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Title: X-ray emission spectroscopy of biomimetic Mn coordination complexes

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. In conclusion, 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.

Authors:
; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Fusion Energy Sciences (FES)
OSTI Identifier:
1364024
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 8; Journal Issue: 12; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Jensen, Scott C., Davis, Katherine M., Sullivan, Brendan, Hartzler, Daniel A., Seidler, Gerald T., Casa, Diego M., Kasman, Elina, Colmer, Hannah E., Massie, Allyssa A., Jackson, Timothy A., and Pushkar, Yulia. X-ray emission spectroscopy of biomimetic Mn coordination complexes. United States: N. p., 2017. Web. doi:10.1021/acs.jpclett.7b01209.
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Jensen, Scott C., Davis, Katherine M., Sullivan, Brendan, Hartzler, Daniel A., Seidler, Gerald T., Casa, Diego M., Kasman, Elina, Colmer, Hannah E., Massie, Allyssa A., Jackson, Timothy A., & Pushkar, Yulia. X-ray emission spectroscopy of biomimetic Mn coordination complexes. United States. https://doi.org/10.1021/acs.jpclett.7b01209
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Jensen, Scott C., Davis, Katherine M., Sullivan, Brendan, Hartzler, Daniel A., Seidler, Gerald T., Casa, Diego M., Kasman, Elina, Colmer, Hannah E., Massie, Allyssa A., Jackson, Timothy A., and Pushkar, Yulia. Fri . "X-ray emission spectroscopy of biomimetic Mn coordination complexes". United States. https://doi.org/10.1021/acs.jpclett.7b01209. https://www.osti.gov/servlets/purl/1364024.
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@article{osti_1364024,
title = {X-ray emission spectroscopy of biomimetic Mn coordination complexes},
author = {Jensen, Scott C. and Davis, Katherine M. and Sullivan, Brendan and Hartzler, Daniel A. and Seidler, Gerald T. and Casa, Diego M. and Kasman, Elina and Colmer, Hannah E. and Massie, Allyssa A. and Jackson, Timothy A. and Pushkar, Yulia},
abstractNote = {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. In conclusion, 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.},
doi = {10.1021/acs.jpclett.7b01209},
journal = {Journal of Physical Chemistry Letters},
number = 12,
volume = 8,
place = {United States},
year = {Fri May 19 00:00:00 EDT 2017},
month = {Fri May 19 00:00:00 EDT 2017}
}
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https://doi.org/10.1021/acs.jpclett.7b01209
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    Works referencing / citing this record:

    Theory of chemical bonds in metalloenzymes XXI. Possible mechanisms of water oxidation in oxygen evolving complex of photosystem II
    journal, December 2017

    What Mn K β spectroscopy reveals concerning the oxidation states of the Mn cluster in photosystem II
    journal, January 2017

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    DIY XES-development of an inexpensive, versatile, and easy to fabricate XES analyzer and sample delivery system
    journal, February 2019

    • Jensen, Scott C.; Sullivan, Brendan; Hartzler, Daniel A.
    • X-Ray Spectrometry, Vol. 48, Issue 5
    • DOI: 10.1002/xrs.3005
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