(1) adding 2-bromo-1, 1, 2-triphenylethylene, 4-formylphenylboronic acid and Na into a sealed tube2CO3And then adding V theretoTHF:VWater (W)Stirring uniformly and introducing nitrogen for 40 minutes, and taking Pd (PPh)3)2Cl2Adding it rapidly, and then N220min, heating to 80 ℃, reacting for 24h, wherein in the step, 2-bromo-1, 1, 2-triphenylethylene and 4-formylphenylboronAcid, Na2CO3And Pd (PPh)3)2Cl2The molar weight ratio of (1) to (2) is 10mmol to 20mmol to 1mmol to 20 mmol. And (3) post-treatment: firstly, extracting, adding anhydrous sodium sulfate into an organic phase, drying, carrying out vacuum filtration, carrying out vacuum concentration on a filtrate, adding silica gel, stirring, and carrying out column chromatography to obtain a compound 1.1H NMR(400MHz,Chloroform-d)δ9.84(s,1H),7.58–7.52(m,2H),7.16–7.12(m,2H),7.06(dtt,J＝5.3,3.8,1.8Hz,9H),6.97(dddd,J＝7.6,5.5,3.8,2.0Hz,6H)。
(2) The compound 4, 7-dibromo-2, 1, 3-benzothiadiazole was placed in a 250mL single-neck round-bottom flask and dissolved with 100mL of ethanol while cooling with an ice-water bath. Then slowly adding NaBH in portions4The reaction was mixed and stirred overnight. The solidified reaction mixture was concentrated in vacuo by a rotary evaporator, then carefully diluted with water, followed by addition of dichloromethane and extraction with saturated brine, drying over anhydrous magnesium sulfate and concentration in vacuo to give compound 2.1H NMR(400MHz,CDCl3) δ 6.85(s,2H),3.89(s, 4H). In this step, the compound 4, 7-dibromo-2, 1, 3-benzothiadiazole, ethanol and NaBH4The molar ratio of (2) to (3) was 10mmol, 100mL, and 20 mmol.
The chemical structure of compound 5 is as follows:
Figure BDA0002566887780000101
(3) compound 1, Ce (NH)4)2(NO3)6Adding a certain amount of hydrogen peroxide into a 250mL single-neck round-bottom flask, adding 100mL acetonitrile for complete dissolution, slowly adding the compound 2 into the system in batches, stirring uniformly, heating to 83 ℃, reacting for 3h, returning the reaction to room temperature, performing suction filtration under reduced pressure to obtain a yellow-white solid compound 3,1H NMR(400MHz,DMSO-d6) δ 13.20(s,1H),8.07(d, J ═ 1.5Hz,2H),7.36(s,2H),7.15(s,10H),7.03(d, J ═ 4.7Hz, 5H). In this step, compound one, Ce (NH)4)2(NO3)6Hydrogen peroxide and compound IIThe ratio of the amounts of (A) to (B) was 4mmol:5mmol:5mmol:5 mmol.
(4) Adding 3, 4-formylphenylboronic acid and Na into the sealed tube2CO3And then adding V theretoTHF:VWater (W)Stirring evenly and introducing N in a ratio of 7:32After about 40 minutes, a certain amount of Pd (PPh) was taken3)4Adding it rapidly, and then N2After about 20 minutes, the temperature was raised to 80 ℃ and the reaction was carried out for 24 hours. Directly carrying out vacuum filtration to obtain a yellow solid compound 4,1H NMR(400MHz,DMSO-d6) δ 12.77(s,1H),10.10(d, J ═ 22.8Hz,2H),8.45(d, J ═ 8.0Hz,2H),8.17 to 7.91(m,8H),7.66(d, J ═ 7.8Hz,1H),7.42(d, J ═ 7.8Hz,1H),7.30 to 7.11(m,12H),7.09 to 6.78(m, 7H). In this step, the compounds tri, 4-formylphenylboronic acid, Na2CO3And Pd (PPh)3)4The molar ratio of (2) to (3) to (6) is 10mmol to 45mmol to 2mmol to 100 mmol.
(5) BFTP (i.e., compound 4) and TAPM are suspended in a certain amount of tetrahydrofuran, DMF, DMAC, dioxane, ethanol, dioxane and mesitylene are used in this experiment, 6M acetic acid is used as a catalyst, and in this step, the amounts of compound 4, TAPM, dioxane and mesitylene are 0.05mmol:0.0125mmol:0.8mL:0.2mL, respectively. The bottles were snap frozen at 77K (liquid nitrogen bath), evacuated to an internal pressure below 8Pa and flame sealed. The reaction was heated at 120 ℃ for 72 hours to give a white solid, which was isolated by filtration and washed with anhydrous acetone, and the resulting powder was immersed in anhydrous DMF for 24 hours and then dried at room temperature. In vacuo at 100 ℃ overnight, a yellow solid was obtained, denoted as compound JUC-555, which is the 3D COFs.
FIGS. 1 to 7 are detection spectra of compounds 2 to 4 obtained in the above steps, respectively.
FIG. 8 is an infrared spectrum of the prepared compound JUC-555, and a black line is a spectrum of ligand TAPM, -NH2The peak of the stretching vibration is 3310-3400 cm-1Can be seen; the red line is the spectrogram of monomer BFTP, and the stretching vibration peak of aldehyde group is 1692cm-1At least one of (1) and (b); blue spectrum JUC-555 at 1624cm-1The peak of stretching vibration of imine bond is observed and originally ranges from 3310 to 3400cm-1And 1692cm-1The stretching vibration peak disappears, and the reaction is proved to be carried out and completed;
FIG. 9 shows preparation of compound JUC-55513C NMR chart in which nuclear magnetic peak at 156ppm confirmed formation of imine bond;
FIG. 10 is a schematic 3D structure of the prepared JUC-555 compound. From the figure, it is evident that the TPE molecules are closely arranged in the three-dimensional pore canal of JUC-555.
FIG. 11 is a PXRD spectrum of prepared JUC-555 compound, where the red line is the experimental value, the blue line is the PAWLEY refinement value, the green line is the error line, and the purple line is the simulated value. It can be clearly seen that the error fluctuation between the simulated value and the experimental value is small, and the structure shown in fig. 10 can be determined.
FIG. 12 is a thermogravimetric analysis of the synthesized JUC-555, with 95% weight retention when the sample is heated to 470 deg.C, demonstrating that the formed JUC-555 has high thermal stability;
FIG. 13 is a graph of nitrogen adsorption and desorption curves for the synthesized JUC-555 showing good BET to 253.1677m2/g；
FIG. 14 is a plot of the pore size distribution of the synthesized JUC-555, described above, illustrating that the covalent organic framework has a uniform pore size, matched by the simulation, of 1.3 nm;
FIG. 15 is a PXRD pattern of the synthesized JUC-555 in different solutions demonstrating its good stability.
FIG. 16 is an ultraviolet absorption spectrum and a light emission spectrum of the monomer (Compound 4) and JUC-555; the maximum absorption peak of the monomer can be seen at 352nm, and the JUC-555 peak is at 339 nm; the maximum emission wavelengths of the monomer and the JUC-555 are 466nm and 482nm respectively;
FIG. 17 is a CIE chromatogram of JUC-555, and a comparison plot under white light illumination with an ultraviolet lamp at 365nm (upper right corner);
FIG. 18 is a graph showing the fluorescence change of a nitrobenzene titration solution in which JUC-555 is uniformly dispersed in a DMF solution;
FIG. 19 shows Stern-
Figure BDA0002566887780000121
plots and KSV；
FIG. 20 shows K measured for p-nitrobenzene in the prior artSVComparing the graphs, it can be seen that the JUC-555 has very sensitive detection capability to nitrobenzene.
Comparative example 1:
compared with example 1, most of the same except that 6M acetic acid was changed to 3M acetic acid in step (5), the product crystallinity was significantly reduced.
Comparative example 2:
compared with example 1, most of them were the same except that in step (5), dioxane in a mixed solvent of dioxane and mesitylene was replaced with an equimolar amount of THF, and the obtained product was a polymer without crystallization.
Comparative example 3:
compared with example 1, most of them are the same except that in step (5), freezing and vacuum-pumping treatments are omitted, so that organic monomers are oxidized, a large amount of colored impurities are generated, and the impurities are difficult to remove.
Comparative example 4:
compared with example 1, most of them are the same, except that in step (5), the temperature of the heating reaction is changed to 80 ℃, and the crystallinity of the product is obviously reduced.
In addition, this example provides only a specific scheme of the 3D COFs structure composed of the COFs skeleton and AIEgens attached to the side chains of the COFs skeleton, which is stated in the present invention, and based on this, those skilled in the art know that the COFs skeleton and AIEgens may be replaced with other groups having corresponding functions, which are commonly used in the art, due to similar action mechanisms or effects.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A fluorescent three-dimensional covalent organic framework material is characterized in that the material is a 3D COFs structure consisting of a COFs framework and AIEgens connected to the side chain of the COFs framework.
2. The fluorescent three-dimensional covalent organic framework material of claim 1, wherein said AIEgens is TPE.
3. The fluorescent three-dimensional covalent organic framework material of claim 2, wherein the chemical structural formula of the 3D COFs structure is as follows:
Figure FDA0002566887770000011
4. a method of preparing a fluorescent three-dimensional covalent organic framework material according to any of claims 1 to 3, comprising the steps of:
(1) taking compound I, Ce (NH)4)2(NO3)6Mixing with hydrogen peroxide, adding acetonitrile for dissolving, adding a compound II, stirring uniformly, heating for reaction, cooling to room temperature, and filtering to obtain a compound III;
(2) taking the compounds of tri, 4-formyl phenylboronic acid and Na2CO3Adding mixed solvent of THF and water, stirring, adding Pd (PPh)3)4Heating for reaction, and filtering to obtain a compound IV;
(3) weighing compounds IV and tetrakis- (4-aminophenyl) -methane, suspending the compounds IV and the tetrakis- (4-aminophenyl) -methane in dioxane and mesitylene, taking acetic acid as a catalyst, freezing, vacuumizing, sealing, heating for reaction, filtering, separating and washing the obtained product, immersing the product in anhydrous DMF, taking out the product, drying, and standing overnight in vacuum to obtain a target product;
wherein, the compound I and the compound II are respectively as follows:
Figure FDA0002566887770000021
5. the method for preparing a fluorescent three-dimensional covalent organic framework material according to claim 4,
the preparation process of the compound I is as follows:
weighing 2-bromo-1, 1, 2-triphenylethylene, 4-formylphenylboronic acid and Na2CO3Adding mixed solvent of THF and water, stirring, and adding Pd (PPh)3)2Cl2Heating for reaction to obtain a compound I, wherein the volume ratio of THF to water in the mixed solvent is 5: 2; the process conditions of the temperature-rising reaction are as follows: reacting for 24 hours at 80 ℃;
the preparation process of the compound II comprises the following steps:
dissolving compound five in ethanol, cooling, and adding NaBH4Mixing and stirring overnight, evaporating and concentrating the obtained reaction mixture, adding water for dilution, extracting and drying to obtain a compound II;
wherein, the chemical structural formula of the compound five is as follows:
Figure FDA0002566887770000022
compound five, ethanol and NaBH4The ratio of the addition amounts of (A) to (B) is 10mmol:100mL of: 20mmol of the active carbon; the temperature of the mixture was 20 ℃ with stirring overnight.
6. The method for preparing the fluorescent three-dimensional covalent organic framework material according to claim 2, wherein in the step (1), compound I, Ce (NH)4)2(NO3)6The ratio of the addition amounts of the hydrogen peroxide and the compound II is 4mmol:5mmol:5mmol:5 mmol.
7. The method for preparing the fluorescent three-dimensional covalent organic framework material according to claim 2, wherein in the step (1), the process conditions of the temperature-raising reaction are as follows: the reaction was carried out at 83 ℃ for 3 h.
8. The method for preparing the fluorescent three-dimensional covalent organic framework material according to claim 2, wherein in the step (2), the compounds tri, 4-formylphenylboronic acid and Na2CO3And Pd (PPh)3)4The addition amount mol ratio of (A) is 10mmol to 45mmol to 2mmol to 100 mmol;
the process conditions of the temperature-rising reaction are as follows: reacting for 24 hours at 80 ℃;
the volume ratio of THF to water in the mixed solvent was 7: 3.
9. The method for preparing a fluorescent three-dimensional covalent organic framework material according to claim 2, wherein in step (3), the addition amount ratio of the compounds of tetra, TAPM, dioxane and mesitylene is 0.05mmol:0.0125mmol:0.8mL:0.2 mL;
the heating reaction process conditions are as follows: reacting for 72 hours at 120 ℃;
immersion time in anhydrous DMF was 24 h.
10. The use of a fluorescent three-dimensional covalent organic framework material according to claim 1 for the detection of hazardous compounds including nitrobenzene compounds, polycyclic aromatic hydrocarbons and sulfur-containing aromatic hydrocarbons.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114773551A (en) * 2022-05-05 2022-07-22 浙江工业大学 Two-dimensional covalent organic framework compound with high fluorescence quantum yield and preparation and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102442873A (en) * 2010-10-08 2012-05-09 国家纳米科学中心 Fluorescence nanometer organic porous material as well as preparation method and application thereof
WO2018070933A1 (en) * 2016-10-10 2018-04-19 National University Of Singapore Fluorescent porous organic frameworks containing molecular rotors for chemical sensing
CN110791046A (en) * 2018-08-01 2020-02-14 孝感市思远新材料科技有限公司 Covalent organic framework film, preparation thereof and application thereof in chiral amine recognition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102442873A (en) * 2010-10-08 2012-05-09 国家纳米科学中心 Fluorescence nanometer organic porous material as well as preparation method and application thereof
WO2018070933A1 (en) * 2016-10-10 2018-04-19 National University Of Singapore Fluorescent porous organic frameworks containing molecular rotors for chemical sensing
CN110791046A (en) * 2018-08-01 2020-02-14 孝感市思远新材料科技有限公司 Covalent organic framework film, preparation thereof and application thereof in chiral amine recognition

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
QIU-YAN LI ET AL: "AIE-active tetraphenylethene functionalized metal–organic framework for selective detection of nitroaromatic explosives and organic photocatalysis", 《CHEMICAL COMMUNICATIONS》 *
XINYU GUAN ET AL: "Design and applications of three dimensionalcovalent organic frameworks", 《CHEMICAL SOCIETY REVIEWS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114773551A (en) * 2022-05-05 2022-07-22 浙江工业大学 Two-dimensional covalent organic framework compound with high fluorescence quantum yield and preparation and application thereof
CN114773551B (en) * 2022-05-05 2023-05-23 浙江工业大学 Two-dimensional covalent organic framework compound with high fluorescence quantum yield, and preparation and application thereof

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