Macrocyclic squaramides as ion pair receptors and fluorescent sensors selective towards sulfates

Through the high dilution technique, we obtained macrocyclic ion pair receptors R1 and R2, an anion receptor R3, and a fluorescent sensor R4 using a combination of particular members of simple libraries consisting of synthesized diamines and methyl squarates, respectively. The receptors were investigated in terms of anion and ion pair binding using the ¹H NMR titration method in DMSO-d₆. 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.