Supporting Information

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

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

X-ray Sciences Division, Argonne, National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
Département de Chimie Physique, Université de Genève, Quai E. Ansermet 30, CH-1211 Genève 4, Switzerland
§ School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, China
Department of Synchrotron Radiation Instrumentation, Lund University, P.O. Box 118, 22100 Lund, Sweden
J. Phys. Chem. C, 2015, 119 (6), pp 3312–3321
DOI: 10.1021/jp5117068
Publication Date (Web): February 3, 2015
Copyright © 2015 American Chemical Society
*E-mail (S.E.C.).


Abstract Image

Characterizing structural distortions in the metastable spin states of d4–d7 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 Jahn–Teller 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 D2 symmetry that originates from a dynamic Jahn–Teller 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.

Supporting Information

Results of the optimization calculations performed for [Fe(terpy)2]2+ in the gas phase and in acetonitrile. This material is available free of charge via the Internet at


Article Views: 487 Times
Received 23 November 2014
Published online 3 February 2015
Published in print 12 February 2015
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