Solid-state 55Mn NMR spectroscopy of bis(μ-oxo) dimanganese(IV) [Mn2O2(salpn)2], a model for the oxygen evolving complex in photosystem II

Paul D. Ellis, Jesse A. Sears, Ping Yang, Michel Dupuis, Thaddeus T. Boron, Vincent L. Pecoraro, Troy A. Stich, R. David Britt, Andrew S. Lipton

Research output: Contribution to journalArticle

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Abstract

We have examined the antiferromagneticly coupled bis(μ-oxo) dimanganese(IV) complex [Mn2O2(salpn)2] (1) with 55Mn solid-state NMR at cryogenic temperatures and first-principle theory. The extracted values of the 55Mn quadrupole coupling constant, CQ, and its asymmetry parameter, ηQ, for 1 are 24.7 MHz and 0.43, respectively. Further, there was a large anisotropic contribution to the shielding of each Mn4+, i.e. a Δσ of 3375 ppm. Utilizing broken symmetry density functional theory, the predicted values of the electric field gradient (EFG) or equivalently the CQ and ηQ at ZORA, PBE QZ4P all electron level of theory are 23.4 MHz and 0.68, respectively, in good agreement with experimental observations.

Original languageEnglish
Pages (from-to)16727-16729
Number of pages3
JournalJournal of the American Chemical Society
Volume132
Issue number47
DOIs
Publication statusPublished - Dec 1 2010

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Photosystem II Protein Complex
Shielding
Cryogenics
Nuclear magnetic resonance spectroscopy
Density functional theory
Magnetic Resonance Spectroscopy
Electric fields
Nuclear magnetic resonance
Electrons
Oxygen
Temperature

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Solid-state 55Mn NMR spectroscopy of bis(μ-oxo) dimanganese(IV) [Mn2O2(salpn)2], a model for the oxygen evolving complex in photosystem II. / Ellis, Paul D.; Sears, Jesse A.; Yang, Ping; Dupuis, Michel; Boron, Thaddeus T.; Pecoraro, Vincent L.; Stich, Troy A.; Britt, R. David; Lipton, Andrew S.

In: Journal of the American Chemical Society, Vol. 132, No. 47, 01.12.2010, p. 16727-16729.

Research output: Contribution to journalArticle

Ellis, Paul D. ; Sears, Jesse A. ; Yang, Ping ; Dupuis, Michel ; Boron, Thaddeus T. ; Pecoraro, Vincent L. ; Stich, Troy A. ; Britt, R. David ; Lipton, Andrew S. / Solid-state 55Mn NMR spectroscopy of bis(μ-oxo) dimanganese(IV) [Mn2O2(salpn)2], a model for the oxygen evolving complex in photosystem II. In: Journal of the American Chemical Society. 2010 ; Vol. 132, No. 47. pp. 16727-16729.
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abstract = "We have examined the antiferromagneticly coupled bis(μ-oxo) dimanganese(IV) complex [Mn2O2(salpn)2] (1) with 55Mn solid-state NMR at cryogenic temperatures and first-principle theory. The extracted values of the 55Mn quadrupole coupling constant, CQ, and its asymmetry parameter, ηQ, for 1 are 24.7 MHz and 0.43, respectively. Further, there was a large anisotropic contribution to the shielding of each Mn4+, i.e. a Δσ of 3375 ppm. Utilizing broken symmetry density functional theory, the predicted values of the electric field gradient (EFG) or equivalently the CQ and ηQ at ZORA, PBE QZ4P all electron level of theory are 23.4 MHz and 0.68, respectively, in good agreement with experimental observations.",
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AU - Ellis, Paul D.

AU - Sears, Jesse A.

AU - Yang, Ping

AU - Dupuis, Michel

AU - Boron, Thaddeus T.

AU - Pecoraro, Vincent L.

AU - Stich, Troy A.

AU - Britt, R. David

AU - Lipton, Andrew S.

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