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Updated: Jun 10, 2025

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
Published on: April 22, 2016
Energy transfer-mediated multiphoton synergistic excitation for selective C(sp3)-H functionalization with
Zhonghe Wang1, Yang Tang1, Songtao Liu1
1State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024, People's Republic of China.
Abstract:
Activation and selective oxidation of inert C(sp3)-H bonds remain one of the most challenging tasks in current synthetic chemistry due to the inherent inertness of C(sp3)-H bonds. In this study, inspired by natural monooxygenases, we developed a coordination polymer with naphthalenediimide (NDI)-based ligands and binuclear iron nodes. The mixed-valence FeIIIFeII species and chlorine radicals (Cl•) are generated via ligand-to-metal charge transfer (LMCT) between FeIII and chlorine ions. These Cl• radicals abstract a hydrogen atom from the inert C(sp3)-H bond of alkanes via hydrogen atom transfer (HAT). In addition, NDI converts oxygen to 1O2 via energy transfer (EnT), which then coordinates to FeII, forming an FeIV = O intermediate for the selective oxidation of C(sp3)-H bonds. This synthetic platform, which combines photoinduced EnT, LMCT and HAT, provides a EnT-mediated parallel multiphoton excitation strategy with kinetic synergy effect for selective C(sp3)-H oxidation under mild conditions and a blueprint for designing coordination polymer-based photocatalysts for C(sp3)-H bond oxidation.
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