Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2′-bipyridine)2(CN)2]

Kasper Skov Kjær, Wenkai Zhang, Roberto Alonso-Mori, Uwe Bergmann, Matthieu Chollet, Ryan G. Hadt, Robert W. Hartsock, Tobias C. B. Harlang, Thomas Kroll, Katharina Kubiček, Henrik T. Lemke, Huiyang W. Liang, Yizhu Liu, Martin Meedom Nielsen, Joseph S. Robinson, Edward I. Solomon, Dimosthenis Sokaras, Tim B. van Driel, Tsu-Chien Weng, Diling ZhuPetter Persson, Kenneth Wärnmark, Villy Sundström, Kelly J. Gaffney

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Abstract

We have used femtosecond resolution UV-visible and Kβ x-ray emission spectroscopy to characterize the electronic excited state dynamics of [Fe(bpy)2(CN)2], where bpy=2,2′-bipyridine, initiated by metal-to-ligand charge transfer (MLCT) excitation. The excited-state absorption in the transient UV-visible spectra, associated with the 2,2′-bipyridine radical anion, provides a robust marker for the MLCT excited state, while the transient Kβ x-ray emission spectra provide a clear measure of intermediate and high spin metal-centered excited states. From these measurements, we conclude that the MLCT state of [Fe(bpy)2(CN)2] undergoes ultrafast spin crossover to a metal-centered quintet excited state through a short lived metal-centered triplet transient species. These measurements of [Fe(bpy)2(CN)2] complement prior measurement performed on [Fe(bpy)3]2+ and [Fe(bpy)(CN)4]2− in dimethylsulfoxide solution and help complete the chemical series [Fe(bpy)N(CN)6–2N]2N-4, where N = 1–3. The measurements confirm that simple ligand modifications can significantly change the relaxation pathways and excited state lifetimes and support the further investigation of light harvesting and photocatalytic applications of 3d transition metal complexes.
Original languageEnglish
Article number044030
JournalStructural Dynamics
Volume4
Issue number4
ISSN2329-7778
DOIs
Publication statusPublished - 2017

Bibliographical note

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Keywords

  • Monte Carlo methods
  • Emission spectra
  • Absorption spectra
  • Excited states
  • Spin crossover

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