Superiority of the Supramolecular Halogen Bond Receptor over Its H-Bond Analogue toward the Efficient Extraction of Perrhenate from Water.

Abstract

A halogen bond-based water-soluble tetrapodal iodoimidazolium receptor, (L-I)(4Br), exhibited a high degree of efficiency (∼96%) in extracting ReO4- from 100% aqueous medium within a wide range of concentrations and of pH values along with excellent reusability. The solid-state X-ray diffraction study showed the trapping of ReO4- by (L-I)(4Br) via the Re-O····I halogen bonding interaction. XPS studies also suggested the interaction between I and ReO4- through polarization of the electron density of I atoms by ReO4-. (L-I)(4Br) is found to be capable of retaining its high extraction efficiency in the presence of competing anions such as F-, Cl-, I-, SO42-, H2PO4-, CO32-, NO3-, BF4-, ClO4-, Cr2O72-, and a mixture of these anions. Interestingly, (L-I)(4Br) was found to be superior in ReO4- extraction as compared to its hydrogen-bond donor analogue, (L-H)(4Br), as confirmed by a series of control experiments and theoretical calculations. Our synthesized dipodal and tripodal halogen bond donor receptors and their H-analogues validated the superiority of these classes of supramolecular halogen bond donor receptors over their hydrogen-bond analogues. (L-I)(4Br) also showed superior practical applicability in terms of the removal of ReO4- at anion concentrations as low as ∼100 ppm, which was a major shortcoming of (L-H)(4Br).