Theoretical Probing of Size-Selective Crown Ether Macrocycle Ligands for Transplutonium Element Separation.

Effective separation and recovery of chemically similar transplutonium elements from adjacent actinides is extremely challenging in spent fuel reprocessing. Deep comprehension of the complexation of transplutonium elements and ligands is significant for the design and development of ligands for the in-group separation of transplutonium elements. Because of experimental difficulties of transplutonium elements, theoretical calculation has become an effective means of exploring transplutonium complexes. In this work, we systematically investigated the coordination mechanism between transplutonium elements (An = Am, Cm, Bk, Cf) and two crown ether macrocyclic ligands [,'- bis[(6-carboxy-2-pyridyl)methyl]-1,10-diaza-18-crown-6 (Hbp18c6) and ,'-bis[(6-methylphosphinic-2-pyridyl)methyl]-1,10-diaza-18-crown-6 (Hbpp18c6)] through quasi-relativistic density functional theory. The extraction complexes of [Anbp18c6] and [Anbpp18c6] possess similar geometrical structures with actinide atoms located in the cavity of the ligands. Bonding nature analysis indicates that the coordination ability of the coordinating atoms in pendent arms is stronger than that in the crown ether macrocycle because of the limitation of the macrocycle. Most of the coordination atoms of the Hbp18c6 ligand have a stronger ability to coordinate with metal ions than those of the Hbpp18c6 ligand. In addition, the bonding strength between the metal ions and ligands gradually weakens from Am to Cf, which is mainly attributed to the size selectivity of the ligands. Thermodynamic analysis shows that the Hbp18c6 ligand has a stronger extraction capacity than the Hbpp18c6 ligand, while the Hbpp18c6 ligand is superior in terms of the in-group separation ability. The extraction capacity of the two ligands for metal ions gradually decreases across the actinide series, indicating that these crown ether macrocycle ligands have size selectivity for these actinide cations as a result of steric constraint of the crown ether ring. We hope that these results offer theoretical clues for the development of macrocycle ligands for in-group transplutonium separation.