Electroactive Anion Receptor with High Affinity for Arsenate

Herein, we present the synthesis and characterization of a macrocyclic polyamide cage that incorporates redox-active 1,4-dithiin units. UV/vis titration experiments with eight anions in acetonitrile revealed high affinity for H₂AsO₄^- (log β₂ = 10.4_-0.4^+0.4) and HCO₃^- (log β₂ = 8.3_-0.4^+0.3) over other common anionic guests, such as Cl^- (log K_1:1 = 3.20_-0.02^+0.03), HSO₄^- (log K_1:1 = 3.57_-0.03^+0.02), and H₂PO₄^- (log K_1:1 = 4.24_-0.04^+0.05), by the selective formation of HG₂ complexes. The recognition of arsenate over phosphate is rare among both proteins and synthetic receptors, and though the origin of selectivity is not known, exploiting the difference in the binding stoichiometry represents an underexplored avenue toward developing receptors that can differentiate between the two anions. Additional analysis by ¹H NMR in 1:3 CD₂Cl₂/MeCN-d₃ found a strong dependence of anion binding stoichiometry with the solvent employed. Finally, titration experiments with cyclic voltammetry provided varying and complex responses for each anion tested, though reaction between the anion and receptors was observed in most cases. These results implicate 1,4-dithiins as interesting recognition moieties in the construction of supramolecular receptors.