Chalcogen Bond Mediated Enhancement of Cooperative Ion-Pair Recognition

Abstract

A series of heteroditopic receptors containing halogen bond (XB) and unprecedented chalcogen bond (ChB) donors integrated into a 3,5-bis-triazole pyridine structure covalently linked to benzo-15-crown-5 ether motifs exhibit remarkable cooperative recognition of halide anions. Multi-nuclear 1H, 13C, 125Te and 19F NMR, ion pair binding investigations reveal sodium cation–benzo-crown ether binding dramatically enhances the recognition of bromide and iodide halide anions, with the chalcogen bonding heteroditopic receptor notably displaying the largest enhancement of halide binding strength of over two hundred-fold, in comparison to the halogen bonding and hydrogen bonding heteroditopic receptor analogues. DFT calculations suggest crown ether sodium cation complexation induces a polarisation of the sigma hole of ChB and XB heteroditopic receptor donors as a significant contribution to the origin of the unique cooperativity exhibited by these systems.