Unravelling of a [High Spin—Low Spin] ↔ [Low Spin—High Spin] Equilibrium in Spin‐Crossover Iron(II) Dinuclear Helicates Using Paramagnetic NMR Spectroscopy

Abstract Spin‐crossover between high‐spin (HS) and low‐spin (LS) states of selected transition metal ions in polynuclear and polymeric compounds is behind their use as multistep switchable materials in breakthrough electronic and spintronic devices. We report the first successful attempt to observe the dynamics of a rarely found broken‐symmetry spin state in binuclear complexes, which mixes the states [HS‐LS] and [LS‐HS] on a millisecond timescale. The slow exchange between these two states, which was identified by paramagnetic NMR spectroscopy in solutions of two spin‐crossover iron(II) binuclear helicates that are amenable to molecular design, opens a path to double quantum dot cellular automata for information storage and processing.