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  Orientational Jahn–Teller Isomerism in the Dark‐Stable State of Nature's Water Oxidase

Drosou, M., Zahariou, G., & Pantazis, D. A. (2021). Orientational Jahn–Teller Isomerism in the Dark‐Stable State of Nature's Water Oxidase. Angewandte Chemie International Edition, 60(24), 13493-13499. doi:10.1002/anie.202103425.

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 Creators:
Drosou, Maria1, Author
Zahariou, Georgia2, Author
Pantazis, Dimitrios A.3, Author           
Affiliations:
1Inorganic Chemistry Laboratory, National and Kapodistrian University of Athens, Panepistimiopolis, Zografou, 15771 Greece, ou_persistent22              
2Institute of Nanoscience & Nanotechnology, NCSR “Demokritos”, Athens, 15310 Greece, ou_persistent22              
3Research Group Pantazis, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541711              

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Free keywords: bioinorganic chemistry; computational chemistry; electronic structure; EPR spectroscopy; photosynthesis
 Abstract: 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.

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Language(s): eng - English
 Dates: 2021-03-092021-04-082021-06-07
 Publication Status: Published in print
 Pages: 7
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/anie.202103425
 Degree: -

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Title: Angewandte Chemie International Edition
  Abbreviation : Angew. Chem., Int. Ed.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 60 (24) Sequence Number: - Start / End Page: 13493 - 13499 Identifier: ISSN: 1433-7851
CoNE: https://pure.mpg.de/cone/journals/resource/1433-7851