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Jens Uhlig. Portrait.

Jens Uhlig

Senior lecturer

Jens Uhlig. Portrait.

HERFD-XANES probes of electronic structures of ironII/IIIcarbene complexes

Author

  • Meiyuan Guo
  • Om Prakash
  • Hao Fan
  • Lisa H.M. de Groot
  • Valtýr Freyr Hlynsson
  • Simon Kaufhold
  • Olga Gordivska
  • Nicolás Velásquez
  • Pavel Chabera
  • Pieter Glatzel
  • Kenneth Wärnmark
  • Petter Persson
  • Jens Uhlig
Show all

Summary, in English

Iron centeredN-heterocyclic carbene (Fe-NHC) complexes have shown long-lived excited states with charge transfer character useful for light harvesting applications. Understanding the nature of the metal-ligand bond is of fundamental importance to rationally tailor the properties of transition metal complexes. The high-energy-resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) has been used to probe the valence orbitals of three carbene complexes, [FeII(bpy)(btz)2](PF6)2(bpy = 2,2′-bipyridine, btz = 3,3′-dimethyl-1,1′-bis(p-tolyl)-4,4′-bis(1,2,3-triazol-5-ylidene)), [FeIII(btz)3](PF6)3, and [FeIII(phtmeimb)2]PF6(phtmeimb = [phenyl(tris(3-methylimidazol-2-ylidene))borate]−). The multiconfigurational restrict active space (RAS) approach has been used to simulate the metal K pre-edge X-ray absorption spectroscopy of these carbene complexes, and have reproduced the metal K pre-edge spectral features in terms of relative intensity and peak positions. The evident intensity difference between the FeIIand the other two FeIIIcomplexes has been elucidated with different intensity mechanisms in the transition. The smaller splitting between the t2gand egcharacter peak for [FeIII(btz)3](PF6)3has been observed in the experimental measurements and been reproduced in the RAS calculations. The results show how the combination of experimental HERFD-XANES measurements andab initioRAS simulations can give quantitative evaluation of the orbital interactions between metal and ligands for such large and strongly interacting systems and thus allow to understand and predict properties of novel complexes.

Department/s

  • Chemical Physics
  • Centre for Analysis and Synthesis
  • NanoLund: Centre for Nanoscience
  • Computational Chemistry
  • eSSENCE: The e-Science Collaboration

Publishing year

2020-04-28

Language

English

Pages

9067-9073

Publication/Series

Physical Chemistry Chemical Physics

Volume

22

Issue

16

Document type

Journal article

Publisher

Royal Society of Chemistry

Topic

  • Physical Chemistry (including Surface- and Colloid Chemistry)
  • Atom and Molecular Physics and Optics

Status

Published

ISBN/ISSN/Other

  • ISSN: 1463-9076