Two‐dimensional β‐ketoenamine linked azo covalent organic frameworks as heterogeneous catalysts for photo‐induced RCMP

Author:

Ding Qiuyu1,Lu Zhen12,Zhao Rui2,Xiao Longqiang123,Hou Linxi123ORCID

Affiliation:

1. Department of Materials‐Oriented Chemical Engineering, College of Chemical Engineering Fuzhou University Fuzhou People's Republic of China

2. Qingyuan Innovation Laboratory Quanzhou People's Republic of China

3. Fujian Key Laboratory of Advanced Manufacturing Technology of Specialty Chemicals Fuzhou University Fuzhou People's Republic of China

Abstract

AbstractPhoto‐induced reversible complexation‐mediated polymerization (RCMP) is a green and economical method to prepare polymers with precise molecular weights, narrow molecular weight distributions and functionally active chain ends. Covalent organic frameworks (COFs) are a promising heterogeneous photocatalyst for mediating RCMP due to their adjustable structure, band gap, and porosity. In this work, 1,3,5‐triformylphloroglucinol (Tp) and p‐azoaniline (Azo) were selected to construct 2D β‐ketoenamine linked Tp‐Azo‐COF as a heterogeneous photocatalyst to trigger RCMP under white light irradiation. A series of polymers with controllable molecular weight and narrow molecular weight distribution were successfully prepared by using Tp‐Azo‐COF as photocatalysis. On/off light experiments confirmed the good spatiotemporal control feature, and chain expansion experiments demonstrated the high “activity” of polymer chain ends. Furthermore, the mechanistic research elucidated that electron transfer between Tp‐Azo‐COF and initiator occurred, allowing the formation of reactive radicals to mediate RCMP. Density functional theory calculations revealed that the coordination of iodine on the initiator to catalyst obviously reduced the bond dissociation energy, leading to enhance in the polymerization rate. This work provides a platform for constructing heterogeneous photocatalysts with more efficient and stable to mediate RCMP.

Funder

National Natural Science Foundation of China

Publisher

Wiley

Subject

Materials Chemistry,Polymers and Plastics,Physical and Theoretical Chemistry

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