The structurally rigid tetradentate N,N′,O,O′-ligands based on phenanthroline for binding of f-elements: The substituents vs. structures of the complexes

• Published in: Inorganica Chimica Acta Vol. 478; pp. 148 - 154
• Main Authors: Borisova, Nataliya E., Kostin, Andrey A., Reshetova, Marina D., Lyssenko, Konstantin A., Belova, Elena V., Myasoedov, Boris F.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 01.06.2018; Elsevier Science Ltd
• Subjects: Actinides; Americium; Binding; Chemical elements; Chemical synthesis; Crystallography; Diffraction; Ions; Lanthanides; Ligands; N,O ligands; Phenanthrolines; X-ray diffraction; X-ray diffraction; Phenanthrolines; Lanthanides; N,O ligands
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2018.03.042

Phenanthroline scaffold for Am/Eu separation get structural evidence. [Display omitted] •Structures of La and Eu complexes with 2,9-phenanthrolinedicarboxamide determined.•A way to the electron-donating 2,9-phenanthrolinedicarboxamides is designed.•Synthesized and characterized substituted 2,9-phenanthrolinedicarboxamide ligands.•Rational way of new diamide-based heterocyclic extractants is supplemented. A new tetradentate N,N′,O,O′-ligands possessing fixed preorganised conformation geometry for metal ion binding are proposed and effectively synthesised. The interaction of the ligands with nitrates of 4f-elements was studied and the complexes were readily prepared. Their structures were studied by various spectroscopic techniques as well as X-ray crystallography. The structures of the lanthanide complexes in comparison with the structure of 5f-element complexes were discussed to illustrate the selectivity of phenanthroline based diamides towards actinides. The influence both of the substituents on the phenanthroline ring and the amidic moiety of the diamides on structures of the complexes is discussed. Several suggestions concerning the rational design of the selective americium extractants based on a phenanthroline scaffold were made starting from structures of the complexes.