Anion-Regulated Molecular Rotor Crystal: The First Case of a Stator-Rotator Double Switch with Relaxation Behavior

Molecular rotational motion is crucial in artificial molecular machines and is expected to be very significant for the development of an electronic information molecular machine as mentioned in the 2016 Nobel Prize. However, controlling multiple motor modes is a huge challenge. Here, we report a case in which the structural phase transition effectively triggers multiple motor modes by regulating the rotational speed of the cation and/or anion. A novel switchable crystalline supramolecular rotor, [(cyclohexylammonium)(18-crown-6)] FSO₃ (1), exhibits prominent temperature-dependent double switching behavior at 157.9 and 389.1 K induced by the variation of the rotational speed of the FSO₃^- anion (which acts as a super miniature rotator) in response to temperature. Moreover, it exhibits significant relaxation behavior and excellent pyroelectric switch characteristics. To the best of our knowledge, this might be the first discovery of the stator-rotator double switch with a relaxation effect, which could be a promising candidate for a slow/fast responsive double switch over a wide temperature range.