@misc{10481/106197,
year = {2025},
month = {7},
url = {https://hdl.handle.net/10481/106197},
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 groundstate, pre-association followed by a static quenching
mechanism. This contrasts with the dynamic quenching
mechanism governing the reductive PCET previously
reported for the same system. Collectively, these findings
establish an unprecedented ambipolar PCET mechanism
with a new class of photocatalytic mediators based on an
earth abundant metal.},
organization = {MICIU/AEI/10.13039/50110001103 (PID2022-143153OAI00, RYC2021-031249-I, PREP2022-
000253)},
publisher = {John Wiley & Sons, Ltd.},
title = {Multisite Proton-Coupled Electron Transfer Facilitates Oxidative Photocatalysis in a Molecular Zr-Based Coordination Compound},
doi = {10.1002/anie.202510723},
author = {Moreno Albarracín, Mercedes and Rodriguez-Jimenez, Alvaro M. and Nuñez, Omar and Garrido-Barros, Pablo},
}