A Metal–Organic Framework as a Multiphoton Excitation Regulator for the Activation of Inert C(sp<sup>3</sup>)−H Bonds and Oxygen
Guanfeng Ji, Liang Zhao, Jianwei Wei, Junkai Cai, Cheng He, Zenggang Du, Wei Cai, Chunying Duan
Abstract
Abstract The activation and oxidization of inert C(sp 3 )−H bonds into value‐added chemicals affords attractively economic and ecological benefits as well as central challenge in modern chemistry. Inspired by the natural enzymatic transformation, herein, we report a new multiphoton excitation approach to activate the inert C(sp 3 )−H bonds and oxygen by integrating the photoinduced electron transfer (PET), ligand‐to‐metal charge transfer (LMCT) and hydrogen atom transfer (HAT) events together into one metal ‐ organic framework. The well‐modified nicotinamide adenine dinucleotide ( NAD + ) mimics oxidized Ce III ‐OEt moieties to generate Ce IV ‐OEt chromophore and its reduced state mimics NAD . via PET. The in situ formed Ce IV ‐OEt moiety triggers a LMCT excitation to form the alkoxy radical EtO . , abstracts a hydrogen atom from the C(sp 3 )−H bond, accompanying the recovery of Ce III ‐OEt and the formation of alkyl radicals. The formed NAD . activates oxygen to regenerate the NAD + for next recycle, wherein, the activated oxygen species interacts with the intermediates for the oxidization functionalization, paving a catalytic avenue for developing scalable and sustainable synthetic strategy.