Lower-rim versus upper-rim functionalization in di-ionizable calix[4]arene-crown-5 isomers. Synthesis and divalent metal ion extraction

Two series of di-ionizable calix4]arene-crown-5 isomers in the cone conformation are synthesized to probe the effect of the pendant acidic group location on their metal ion extraction properties. In one series, the ionizable groups are attached to the lower rim of the calix4]arene scaffold, which orients them near the crown ether cavity. In the second series, the ionizable groups are connected to the upper rim positioning them away from the crown ether ring, but close to the hydrophobic pocket of the calix4]arene unit. The metal ion extraction behaviors of the two series of ligands are compared in extractions of alkaline earth metal cations, Hg²⁺, and Pb²⁺.