Hard-Soft Cooperativity of an Allosteric Tweezer.

Drawing inspiration from allosteric proteins, a zigzag-shaped π-conjugation was structurally engineered into a tweezer-like ionophore having multiple disparate binding sites. When a soft metal ion binds to the central tridentate ligand motif, the rigid backbone folds, bringing two macrocyclic arms into close proximity. Stabilized by a coordinating anion, the tweezer-like conformation of the resulting metalloligand recruits a hard cation to form a sandwich-like complex with a remarkably enhanced binding affinity and selectivity.