TY - JOUR
T1 - X-ray Emission Spectroscopy of Mn Coordination Complexes Toward Interpreting the Electronic Structure of the Oxygen-Evolving Complex of Photosystem II
AU - Davis, Katherine M.
AU - Palenik, Mark C.
AU - Yan, Lifen
AU - Smith, Paul F.
AU - Seidler, Gerald T.
AU - Dismukes, G. Charles
AU - Pushkar, Yulia N.
N1 - Funding Information:
This material is based upon work supported by the National Science Foundation, Division of Chemistry CHE-1350909 (Y.P.) and CHE-1213772 (G.C.D.), and NSF Graduate Research Fellowships under Grant No. DGE0833366 (K.D.) and DGE0903675 (P.F.S.). G.T.S. acknowledges support of this research program by the U.S. Department of Energy, Basic Energy Sciences, by Grant No. DE-FG02-09ER16106. Sector 20 facilities at the Advanced Photon Source, and research at these facilities are supported by the U.S. Department of Energy?Basic Energy Sciences, the Canadian Light Source and its funding partners, the University of Washington, and the Advanced Photon Source. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357. We thank Dr. Steve Heald and Dr. Dale Brewe for help with experiments at Beamline 20-BM and ID-20, APS. Access to EPR was provided by the Amy Instrumentation Facility, Department of Chemistry, under the supervision of Dr. Michael Everly.
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/2/18
Y1 - 2016/2/18
N2 - X-ray emission (XES) spectroscopy is an attractive technique for analysis of the electronic structure of molecules, materials, and metalloproteins. However, a better understanding of XES results is required. Using a combination of experiment and ground-state density functional theory analysis, we rationalize differences in the X-ray emission spectra of multinuclear Mn complexes. Model compounds, including dinuclear [Mn2O2L′4](ClO4)3 (L′= 2,2′-bipyridyl, [1]) and two examples from the Mn4O4L6 "cubane " family of model compounds (L = (p-R-C6H4)PO2¯, R = OCH3 [2], CH3 [3]), were compared with the Oxygen Evolving Complex of Photosystem II. Our analysis shows that changes in the structure of the Mn complexes, resulting in changes to the spin polarization, can introduce significant spectral shifts in compounds of the same formal redox state. The implications of changes in spin polarization for understanding photosynthetic water-splitting catalysis is discussed.
AB - X-ray emission (XES) spectroscopy is an attractive technique for analysis of the electronic structure of molecules, materials, and metalloproteins. However, a better understanding of XES results is required. Using a combination of experiment and ground-state density functional theory analysis, we rationalize differences in the X-ray emission spectra of multinuclear Mn complexes. Model compounds, including dinuclear [Mn2O2L′4](ClO4)3 (L′= 2,2′-bipyridyl, [1]) and two examples from the Mn4O4L6 "cubane " family of model compounds (L = (p-R-C6H4)PO2¯, R = OCH3 [2], CH3 [3]), were compared with the Oxygen Evolving Complex of Photosystem II. Our analysis shows that changes in the structure of the Mn complexes, resulting in changes to the spin polarization, can introduce significant spectral shifts in compounds of the same formal redox state. The implications of changes in spin polarization for understanding photosynthetic water-splitting catalysis is discussed.
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U2 - 10.1021/acs.jpcc.5b10610
DO - 10.1021/acs.jpcc.5b10610
M3 - Article
AN - SCOPUS:84958965276
VL - 120
SP - 3326
EP - 3333
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 6
ER -