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

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Robert H. Temperton
Meiyuan Guo
Giulio D’Acunto
Niclas Johansson
Nils W. Rosemann
Om Prakash
Kenneth Wärnmark
Joachim Schnadt
Jens Uhlig
Petter Persson
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[1] Lund University,MAX IV Laboratory
[2] University of Nottingham,School of Physics and Astronomy
[3] Lund Institute of Advanced Neutron and X-ray Science,Division of Chemical Physics, Department of Chemistry
[4] Lund University,Division of Synchrotron Radiation Research, Department of Physics
[5] Lund University,Department of Chemistry, Centre for Analysis and Synthesis
[6] Lund University,Division of Theoretical Chemistry, Department of Chemistry
[7] Lund University,undefined
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Two photoactive iron N-heterocyclic carbene complexes [FeII(btz)2(bpy)]2+\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${[\hbox {Fe}^{{{\rm{II}}}}(\hbox {btz})_2(\hbox {bpy})]^{2+}}$$\end{document} and [FeIII(btz)3]3+\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${[\hbox {Fe}^{{\rm{III}}}(\hbox {btz})_3]^{3+}}$$\end{document}, 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 t2g\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${\hbox {t}_{{\rm{2g}}}}$$\end{document} levels with occupied ligand π\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\pi$$\end{document} orbitals but weak mixing with the corresponding unoccupied ligand orbitals. This highlights the importance of π\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\pi$$\end{document}-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 FeIII\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\hbox {Fe}^{{\rm{III}}}$$\end{document} 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 FeIII\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\hbox {Fe}^{{\rm{III}}}$$\end{document} photosensitizers from those of more traditional FeII\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\hbox {Fe}^{{\rm{II}}}$$\end{document} complexes.
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