Chalcogen Bonding in Selective Recognition and Liquid-Liquid Extraction of Perrhenate

Efficient recognition and extraction of hazardous anionic pollutants from water medium is of great significance for environmental concerns, representing a challenging area of research in supramolecular chemistry. In this study, we present, for the first time, a comprehensive demonstration of the ability of chalcogen bonding (ChB) to recognize and remove the ReO₄ ^- from 100 % water medium. The anion recognition ability is well elucidated through solution phase NMR and ITC studies, which clearly reveal the selective binding of ReO₄ ^- over other oxo-anions. Moreover, the selenoimidazolium scaffold effectively engages in Se•••O ChB interaction with ReO₄ ^- as confirmed by X-ray crystal structure and XPS analysis. More importantly, the binding of ReO₄ ^- with different prolongations of the σ-holes, along with Se•••Se chalcogen bonding interactions, lead to the formation of a 1D supramolecular assembly. Eventually, ChB receptor Se₄Me-Br exhibits ~62 % ReO₄ ^- extraction efficiency through precipitation as the extraction method. Furthermore, in efforts to enhance efficiency, a hydrophobic ChB receptor Se₄Do-PF₆ has been prepared, achieving an efficiency of up to ~93 % at a very low concentration (~5 ppm) by liquid-liquid extraction.