Τίτλος:
Orientational Jahn–Teller Isomerism in the Dark-Stable State of Nature's Water Oxidase
Γλώσσες Τεκμηρίου:
Αγγλικά
Περίληψη:
The tetramanganese–calcium cluster of the oxygen-evolving complex of photosystem II adopts electronically and magnetically distinct but interconvertible valence isomeric forms in its first light-driven oxidized catalytic state, S2. This bistability is implicated in gating the final catalytic states preceding O−O bond formation, but it is unknown how the biological system enables its emergence and controls its effect. Here we show that the Mn4CaO5 cluster in the resting (dark-stable) S1 state adopts orientational Jahn–Teller isomeric forms arising from a directional change in electronic configuration of the “dangler” MnIII ion. The isomers are consistent with available structural data and explain previously unresolved electron paramagnetic resonance spectroscopic observations on the S1 state. This unique isomerism in the resting state is shown to be the electronic origin of valence isomerism in the S2 state, establishing a functional role of orientational Jahn–Teller isomerism unprecedented in biological or artificial catalysis. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
Συγγραφείς:
Drosou, M.
Zahariou, G.
Pantazis, D.A.
Περιοδικό:
Angewandte Chemie. International Edition
Εκδότης:
John Wiley and Sons Inc
Λέξεις-κλειδιά:
Calcium compounds; Manganese compounds; Paramagnetic resonance; Stereochemistry, Bond formation; Directional changes; Electronic configuration; Electronic origin; Isomeric forms; Oxygen-evolving complexes; Photosystem II; Structural data, Isomers, calcium; coordination compound; manganese; oxygen; water, catalysis; chemistry; electron spin resonance; isomerism; metabolism; photosystem II, Calcium; Catalysis; Coordination Complexes; Electron Spin Resonance Spectroscopy; Isomerism; Manganese; Oxygen; Photosystem II Protein Complex; Water
DOI:
10.1002/anie.202103425
