The role of ligand-field states in the ultrafast photophysical cycle of the prototypical iron(II) spin-crossover compound [Fe(ptz)6](BF4)2 - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Angewandte Chemie International Edition Année : 2014

The role of ligand-field states in the ultrafast photophysical cycle of the prototypical iron(II) spin-crossover compound [Fe(ptz)6](BF4)2

Andrea Marino
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Marina Servol
Maciej Lorenc
Eric Collet

Résumé

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 1MLCT to the high-spin state via the 3MLCT 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.
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hal-00959758 , version 1 (18-03-2014)

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Andrea Marino, Pradip Chakraborty, Marina Servol, Maciej Lorenc, Eric Collet, et al.. The role of ligand-field states in the ultrafast photophysical cycle of the prototypical iron(II) spin-crossover compound [Fe(ptz)6](BF4)2. Angewandte Chemie International Edition, 2014, 53 (15), pp.3863-3867, 10.1002/anie.201310884. ⟨10.1002/anie.201310884⟩. ⟨hal-00959758⟩
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