New asymmetric tetradentate phenanthroline chelators with pyrazole and amide groups for complexation and solvent extraction of Ln(iii)/Am(iii)

Abstract

To tune the complexation and solvent extraction performance of the ligands with a 1,10-phenanthroline core for trivalent actinides (An³⁺) and lanthanides (Ln³⁺), we synthesized two new asymmetric tetradentate ligands with pyrazole and amide groups, i.e., L1 (N,N-diethyl-9-(5-ethyl-1H-pyrazol-3-yl)-1,10-phenanthroline-2-carboxamide) and its analogue L2 with longer alkyl chains (N,N-dihexyl). The complexation of the ligands with Ln³⁺ was confirmed by ¹H NMR titration and X-ray crystallography, and stability constants were measured in methanol by spectrophotometric titration. The asymmetric ligands exhibited an improved performance in terms of selective solvent extraction of Am³⁺ over Eu³⁺ in strongly acidic solutions compared to their symmetric analogues. The improved selectivity of the asymmetric ligands was interpreted theoretically by density functional theory simulations. This study implies that combining different functional groups to construct asymmetric ligands may be an efficient way to tune ligand performance with regard to An³⁺ separation from Ln³⁺.