Does Larger Cavity-Size Really Help Bigger Anions to Bind? A Scrutiny on Core-Expanded Calix[4]pyrroles and Their...

Calix[4]pyrroles are an important class of oligopyrrolic macrocycles and have found applications in many diverse fields including anion recognition. To modulate the properties of the calix[4]pyrrole, several structural modifications are realized. The core-expansion has attracted extra attention as it provides larger cavity-size compared to parent calix[4]pyrrole(s). This review highlights the synthetic development of various core-expanded calix[4]pyrroles and their applications in anion-binding properties. Emphasis is given to the changes in the binding properties observed with expanded versions of calix[4]pyrrole(s) in both solution and the solid states. The expanded versions of calix[4]pyrrole do not always show higher binding affinities for larger anions as anticipated. Rather, they display reduced affinities with the anions. The truncated form or asymmetric nature of the expanded versions of calix[4]pyrrole does not probably allow to access all the available binding sites for the anions and hence reduced binding affinities are observed. The receptors which contain a greater number of binding sites and are somehow rigid or preorganized apparently show enhanced binding affinities for anions. The relative binding constants for halide series indicate that the enlarged molecules are more beneficial for largest iodide among others. However, most of the receptors show selectivity towards smallest fluoride over other anions studied.