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Chalcogen Bond Mediated Enhancement of Cooperative Ion‐Pair Recognition
Author(s) -
Bunchuay Thanthapatra,
Docker Andrew,
Eiamprasert Utt,
Surawatanawong Panida,
Brown Asha,
Beer Paul D.
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202001125
Subject(s) - chemistry , crown ether , halogen bond , hydrogen bond , halide , chalcogen , bromide , supramolecular chemistry , covalent bond , crystallography , iodide , ether , pyridine , stereochemistry , ion , inorganic chemistry , molecule , medicinal chemistry , crystal structure , organic chemistry
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 1 H, 13 C, 125 Te and 19 F 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.