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Title: Probing the oxidation state of transition metal complexes: a case study on how charge and spin densities determine Mn L-edge X-ray absorption energies

Abstract

Transition metals in inorganic systems and metalloproteins can occur in different oxidation states, which makes them ideal redox-active catalysts. To gain a mechanistic understanding of the catalytic reactions, knowledge of the oxidation state of the active metals, ideally in operando, is therefore critical. L-edge X-ray absorption spectroscopy (XAS) is a powerful technique that is frequently used to infer the oxidation state via a distinct blue shift of L-edge absorption energies with increasing oxidation state. A unified description accounting for quantum-chemical notions whereupon oxidation does not occur locally on the metal but on the whole molecule and the basic understanding that L-edge XAS probes the electronic structure locally at the metal has been missing to date. Here we quantify how charge and spin densities change at the metal and throughout the molecule for both redox and core-excitation processes. We explain the origin of the L-edge XAS shift between the high-spin complexes MnII(acac)2 and MnIII(acac)3 as representative model systems and use ab initio theory to uncouple effects of oxidation-state changes from geometric effects. The shift reflects an increased electron affinity of MnIII in the core-excited states compared to the ground state due to a contraction of the Mn 3d shell upon core-excitationmore » with accompanied changes in the classical Coulomb interactions. This new picture quantifies how the metal-centered core hole probes changes in formal oxidation state and encloses and substantiates earlier explanations. The approach is broadly applicable to mechanistic studies of redox-catalytic reactions in molecular systems where charge and spin localization/delocalization determine reaction pathways.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4];  [2]; ORCiD logo [5];  [1]; ORCiD logo [6]; ORCiD logo [7]; ORCiD logo [8];  [4]; ORCiD logo [9];  [6]; ORCiD logo [6]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Institute for Methods and Instrumentation for Synchrotron Radiation Research; Helmholtz-Zentrum Berlin für Materialien und Energie GmbH; 12489 Berlin; Germany
  2. Department of Chemistry-Ångström Laboratory; Uppsala University; Sweden
  3. SSRL; SLAC National Accelerator Laboratory; Menlo Park; USA
  4. Institute for Nanometre Optics and Technology; Helmholtz-Zentrum Berlin für Materialien und Energie GmbH; 12489 Berlin; Germany
  5. The School of Chemistry; The University of Manchester at Harwell; OX11 OFA; UK
  6. Molecular Biophysics and Integrated Bioimaging Division; Lawrence Berkeley National Laboratory; Berkeley; USA
  7. Molecular Biophysics and Integrated Bioimaging Division; Lawrence Berkeley National Laboratory; Berkeley; USA; LCLS
  8. Institute for Methods and Instrumentation for Synchrotron Radiation Research; Helmholtz-Zentrum Berlin für Materialien und Energie GmbH; 12489 Berlin; Germany; Institut für Physik und Astronomie
  9. Stanford PULSE Institute; SLAC National Accelerator Laboratory; Menlo Park; USA
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; Human Frontier Science Program (HFSP), Strasbourg (France); Swedish Research Council (SRC); Knut and Alice Wallenberg Foundation (Sweden); National Institutes of Health (NIH); USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1461356
Alternate Identifier(s):
OSTI ID: 1476324; OSTI ID: 1506286
Grant/Contract Number:  
AC02-76SF00515; AC02-05CH11231; RGP0063/2013; P41GM103393; KAW-2013.0020; GM110501; GM55302
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 9 Journal Issue: 33; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kubin, Markus, Guo, Meiyuan, Kroll, Thomas, Löchel, Heike, Källman, Erik, Baker, Michael L., Mitzner, Rolf, Gul, Sheraz, Kern, Jan, Föhlisch, Alexander, Erko, Alexei, Bergmann, Uwe, Yachandra, Vittal, Yano, Junko, Lundberg, Marcus, and Wernet, Philippe. Probing the oxidation state of transition metal complexes: a case study on how charge and spin densities determine Mn L-edge X-ray absorption energies. United Kingdom: N. p., 2018. Web. doi:10.1039/C8SC00550H.
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Kubin, Markus, Guo, Meiyuan, Kroll, Thomas, Löchel, Heike, Källman, Erik, Baker, Michael L., Mitzner, Rolf, Gul, Sheraz, Kern, Jan, Föhlisch, Alexander, Erko, Alexei, Bergmann, Uwe, Yachandra, Vittal, Yano, Junko, Lundberg, Marcus, & Wernet, Philippe. Probing the oxidation state of transition metal complexes: a case study on how charge and spin densities determine Mn L-edge X-ray absorption energies. United Kingdom. https://doi.org/10.1039/C8SC00550H
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Kubin, Markus, Guo, Meiyuan, Kroll, Thomas, Löchel, Heike, Källman, Erik, Baker, Michael L., Mitzner, Rolf, Gul, Sheraz, Kern, Jan, Föhlisch, Alexander, Erko, Alexei, Bergmann, Uwe, Yachandra, Vittal, Yano, Junko, Lundberg, Marcus, and Wernet, Philippe. Tue . "Probing the oxidation state of transition metal complexes: a case study on how charge and spin densities determine Mn L-edge X-ray absorption energies". United Kingdom. https://doi.org/10.1039/C8SC00550H.
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@article{osti_1461356,
title = {Probing the oxidation state of transition metal complexes: a case study on how charge and spin densities determine Mn L-edge X-ray absorption energies},
author = {Kubin, Markus and Guo, Meiyuan and Kroll, Thomas and Löchel, Heike and Källman, Erik and Baker, Michael L. and Mitzner, Rolf and Gul, Sheraz and Kern, Jan and Föhlisch, Alexander and Erko, Alexei and Bergmann, Uwe and Yachandra, Vittal and Yano, Junko and Lundberg, Marcus and Wernet, Philippe},
abstractNote = {Transition metals in inorganic systems and metalloproteins can occur in different oxidation states, which makes them ideal redox-active catalysts. To gain a mechanistic understanding of the catalytic reactions, knowledge of the oxidation state of the active metals, ideally in operando, is therefore critical. L-edge X-ray absorption spectroscopy (XAS) is a powerful technique that is frequently used to infer the oxidation state via a distinct blue shift of L-edge absorption energies with increasing oxidation state. A unified description accounting for quantum-chemical notions whereupon oxidation does not occur locally on the metal but on the whole molecule and the basic understanding that L-edge XAS probes the electronic structure locally at the metal has been missing to date. Here we quantify how charge and spin densities change at the metal and throughout the molecule for both redox and core-excitation processes. We explain the origin of the L-edge XAS shift between the high-spin complexes MnII(acac)2 and MnIII(acac)3 as representative model systems and use ab initio theory to uncouple effects of oxidation-state changes from geometric effects. The shift reflects an increased electron affinity of MnIII in the core-excited states compared to the ground state due to a contraction of the Mn 3d shell upon core-excitation with accompanied changes in the classical Coulomb interactions. This new picture quantifies how the metal-centered core hole probes changes in formal oxidation state and encloses and substantiates earlier explanations. The approach is broadly applicable to mechanistic studies of redox-catalytic reactions in molecular systems where charge and spin localization/delocalization determine reaction pathways.},
doi = {10.1039/C8SC00550H},
journal = {Chemical Science},
number = 33,
volume = 9,
place = {United Kingdom},
year = {Tue Jul 17 00:00:00 EDT 2018},
month = {Tue Jul 17 00:00:00 EDT 2018}
}
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