Abstract 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 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, ·OH) pathways is analyzed. Structure-activity relationships governing the activation of aromatic, benzylic, allylic, and aliphatic C-H bonds are elucidated. Finally, perspectives on operando characterization, precision synthesis, green manufacturing, and AI-assisted design are provided to guide next-generation photocatalysts.
Lv et al. (Fri,) studied this question.