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An N-pivot diglycolamide extractant (DGA-TREN) was synthesized for the first time and its complexation behaviour was studied towards trivalent lanthanide/actinide ions. The solvent extraction studies suggested a unique selectivity reversal in the extraction of trivalent actinides versus trivalent lanthanides which was observed performing extraction studies in an ionic liquid vis-à-vis a molecular diluent for a tripodal TREN-based diglycolamide ligand (DGA-TREN) vs. a tripodal diglycolamide ligand (T-DGA) which may have great significance in radioactive waste remediation. The nature of the bonding to Eu(3+) ion was investigated by EXAFS as well as by DFT calculations.

This paper reports the solvent extraction of Am and Eu using N,N,N',N',N'',N''-hexa-n-octylnitrilotriacetamide (HONTA) as the extractant in n-dodecane. The results are in variance with those reported previously with respect to the nature of the extracted species. The solvent extraction data were entirely different from those reported previously as the extracted species conformed to 1 : 2 (M : L) species for both Am and Eu ions. The structure of the extracted complex was determined by EXAFS demonstrating the three amidic 'O' atoms of the HONTA complex with the Eu ion. In the case of the Am ion, the pivotal 'N' atom is suggested to bond to the metal ion, which may explain the significantly more favourable extraction of Amvis-à-vis Eu. The absence of HO molecules in the inner coordination sphere of the Eu-HONTA extract was confirmed by luminescence spectroscopic measurements. Complexation studies in MeOH and EtOH indicated the formation of both 1 : 1 and 1 : 2 complexes with Nd ions. The results are explained on the basis of DFT calculations using HMNTA, the corresponding hexamethyl analogue of HONTA.

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