The selectivity of reversible oxy-anion binding in aqueous solution at a chiral europium and terbium center: Signaling of carbonate chelation by changes in the form and circular polarization of luminescence emission

Reversible anion binding in aqueous media at chiral Eu-III and Tbm centers has been characterized by H-1 NMR and by changes in the emission intensity and circular polarization following direct or sensitized (365 nm) excitatio n via an alkylphenanthridinium chromophore. Using a series of heptadentate tri-amide or polycarboxylate ligands, the affinity for CO32-/HCO3-, phospha te, lactate, citrate, acetate, and malonate at pH 7.4 was found Co decrease as a function of the overall negative charge on the complex: citrate and m alonate bound most strongly, and lactate and hydrogen carbonate also formed chelated ternary complexes in, which displacement of both of the metal-bou nd water molecules occurred, which was confirmed by VT 17-O NMR measurement s of-the corresponding Gd complexes. The binding of carbonate was studied i n particular, and H-1 NMR and CPL data were obtained that were consistent w ith the formation of a complex with a reduced helical twist about the metal center. Monohydrogen phosphate was bound in a monodentate manner, giving a mono; aqua adduct. The binding of carbonate to cationic Eu complexes in th e presence of a simulated extra-cellular anionic background at pH 7.4 was m onitored by variation in the emission intensity, ratio of intensities (615/ 594 nm), and dissymmetry factors as a function of added total carbonate.