Solvent Extraction and Conformation Rigidity: Actinide(IV) and Actinide(VI) Come Together

• Published in: Inorganic chemistry 2022-12, Vol.61 (51), p.20774-20784
• Main Authors: Borisova, Nataliya E., Fedoseev, Alexandre M., Kostikova, Galina V., Matveev, Petr I., Starostin, Leonid Yu, Sokolova, Marina N., Evsiunina, Mariia V.
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.2c02578

The first comprehensive structural and extraction study of a 2,2′-bipyridine-6,6′-dicarboxamide (L diamide) extractant for U, Np, Pu, Th, Am, and Eu ions showed great potential for actinide separation due to steric hindrance of the amidic side phenyl ring of the given compound. The study of the complexes of An­(VI) and Th­(IV) with 2,2′-bipyridyldicarboxamide-type extractants demonstrated the structure of the extraction species for the first time. Investigation of the extraction properties with the radiometric and millimolar quantities of actinides showed similar extraction trends. For the first time, a metal-ion-induced phenyl-ring rotation restriction was found for the U, Th, and Eu complexes by employing temperature-dependent dynamic NMR. A study of the solution behavior of the complexes accompanied by density functional theory modeling studies elucidated the mechanism of the unusual C–N bond rotation restriction induced by metal coordination.