Photoexcitation and relaxation properties of a spin-crossover solid in the case of a stable high-spin state

Abstract

The molecular solid [Fe^IIL₂](ClO₄)₂·CH₃CN where L is 2,6-bis(3,5-dimethylpyrazol-1-ylmethyl)pyridine provides a stable high-spin (HS) state at low temperature. Photoexcitation and subsequent relaxation have been studied using light-induced excited state spin trapping [LIESST(H → L)] in the 700−850 nm range, determination of T_LIESST, relaxation curves at different temperatures, and temperature dependence of the light-induced spin equilibrium under constant irradiation. The measured photoinduced population of the metastable low-spin (LS) state (<30%) was drastically limited by the concomitant L → H photoprocess. The absence of static light-induced thermal hysteresis and the stretched exponential shape of the relaxation curves respectively revealed the absence of sizable interactions and a large spreading of the activation energies attributed to the ligand flexibility. The whole data set has been simulated using a linear rate equation, with a simplified correction for the bulk extinction of light in the powder sample.