Host–guest complexes of mixed glycol-bipyridine cryptands: prediction of ion selectivity by quantum chemical calculations, part V

The selectivity of the cryptands [2.2.bpy] and [2.bpy.bpy] for the endohedral complexation of alkali, alkaline-earth and earth metal ions was predicted on the basis of the DFT (B3LYP/LANL2DZp) calculated structures and complex-formation energies. The cavity size in both cryptands lay between that for [2.2.2] and [bpy.bpy.bpy], such that the complexation of K(+), Sr(2+) and Tl(3+) is most favorable. While the [2.2.bpy] is moderately larger, preferring Rb(+) complexation and demonstrating equal priority for Sr(2+) and Ba(2+), the slightly smaller [2.bpy.bpy] yields more stable cryptates with Na(+) and Ca(2+). Although the CH2-units containing molecular bars fixed at the bridgehead nitrogen atoms determine the flexibility of the cryptands, the twist angles associated with the bipyridine and glycol building blocks also contribute considerably.