meso-Bis(ethynyl) Versus meso-Bis(aryl) Calix[4]pyrroles: Dimensionally Well-Modulated Receptors That Can Regulate the Anion Binding Domains

meso-Substituted calix[4]pyrroles 2–6 containing a direct meso-ethynyl linker displayed high binding affinities and unique conformational features on halide anion binding. A general conformational bias for the equatorial alignments of the meso-(aryl)ethynyl groups was observed in the host–halide complexes which was attributed to the repulsive anion–alkyne interactions and released steric strain. Such conformational features of host–halide complexes persisted even in the case of calix[4]pyrrole 6 bearing cationic meso components, which displayed the highest binding affinity for chloride anions among known meso-aryl calix[4]pyrroles. Synthetic details, conformational features, and comparative halide anion binding properties of this series of calix[4]pyrroles are described.