Post‐Modification of MOF with Electron Donor for Efficient Photocatalytic Oxidative Organic Transformations

Construction of donor-accepter systems via self-assembling electron donor and acceptor chromophores within one single metal-organic framework (MOF) for advanced artificial photosynthesis is of great intertest yet a major challenge. Herein, an electron donor porphyrin 5-(4-carboxyphenyl)-10,15,20-triphenylporphyrin (PCOOH) was successfully integrated into a highly stable and porous electron acceptor naphthalene diimide (NDI)-based MOF (Zr-NDI) through the postmodified approach of solvent-assisted ligand incorporation (SALI). Benefiting from the efficient photoinduced electron transfer (PET) from the donor PCOOH anchored on the Zr-nodes to the acceptor NDI ligand, which contributes to the abundant generation of reactive oxygen species (ROS) of superoxide radical (O₂ ^•-), the resulting MOF Zr-NDI-PCOOH exhibited superior photocatalytic activities that among the highest levels of MOF-based photocatalysts to aerobic oxidation reactions, including hydroxylation of arylboronic acids and homocoupling of amines. This work exemplifies an avenue to develop high-efficiency MOF-based donor-acceptor systems for advanced artificial photosynthesis through facile post-modified approach.