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Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes

Two photoactive iron N-heterocyclic carbene complexes [Formula: see text] and [Formula: see text] , where btz is 3,3’-dimethyl-1,1’-bis(p-tolyl)-4,4’-bis(1,2,3-triazol-5-ylidene) and bpy is 2,2’-bipyridine, have been investigated by Resonant Photoelectron Spectroscopy (RPES). Tuning the incident X-r...

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Autores principales: Temperton, Robert H., Guo, Meiyuan, D’Acunto, Giulio, Johansson, Niclas, Rosemann, Nils W., Prakash, Om, Wärnmark, Kenneth, Schnadt, Joachim, Uhlig, Jens, Persson, Petter
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8590020/
https://www.ncbi.nlm.nih.gov/pubmed/34772983
http://dx.doi.org/10.1038/s41598-021-01509-7
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author Temperton, Robert H.
Guo, Meiyuan
D’Acunto, Giulio
Johansson, Niclas
Rosemann, Nils W.
Prakash, Om
Wärnmark, Kenneth
Schnadt, Joachim
Uhlig, Jens
Persson, Petter
author_facet Temperton, Robert H.
Guo, Meiyuan
D’Acunto, Giulio
Johansson, Niclas
Rosemann, Nils W.
Prakash, Om
Wärnmark, Kenneth
Schnadt, Joachim
Uhlig, Jens
Persson, Petter
author_sort Temperton, Robert H.
collection PubMed
description Two photoactive iron N-heterocyclic carbene complexes [Formula: see text] and [Formula: see text] , where btz is 3,3’-dimethyl-1,1’-bis(p-tolyl)-4,4’-bis(1,2,3-triazol-5-ylidene) and bpy is 2,2’-bipyridine, have been investigated by Resonant Photoelectron Spectroscopy (RPES). Tuning the incident X-ray photon energy to match core-valence excitations provides a site specific probe of the electronic structure properties and ligand-field interactions, as well as information about the resonantly photo-oxidised final states. Comparing measurements of the Fe centre and the surrounding ligands demonstrate strong mixing of the Fe [Formula: see text] levels with occupied ligand [Formula: see text] orbitals but weak mixing with the corresponding unoccupied ligand orbitals. This highlights the importance of [Formula: see text] -accepting and -donating considerations in ligand design strategies for photofunctional iron carbene complexes. Spin-propensity is also observed as a final-state effect in the RPES measurements of the open-shell [Formula: see text] complex. Vibronic coupling is evident in both complexes, where the energy dispersion hints at a vibrationally hot final state. The results demonstrate the significant impact of the iron oxidation state on the frontier electronic structure and highlights the differences between the emerging class of [Formula: see text] photosensitizers from those of more traditional [Formula: see text] complexes.
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spelling pubmed-85900202021-11-16 Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes Temperton, Robert H. Guo, Meiyuan D’Acunto, Giulio Johansson, Niclas Rosemann, Nils W. Prakash, Om Wärnmark, Kenneth Schnadt, Joachim Uhlig, Jens Persson, Petter Sci Rep Article Two photoactive iron N-heterocyclic carbene complexes [Formula: see text] and [Formula: see text] , where btz is 3,3’-dimethyl-1,1’-bis(p-tolyl)-4,4’-bis(1,2,3-triazol-5-ylidene) and bpy is 2,2’-bipyridine, have been investigated by Resonant Photoelectron Spectroscopy (RPES). Tuning the incident X-ray photon energy to match core-valence excitations provides a site specific probe of the electronic structure properties and ligand-field interactions, as well as information about the resonantly photo-oxidised final states. Comparing measurements of the Fe centre and the surrounding ligands demonstrate strong mixing of the Fe [Formula: see text] levels with occupied ligand [Formula: see text] orbitals but weak mixing with the corresponding unoccupied ligand orbitals. This highlights the importance of [Formula: see text] -accepting and -donating considerations in ligand design strategies for photofunctional iron carbene complexes. Spin-propensity is also observed as a final-state effect in the RPES measurements of the open-shell [Formula: see text] complex. Vibronic coupling is evident in both complexes, where the energy dispersion hints at a vibrationally hot final state. The results demonstrate the significant impact of the iron oxidation state on the frontier electronic structure and highlights the differences between the emerging class of [Formula: see text] photosensitizers from those of more traditional [Formula: see text] complexes. Nature Publishing Group UK 2021-11-12 /pmc/articles/PMC8590020/ /pubmed/34772983 http://dx.doi.org/10.1038/s41598-021-01509-7 Text en © The Author(s) 2021 https://creativecommons.org/licenses/by/4.0/Open AccessThis 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 licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence 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 licence, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Temperton, Robert H.
Guo, Meiyuan
D’Acunto, Giulio
Johansson, Niclas
Rosemann, Nils W.
Prakash, Om
Wärnmark, Kenneth
Schnadt, Joachim
Uhlig, Jens
Persson, Petter
Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes
title Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes
title_full Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes
title_fullStr Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes
title_full_unstemmed Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes
title_short Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes
title_sort resonant x-ray photo-oxidation of light-harvesting iron (ii/iii) n-heterocyclic carbene complexes
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8590020/
https://www.ncbi.nlm.nih.gov/pubmed/34772983
http://dx.doi.org/10.1038/s41598-021-01509-7
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