The activation and oxidization of inert C(sp 3 )ÀH bonds into value-added chemicals affords attractively economic and ecological benefits as well as central challenge in modern chemistry.I nspired by the natural enzymatic transformation, herein, we report an ew multiphoton excitation approach to activate the inert C(sp 3 ) À Hb onds 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 wellmodified nicotinamide adenine dinucleotide (NAD + )m imics oxidized Ce III -OEt moieties to generate Ce IV -OEt chromophore and its reduced state mimics NADC via PET.The in situ formed Ce IV -OEt moiety triggers aL MCT excitation to form the alkoxy radical EtOC,a bstracts ah ydrogen atom from the C(sp 3 )ÀHb ond, accompanying the recovery of Ce III -OEt and the formation of alkylr adicals.T he formed NADC activates oxygen to regenerate the NAD + for next recycle,w herein, the activated oxygen species interacts with the intermediates for the oxidization functionalization, paving ac atalytic avenue for developing scalable and sustainable synthetic strategy.

Metal−organic frameworks (MOFs) have gained attention as multifunctional catalytic platforms, allowing us to gain important insights into synergistically activating both C−H bonds and oxygen for improving oxidation. Herein, by ingenious incorporation of anthraquinone, we report an anthraquinone-based MOF as a bifunctional heterogeneous photocatalytic platform to simultaneously activate inert C(sp 3 )−H bonds and oxygen for C− H bond oxidation. Making use of the rigid framework with the fixation and isolation effect, both a great chemical stability and bifunctional synergistic photocatalytic effects were obtained through the immobilization of anthraquinone into a MOF. Importantly, while decorating two carboxyl groups on anthraquinone, the carbonyl groups of anthraquinone photosensitizers were not involved in coordinating the self-assembly and orderly arranged on the wall of channels that were constructed through a π−π interaction between the anthraquinone moieties in the adjacent layers, which was beneficial to form and stabilize the excited-state radical intermediates in the molecule-fenced channels, and the close proximity between the catalytic sites and the substrates to abstract a hydrogen atom from the substrate through the hydrogen atom transfer process aimed at activating the inertness of C−H bonds. Moreover, highdensity-distributed anthraquinone dyes in the confined channels would activate oxygen to form singlet oxygen ( 1 O 2 ) through an energy transfer pathway, further promoting inert C(sp 3 )−H bond oxidation efficiency. Under visible light irradiation, this anthraquinone-based MOF was successfully applied to explore activation and oxidation of a series of substrates containing benzylic C(sp 3 )−H bonds in the presence of air or oxygen to produce the corresponding carbonyl products. This bifunctional photocatalytic platform based on a heterogeneous MOF provides an available catalytic avenue to develop a scalable and sustainable synthetic strategy using green and sustainable oxygen as the potent oxidant.

The activation and oxidization of inert C(sp 3 )ÀH bonds into value-added chemicals affords attractively economic and ecological benefits as well as central challenge in modern chemistry.I nspired by the natural enzymatic transformation, herein, we report an ew multiphoton excitation approach to activate the inert C(sp 3 ) À Hb onds 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 wellmodified nicotinamide adenine dinucleotide (NAD + )m imics oxidized Ce III -OEt moieties to generate Ce IV -OEt chromophore and its reduced state mimics NADC via PET.The in situ formed Ce IV -OEt moiety triggers aL MCT excitation to form the alkoxy radical EtOC,a bstracts ah ydrogen atom from the C(sp 3 )ÀHb ond, accompanying the recovery of Ce III -OEt and the formation of alkylr adicals.T he formed NADC activates oxygen to regenerate the NAD + for next recycle,w herein, the activated oxygen species interacts with the intermediates for the oxidization functionalization, paving ac atalytic avenue for developing scalable and sustainable synthetic strategy.