Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid-Liquid and 2D-Confined Interfaces

Understanding the interaction of ions with organic receptors in confined space is of fundamental importance and could advance nanoelectronics and sensor design. In this work, metal ion complexation of conformationally varied thiacalix[4]monocrowns bearing lower-rim hydroxy (type I), dodecyloxy (type II), or methoxy (type III) fragments was evaluated. At the liquid-liquid interface, alkylated thiacalixcrowns-5(6) selectively extract alkali metal ions according to the induced-fit concept, whereas crown-4 receptors were ineffective due to distortion of the crown-ether cavity, as predicted by quantum-chemical calculations. In type-I ligands, alkali-metal ion extraction by the solvent-accessible crown-ether cavity was prevented, which resulted in competitive Ag⁺ extraction by sulfide bridges. Surprisingly, amphiphilic type-I/II conjugates moderately extracted other metal ions, which was attributed to calixarene aggregation in salt aqueous phase and supported by dynamic light scattering measurements. Cation-monolayer interactions at the air-water interface were monitored by surface pressure/potential measurements and UV/visible reflection-absorption spectroscopy. Topology-varied selectivity was evidenced, towards Sr²⁺ (crown-4), K⁺ (crown-5), and Ag⁺ (crown-6) in type-I receptors and Na⁺ (crown-4), Ca²⁺ (crown-5), and Cs⁺ (crown-6) in type-II receptors. Nuclear magnetic resonance and electronic absorption spectroscopy revealed exocyclic coordination in type-I ligands and cation-π interactions in type-II ligands.