Conformational features of calix[4]arenes with alkali metal cations: A quantum chemical investigation with density functional theory

A variety of conformations for three model calix4]arenes with 8 or 12 OH groups have been investigated by calculations at density functional (RI-BP86) and RI-MP2 level of approximation. The calixarenes form stable complexes with the alkali metal cations of lithium up to caesium. For the investigations all-valence electron basis sets as well as various effective core potentials were probed. The stabilities of complexes were analysed in comparison with the corresponding benzene complexes, M⁺·C₆H₆. The formation of the calixarene metal complexes is considered in two steps, (a) in a distortion from the equilibrium conformation of the free calixarenes and (b) subsequent complexation. The distortion energies are small for the ‘crown’ and larger for the ‘boat’ conformations. On the other hand the latter are more stabilized by significant interaction energy of the cation with two adjacent π-systems of the aromatic rings. As a result, these two conformations are of similar stabilities for K⁺ to Cs⁺ complexes with resorc4]arenes, with a slight advantage for the ‘boat’ structure. The most stable conformation for the coordination products of these cations with the calix4]arene with 12 OH groups is a slightly flattened ‘crown’ that is derived by maximum hydrogen bonding of the OH-groups and the most effective cation-π interactions. Special cases are complexes of Li⁺ and Na⁺ which in most instances prefer the coordination on the oxygen atoms of the upper rim of the calixarene cavities and thus form ‘boat’-like structures.