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Janus-type emission from a cyclometalated iron(iii) complex

Although iron is a dream candidate to substitute noble metals in photoactive complexes, realization of emissive and photoactive iron compounds is demanding due to the fast deactivation of their charge-transfer states. Emissive iron compounds are scarce and dual emission has not been observed before....

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Autores principales: Steube, Jakob, Kruse, Ayla, Bokareva, Olga S., Reuter, Thomas, Demeshko, Serhiy, Schoch, Roland, Argüello Cordero, Miguel A., Krishna, Athul, Hohloch, Stephan, Meyer, Franc, Heinze, Katja, Kühn, Oliver, Lochbrunner, Stefan, Bauer, Matthias
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10070185/
https://www.ncbi.nlm.nih.gov/pubmed/36849804
http://dx.doi.org/10.1038/s41557-023-01137-w
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author Steube, Jakob
Kruse, Ayla
Bokareva, Olga S.
Reuter, Thomas
Demeshko, Serhiy
Schoch, Roland
Argüello Cordero, Miguel A.
Krishna, Athul
Hohloch, Stephan
Meyer, Franc
Heinze, Katja
Kühn, Oliver
Lochbrunner, Stefan
Bauer, Matthias
author_facet Steube, Jakob
Kruse, Ayla
Bokareva, Olga S.
Reuter, Thomas
Demeshko, Serhiy
Schoch, Roland
Argüello Cordero, Miguel A.
Krishna, Athul
Hohloch, Stephan
Meyer, Franc
Heinze, Katja
Kühn, Oliver
Lochbrunner, Stefan
Bauer, Matthias
author_sort Steube, Jakob
collection PubMed
description Although iron is a dream candidate to substitute noble metals in photoactive complexes, realization of emissive and photoactive iron compounds is demanding due to the fast deactivation of their charge-transfer states. Emissive iron compounds are scarce and dual emission has not been observed before. Here we report the Fe(III) complex [Fe(ImP)(2)][PF(6)] (HImP = 1,1′-(1,3-phenylene)bis(3-methyl-1-imidazol-2-ylidene)), showing a Janus-type dual emission from ligand-to-metal charge transfer (LMCT)- and metal-to-ligand charge transfer (MLCT)-dominated states. This behaviour is achieved by a ligand design that combines four N-heterocyclic carbenes with two cyclometalating aryl units. The low-lying π* levels of the cyclometalating units lead to energetically accessible MLCT states that cannot evolve into LMCT states. With a lifetime of 4.6 ns, the strongly reducing and oxidizing MLCT-dominated state can initiate electron transfer reactions, which could constitute a basis for future applications of iron in photoredox catalysis. [Image: see text]
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spelling pubmed-100701852023-04-05 Janus-type emission from a cyclometalated iron(iii) complex Steube, Jakob Kruse, Ayla Bokareva, Olga S. Reuter, Thomas Demeshko, Serhiy Schoch, Roland Argüello Cordero, Miguel A. Krishna, Athul Hohloch, Stephan Meyer, Franc Heinze, Katja Kühn, Oliver Lochbrunner, Stefan Bauer, Matthias Nat Chem Article Although iron is a dream candidate to substitute noble metals in photoactive complexes, realization of emissive and photoactive iron compounds is demanding due to the fast deactivation of their charge-transfer states. Emissive iron compounds are scarce and dual emission has not been observed before. Here we report the Fe(III) complex [Fe(ImP)(2)][PF(6)] (HImP = 1,1′-(1,3-phenylene)bis(3-methyl-1-imidazol-2-ylidene)), showing a Janus-type dual emission from ligand-to-metal charge transfer (LMCT)- and metal-to-ligand charge transfer (MLCT)-dominated states. This behaviour is achieved by a ligand design that combines four N-heterocyclic carbenes with two cyclometalating aryl units. The low-lying π* levels of the cyclometalating units lead to energetically accessible MLCT states that cannot evolve into LMCT states. With a lifetime of 4.6 ns, the strongly reducing and oxidizing MLCT-dominated state can initiate electron transfer reactions, which could constitute a basis for future applications of iron in photoredox catalysis. [Image: see text] Nature Publishing Group UK 2023-02-27 2023 /pmc/articles/PMC10070185/ /pubmed/36849804 http://dx.doi.org/10.1038/s41557-023-01137-w Text en © The Author(s) 2023 https://creativecommons.org/licenses/by/4.0/ 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/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Steube, Jakob
Kruse, Ayla
Bokareva, Olga S.
Reuter, Thomas
Demeshko, Serhiy
Schoch, Roland
Argüello Cordero, Miguel A.
Krishna, Athul
Hohloch, Stephan
Meyer, Franc
Heinze, Katja
Kühn, Oliver
Lochbrunner, Stefan
Bauer, Matthias
Janus-type emission from a cyclometalated iron(iii) complex
title Janus-type emission from a cyclometalated iron(iii) complex
title_full Janus-type emission from a cyclometalated iron(iii) complex
title_fullStr Janus-type emission from a cyclometalated iron(iii) complex
title_full_unstemmed Janus-type emission from a cyclometalated iron(iii) complex
title_short Janus-type emission from a cyclometalated iron(iii) complex
title_sort janus-type emission from a cyclometalated iron(iii) complex
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10070185/
https://www.ncbi.nlm.nih.gov/pubmed/36849804
http://dx.doi.org/10.1038/s41557-023-01137-w
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