Highly efficient N‑pivot tripodal diglycolamide ligands for trivalent f‑cations: Synthesis, extraction, spectroscopy, and density functional theory studies

A series of four N-pivot tripodal diglycolamide (DGA) ligands, where three DGA moieties are attached to the central N atom via spacers of different lengths and with varying alkyl substituents on the amidic nitrogen of DGA (L_I−L_IV), were studied for their extraction and complexation ability toward trivalent lanthanide/actinide ions, including solvent extraction, complexation using spectrophotometric titrations, and luminescence spectroscopic studies. Introduction of a methyl group on the amidic nitrogen atom gives rise to a 400 fold increase of the Eu distribution (D) value [L_III (NMe) vs L_II (NH)] at 1 M HNO₃. Enlargement of the spacer length between the pivotal N atom and the DGA moieties with one carbon atom results in a 14 times higher D_Eu value [L_I (C3) vs L_II (C2)]. Slope analyses showed that Eu³⁺ was extracted as a bis-solvated species with all four ligands. The compositions of the Eu³⁺/L complexes were further confirmed by spectroscopic measurements, its formation constants following the order: L_III > L_IV > L_I > L_II. Luminescence spectroscopy and electrospray ionization mass spectrometry revealed that all four ligands form [Eu(L)₂(NO₃)₃] complexes. Density functional theory and thermodynamic parameters corroborated the existence of [Eu(L)₂(NO₃)₃] complexes.