Novel caesium-selective, 1,3-alternate calix[4]arene-bis(crown-6-ethers) with proton-ionizable groups for enhanced extraction efficiency

Synthesis of a series of novel 1,3-alternate calix[4]arene-bis(crown-6-ethers) with a proton-ionizable group (PIG) located in front of one crown ether cavity is reported. Variation of the X group in the N-(X-sulfonyl) carbamoyl substituent on the calixbiscrowns provides variation of acidity of the PIG. NMR spectroscopic studies demonstrate that the position of the PIG within the molecule allows it to participate in cooperative metal ion coordination by the ligand. In solvent extraction of alkali metal cations from aqueous solutions of varying pH into chloroform, the novel ionophores possess enhanced efficiency relative to a non-ionizable analog, while retaining high Cs+ selectivity. The Cs+ extraction constants of the proton-ionizable calixbiscrowns are proportional to their acidities. Under the conditions employed, 1 : 1 complexes of the ionized calixbiscrowns with Cs+ are the dominant species extracted into the organic phase.