Substituent Effect on the Selective Separation and Complexation of Trivalent Americium and Lanthanides by N,O-Hybrid 2,9-Diamide-1,10-phenanthroline Ligands in Ionic Liquid.

The extraction and complexation of trivalent americium (Am) and lanthanides (Ln) by four 2,9-diamide-1,10-phenanthroline (DAPhen) ligands with different alkyl substituent groups on the diamide moiety in an ionic liquid (IL), C4mimNTf2, were studied through a combination of batch extraction, spectroscopic, and calorimetric approaches. All four DAPhen ligands can achieve selective separation of Am(III) from Eu(III), but the detailed extractability and the extraction kinetics are affected significantly by the length of the alkyl substituent groups. UV-vis absorption spectrophotometric titrations indicate that Ln(III) coordinates with all four ligands in a 1:2 mode in the ionic liquid and the binding strength decreases with the increase of the alkyl chain length. The complexation of the DAPhen ligands with Ln(III) in the ionic liquid is driven by highly positive entropies and opposed by endothermic enthalpies. A luminescence spectroscopy study suggests that each DAPhen ligand coordinates in a tetradentate form with Eu(III). This work further unravels the unique extraction and coordination behavior in an ionic liquid system and offers additional guidelines to design more efficient DAPhen ligands for Ln(III)/An(III) separation.