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

Zhang, X.; Daku, M. L. Lawson; Zhang, J.; Suarez-Alcantara, K.; Jennings, G.; Kurtz, C. A. and Canton, Sophie LU (2015) In Journal of Physical Chemistry C 119(6). p.3312-3321
Abstract
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,... (More)
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. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Physical Chemistry C
volume
119
issue
6
pages
3312 - 3321
publisher
The American Chemical Society
external identifiers
  • wos:000349578400046
  • scopus:84923165946
ISSN
1932-7447
DOI
10.1021/jp5117068
language
English
LU publication?
yes
id
29c42589-8ba4-4a8a-aaae-514d41625c83 (old id 5160164)
date added to LUP
2015-03-25 08:40:39
date last changed
2017-07-23 03:25:25
@article{29c42589-8ba4-4a8a-aaae-514d41625c83,
  abstract     = {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.},
  author       = {Zhang, X. and Daku, M. L. Lawson and Zhang, J. and Suarez-Alcantara, K. and Jennings, G. and Kurtz, C. A. and Canton, Sophie},
  issn         = {1932-7447},
  language     = {eng},
  number       = {6},
  pages        = {3312--3321},
  publisher    = {The American Chemical Society},
  series       = {Journal of Physical Chemistry C},
  title        = {Dynamic Jahn-Teller Effect in the Metastable High-Spin State of Solvated [Fe(terpy)(2)](2+)},
  url          = {http://dx.doi.org/10.1021/jp5117068},
  volume       = {119},
  year         = {2015},
}