Hyperfine coupling to the bridging 17O in the Di-μ-oxo core of a MnIII-MnIV model significant to the core electronic structure of the O2-evolving complex in photosystem II

Oleg M. Usov, Vladimir M. Grigoryants, Ranitendranath Tagore, Gary W Brudvig, Charles P. Scholes

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Abstract

Di-μ-oxo MnIII-MnIV dimers are models for coupled, mixed-valence manganese in the oxygen-evolving centers of green plants. Using a recently reported method of exchanging water oxygen into the di-μ-oxo cross-bridges (Tagore, R.; Chen, H.; Crabtree, R. H.; Brudvig, G. W. J. Am. Chem. Soc. 2006, 128, 9457-9465), we have incorporated 17O into the μ-oxo cross bridges of the MnIII-MnIV bipyridyl dimer for study of oxygen electron-spin hyperfine couplings by electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR). The ENDOR evidence was for a di-μ-oxo 17O hyperfine coupling of 12.8 ± 1.0 MHz. Narrow and highly resolved EPR features from dimers exchanged with H2 16O (I = 0) became broadened when the dimer was prepared by exchanging the cross bridging oxygens with H2 17O (I = 5/2). The EPR broadening due to 17O was quantitatively reproduced by a model where the dimer has two equivalent di-μ-oxo cross-bridging 17Ο, and the 17O hyperfine coupling was highly consistent with that determined by ENDOR. This work explicitly points out evidence for covalent spin transfer to the cross-bridging di-μ-oxo oxygens which provide chemical bonds and antiferromagentic coupling between the mixed-valence manganese centers.

Original languageEnglish
Pages (from-to)11886-11887
Number of pages2
JournalJournal of the American Chemical Society
Volume129
Issue number39
DOIs
Publication statusPublished - Oct 3 2007

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Photosystem II Protein Complex
Electron Spin Resonance Spectroscopy
Dimers
Electronic structure
Oxygen
Paramagnetic resonance
Electrons
Manganese
2,2'-Dipyridyl
Viridiplantae
Chemical bonds
Water

ASJC Scopus subject areas

  • Chemistry(all)

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Hyperfine coupling to the bridging 17O in the Di-μ-oxo core of a MnIII-MnIV model significant to the core electronic structure of the O2-evolving complex in photosystem II. / Usov, Oleg M.; Grigoryants, Vladimir M.; Tagore, Ranitendranath; Brudvig, Gary W; Scholes, Charles P.

In: Journal of the American Chemical Society, Vol. 129, No. 39, 03.10.2007, p. 11886-11887.

Research output: Contribution to journalArticle

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AU - Grigoryants, Vladimir M.

AU - Tagore, Ranitendranath

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AU - Scholes, Charles P.

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