Selective Separation and Complexation of Trivalent Actinide and Lanthanide by a Tetradentate Soft–Hard Donor Ligand: Solvent Extraction, Spectroscopy, and DFT Calculations

Recently, phenanthroline-based ligands have received increasing attention due to their excellent separation capabilities for trivalent actinides over lanthanide. In this work, we designed a soft–hard donor combined tetradentate phenanthroline-based extractant, tetraethyl (1,10-phenanthrolin-2,9-diyl)­phosphonate (C2-POPhen), for the selective separation of trivalent Am­(III) over Ln­(III) from HNO3 media. The solvent extraction and complexation behaviors of Am­(III) and Ln­(III) by C2-POPhen were investigated both experimentally and theoretically. C2-POPhen could selectively extract Am­(III) over Eu­(III) with an extremely fast extraction kinetics. NMR titration studies suggest that only 1:1 complexes of Ln­(III) with C2-POPhen formed in CH3OH in the presence of a significant amount of nitrate, while both 1:1 and 2:1 complexes species could form between C2-POPhen and Ln­(III) perchlorate in CH3OH without nitrate ions. The stability constants for the complexation of Am­(III) and Ln­(III) with C2-POPhen in CH3OH were determined by spectrophotometric titrations and the Am­(III) complexes are approximately 1 order of magnitude stronger than those of Ln­(III), which is consistent with the extraction results. Theoretical calculations indicate that the Am–N bonds in Am/C2-POPhen complexes possess more covalent characters than the Eu–N bonds in Eu/C2-POPhen complexes, shedding light on the underlying chemical force responsible for the Am/Eu selectivity by C2-POPhen. This work represents the first report utilizing phenanthroline-based phosphonate ligands for selective separation of actinides from highly acidic solutions