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

Abstract Two photoactive iron N-heterocyclic carbene complexes $${[\hbox {Fe}^{{{\rm{II}}}}(\hbox {btz})_2(\hbox {bpy})]^{2+}}$$ [ Fe II ( btz ) 2 ( bpy ) ] 2 + and $${[\hbox {Fe}^{{\rm{III}}}(\hbox {btz})_3]^{3+}}$$ [ Fe III ( btz ) 3 ] 3 + , where btz is 3,3’-dimethyl-1,1’-bis(p-tolyl)-4,4’-bis(1,...

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Autores principales:	Robert H. Temperton, Meiyuan Guo, Giulio D’Acunto, Niclas Johansson, Nils W. Rosemann, Om Prakash, Kenneth Wärnmark, Joachim Schnadt, Jens Uhlig, Petter Persson
Formato:	article
Lenguaje:	EN
Publicado:	Nature Portfolio 2021
Materias:	Medicine R Science Q
Acceso en línea:	https://doaj.org/article/d27330a5170b48d381baf23c66e61dd2
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spelling	oai:doaj.org-article:d27330a5170b48d381baf23c66e61dd22021-11-14T12:22:49ZResonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes10.1038/s41598-021-01509-72045-2322https://doaj.org/article/d27330a5170b48d381baf23c66e61dd22021-11-01T00:00:00Zhttps://doi.org/10.1038/s41598-021-01509-7https://doaj.org/toc/2045-2322Abstract Two photoactive iron N-heterocyclic carbene complexes $${[\hbox {Fe}^{{{\rm{II}}}}(\hbox {btz})_2(\hbox {bpy})]^{2+}}$$ [ Fe II ( btz ) 2 ( bpy ) ] 2 + and $${[\hbox {Fe}^{{\rm{III}}}(\hbox {btz})_3]^{3+}}$$ [ Fe III ( btz ) 3 ] 3 + , 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 $${\hbox {t}_{{\rm{2g}}}}$$ t 2 g levels with occupied ligand $$\pi$$ π orbitals but weak mixing with the corresponding unoccupied ligand orbitals. This highlights the importance of $$\pi$$ π -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 $$\hbox {Fe}^{{\rm{III}}}$$ Fe III 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 $$\hbox {Fe}^{{\rm{III}}}$$ Fe III photosensitizers from those of more traditional $$\hbox {Fe}^{{\rm{II}}}$$ Fe II complexes.Robert H. TempertonMeiyuan GuoGiulio D’AcuntoNiclas JohanssonNils W. RosemannOm PrakashKenneth WärnmarkJoachim SchnadtJens UhligPetter PerssonNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 11, Iss 1, Pp 1-14 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	Medicine R Science Q
spellingShingle	Medicine R Science Q Robert H. Temperton Meiyuan Guo Giulio D’Acunto Niclas Johansson Nils W. Rosemann Om Prakash Kenneth Wärnmark Joachim Schnadt Jens Uhlig Petter Persson Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes
description	Abstract Two photoactive iron N-heterocyclic carbene complexes $${[\hbox {Fe}^{{{\rm{II}}}}(\hbox {btz})_2(\hbox {bpy})]^{2+}}$$ [ Fe II ( btz ) 2 ( bpy ) ] 2 + and $${[\hbox {Fe}^{{\rm{III}}}(\hbox {btz})_3]^{3+}}$$ [ Fe III ( btz ) 3 ] 3 + , 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 $${\hbox {t}_{{\rm{2g}}}}$$ t 2 g levels with occupied ligand $$\pi$$ π orbitals but weak mixing with the corresponding unoccupied ligand orbitals. This highlights the importance of $$\pi$$ π -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 $$\hbox {Fe}^{{\rm{III}}}$$ Fe III 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 $$\hbox {Fe}^{{\rm{III}}}$$ Fe III photosensitizers from those of more traditional $$\hbox {Fe}^{{\rm{II}}}$$ Fe II complexes.
format	article
author	Robert H. Temperton Meiyuan Guo Giulio D’Acunto Niclas Johansson Nils W. Rosemann Om Prakash Kenneth Wärnmark Joachim Schnadt Jens Uhlig Petter Persson
author_facet	Robert H. Temperton Meiyuan Guo Giulio D’Acunto Niclas Johansson Nils W. Rosemann Om Prakash Kenneth Wärnmark Joachim Schnadt Jens Uhlig Petter Persson
author_sort	Robert H. Temperton
title	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_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_sort	resonant x-ray photo-oxidation of light-harvesting iron (ii/iii) n-heterocyclic carbene complexes
publisher	Nature Portfolio
publishDate	2021
url	https://doaj.org/article/d27330a5170b48d381baf23c66e61dd2
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Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes

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