ON/OFF Photo(switching) along with Reversible Spin-State Change and Single-Crystal-to-Single-Crystal Transformation in a Mixed- Valence Fe(II)Fe(III) Molecular System

A mixed-valence Fe(II)Fe(III) molecular system, {[Fe(pzTp)(CN)3]2[Fe(bik)2]2}center dot [Fe(pzTp)(CN)3]2 center dot 4MeOH (1 center dot 4MeOH) (bik = bis-(1-methylimidazolyl)-2-methanone, pzTp = tetrakis(pyrazolyl)borate), exhibits single-crystal-to-single-crystal (SC-SC) transformation while increasing the temperature and is converted into {[Fe(pzTp)(CN)3]2[Fe(bik)2]2}center dot[Fe(pzTp)-(CN)3]2 (1). Both complexes exhibit thermo-induced spin-state switching behavior along with reversible SC-SC transformation, where the low-temperature [FeIIILSFeIILS]2 phase transforms into a high-temperature [FeIIILSFeIIHS]2 phase. 1 center dot 4MeOH exhibits an abrupt spin-state switching with T1/2 at 355 K, whereas 1 undergoes a gradual and reversible spin-state switching with a lower T1/2 at 338 K. Astonishingly, 1 exhibits ON/OFF photo-induced spin-state switching with TLIESST = 67 K, whereas 1 center dot 4MeOH does not show such an effect.

Automated summary

This article describes a mixed-valence Fe(II)Fe(III) molecular system that undergoes single-crystal-to-single-crystal transformation with increasing temperature, along with thermo-induced spin-state switching behavior. One of the compounds also exhibits photo-induced spin-state switching.