CN113817161B - Process for the preparation of amide-linked covalent organic frameworks - Google Patents
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Abstract
The invention discloses a preparation method of an amido bond linked covalent organic framework, which comprises the following steps: in solvent, the covalent organic framework linking imine bonds ‑ HSO 5 By oxidation to give said amide linkageA covalent organic framework. The preparation method of the invention has one or more of the following advantages: high efficiency and universality, and can realize amplified preparation.
Description
Technical Field
The invention relates to a preparation method of an amido bond linked covalent organic framework.
Background
Covalent Organic Frameworks (COFs) are a class of crystalline Organic porous polymers formed by the development of building blocks through Covalent bond connection according to the principle of framework chemistry. In 2005, the Yaghi topic group first reported such structures (
A.P.; benin, a.i.; lockwig, n.w.; o' Keeffe, m.; matzger, a.j.; yaghi, o.m. science 2005,310, 1166). Through many years of development, covalent organic frameworks have made significant advances in both structural design and functional application (Geng, K.; he, T.; liu, R.; dalapati, S.; tan, K.T.; li, Z.; tao, S.; gong, Y.; jiang, Q.; jiang, G.Chem.Rev.2020,120,8814). Due to the characteristics of crystallinity, porosity, large specific surface area, low density, high stability, structure designability and the like of the covalent organic frameworks, the covalent organic frameworks have great application potential in many fields such as substance adsorption and separation, catalysis, drug delivery, photoelectric materials and the like. However, since the formation of covalent organic frameworks is usually based on dynamic covalent bonds, the chemical stability of the covalent organic frameworks is somewhat reduced while the crystallinity is satisfied. Therefore, it is of great value to develop synthetic methods for covalent organic frameworks with high chemical stability and high crystallinity.
Subsequently developed covalent organic frameworks linked by-C = N-possess higher chemical stability and are easier to prepare than the covalent organic frameworks linked by B-O bonds originally reported. Among the covalent organic frameworks reported so far, the covalent organic frameworks linked by-C = N-account for approximately two thirds or more of the total number. However, the structure of the covalent organic framework structure connected by-C = N-is still easy to be damaged under the severe environment of strong acid and the like, thereby limiting the practical application of the material. Polyamides (commonly known as nylons) are a large class of polymers connected by amide bonds, and have been widely used in industry and life, and have important commercial application values. Compared with a C = N bond, the amido bond has higher chemical stability and stronger polarity, improves the hydrophilicity of the structure, and has larger application potential. However, the reversibility of amidation reaction is very low, and it is difficult to obtain a covalent organic framework material with high crystallinity and amido bond connection by a direct polymerization method. The preparation methods of the amide bond linked covalent organic framework reported in the literature at present have the following three methods: yaghi et al, 2016,138,15519, used a Pinnick-like oxidation reaction to convert a-C = N-linked covalent organic framework to an amide-linked covalent organic framework using sodium chlorite as an oxidant (Waller, P.J.; lyle, S.J.; osborn Popp, T.M.; diercks, C.S.; reimer, J.A.; yaghi, O.M.J.Am.Chem.Soc.2016,138, 15519.). This method requires a long reaction time (at least 48 hours), and is complicated in operation steps, thus having great limitations. In 2017, the Rosseinsky group reported methods for the synthesis of covalent amide frameworks by high temperature and pressure facilitated reversible repair of polymerization products of acid chloride monomers and amine monomers (Stewart, D.; antypov, D.; dyer, M.S.; pitcher, M.J.; katsouldis, A.P.; chater, P.A.; blanc, F.; rosseinsky, M.J.Nat. Commun.2017,8, 1102.). However, the material obtained by the method has low crystallinity, the reaction temperature is as high as 250 ℃, and the reaction time is long (3 days), so the method has low practical application value. In 2020, yan project group reported a method for constructing an amide-linked covalent organic framework by a strategy of linker exchange (Qian, H.L.; meng, F.L.; yang, C.X.; yan, X.P.Angew.chem.int.Ed.2020,59, 17607), but this method also has the disadvantages of long reaction time (48 hours), inconvenient operation (low temperature), low universality, etc. In addition, these methods all achieve only a small synthesis of milligram-grade product. Therefore, the preparation methods of the amide bond linked covalent organic framework materials reported so far have great limitations, and the amide bond linked covalent organic frameworks cannot be efficiently and simply obtained, and cannot be synthesized in large quantities.
Disclosure of Invention
The invention aims to solve the technical problems of time consumption, energy consumption, complex operation steps, inconvenience for scale-up production and the like in the conventional method for preparing the amide bond-linked covalent organic framework.
The invention solves the technical problems through the following technical scheme.
The invention provides a preparation method of an amide bond linked covalent organic framework, which comprises the following steps: in a solvent, a covalent organic framework linking imine linkages (i.e., -C = N-) - HSO 5 Carrying out oxidation reaction under the action of (3) to obtain the covalent organic framework connected with the amide bond.
In some embodiments, the imine-linked covalent organic framework can have a one-, two-, or three-dimensional structure.
In some embodiments, the covalent organic framework of the imine bond is linked such that both ends of the imine bond are linked to aromatic carbon atoms.
In some embodiments, the covalent organic framework of the imine bond is linked such that both ends of the imine bond are attached to carbon atoms of the aryl ring. The aryl rings attached to both ends of the imine bond may be the same or different. Examples of such aryl rings include, but are not limited to, benzene, naphthalene, anthracene, phenanthrene, pyrene rings. The aryl ring may be unsubstituted or substituted by one or more C 1-4 Alkyl (e.g., methyl) substituted, e.g., the aryl ring may be unsubstituted or substituted with one methyl group.
In some embodiments, the covalent organic framework of the imine bond is linked such that both ends of the imine bond are attached to carbon atoms of the phenyl ring.
In some embodiments, the imine-linked covalent organic framework is comprised of imine linkages and one or more of the following structures:
the aryl rings contained in the above structures may be unsubstituted or substituted by one or more C 1-4 Alkyl (e.g., methyl) substituents, for example, the aryl ring contained in the above structure may be unsubstituted or substituted with one methyl group.
In some embodiments, the imine-linked covalent organic framework consists of structural units a and B interconnected:
the structural unit A is
The structural unit B is
The aryl rings contained in the structural units A and B may be unsubstituted or substituted by one or more C 1-4 Alkyl (e.g., methyl) is substituted, e.g., unsubstituted or substituted with one methyl group.
In some embodiments, the imine-linked covalent organic framework is composed of structural units a and B of any one of the following groups linked to each other:
(1) The structural unit A is
Structural unit B is
(2) Structural unit A is
Structural unit B is
(3) Structural unit A is
Structural unit B is
(4) The structural unit A is
Structural unit B is
(5) Structural unit A is
Structural unit B is
(6) Structural unit A is
Structural unit B is
(7) Structural unit A is
Structural unit B is
The aryl rings contained in the structural units A and B may be unsubstituted or substituted by one or more C 1-4 Alkyl (e.g., methyl) is substituted, e.g., unsubstituted or substituted with one methyl group.
In some embodiments, in said structural unit A and said structural unit B,
containing benzene rings unsubstituted or substituted by one or more C 1-4 Alkyl (e.g. methyl) substitution, e.g.Is unsubstituted or substituted by one methyl group (e.g.
) And aryl rings contained in other structures are all unsubstituted.
In some embodiments, the imine-linked covalent organic framework has a structure represented by formula I, III, V, VII, IX, XI, XIII, XV, or XVII.
In some embodiments, the amide linked covalent organic framework has a structure according to formula II, IV, VI, VIII, X, XII, XIV, XVI, or XVIII.
In some embodiments of the present invention, the substrate is, - HSO 5 may be provided in the form of various conventional salts for use in the oxidation reaction. Examples of such salts include, but are not limited to, naHSO 5 、NaHSO 5 Compound salt, KHSO 5 、KHSO 5 Complex salt, ca (HSO) 5 ) 2 、Ca(HSO 5 ) 2 Complex salt, mg (HSO) 5 ) 2 、Mg(HSO 5 ) 2 One or more of complex salts. The NaHSO 5 Examples of complex salts include, but are not limited to, na 2 SO 4 ·NaHSO 4 ·2NaHSO 5 . The KHSO 5 Examples of complex salts include, but are not limited to, 2KHSO 5 ·KHSO 4 ·K 2 SO 4 . Preferably, the first and second electrodes are formed of a metal, - HSO 5 in KHSO 5 And/or a complex salt thereof, for use in the oxidation reaction.
In some embodiments, there is provided - HSO 5 May be 1 to 5 times, preferably 2 to 3 times the molar amount of the imine-linked covalent organic framework.
In some embodiments, the oxidation reaction may be carried out in the absence of an acid or in the presence of an acid. Generally, the addition of an acid is advantageous to enhance the reaction effect. The acid may be an acid conventional in the art for such reactions, including but not limited to acetic acid. The amount of the acid may be conventional in the art.
In some embodiments, the organic solvent may be a solvent conventional in such reactions in the art, preferably N, N-dimethylformamide, further preferably anhydrous N, N-dimethylformamide. The organic solvent may be used in an amount conventional in the art.
In some embodiments, the oxidation reaction may be carried out at a temperature of 0 to 80 ℃ (preferably 20 to 30 ℃, e.g., 25 ℃).
In some embodiments, the oxidation reaction may be performed under a gas blanket. The gas may be conventional in the art, including but not limited to one or more of nitrogen, argon, and helium.
In the present invention, the time of the oxidation reaction may be adjusted conventionally according to the reaction monitoring result, the reaction scale, and the like. In some embodiments, the time for the oxidation reaction may be 0.5 to 10 hours, such as 4 to 6 hours (e.g., 5 hours).
In some embodiments, the preparation method may further comprise a post-treatment step after the oxidation reaction is completed. The post-treatment step may be conventional in the art and may, for example, comprise the steps of: and (3) carrying out solid-liquid separation on the reaction liquid, washing the obtained solid, extracting by using an organic solvent, and drying to obtain the amide bond linked covalent organic framework. The washing may be with Na 2 S 2 O 3 The aqueous solution, water and tetrahydrofuran are washed in this order. The organic solvent extraction may be performed by using methanol and tetrahydrofuran, respectively.
In the present invention, the imine-linked covalent organic framework can be obtained by preparation methods conventional in the art. See the following documents: zhanhongjiang et al, covalent organic framework materials based on schiff base reactions, chemical evolution, 2018,30,365; weihao et al, development of covalent organic framework materials, reports on physicochemical science, 2017,33,1960; segura et al, commercial organic frames based on Schiff-base chemistry, synthesis, properties and potential applications, chem.Soc.Rev.,2016,45,5635. A typical solvothermal preparation process may comprise the steps of: placing the raw materials and the solvent in a sealed tube, carrying out ultrasonic treatment for a few minutes to uniformly mix the raw materials and the solvent, adding an acetic acid aqueous solution as a catalyst, carrying out air extraction treatment on the sealed tube, carrying out melt sealing under vacuum, and then standing for 3 days at 120 ℃. Filtering, washing the obtained solid, and drying in vacuum to obtain the covalent organic framework material.
The positive progress effects of the invention are as follows: the method of the invention for preparing an amide-linked covalent organic framework has one or more of the following advantages:
(1) Compared with the methods reported before, the method provided by the invention is not only quick, but also simple in operation steps, avoids complex procedures and is beneficial to practical application;
(2) The method has universality and shows good implementation effect on covalent organic frameworks with different structures and different dimensions;
(3) The method takes the covalent organic framework connected by imine bonds with wide sources as a precursor, the covalent organic framework connected by imine bonds accounts for more than two thirds of the total number of the covalent organic frameworks reported at present, the preparation is easy, and the structure is various, so the method can obtain a large amount of covalent organic frameworks connected by amide bonds with various structures;
(4) The method of the invention can realize scale-up preparation, and the methods reported in the prior art are limited to milligram scale.
Drawings
FIG. 1 is a powder X-ray diffraction pattern of covalent organic frameworks I and II.
FIG. 2 is an infrared spectrum of covalent organic frameworks I and II.
FIG. 3 shows covalent organic frameworks I and II 13 C solid nuclear magnetic diagram.
FIG. 4 is a plot of the sorption isotherms for nitrogen for covalent organic frameworks I and II.
FIG. 5 is a powder X-ray diffraction pattern of covalent organic frameworks III and IV.
FIG. 6 is an infrared spectrum of covalent organic frameworks III and IV.
FIG. 7 shows covalent organic frameworks III and IV 13 C solid nuclear magnetic diagram.
FIG. 8 is a nitrogen desorption isotherm plot of covalent organic frameworks III and IV.
FIG. 9 is a powder X-ray diffraction diagram of covalent organic frameworks V and VI.
FIG. 10 is an infrared spectrum of covalent organic frameworks V and VI.
FIG. 11 shows covalent organic frameworks V and VI 13 C solid nuclear magnetic diagram.
FIG. 12 is a nitrogen desorption isotherm plot of covalent organic frameworks V and VI.
FIG. 13 is a powder X-ray diffraction pattern of covalent organic frameworks VII and VIII.
FIG. 14 is an infrared spectrum of covalent organic frameworks VII and VIII.
FIG. 15 is a powder X-ray diffraction pattern of covalent organic frameworks IX and X.
FIG. 16 is an infrared spectrum of covalent organic frameworks IX and X.
FIG. 17 is a powder X-ray diffraction pattern of covalent organic frameworks XI and XII.
FIG. 18 is an infrared spectrum of covalent organic frameworks XI and XII.
FIG. 19 is a powder X-ray diffraction pattern of covalent organic frameworks XIII and XIV.
FIG. 20 is an infrared spectrum of covalent organic frameworks XIII and XIV.
FIG. 21 is a powder X-ray diffraction pattern of covalent organic frameworks XV and XVI.
FIG. 22 is an infrared spectrum of covalent organic frameworks XV and XVI.
FIG. 23 is a powder X-ray diffraction pattern of covalent organic frameworks XVII and XVIII.
FIG. 24 is an infrared spectrum of covalent organic frameworks XVII and XVIII.
FIG. 25 is a graph of the infrared spectra of covalent organic framework I before and after oxidation in the absence of acid.
FIG. 26 shows the use of Pd (OAc) 2 Infrared spectrum of oxidation of the/t-BuOOH system.
FIG. 27 shows a case where the catalyst is used in the reaction solution H 2 O 2 Infrared spectrum of oxidation of the/HOAc system.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods not specified in the following examples may be selected according to conventional methods and conditions, or according to the commercial instructions.
Example 1
Covalent organic frameworks I (30 mg) and KHSO 5 (86mg, 3 equiv.) was added to anhydrous N, N-dimethylformamide (2 ml), and then 0.1ml of glacial acetic acid was added thereto, and nitrogen gas was rapidly purged several times, sealed, and stirred at 25 ℃ for reaction for 5 hours. Filtering, and using 10% of filter cake to obtain Na% 2 S 2 O 3 Aqueous solution, water and tetrahydrofuran. The resulting solid was then subjected to Soxhlet extraction with anhydrous methanol and tetrahydrofuran, respectively, for 5 hours and vacuum dried at 100 ℃ for 2 hours to give a brown solid (30mg, 90%).
As can be seen from fig. 1, the X-ray diffraction peaks of the powder before and after oxidation remained essentially unchanged, indicating that the amide bond linked covalent organic framework obtained after oxidation has a similar crystal structure to its precursor (-C = N-linked covalent organic framework). Wherein, the diffraction peaks of the covalent organic framework II at 2Theta =2.76 °,5.46 ° and 7.20 ° respectively correspond to the diffraction of the (100), (200) and (210) crystal planes, and the AA stacking structure has P6 symmetry.
As can be seen from FIG. 2, at 1620cm -1 The characteristic peak corresponding to-C = N-had disappeared, corresponding to 1655cm -1 The formation of amide (C (O) NH) is evidenced by the characteristic peak at (A).
From fig. 3 it can be seen that the carbon signal corresponding to-C = N-has disappeared at 158ppm and instead the carbon signal of the amide bond appears at 164ppm, further demonstrating the complete conversion of the covalent organic framework i into the covalent organic framework ii.
From the nitrogen adsorption isotherm data of FIG. 4, it can be calculated that the BET specific surface area of the covalently organic framework II obtained after oxidation is 728m 2 G, albeit in comparison with Structure I (specific surface area 1171 m) 2 The/g) is reduced because of the greater structural flexibility of II.
Working examples for the amplification of preparation
Covalent organic frameworks I (1 g) and KHSO 5 (3.2 g,3 equiv.) was added to anhydrous N, N-dimethylformamide (30 ml), and 1.5ml of glacial acetic acid was added thereto, and nitrogen gas was rapidly purged several times, sealed, and stirred at 25 ℃ for reaction for 5 hours. Filtering, the filter cake is 10% Na 2 S 2 O 3 Aqueous solution, water and tetrahydrofuran. The resulting solid was then subjected to Soxhlet extraction with anhydrous methanol and tetrahydrofuran, respectively, for 5 hours, and vacuum-dried at 100 ℃ for 2 hours to give a brown solid (1.1 g). The structural characterization results of the covalent organic framework II obtained in the scale-up preparation are similar to those of example 1.
Example 2
Covalent organic framework III (30 mg) and KHSO 5 (48mg, 2equiv.) was added to anhydrous N, N-dimethylformamide (2 ml), 0.1ml of glacial acetic acid was added thereto, nitrogen gas was rapidly purged several times, and the mixture was sealed and stirred at 25 ℃ for reaction for 5 hours. Filtering, and using 10% of filter cake to obtain Na% 2 S 2 O 3 Aqueous solution, water and tetrahydrofuran. The resulting solid was then subjected to Soxhlet extraction with anhydrous methanol and tetrahydrofuran, respectively, for 5 hours and vacuum dried at 100 ℃ for 2 hours to give a brown solid (30mg, 92%).
As can be seen in fig. 5, the X-ray diffraction peaks of the powder before and after oxidation remained essentially unchanged, indicating that the amide bond linked covalent organic framework obtained after oxidation has a similar crystal structure to the precursor covalent organic framework. Wherein the diffraction peaks of the covalent organic framework iv at 2theta =3.76 °,5.38 °,7.49 °,11.22 ° correspond to the diffraction of the (110), (020), (220) and (330) crystal planes, respectively, and have an AA packing structure with CMM2 symmetry.
As can be seen from FIG. 6, at 1620cm -1 The characteristic peak corresponding to-C = N-had disappeared, corresponding to 1655cm -1 The characteristic peak at (a), evidencing the formation of C (O) NH.
As can be seen from fig. 7, the carbon signal corresponding to-C = N-has disappeared at 156ppm and instead the carbon signal of the amide bond appears at 165ppm, further demonstrating the complete conversion of the covalent organic framework iii into the covalent organic framework iv.
From the nitrogen adsorption isotherm data of FIG. 8, it can be calculated that the BET specific surface area of the covalently organic framework IV obtained after oxidation is 1015m 2 /g。
Example 3
Covalent organic framework V (40 mg) and KHSO 5 (73mg, 2equiv.) was added to anhydrous N, N-dimethylformamide (2 ml), and then 0.1ml of glacial acetic acid was added thereto, and nitrogen gas was rapidly purged several times, sealed, and stirred at 25 ℃ for reaction for 5 hours. Filtering, and using 10% of filter cake to obtain Na% 2 S 2 O 3 Aqueous solution, water and tetrahydrofuran. The resulting solid was then subjected to Soxhlet extraction with anhydrous methanol and tetrahydrofuran, respectively, for 5 hours and vacuum dried at 100 ℃ for 2 hours to give a brown solid (26mg, 59%).
As can be seen from fig. 9, the X-ray diffraction peaks of the powder before and after oxidation remained essentially unchanged, indicating that the amide bond linked covalent organic framework obtained after oxidation has a similar crystal structure to the precursor. Wherein, the diffraction peak of the covalent organic framework VI at 2Theta =5.12 degrees and 10.29 degrees respectively corresponds to the diffraction of (100) and (020) crystal planes, and has an AA stacking structure with P1 symmetry.
As can be seen from FIG. 10, at 1620cm -1 The characteristic peak corresponding to-C = N-had disappeared, corresponding to 1656cm -1 The characteristic peak shows the formation of C (O) NH, and the C-H content is 2921cm -1 ，2867cm -1 The vibration signal peak is still remained after oxidation, which proves that methyl is not affected in the oxidation process, and the preparation method of the invention has better functional group compatibility.
As can be seen from fig. 11, the carbon signal corresponding to-C = N-at 157ppm had disappeared, and instead the carbon signal of the amide bond appeared at 165 ppm. And the methyl carbon signal at 18ppm was retained. This is consistent with the conclusions drawn in the infrared spectrum.
From the nitrogen adsorption isotherm data of FIG. 12, it can be calculated that the BET specific surface area of the covalently organic framework VI obtained after oxidation is 795m 2 /g。
Example 4
Combining three-dimensional covalent organic framework VII (20 mg) and KHSO 5 (32mg, 2equiv.) was added to anhydrous N, N-dimethylformamide (2 ml), and then 0.1ml of glacial acetic acid was added, nitrogen gas was rapidly purged several times, sealed, and stirred at 25 ℃ for reaction for 5 hours. Filtering, the filter cake is 10% Na 2 S 2 O 3 Aqueous solution, water and tetrahydrofuran. The resulting solid was then subjected to Soxhlet extraction with anhydrous methanol and tetrahydrofuran, respectively, for 5 hours and vacuum dried at 100 ℃ for 2 hours to give a brown solid (12.1mg, 56%).
As can be seen in fig. 13, the powder X-ray diffraction peaks remained essentially unchanged before and after oxidation, indicating that the amide bond linked covalent organic framework obtained after oxidation has a similar crystal structure to the precursor.
From FIG. 14It can be seen that the length of the groove is 1624cm -1 The characteristic peak corresponding to-C = N-had disappeared, corresponding to 1668cm -1 A characteristic peak at, and at 3325cm -1 A stretching vibration peak of N-H appears, confirming the formation of C (O) NH.
Example 5
Covalent organic frameworks IX (30 mg) and KHSO 5 (48mg, 2equiv.) was added to anhydrous N, N-dimethylformamide (2 ml), 0.1ml of glacial acetic acid was added thereto, nitrogen gas was rapidly purged several times, and the mixture was sealed and stirred at 25 ℃ for reaction for 5 hours. Filtering, the filter cake is 10% Na 2 S 2 O 3 Aqueous solution, water and tetrahydrofuran. The resulting solid was then subjected to Soxhlet extraction with anhydrous methanol and tetrahydrofuran, respectively, for 5 hours and vacuum dried at 100 ℃ for 2 hours to give a brown solid (29.4 mg, 90.5%).
As can be seen in fig. 15, the powder X-ray diffraction peaks remained essentially unchanged before and after oxidation, indicating that the amide bond linked covalent organic framework obtained after oxidation has a similar crystal structure to the precursor.
As can be seen from FIG. 16, at 1620cm -1 The characteristic peak corresponding to-C = N-had disappeared, corresponding to 1653cm -1 The characteristic peak at (a), evidencing the formation of C (O) NH.
Example 6
Covalently attaching an organic framework XI (30 mg) to KHSO 5 (63mg, 2equiv.) to anhydrous N, N-dimethylformamide (2 ml), adding 0.1ml glacial acetic acid, rapidly changing nitrogen gas several times, sealing, and reacting at 25 deg.C under stirring for 5 hrThen (c) is performed. Filtering, the filter cake is 10% Na 2 S 2 O 3 Aqueous solution, water and tetrahydrofuran. The resulting solid was then subjected to Soxhlet extraction with dry methanol and tetrahydrofuran, respectively, for 5 hours and vacuum dried at 100 ℃ for 2 hours to give a brown solid (22.4 mg, 67.3%).
As can be seen in fig. 17, the powder X-ray diffraction peaks remained essentially unchanged before and after oxidation, indicating that the amide bond linked covalent organic framework obtained after oxidation has a similar crystal structure to the precursor.
As can be seen from FIG. 18, at 1619cm -1 The characteristic peak corresponding to-C = N-had disappeared, corresponding to 1659cm -1 The characteristic peak at (a), evidencing the formation of C (O) NH.
Example 7
Covalent organic frameworks XIII (20 mg) and KHSO 5 (27mg, 2equiv.) was added to anhydrous N, N-dimethylformamide (2 ml), and then 0.1ml glacial acetic acid was added thereto, and nitrogen gas was rapidly purged several times, sealed, and stirred at 25 ℃ for reaction for 5 hours. Filtering, the filter cake is 10% Na 2 S 2 O 3 Aqueous solution, water and tetrahydrofuran. The resulting solid was then subjected to Soxhlet extraction with anhydrous methanol and tetrahydrofuran, respectively, for 5 hours and vacuum dried at 100 ℃ for 2 hours to give a brown solid (20.5mg, 95.8%).
As can be seen in fig. 19, the powder X-ray diffraction peaks remained essentially unchanged before and after oxidation, indicating that the amide bond linked covalent organic framework obtained after oxidation has a similar crystal structure to the precursor.
As can be seen from FIG. 20, at 1619cm -1 The characteristic peak corresponding to-C = N-had disappeared, corresponding to 1656cm -1 The characteristic peak at (a), evidencing the formation of C (O) NH.
Example 8
Covalent organic frameworks XV (30 mg) and KHSO 5 (59mg, 2equiv.) was added to anhydrous N, N-dimethylformamide (2 ml), and then 0.1ml of glacial acetic acid was added, nitrogen gas was rapidly purged several times, sealed, and stirred at 25 ℃ for reaction for 5 hours. Filtering, and using 10% of filter cake to obtain Na% 2 S 2 O 3 Aqueous solution, water and tetrahydrofuran. The resulting solid was then subjected to Soxhlet extraction with anhydrous methanol and tetrahydrofuran, respectively, for 5 hours and vacuum dried at 100 ℃ for 2 hours to give a brown solid (21.3mg, 64.4%).
As can be seen in fig. 21, the powder X-ray diffraction peaks remained essentially unchanged before and after oxidation, indicating that the amide bond linked covalent organic framework obtained after oxidation has a similar crystal structure to the precursor.
As can be seen from FIG. 22, at 1660cm -1 The characteristic peak of the amide carbonyl appears, demonstrating the formation of C (O) NH.
Example 9
One-dimensional covalent organic frameworks XV II (30 mg) and KHSO 5 (34mg, 2equiv.) was added to anhydrous N, N-dimethylformamide (2 ml), 0.1ml glacial acetic acid was added thereto, nitrogen gas was rapidly purged several times, and the mixture was sealed and stirred at 25 ℃ for reaction for 5 hours. Filtering, the filter cake is 10% Na 2 S 2 O 3 Aqueous solution, water and tetrahydrofuran. The resulting solid was then subjected to Soxhlet extraction with anhydrous methanol and tetrahydrofuran, respectively, for 5 hours and vacuum drying at 100 ℃ for 2 hours to give a tan solid (24.3mg, 72.1%).
As can be seen from fig. 23, the powder X-ray diffraction results of the oxidized product still have a main peak and a partial fine peak similar to those of the covalent organic framework before oxidation, indicating that the amide bond linked covalent organic framework obtained after oxidation has a crystal structure similar to that of the precursor.
As can be seen in FIG. 24, the imine bond after oxidation is 1620cm -1 The signal peak at (A) is greatly diminished and disappears, indicating that conversion has occurred.
Example 10
Covalently attaching organic framework I (10 mg) and KHSO 5 (14mg, 1.5equiv.) and N, N-dimethylformamide (1 mL) as a solvent were charged into a reaction vessel and reacted at room temperature for 1.5 hours. After the reaction was completed, it was cooled and filtered to obtain a brown solid, which was then dried in vacuo. From the results of the infrared spectroscopy (FIG. 25), the imine bond in the covalent organic framework I has been converted into an amide bond, yielding a covalent organic framework II, the structural characterization data of which is similar to that of example 1, as shown in FIG. 25.
Comparative example 1
Covalent organic frameworks I (10 mg), pd (OAc) 2 (1.2mg, 1.5 equiv.), t-BuOOH (70%, 41. Mu.L, 6 equiv.) and 1, 2-dichloroethane (1.5 mL) as a solvent were charged into a reaction vessel and reacted at 120 ℃ for 5 hours. After the reaction is finished, cooling and filtering are carried out to obtain yellow solid, and vacuum drying is carried out. From the results of the infrared spectroscopy (FIG. 26), the imine bond in the covalent organic framework I was not converted into an amide bond.
Comparative example 2
Covalent organic frameworks I (10 mg), H 2 O 2 (30%, 100. Mu.L), glacial acetic acid (50. Mu.L) and acetonitrile (1 mL) as a solvent were added to the reaction vessel and reacted at 50 ℃ for 8 hours. After the reaction is finished, cooling and filtering are carried out to obtain a brown yellow solid, and vacuum drying is carried out. From the results of the infrared spectroscopy (FIG. 27), the imine bond in the covalent organic framework I was not converted into an amide bond.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes or modifications to these embodiments may be made by those skilled in the art without departing from the principle and spirit of this invention, and these changes and modifications are within the scope of this invention.
Claims (13)
1. A method for preparing an amide bond linked covalent organic framework comprising the steps of: in a solvent, a covalent organic framework linking imine bonds - HSO 5 Carrying out oxidation reaction under the action of (a) to obtain a covalent organic framework connected with the amide bond; in the covalent organic framework connected by the imine bond, two ends of the imine bond are connected with carbon atoms on an aryl ring.
2. The method of claim 1, wherein the aryl ring is independently a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, or a pyrene ring.
3. The process according to claim 2, wherein the imine bond is bonded at both ends to carbon atoms on the benzene ring.
4. The method of claim 3, wherein said aryl ring is unsubstituted or substituted with one or more C 1-4 Alkyl substitution.
5. The method of claim 1, wherein the imine-linked covalent organic framework consists of imine linkages and one or more of the following structures:
the aryl rings of the above structures being unsubstituted or substituted by one or more C 1-4 Alkyl substitution.
6. The method of claim 1, wherein the imine-linked covalent organic framework is composed of structural units a and B linked to each other:
the structural unit A is
The structural unit B is
The aryl rings contained in said structural units A and B being unsubstituted or substituted by one or more C 1-4 Alkyl substitution.
7. The method of claim 1, wherein said imine-linked covalent organic framework is composed of structural units A and B linked to each other from any of the following groups:
(1) Structural unit A is
Structural unit B is
(2) The structural unit A is
Structural unit B is
(3) The structural unit A is
Structural unit B is
(4) The structural unit A is
Structural unit B is
(5) Structural unit A is
Structural unit B is
(6) The structural unit A is
Structural unit B is
(7) The structural unit A is
Structural unit B is
The aryl rings contained in said structural units A and B being unsubstituted or substituted by one or more C 1-4 Alkyl substitution.
8. The method of any one of claims 4 to 7, wherein the coating is coated with one or more C 1-4 Alkyl substitution refers to substitution by one methyl group.
9. The method according to any one of claims 1 to 7, - HSO 5 with NaHSO 5 、NaHSO 5 Compound salt, KHSO 5 、KHSO 5 Complex salt, ca (HSO) 5 ) 2 、Ca(HSO 5 ) 2 Complex salt, mg (HSO) 5 ) 2 、Mg(HSO 5 ) 2 One or more of the complex salts are provided for use in the oxidation reaction.
10. The method of claim 9, wherein said NaHSO is used as a carrier of said reaction 5 The compound salt is Na 2 SO 4 ·NaHSO 4 ·2NaHSO 5 ；
And/or, said KHSO 5 The compound salt is 2KHSO 5 ·KHSO 4 ·K 2 SO 4 ；
And/or the presence of a gas in the gas, - HSO 5 with KHSO 5 And/or a complex salt thereof, for use in the oxidation reaction.
11. The method of any one of claims 1-7, wherein providing is performed by - HSO 5 The molar amount of the material(s) is 1-5 times that of the covalent organic framework linked by the imine bond;
and/or, the oxidation reaction is carried out in the presence or absence of an acid;
and/or the solvent is N, N-dimethylformamide;
and/or the oxidation reaction is carried out at a temperature of 0-80 ℃;
and/or the oxidation reaction is carried out under the protection of gas;
and/or the time of the oxidation reaction is 0.5 to 10 hours.
12. The method of claim 11, wherein providing is performed by - HSO 5 In a molar amount of said imine bond linkage2-3 times the molar amount of the covalent organic framework of (a);
and/or, the oxidation reaction is carried out in the presence of an acid; when the oxidation reaction is carried out in the presence of an acid, the acid is acetic acid;
and/or the solvent is anhydrous N, N-dimethylformamide;
and/or, the oxidation reaction is carried out at a temperature of 20-30 ℃;
and/or the time of the oxidation reaction is 4 to 6 hours.
13. The method of claim 12, wherein the oxidation reaction is carried out at a temperature of 25 ℃.
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