Readily Prepared Metallo‐Supramolecular Triple Helicates Designed to Exhibit Spin‐Crossover Behaviour

New dinuclear supramolecular cylinders have been designed to exhibit spin-crossover behaviour, a form of molecular bistability. This has been achieved within the framework of our imine-based approach to supramolecular architecture by switching from pyridylimine systems to imidazolimines. Spin-crossover behaviour is achieved while retaining the simplicity and ease-of-synthesis of our molecular design. The imidazole groups used also introduce additional NH groups that engage in hydrogen-bonding to anions and solvents. In the case of the iron(II) tetrafluoroborate complex this hydrogen bonding links supramolecular cylinders into an extended two-dimensional array. Consistent with this, a sharper spin-crossover transition is observed for this compound than for the corresponding hexafluorophosphate salt. More subtle anion effects are indicated in the perchlorate salt which gives a two-step spin conversion, thereby displaying tristability.