Selective Extraction of Americium(III) over Europium(III) with the Pyridylpyrazole Based Tetradentate Ligands: Experimental and Theoretical Study

1,3-Bis­[3-(2-pyridyl)­pyrazol-1-yl]­propane (Bippp) and 1,2-bis­[3-(2-pyridyl)­pyrazyl-1-methyl]­benzene (Dbnpp), the pyridylpyrazole based tetradentate ligands, were synthesized and characterized by MS, NMR, and FT-IR. The solvent extraction and complexation behaviors of Am­(III) and Eu­(III) with the ligands were investigated experimentally and theoretically. In the presence of 2-bromohexanoic acid, the two ligands can effectively extract Am­(III) over Eu­(III) and other rare earth­(III) metals (RE­(III)) in HNO₃ solution with the separation factors (<i>SF</i>_Am/RE) ranging from 15 to 60. Slope analyses showed that both Am­(III) and Eu­(III) were extracted as monosolvated species, which agrees well with the results observed from X-ray crystallography and MS analyses. The stability constants (log <i>K</i>) obtained from UV–vis titration for Eu­(III) complexes with Bippp and Dbnpp are 4.75 ± 0.03 and 4.45 ± 0.04, respectively. Both UV–vis titration and solvent extraction studies indicated that Bippp had stronger affinity for Eu­(III) than Dbnpp, which is confirmed by density functional theory (DFT) calculations. DFT calculations revealed that the AmL­(NO₃)₃ (L = Bippp and Dbnpp) complexes are thermodynamically more stable in water than their Eu­(III) analogues, which is caused by greater covalency of the Am–N than Eu–N bonds. Theoretical studies gave an insight into the nature of the M­(III)–ligand bonding interactions