Harnessing Radicals in Confined Supramolecular Environments Made Possible by MOFs

Abstract Researching and utilizing radical intermediates in organic synthetic chemistry have innovated discoveries in methodology and theory. Reactions concerning free radical species opened new pathways beyond the frame of the two‐electron mechanism while commonly characterized as rampant processes lacking selectivity. As a result, research in this field has always focused on the controllable generation of radical species and determining factors of selectivity. Metal‐organic frameworks (MOFs) have emerged as compelling candidates as catalysts in radical chemistry. From a catalytic point of view, the porous nature of MOFs entails an inner phase for the reaction that could offer possibilities for the regulation of reactivity and selectivity. From a material science perspecti ve, MOFs are organic‐inorganic hybrid materials that integrate functional units in organic compounds and complex forms in the tunable long‐ranged periodic structure. In this account, we summarized our progress in the application of MOFs in radical chemistry in three parts: (1) The generation of radical species; (2) The weak interactions and site selectivity; (3) Regio‐ and stereo‐selectivity. The unique role of MOFs play in these paradigms is demonstrated in a supramolecular narrative through the analyses of the multi‐constituent collaboration within the MOF and the interactions between MOFs and the intermediates during the reactions.