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Spectral Signatures of Oxidation States in a Manganese‐Oxo Cubane Water Oxidation Catalyst
We report IR and UV/Vis spectroscopic signatures that allow discriminating between the oxidation states of the manganese‐based water oxidation catalyst [(Mn(4)O(4))(V(4)O(13))(OAc)(3)](3−). Simulated IR spectra show that V=O stretching vibrations in the 900–1000 cm(−1) region shift consistently by a...
Autores principales: | , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9293465/ https://www.ncbi.nlm.nih.gov/pubmed/34523763 http://dx.doi.org/10.1002/chem.202102583 |
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author | Mai, Sebastian Klingler, Sarah Trentin, Ivan Kund, Julian Holzer, Marcus Andreeva, Anastasia Stach, Robert Kranz, Christine Streb, Carsten Mizaikoff, Boris González, Leticia |
author_facet | Mai, Sebastian Klingler, Sarah Trentin, Ivan Kund, Julian Holzer, Marcus Andreeva, Anastasia Stach, Robert Kranz, Christine Streb, Carsten Mizaikoff, Boris González, Leticia |
author_sort | Mai, Sebastian |
collection | PubMed |
description | We report IR and UV/Vis spectroscopic signatures that allow discriminating between the oxidation states of the manganese‐based water oxidation catalyst [(Mn(4)O(4))(V(4)O(13))(OAc)(3)](3−). Simulated IR spectra show that V=O stretching vibrations in the 900–1000 cm(−1) region shift consistently by about 20 cm(−1) per oxidation equivalent. Multiple bands in the 1450–1550 cm(−1) region also change systematically upon oxidation/reduction. The computed UV/Vis spectra predict that the spectral range above 350 nm is characteristic of the managanese‐oxo cubane oxidation state, whereas transitions at higher energy are due to the vanadate ligand. The presence of absorption signals above 680 nm is indicative of the presence of Mn(III) atoms. Spectroelectrochemical measurements of the oxidation from [Mn [Formula: see text] Mn [Formula: see text] ] to [Mn [Formula: see text] ] showed that the change in oxidation state can indeed be tracked by both IR and UV/Vis spectroscopy. |
format | Online Article Text |
id | pubmed-9293465 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-92934652022-07-20 Spectral Signatures of Oxidation States in a Manganese‐Oxo Cubane Water Oxidation Catalyst Mai, Sebastian Klingler, Sarah Trentin, Ivan Kund, Julian Holzer, Marcus Andreeva, Anastasia Stach, Robert Kranz, Christine Streb, Carsten Mizaikoff, Boris González, Leticia Chemistry Full Papers We report IR and UV/Vis spectroscopic signatures that allow discriminating between the oxidation states of the manganese‐based water oxidation catalyst [(Mn(4)O(4))(V(4)O(13))(OAc)(3)](3−). Simulated IR spectra show that V=O stretching vibrations in the 900–1000 cm(−1) region shift consistently by about 20 cm(−1) per oxidation equivalent. Multiple bands in the 1450–1550 cm(−1) region also change systematically upon oxidation/reduction. The computed UV/Vis spectra predict that the spectral range above 350 nm is characteristic of the managanese‐oxo cubane oxidation state, whereas transitions at higher energy are due to the vanadate ligand. The presence of absorption signals above 680 nm is indicative of the presence of Mn(III) atoms. Spectroelectrochemical measurements of the oxidation from [Mn [Formula: see text] Mn [Formula: see text] ] to [Mn [Formula: see text] ] showed that the change in oxidation state can indeed be tracked by both IR and UV/Vis spectroscopy. John Wiley and Sons Inc. 2021-10-15 2021-12-06 /pmc/articles/PMC9293465/ /pubmed/34523763 http://dx.doi.org/10.1002/chem.202102583 Text en © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Full Papers Mai, Sebastian Klingler, Sarah Trentin, Ivan Kund, Julian Holzer, Marcus Andreeva, Anastasia Stach, Robert Kranz, Christine Streb, Carsten Mizaikoff, Boris González, Leticia Spectral Signatures of Oxidation States in a Manganese‐Oxo Cubane Water Oxidation Catalyst |
title | Spectral Signatures of Oxidation States in a Manganese‐Oxo Cubane Water Oxidation Catalyst |
title_full | Spectral Signatures of Oxidation States in a Manganese‐Oxo Cubane Water Oxidation Catalyst |
title_fullStr | Spectral Signatures of Oxidation States in a Manganese‐Oxo Cubane Water Oxidation Catalyst |
title_full_unstemmed | Spectral Signatures of Oxidation States in a Manganese‐Oxo Cubane Water Oxidation Catalyst |
title_short | Spectral Signatures of Oxidation States in a Manganese‐Oxo Cubane Water Oxidation Catalyst |
title_sort | spectral signatures of oxidation states in a manganese‐oxo cubane water oxidation catalyst |
topic | Full Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9293465/ https://www.ncbi.nlm.nih.gov/pubmed/34523763 http://dx.doi.org/10.1002/chem.202102583 |
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