Dynamic Jahn-Teller Effect in the Metastable High-Spin State of Solvated [Fe(terpy)(2)](2+)

Research output: Contribution to journalArticle


Characterizing structural distortions in the metastable spin states of d(4)d(7) transition metal ion complexes is crucial to understand the nature of their bistability and eventually control their switching dynamics. In particular, the impact of the JahnTeller effect needs to be assessed for any electronic configuration that could be effectively degenerate, as in e.g. the high-spin (HS) manifold of highly symmetric homoleptic FeII complexes. However, capturing its manifestations remains challenging since crystallization generally alters the molecular conformations and their interconversion. With the rapid progress of ultrafast X-ray absorption spectroscopy, it is now possible to collect data with unprecedented signal-to-noise ratio, opening up for detailed structural characterization of transient species in the homogeneous solution phase. By combining the analysis of picosecond X-ray absorption spectra with DFT simulations, the structure of the photoinduced HS state is elucidated for solvated [Fe(terpy)(2)](2+) (terpy = 2,2':6',2 ''-terpyridine). This species can be viewed as the average 5B structure in D-2 symmetry that originates from a dynamic JahnTeller effect in the HS manifold. These results evidence the active role played by this particular instance of vibronic coupling in the formation of the HS state for this benchmark molecule. Ultimately, correlating the interplay between intramolecular and intermolecular degrees of freedom to conformational strain and distortions in real time should contribute to the development of advanced functionalities in transition metal ion complexes.


  • X. Zhang
  • M. L. Lawson Daku
  • J. Zhang
  • K. Suarez-Alcantara
  • G. Jennings
  • C. A. Kurtz
  • Sophie Canton
Research areas and keywords

Subject classification (UKÄ) – MANDATORY

  • Atom and Molecular Physics and Optics
Original languageEnglish
Pages (from-to)3312-3321
JournalJournal of Physical Chemistry C
Issue number6
StatePublished - 2015
Publication categoryResearch

Bibliographic note

The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)