Light-controlled switching of the spin state of iron(III)

Controlled switching of the spin state of transition metal ions, particularly of Fe(II) and Fe(III), is a prerequisite to achieve selectivity, efficiency, and catalysis in a number of metalloenzymes. Here we report on an iron(III) porphyrin with a photochromic axial ligand which, upon irradiation wi...

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Autores principales: Shankar, Sreejith, Peters, Morten, Steinborn, Kim, Krahwinkel, Bahne, Sönnichsen, Frank D., Grote, Dirk, Sander, Wolfram, Lohmiller, Thomas, Rüdiger, Olaf, Herges, Rainer
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2018
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Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6232099/
https://www.ncbi.nlm.nih.gov/pubmed/30420598
http://dx.doi.org/10.1038/s41467-018-07023-1
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author Shankar, Sreejith
Peters, Morten
Steinborn, Kim
Krahwinkel, Bahne
Sönnichsen, Frank D.
Grote, Dirk
Sander, Wolfram
Lohmiller, Thomas
Rüdiger, Olaf
Herges, Rainer
author_facet Shankar, Sreejith
Peters, Morten
Steinborn, Kim
Krahwinkel, Bahne
Sönnichsen, Frank D.
Grote, Dirk
Sander, Wolfram
Lohmiller, Thomas
Rüdiger, Olaf
Herges, Rainer
author_sort Shankar, Sreejith
collection PubMed
description Controlled switching of the spin state of transition metal ions, particularly of Fe(II) and Fe(III), is a prerequisite to achieve selectivity, efficiency, and catalysis in a number of metalloenzymes. Here we report on an iron(III) porphyrin with a photochromic axial ligand which, upon irradiation with two different wavelengths reversibly switches its spin state between low-spin (S = (1)/(2)) and high-spin (S = (5)/(2)) in solution (DMSO-acetone, 2:598). The switching efficiency is 76% at room temperature. The system is neither oxygen nor water sensitive, and no fatigue was observed after more than 1000 switching cycles. Concomitant with the spin-flip is a change in redox potential by ~60 mV. Besides serving as a simple model for the first step of the cytochrome P450 catalytic cycle, the spin switch can be used to switch the spin-lattice relaxation time T(1) of the water protons by a factor of 15.
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spelling pubmed-62320992018-11-14 Light-controlled switching of the spin state of iron(III) Shankar, Sreejith Peters, Morten Steinborn, Kim Krahwinkel, Bahne Sönnichsen, Frank D. Grote, Dirk Sander, Wolfram Lohmiller, Thomas Rüdiger, Olaf Herges, Rainer Nat Commun Article Controlled switching of the spin state of transition metal ions, particularly of Fe(II) and Fe(III), is a prerequisite to achieve selectivity, efficiency, and catalysis in a number of metalloenzymes. Here we report on an iron(III) porphyrin with a photochromic axial ligand which, upon irradiation with two different wavelengths reversibly switches its spin state between low-spin (S = (1)/(2)) and high-spin (S = (5)/(2)) in solution (DMSO-acetone, 2:598). The switching efficiency is 76% at room temperature. The system is neither oxygen nor water sensitive, and no fatigue was observed after more than 1000 switching cycles. Concomitant with the spin-flip is a change in redox potential by ~60 mV. Besides serving as a simple model for the first step of the cytochrome P450 catalytic cycle, the spin switch can be used to switch the spin-lattice relaxation time T(1) of the water protons by a factor of 15. Nature Publishing Group UK 2018-11-12 /pmc/articles/PMC6232099/ /pubmed/30420598 http://dx.doi.org/10.1038/s41467-018-07023-1 Text en © The Author(s) 2018 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
spellingShingle Article
Shankar, Sreejith
Peters, Morten
Steinborn, Kim
Krahwinkel, Bahne
Sönnichsen, Frank D.
Grote, Dirk
Sander, Wolfram
Lohmiller, Thomas
Rüdiger, Olaf
Herges, Rainer
Light-controlled switching of the spin state of iron(III)
title Light-controlled switching of the spin state of iron(III)
title_full Light-controlled switching of the spin state of iron(III)
title_fullStr Light-controlled switching of the spin state of iron(III)
title_full_unstemmed Light-controlled switching of the spin state of iron(III)
title_short Light-controlled switching of the spin state of iron(III)
title_sort light-controlled switching of the spin state of iron(iii)
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6232099/
https://www.ncbi.nlm.nih.gov/pubmed/30420598
http://dx.doi.org/10.1038/s41467-018-07023-1
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