Influence of a N-Heterocyclic Core on the Binding Capability of N,O-Hybrid Diamide Ligands toward Trivalent Lanthanides and Actinides

N,O-hybrid diamide ligands with N-heterocyclic skeletons are one of the promising extractants for the selective separation of actinides over lanthanides in a highly acidic HNO3 solution. In this work, three hard-soft donor mixed diamide ligands, pyridine-2,6-diylbis(pyrrolidin-1-ylmethanone) (Pyr-PyDA), 2,2'-bipyridine-6,6'-diylbis( pyr-rolidine-1-ylmethanone) (Pyr-BPyDA), and (1,10-phenanthroline-2,9-diyl)bis(pyrrolidin-1-ylmethanone) (Pyr-DAPhen), were synthesized and used to probe the influence of N-heterocyclic cores on the complexation and extraction behaviors with trivalent lanthanides and actinides. H-1 NMR titration experiments demonstrated that 1:1 metal-to-ligand complexes were mainly formed between the three ligands and lanthanides, but 1:2 type complexes were also formed between tridentate Pyr-PyDA and Lu(III). The stability constants (log beta) of these three ligands with two typical lanthanides, Nd(III) and Eu(III), were determined through spectrophotometric titration. It is found that Pyr-DAPhen formed the most stable complexes, while Pyr-PyDA formed the most unstable complexes with lanthanides, which coincided well with the following solvent extraction results. The solid-state structures of 1:1 type complexes of these three ligands with La(III), Nd(III), and Er(III) in nitrate media were identified by a single-crystal X-ray diffraction technique. Nd(III) and Er(III) were 10-coordinated with Pyr-PyDA, Pyr-BPyDA, and Pyr-DAPhen via one ligand molecule and three nitrate ions. La(III), because of its larger ionic radius, was 11-coordinated with Pyr-DAPhen through one ligand molecule, three nitrate ions, and one methanol molecule. Solvent extraction experiments showed that the preorganized phenanthroline-derived Pyr-DAPhen had the best extraction performance for trivalent actinide among the three ligands tested. This work provides some experimental insights into the design of more efficient ligands for trivalent actinide separation by adjusting the N-heterocyclic cores.

Automated summary

N,O-hybrid diamide ligands with N-heterocyclic skeletons show promising extractant properties for selective actinide separation over lanthanides in highly acidic solutions. In this study, three mixed diamide ligands were synthesized and their complexation behaviors with lanthanides and actinides were investigated. The stability of complexes, as well as the solid-state structures of 1:1 complexes, were determined, providing insights into designing more efficient ligands for trivalent actinide separation.