4.8 Article

Rationally fabricating 3D porphyrinic covalent organic frameworks with scu topology as highly efficient photocatalysts

期刊

CHEM
卷 8, 期 11, 页码 3064-3080

出版社

CELL PRESS
DOI: 10.1016/j.chempr.2022.07.016

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资金

  1. National Natural Science Foundation of China [22001131]
  2. Frontiers Science Center for New Organic Matter [63181206]
  3. 111 projects [B12015]
  4. Postdoctoral Science Foundation of China [2019M660974]

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In this study, two highly crystalline three-dimensional COFs were synthesized and their topological structures were determined. These COFs exhibit good photoelectric activity and structural stability, making them highly efficient photocatalysts for various reactions.
The exploration of highly crystalline three-dimensional (3D) cova-lent organic frameworks (COFs) with new topologies remains chal-lenging. In this work, we rationally designed and synthesized two highly crystalline 3D COFs, constructed by an octatopic linker and porphyrin-based tetratopic linkers through an [8 + 4] approach. The COF structures were successfully determined as non -interpene-trated scu topology using the continuous rotation electron diffrac-tion (cRED) technique and structural simulation. The scu network was further verified by both high-resolution transmission electron microscopy (TEM) and pore size distribution based on N2 sorption isotherms. Due to the exposed catalytic porphyrin sites, good pho-toelectric activity, and high structure robustness, these COFs can serve as highly efficient heterogeneous photocatalysts for various reactions, including oxidative amine coupling and cycloaddition reactions between tertiary aniline and maleimide, with a broad substrate scope (22 examples). This work enriches the topological varieties of 3D COFs and provides a class of highly efficient photo -catalysts.

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