Effect of steric crowding on ion selectivity for calix-crown hybrid ionophores: experimental, molecular modeling and crystallographic studies

Abstract

A number of calix[4]arene-azacrowns with variation in ring size and substituents at the upper and lower rims have been synthesized to investigate the effect of steric crowding towards ion selectivity. The structural elucidation of these ionophores has been carried out mainly by ¹H NMR and ES-MS in solution and by single crystal X-ray study in the solid state. Interaction of these ionophores with a large number of cations has been investigated by NMR studies. The ionophore with tert-butyl at the upper rim (3) exhibits selectivity towards Na⁺ only whereas an ionophore of the same size but without tert-butyl at the upper rim (1) shows selectivity towards both Na⁺ and K⁺. An ionophore of the same size but with three tosyl substituents at the lower rim (4) exhibits no complexation with any cation. The ionophore with the larger crown ring and without tert-butyl at the upper rim (2) exhibits complexation with K⁺, Rb⁺, Ba²⁺ and weak interaction with Na⁺. Binding constants with these metal ions have been determined by NMR titration. Molecular modeling studies performed by a molecular mechanics force field (MMFF94) using the Monte Carlo search method and DFT calculations predicted the observed higher selectivity for sterically crowded receptor.