Single-Crystal to Single-Crystal Transformation of a Spin-Crossover Hybrid Perovskite via Thermal-Induced Cyanide Linkage Isomerization

Linkage isomers involving changes in the bonding mode of ambidentate ligands have potential applications in data storage, molecular machines, and motors. However, the observation of the cyanide-linkage-isomerism-induced spin change (CLIISC) effect characterized by single-crystal X-ray diffraction remains a considerable challenge. Meanwhile, the high-spin and low-spin states can be reversibly switched in spin-crossover (SCO) compounds, which provide the potential for applications to data storage, switches, and sensors. Here, a new perovskite-type SCO framework (PPN)­[Fe­{Ag­(CN)₂}₃] (PPN⁺ = bis­(trisphenylphosphine)­iminium cation) is synthesized, which displays the unprecedented aging and temperature dependences of hysteretic multistep SCO behaviors near room temperature. Moreover, the thermal-induced cyanide linkage isomerization from Fe^II–NC–Ag^I to Fe^II–CN–Ag^I is revealed by single-crystal X-ray diffraction, Raman, and Mössbauer spectra, which is associated with a transition from the mixed spin state to the low-spin state and a dramatic volume shrinkage. Considering the wide use of cyanogen in magnetic systems, the association of CLIISC and SCO opens a new dimension to modulate the spin state and realize a colossal negative thermal expansion.