Competing Supramolecular Interactions Give a New Twist to Terpyridyl Chemistry: Anion‐ and Solvent‐Induced Formation of Spiral Arrays in Silver(I) Complexes of a Simple Terpyridine

Multiple competing molecular interactions (metal–ligand, π‐stacking and hydrogen‐bonding) in the silver(I) complexes of 4′‐thiomethyl‐2,2′:6′,2″‐terpyridine give rise to a range of different molecular architectures, in which the metal–ligand coordination requirements are satisfied in quite different ways. Polynuclear supramolecular spirals, aggregated mononuclear and aggregated dinuclear units are all structurally characterised. The metallo‐supramolecular architecture obtained displays a remarkable dependence both on the choice of non‐coordinated anion and the type of solvent used (coordinating or non‐coordinating). The anion dependence is particularly surprising, since the anions are not integrated into the centre of the supramolecular structure. The solution behaviour is also solvent and anion dependent, with aggregation of planar mononuclear cations observed in acetonitrile, but oligonuclear spiral species implicated in nitromethane. The extraordinarily variable geometries of these systems suggest that they provide a novel example of the “frustration” principle, in which opposing tendencies cannot simultaneously be satisfied and identify an alternative approach to the design of metallo‐supramolecular systems whose structure is responsive to external agents.