Lariat Ether Receptor Systems Show Experimental Evidence for Alkali Metal Cation−π Interactions

Abstract
Cation−π interactions occur between cations and electron-rich species such as double bonds, triple bonds, and arenes. The π-electron system may be neutral or anionic, but the latter are less relevant to biology, at least so far as is currently known. Among the 20 essential amino acids, there are four aromatic residues. These are benzene, phenol, indole, and imidazole, on the side chains of phenylalanine, tyrosine, tryptophan, and histidine, respectively. Of these, imidazole is expected to be a σ-donor, and benzene, phenol, and indole are antipicated to serve as π-donors. Sodium and potassium are the most abundant cations in living systems. This Account describes an experimental system that has been developed to probe, especially by X-ray crystallography, the interactions that occur between Na+ or K+ and the neutral arenes of particular biological significance.