Recent progress in the development of MOFs/POMOFs for light-mediated C–H bond activation

The activation of inert C–H bonds under mild conditions with high selectivity remains a central challenge in catalysis. Metal–organic frameworks (MOFs) and polyoxometalate-based MOFs (POMOFs) offer atomically precise, tunable structures that integrate light absorption, charge separation, and catalytic sites. This review systematically summarizes recent progress in the development of MOFs/POMOFs for light-mediated C–H bond activation over the past decade. We discuss design strategies for active sites, including metal nodes, functionalized ligands, guest encapsulation, defect engineering, and single-site regulation. The synergistic role of POMs as electron sponges in promoting charge separation and modulating reactive oxygen species (·O₂⁻, ¹O₂, and ·OH) pathways is discussed. Structure–activity relationships governing the activation of aromatic, benzylic, allylic, and aliphatic C–H bonds are discussed. Finally, perspectives on operando characterization, precision synthesis, green manufacturing, and AI-assisted design are provided to guide the development of next-generation photocatalysts.