摘要：SummaryThe photosynthetic water-oxidation reaction is catalyzed by the oxygen-evolving complex in photosystem II (PSII) that comprises the Mn4CaO5cluster, with participation of the redox-active tyrosine residue (YZ) and a hydrogen-bonded network of amino acids and water molecules. It has been proposed that the strong hydrogen bond between YZand D1-His190 likely renders YZkinetically and thermodynamically competent leading to highly efficient water oxidation. However, a detailed understanding of the proton-coupled electron transfer (PCET) at YZremains elusive owing to the transient nature of its intermediate states involving YZ⋅. Herein, we employ a combination of high-resolution two-dimensional14N hyperfine sublevel correlation spectroscopy and density functional theory methods to investigate a bioinspired artificial photosynthetic reaction center that mimics the PCET process involving the YZresidue of PSII. Our results underscore the importance of proximal water molecules and charge delocalization on the electronic structure of the artificial reaction center.Graphical AbstractDisplay OmittedHighlights•Structural factors are critical in the design of artificial photosynthetic systems•Correlation between hyperfine couplings of the N atoms and electron spin density•Spin density distribution affected by charge delocalization and explicit waters•Spin density modulation by electronic coupling as observed with P680and YZin PSIISpectroscopy; Organic Reaction; Computational Chemistry
