Post‐synthetic anchoring of an iodinated <scp>BOPHY</scp> photosensitizer into defect‐engineered <scp>UiO</scp> ‐67 for enhanced photocatalytic oxidation

Abstract Metal–organic frameworks (MOFs) offer a versatile platform for integrating photoactive chromophores to enable selective photocatalysis under mild conditions. Here, we report the fabrication of I‐BOPHY‐functionalized UiO‐67 (I‐BOPHY@UiO‐67) by embedding a newly designed triplet photosensitizer ligand, I‐BOPHYPhCOOH, into UiO‐67 with tunable ligand defect levels. Comprehensive optical spectroscopy revealed not only strong visible‐light absorption but also a highly efficient energy transfer pathway from the MOF's linkers to the anchored (bis(difluoroboron)‐1,2‐bis((1 H ‐pyrrol‐2‐yl)methylene)hydrazine) (BOPHY) photosensitizers. The composites demonstrated exceptional photocatalytic activity in the selective photooxidation of thioanisole to sulfoxide, achieving near‐quantitative conversion with no sulfone formation, in stark contrast to pristine UiO‐67 which showed negligible activity. These results establish the critical role of the I‐BOPHY ligand in driving triplet‐sensitized photocatalysis via an antenna effect and highlight MOF‐based architectures as promising platforms for green oxidative transformations.