First 24-Membered Macrocyclic 1,10-Phenanthroline-2,9-Diamides-An Efficient Switch from Acidic to Alkaline Extraction of f-Elements

Pavel S Lemport; Valentine S Petrov; Petr I Matveev; Uliana M Leksina; Vitaly A Roznyatovsky; Igor P Gloriozov; Alexandr V Yatsenko; Viktor A Tafeenko; Pavel V Dorovatovskii; Viktor N Khrustalev; Gleb S Budylin; Evgeny A Shirshin; Vitaliy Yu Markov; Alexey A Goryunkov; Vladimir G Petrov; Yuri A Ustynyuk; Valentine G Nenajdenko

doi:10.3390/ijms241210261

First 24-Membered Macrocyclic 1,10-Phenanthroline-2,9-Diamides-An Efficient Switch from Acidic to Alkaline Extraction of f-Elements

Int J Mol Sci. 2023 Jun 17;24(12):10261. doi: 10.3390/ijms241210261.

Authors

Pavel S Lemport¹, Valentine S Petrov¹, Petr I Matveev¹, Uliana M Leksina¹, Vitaly A Roznyatovsky¹, Igor P Gloriozov¹, Alexandr V Yatsenko¹, Viktor A Tafeenko¹, Pavel V Dorovatovskii², Viktor N Khrustalev^{3

4}, Gleb S Budylin⁵, Evgeny A Shirshin^{5

6}, Vitaliy Yu Markov¹, Alexey A Goryunkov¹, Vladimir G Petrov¹, Yuri A Ustynyuk¹, Valentine G Nenajdenko¹

Affiliations

¹ Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1 bld. 3, Moscow 119991, Russia.
² National Research Center "Kurchatov Institute", Moscow 123182, Russia.
³ Department of Inorganic Chemistry, Peoples' Friendship University of Russia (RUDN University), Moscow 115419, Russia.
⁴ N.D. Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences, Moscow 119991, Russia.
⁵ Laboratory of Clinical Biophotonics, Biomedical Science and Technology Park, Sechenov First Moscow State Medical University, Moscow 119991, Russia.
⁶ Faculty of Physics, M.V. Lomonosov Moscow State University, Moscow 119991, Russia.

Abstract

A reaction of acyl chlorides derived from 1,10-phenanthroline-2,9-dicarboxylic acids with piperazine allows the preparation of the corresponding 24-membered macrocycles in good yield. The structural and spectral properties of these new macrocyclic ligands were thoroughly investigated, revealing promising coordination properties towards f-elements (Am, Eu). It was shown that the prepared ligands can be used for selective extraction of Am(III) from alkaline-carbonate media in presence of Eu(III) with an SF_Am/Eu up to 40. Their extraction efficiency is higher than calixarene-type extraction of the Am(III) and Eu(III) pair. Composition of macrocycle-metal complex with Eu(III) was investigated by luminescence and UV-vis spectroscopy. The possibility of such ligands to form complexes of L:Eu = 1:2 stoichiometry is revealed.

Keywords: DFT; NMR; XRD; actinide; lanthanide; macrocycle; phenanthroline; solvent extraction.

MeSH terms

Coordination Complexes* / chemistry
Diamide*
Ligands
Models, Molecular

Substances

1,10-phenanthroline
Diamide
Ligands
Coordination Complexes

Grants and funding

21-73-10067/Russian Science Foundation