Two-dimensional 14N HYSCOREspectroscopy of the coordination geometry of ligands in dimanganese di-μ-oxo mimics of the oxygen evolving complex of photosystem II

Literature Information

Publication Date 2012-03-20
DOI 10.1039/C2CP40416H
Impact Factor 3.676
Authors

Ruchira Chatterjee, Sergey Milikisiyants, K. V. Lakshmi


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Abstract

We use two-dimensional hyperfine sublevel correlation (HYSCORE) spectroscopy to investigate the coordination geometry of the nitrogen ligands of biomimetic models of the oxygen-evolving complex of photosystem II. In the 2D HYSCORE spectroscopy study, [(bpy)2MnIII(μ-O)2MnIV(bpy)2](ClO4)3 (bpy, 2,2′-bipyridine) (1) and [H2O(terpy)MnIII(μ-O)2MnIV(terpy)OH2](NO3)3 (terpy = 2,2′:6′,2″-terpyridine) (2) exhibit electron-nuclear hyperfine interactions that depend on both the oxidation state of the manganese ion and the geometry of the nitrogen ligand. We observe four types of 14N hyperfine interactions corresponding to the Mn(III) and Mn(IV) ion of each mixed-valence complex and the equatorial and axial geometry of the ligand, respectively. The strongest and the weakest hyperfine interactions arise from the axial and equatorial ligands of the Mn(III) ion, respectively. The hyperfine interactions of intermediate strength are due to the axial and equatorial ligands of the Mn(IV) ion. Based on the results of this study, we assign the location and ligand geometry of the Mn(III) ion of the tetranuclear manganese–calcium–oxo cluster in the S2 state of photosystem II.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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