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

Department of Chemical and Biological Engineering

Pacific Northwest National Laboratory
Environmental Molecular Sciences Laboratory
University of Michigan, Ann Arbor
University of California at Davis

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

11 Scopus citations

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
State	Published - Dec 1 2010

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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

@article{34b967081b6244aaa52649568fcd724c,

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.\}",

year = "2010",

month = dec,

day = "1",

doi = "10.1021/ja1054252",

language = "English",

volume = "132",

pages = "16727--16729",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Solid-state 55Mn NMR spectroscopy of bis(μ-oxo) dimanganese(IV) [Mn2O2(salpn)2], a model for the oxygen evolving complex in photosystem II

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.

PY - 2010/12/1

Y1 - 2010/12/1

N2 - 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.

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.

UR - https://www.scopus.com/pages/publications/78649509423

U2 - 10.1021/ja1054252

DO - 10.1021/ja1054252

M3 - Article

C2 - 21058720

AN - SCOPUS:78649509423

SN - 0002-7863

VL - 132

SP - 16727

EP - 16729

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 47

ER -

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

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