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Scientific article
English

The Role of Ligand-Field States in the Ultrafast Photophysical Cycle of the Prototypical Iron(II) Spin-Crossover Compound [Fe(ptz)6](BF4)2

Published inAngewandte Chemie, vol. 53, no. 15, p. 3863-3867
Publication date2014
Abstract

Light-induced excited spin state trapping (LIESST) in iron(II) spin-crossover compounds, i.e., the light-induced population of the high-spin (S=2) state below the thermal transition temperature, was discovered thirty years ago. For irradiation into metal-ligand charge transfer (MLCT) bands of the low-spin (S=0) species the acknowledged sequence takes the system from the initially excited 1MLCT to the high-spin state via the 3MLCT state within ~150 fs, thereby bypassing low-lying ligand-field (LF) states. Nevertheless, these play role, as borne out by the observation of LIESST and reverse-LIESST on irradiation directly into the LF bands for systems with only high-energy MLCT states. Herein we elucidate the ultrafast reverse-LIESST pathway by identifying the lowest energy S=1 LF state as intermediate state with a lifetime of 39 ps for the light-induced high-spin to low-spin conversion on irradiation into the spin-allowed LF transition of the high-spin species in the NIR.

Keywords
  • Intersystem crossing
  • LIESST
  • Ligand-field states
  • Spin crossover
  • Ultrafast spectroscopy
Research group
Citation (ISO format)
MARINO, Andrea et al. The Role of Ligand-Field States in the Ultrafast Photophysical Cycle of the Prototypical Iron(II) Spin-Crossover Compound [Fe(ptz)<sub>6</sub>](BF<sub>4</sub>)<sub>2</sub>. In: Angewandte Chemie, 2014, vol. 53, n° 15, p. 3863–3867. doi: 10.1002/anie.201310884
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ISSN of the journal1433-7851
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