X-ray Emission Spectroscopy of Biomimetic Mn Coordination Complexes

The Journal of Physical Chemistry Letters
Scott C JensenYulia Pushkar

Abstract

Understanding the function of Mn ions in biological and chemical redox catalysis requires precise knowledge of their electronic structure. X-ray emission spectroscopy (XES) is an emerging technique with a growing application to biological and biomimetic systems. Here, we report an improved, cost-effective spectrometer used to analyze two biomimetic coordination compounds, [MnIV(OH)2(Me2EBC)]2+ and [MnIV(O)(OH)(Me2EBC)]+, the second of which contains a key MnIV═O structural fragment. Despite having the same formal oxidation state (MnIV) and tetradentate ligands, XES spectra from these two compounds demonstrate different electronic structures. Experimental measurements and DFT calculations yield different localized spin densities for the two complexes resulting from MnIV-OH conversion to MnIV═O. The relevance of the observed spectroscopic changes is discussed for applications in analyzing complex biological systems such as photosystem II. A model of the S3 intermediate state of photosystem II containing a MnIV═O fragment is compared to recent time-resolved X-ray diffraction data of the same state.

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Citations

Oct 6, 2018·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Simon PetrieRon J Pace
Mar 7, 2020·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Simon PetrieRon J Pace
Oct 7, 2017·Physical Chemistry Chemical Physics : PCCP·Simon PetrieRon J Pace
Jun 25, 2019·Physical Review. X·Katherine M DavisYulia Pushkar
May 12, 2020·Analytical Sciences : the International Journal of the Japan Society for Analytical Chemistry·Hisashi Hayashi, Mao Takaishi
Oct 24, 2017·Journal of the American Chemical Society·Mian GuoWonwoo Nam
May 7, 2020·The Journal of Physical Chemistry Letters·Thomas A Corry, Patrick J O'Malley

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