Decoding Framework Dynamics in a Spin Crossover Flexible Metal–Organic Framework

Abstract Functional spin crossover (SCO) metal–organic frameworks (MOFs) hold promise for miniaturized spin‐based devices due to their tuneable molecule‐based properties near room temperature. SCO describes the phenomenon where transition metal ions switch between high spin (HS) and low spin (LS) states upon external stimuli. However, even simple guest molecules like water can significantly alter the properties of these materials. Understanding the interplay between SCO and these molecules is therefore crucial. This work investigates this interplay in a fascinating 3D Fe(II) SCO‐MOF, recently reported to exhibit reversible conductivity even in bulk. A combined experimental and computational approach is employed to explore how guest molecule uptake/release influences SCO dynamics including a transition from partial HS/LS to a fully LS state at high temperatures, (named reverse SCO) and ligand disorder‐order behavior. The findings reveal a solid‐state mechanism that differs from those previously described.