Engineering Redox‐Active Metal Sites into Covalent Organic Frameworks for Efficient Photocatalytic Activation and Aerobic Oxidation of C(sp ³ )─H Bonds

Abstract Partial oxidation of alkanes with green O ₂ source for valuable oxygenated products is one of the most challenging tasks in chemistry due to the difficulty of the activation of both inert C(sp ³ )─H bonds and unreactive O ₂ molecules. Taking advantage of the structural designability of covalent organic frameworks (COFs) for incorporating diverse functional groups and embedding redox‐active Fe/Cu ions into a bipyridine‐based COF ( BPY‐COF ), metalated COFs ( M@COF s; M = Fe, Cu) with open coordinative metal sites are obtained as heterogeneous photocatalysts for the activation and aerobic oxidation of alkanes under mild conditions. Photoinduced activation of the C(sp ³ )–H bonds is achieved via hydrogen atom transfer (HAT) by chlorine radicals ( Cl •), which are generated via ligand‐to‐metal charge transfer (LMCT) between the metal centers in the M@COF s and chlorine ions; and the M@COF s with good photoelectric performance can activate O ₂ via photoinduced electron transfer (PET). Through dynamic matching of the photoinduced C–H bond and oxygen activation processes, a highly efficient partial oxidation transformation of alkanes is achieved. This study paves the way for the application of multifunctional COF materials in energy and chemical feedstock‐related fields.