Electron transfer coupled spin transition in cyano-bridged mixed-valence {FeIII2FeII2} molecular squares

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The research on electron transfer coupled spin transition regulating the valence state and spin state transition of metal ions is promising and challenging. Herein, we report a cyano-bridged {FeIII2FeII2} molecular square complex, {[Fe(Tp)(CN)3]2 [Fe(bnbpen)]2}(ClO4)2·8CH3OH (1·8CH3OH, bnbpen = N,N'-bis-(2-naphthylmethyl)-N,N'-bis(2-picolayl)-ethylenediamine), and its free of solvents form (1). Combined single-crystal X-ray diffraction, temperature-dependent infrared (IR) spectra, magnetic measurements, and Mössbauer spectra reveal that 1·8CH3OH and 1 exhibit reversible one-step and two-step electron transfer coupled spin transition (ETCST) with temperature change, between the low-temperature state {FeII,LS(μ-CN)FeIII,LS}2 (LS = low spin, HS = high spin) and the high-temperature state {FeIII,LS(μ-CN)FeII,HS}2, respectively.