Search

CN-122011404-A - Acylhydrazone covalent organic framework material with pentadentate coordination environment, and preparation method and application thereof

CN122011404ACN 122011404 ACN122011404 ACN 122011404ACN-122011404-A

Abstract

The invention belongs to the technical field of covalent organic framework functional materials, and particularly relates to an acylhydrazone covalent organic framework material with a pentadentate coordination environment, and a preparation method and application thereof. The invention discloses an acylhydrazone Covalent Organic Frameworks (COFs) with a pentadentate coordination center. The COFs are constructed by the cooperative driving of covalent bonds and coordination bonds, so that covalent assembly and metal coordination processes are synchronously realized, and the unification of multiple structures, high crystallinity and excellent chemical stability is realized. The unique U-shaped five-tooth coordination center induced by the metal template can realize the conversion of U-shaped and W-shaped structures along with the reversible deintercalation of metal ions, and the coordination center can be converted into a J-shaped structure by introducing metal ions such as Cu 2+ through a re-metallization strategy, thereby realizing U in the same COFs framework W J' three configurations, and endows the three configurations with application potential in the fields of photocatalytic coenzyme NAD + regeneration and the like.

Inventors

  • SU CHENGYONG
  • XU HAISEN
  • HUANG SI

Assignees

  • 中山大学

Dates

Publication Date
20260512
Application Date
20251231

Claims (10)

  1. 1. An acylhydrazone covalent organic framework material characterized in that the acylhydrazone covalent organic framework material has any one of the following repeating unit structures: Wherein each R 1 、R 2 is independently selected from hydrogen, C 1~10 alkyl, or C 1~10 alkoxy, and each R 3 、R 4 、R 5 、R 6 is independently selected from hydrogen, C 1~10 alkyl, or C 1~10 alkoxy.
  2. 2. The preparation method of the acylhydrazone covalent organic framework material is characterized by comprising the following steps of: s1, uniformly mixing an acetal monomer, a hydrazide monomer, metal salt, an organic solvent and water, heating after freezing and degassing treatment, completely reacting, and performing aftertreatment to obtain an acylhydrazone covalent organic framework material COF-LIFM-13; S2, demetallizing the COF-LIFM-13 obtained in the step S1 to obtain a demetallized acylhydrazone covalent organic framework material COF-LIFM-13-De; S3, mixing the COF-LIFM-13-De obtained in the step S2 with a solution containing metal salt, and performing post-metallization treatment to obtain a re-metallized acylhydrazone covalent organic framework material COF-LIFM-13-M; When the metal ion types of the metal salts in the step S3 and the step S1 are the same, the COF-LIFM-13-M and the COF-LIFM-13 are the same; when the metal ion types of the metal salts in the step S3 and the step S1 are different, the COF-LIFM-13-M and the COF-LIFM-13 are different; the COF-LIFM-13, COF-LIFM-13-De or COF-LIFM-13-M is the acylhydrazone covalent organic framework material; wherein the structural formula of the acetal monomer is as follows: Each R 3 、R 4 、R 5 、R 6 is independently selected from hydrogen, C 1~10 alkyl, or C 1~10 alkoxy; The structural formula of the hydrazide monomer is as follows: Each R 1 、R 2 is independently selected from hydrogen, C 1~10 alkyl, or C 1~10 alkoxy; The metal ions of the metal salts in step S1 and step S3 are each independently selected from at least one of Zn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Mn 2+ 、Cd 2+ 、Ag + .
  3. 3. The method of claim 2, wherein each R 3 、R 4 、R 5 、R 6 is independently selected from C 5~8 alkoxy.
  4. 4. The method of claim 2, wherein each R 1 、R 2 is independently selected from hydrogen or C 1~6 alkoxy.
  5. 5. The method according to any one of claims 2 to 4, wherein the molar ratio of the acetal monomer to the hydrazide monomer is 1 (1 to 4).
  6. 6. The method according to any one of claims 2 to 4, wherein the molar ratio of the acetal monomer to the metal salt is 1 (1 to 8).
  7. 7. The method according to any one of claims 2 to 4, wherein the organic solvent is one or more selected from acetonitrile, mesitylene, benzyl alcohol, methanol, n-butanol, o-dichlorobenzene, and 1, 4-dioxane.
  8. 8. The method according to any one of claims 2 to 4, wherein the volume ratio of water to the organic solvent is 1 (2 to 5).
  9. 9. The acylhydrazone covalent organic framework material prepared by the preparation method of any one of claims 2-8.
  10. 10. Use of the acylhydrazone covalent organic framework material of claim 1 or the acylhydrazone covalent organic framework material of claim 9 for photocatalyzing the conversion of NADH to NAD + .

Description

Acylhydrazone covalent organic framework material with pentadentate coordination environment, and preparation method and application thereof Technical Field The invention belongs to the technical field of covalent organic framework functional materials. More particularly relates to an acylhydrazone covalent organic framework material with a pentadentate coordination environment, and a preparation method and application thereof. Background Covalent organic frameworks (Covalent Organic Frameworks, COFs) are crystalline porous materials formed by covalent bonding of organic building blocks, the structure and function of which are highly dependent on the diversity of the bonding chemistry. By selecting the connection mode of constructing the primitives and regulating, the directional design and functional customization of the COFs can be realized theoretically. Since the first COFs report in 2005, researchers have developed a variety of ligation chemistries such as imines, borates, acylhydrazones, and have successfully constructed numerous COFs structures. However, due to the inherent limitation of the carbon atom hybridization mode in the organic building block, the structure type of the currently reported COFs is still single, and especially the two-dimensional COFs only show more than ten topological networks, which severely limits the expansion space of the functional oriented material customization and practical application. In this context, synthesis studies of COFs are gradually moving from static structures to dynamic system designs. Inspired by the realization of functional conversion of a biomolecular machine through conformational change, the introduction of controllable structural responsiveness and conversion capability into COFs is regarded as an important way to break through structural limitations and enrich functional expression. The COFs can be induced to generate reversible changes of pore channel size, surface chemistry or interlayer distance through external stimulation such as light, heat, pH or guest molecules, so that the behavior of the COFs in the fields of catalysis, adsorption, recognition and the like can be dynamically regulated and controlled. Although the dynamic design concept shows great potential, the development of the dynamic design concept still faces significant challenges, namely, on one hand, the synthesis difficulty exists in the accurate construction of a complex topology COFs framework, and on the other hand, how to realize the efficient and reversible switching of materials between different configurations, and maintain the structural integrity and the cyclic stability, and the key scientific problem which is not completely solved is still remained. Therefore, the development of novel connection chemistry and the innovation of dynamic construction strategies are advanced, and controllable configuration conversion and function regulation in the complex topology COFs are further realized, so that the method has important significance for expanding the structure type and application prospect of the COFs system. Disclosure of Invention The invention aims to overcome the defects and the shortcomings that the traditional COFs structure is limited in type and difficult to realize dynamic configuration conversion so as to restrict application expansion, and provides an acylhydrazone covalent organic framework material with dynamic conversion characteristics. Another object of the invention is to provide a method for preparing an acylhydrazone covalent organic framework material. It is still another object of the present invention to provide the acylhydrazone covalent organic framework material obtained by the preparation method. It is a further object of the present invention to provide the use of the above acylhydrazone covalent organic framework material. The above object of the present invention is achieved by the following technical scheme: The invention protects an acylhydrazone covalent organic framework material, which has any one of the following structures: ; Wherein each R 1、R2 is independently selected from hydrogen, C 1~10 alkyl, or C 1~10 alkoxy, and each R 3、R4、R5、R6 is independently selected from hydrogen, C 1~10 alkyl, or C 1~10 alkoxy. The invention discloses an acylhydrazone Covalent Organic Frameworks (COFs) with a pentadentate coordination center for the first time, wherein the COFs are constructed by a covalent bond and a coordination bond in a collaborative driving way, so that covalent assembly and metal coordination processes are synchronously realized, and the unification of multiple structures, high crystallinity and excellent chemical stability is realized. The unique U-shaped five-tooth coordination center induced by the metal template can realize the conversion of U-shaped and W-shaped structures along with the reversible deintercalation of metal ions, and the coordination center can be converted into a J-shaped structure by introducing metal ion