Mapping Out the Diversity of Lanthanide(III) Coordination Complexes Involving p-Sulfonatocalix[4,6]arenes

Abstract

Structurally authenticated complexes of the cone-shaped p-sulfonatocalix[4]arene and conformationally flexible p-sulfonatocalix[6]arene devoid of co-ligands/ancillary molecules are limited. Early and late members of the lanthanide series as their trivalent ions, La3+, Er3+, and Yb3+, form complexes from aqueous media under these conditions. For La3+ and Er3+, distinct hydrophobic and hydrophilic bilayers are formed with p-sulfonatocalix[4]arene, whereas for Yb3+, two complexes form that deviate from the well-known bilayer arrangement of calixarenes. Replacing the calixarene with p-sulfonatocalix[6]arene results in a hydrogen-bonded network with alternating hydrophobic–hydrophilic layers associated with primary coordination of Yb3+, with the larger macrocyclic calixarene in a partial cone conformation.