Multisite Proton-Coupled Electron Transfer Facilitates Oxidative Photocatalysis in a Molecular Zr-Based Coordination Compound.

ABSTRACT: The development of mediators that harness visible light to drive proton-coupled electron transfer (PCET) offers a promising pathway to achieving challenging redox transformations in a more sustainable manner and with enhanced thermochemical efficiency. However, designing photocatalytic systems based on earth-abundant metals while gaining precise control over their excited-state reactivity remains a significant challenge. Here, deprotonation of the hydroxy ligands in the Zr₃(O)(OH)₃ nodes of a photoactive coordination cage is shown to unlock the photocatalytic oxidation of strong O─H and C─H bonds (70-100 kcal mol⁻¹). Mechanistic investigations reveal that this oxidative process proceeds via a multisite PCET pathway involving ground-state, pre-association followed by a static que

SUBMITTER: Moreno-Albarracin M 

PROVIDER: S-EPMC12435420 | biostudies-literature | 2025 Sep

REPOSITORIES: biostudies-literature