title: The role of ligand-field states in the ultrafast photophysical cycle of the prototypical iron(II) spin-crossover compound [Fe(ptz)(6)](BF(4))(2).
abstract: Light-induced excited spin-state trapping (LIESST) in iron(II) spin-crossover compounds, that is, 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 (1) MLCT to the high-spin state via the (3) MLCT state within ca. 150 fs, thereby bypassing low-lying ligand-field (LF) states. Nevertheless, these play a 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 an 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.
authors.affiliation: Institut de Physique de Rennes, UMR CNRS 6251, University of Rennes 1, 35042 Rennes (France).
authors.forename: Andrea
authors.initials: A
authors.lastname: Marino
authors.forename: Pradip
authors.initials: P
authors.lastname: Chakraborty
authors.forename: Marina
authors.initials: M
authors.lastname: Servol
authors.forename: Maciej
authors.initials: M
authors.lastname: Lorenc
authors.forename: Eric
authors.initials: E
authors.lastname: Collet
authors.forename: Andreas
authors.initials: A
authors.lastname: Hauser
keywords: LIESST; intersystem crossing; ligand-field states; spin crossover; ultrafast spectroscopy