Mixed-Component Metal-Organic Framework for Boosting Synergistic Photoactivation of C(sp³)-H and Oxygen

Synergistic catalysis is an efficient and powerful strategy for simultaneously activating reactants by multiple active sites to promote the efficiency of difficult and challenging catalytic reactions. Meanwhile, enzymes with multi-active-site synergistic catalytic properties possessing high efficiency and high selectivity have become the goal pursued in the field of catalytic chemistry in recent years. Metal-organic frameworks (MOFs), as an effective heterogeneous catalytic platform, that can integrate multiple active sites for synergistic catalysis like enzymatic systems have recently attracted interest. Herein, we report a doubly interpenetrated metal-organic framework with dual active sites, Mn^III-porphyrin sites to directly activate molecular oxygen and fluoren-9-one sites to produce a hydrogen atom transfer (HAT) agent by the proton-coupled electron transfer (PCET) process to simultaneously activate inert C(sp³)-H bonds for efficient inert C(sp³)-H bond oxidation under mild conditions. The bifunctional mixed-component MOF structure forced the two catalytic sites closer together to a more suitable distance, exhibiting high photocatalytic activity for inert C(sp³)-H bond oxidation with almost unique selectivity under mild conditions. The density functional theory (DFT) calculation of free energy during the whole catalytic process demonstrated that it is likely that the synergistic catalytic process occurred in the interframework to accelerate the catalytic reaction. The assembling mixed-component MOF for synergistic catalysis would be a prospective approach for the inert C(sp³)-H photoactivation and functionalization.