Macrocyclic squaramides as ion pair receptors and fluorescent sensors selective towards sulfates
Marta Zaleskaya-Hernik, Damian Jagleniec, J. Romański
Abstract
. We found that the major contribution to the anion binding comes from the interaction with the squaramide protons rather than with the amide functions of the receptors. The receptors demonstrated the highest affinity towards benzoates and sulfates over the anions tested, and in the case of sulfate binding more complex equilibria in solution were observed. Unlike the anion receptor R3, the ion pair receptor R1 was found to recognize anions in an enhanced manner with the assistance of sodium or potassium cations. Tethering of a simple fluorophore in close proximity to the amide function of receptor R4 resulted in an optical ion pair sensor selective towards sulfates. DFT calculations carried out for the 1 : 1 complexes of R3 with the anions helped clarify this selectivity, showing more effective participation of tetrahedral sulfate anions in binding with the amide function than in the case of benzoates or chlorides.