Highly Efficient Extraction of Trivalent f‐Cations Using Several N‐Pivot Tripodal Diglycolamide Ligands in an Ionic Liquid: The Role of Ligand Structure on Metal Ion Complexation

Abstract

Complexation of trivalent lanthanides and actinides was studied in a room temperature ionic liquid (RTIL) using five N‐pivot tripodal diglycolamide ligands (LI–LV) having different structural features, viz. spacer lengths and substituents. The nature of the metal/Ligand complex changed with the substitution of N atom near the tripodal platform from ML with LIII and LIV to ML2 with LI, LII and LV (where M = Eu3+/Nd3+/Am3+). With 0.2 mmol/L ligands, the distribution ratio of Am3+ at 1 m HNO3 followed the order: LI (210) > LII (42) > LIII (2.1) > LV (0.7) > LIV (0.2). The formation constants between Nd3+ and the ligands (log βML,ML2) followed an identical order, viz. LI > LII > LIII > LV > LIV. The extraction of Am3+ or Eu3+ with all the ligands followed a cation‐exchange extraction mechanism, which is in sharp contrast to the results obtained in a molecular solvent (n‐dodecane), where a solvation extraction mechanism prevalied. Luminescence studies on the Eu3+ extract in RTIL confimed the absence of water molecules in the inner coordination sphere of the complex. EXAFS studies indicated that all three DGA arms were binding to the Eu3+ cation.