Macrocyclic squaramides: anion receptors with high sulfate binding affinity and selectivity in aqueous media†

Abstract

Macrocyclic squaramide derivatives bind sulfate ions with high selectivity and affinity in aqueous mixtures.

Abstract

A number of macrocyclic squaramide-containing receptors (MSQs) have been designed and synthesised and their interaction with a range of inorganic anions was studied in solution by ¹H NMR spectroscopy and ESI-HRMS. The binding data revealed remarkable binding of sulfate in aqueous mixtures from 0.5 to 50% v/v H ₂O/DMSO- d ₆. The larger [3]-MSQs were found to better match the size and shape of the sulfate ion than the [2]-MSQs, providing high affinity and selectivity for sulfate while other tetrahedral divalent anions such as selenate, phosphate species and chromate have substantially lower binding affinities. In mixtures of anions mimicking the composition of either nuclear waste or plasma, the [3]-MSQs were still able to bind sulfate ions with high affinity.

Notes

†Electronic supplementary information (ESI) available: Experimental procedures, ¹H and ¹³C NMR spectra, titration data, X-ray crystallography summary, mass spectra. CCDC 1457412–1457415. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc01011c