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

doi:10.1021/ja1054252

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

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article › peer-review

8 Citations (Scopus)

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, C_Q, and its asymmetry parameter, η_Q, 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 C_Q and η_Q at ZORA, PBE QZ4P all electron level of theory are 23.4 MHz and 0.68, respectively, in good agreement with experimental observations.

Original language	English
Pages (from-to)	16727-16729
Number of pages	3
Journal	Journal of the American Chemical Society
Volume	132
Issue number	47
DOIs	https://doi.org/10.1021/ja1054252
Publication status	Published - Dec 1 2010

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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Ellis, P. D., Sears, J. A., Yang, P., Dupuis, M., Boron, T. T., Pecoraro, V. L., Stich, T. A., Britt, R. D., & Lipton, A. S. (2010). Solid-state ⁵⁵Mn NMR spectroscopy of bis(μ-oxo) dimanganese(IV) [Mn₂O₂(salpn)₂], a model for the oxygen evolving complex in photosystem II. Journal of the American Chemical Society, 132(47), 16727-16729. https://doi.org/10.1021/ja1054252

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 journal › Article › peer-review

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

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.",

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

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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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AB - 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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