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Updated: Mar 21, 2026

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
A Case of Macrocyclic N,N'-Diphenyl-Substituted Phenanthrolinediamides: Molecular Dynamics and Eu3+/Am3+ Binding
Valentine S Petrov1, Mariia V Evsiunina1, Roman V Zonov1
1Department of Chemistry, Lomonosov Moscow State University, Leninskie gory 1 bld. 3, Moscow 119991, Russia.
Abstract:
A set of 12 novel macrocyclic 1,10-phenanthroline-2,9-dicarboxamides (DAPhen's) with variable ring size were synthesized. A variety of ligands were prepared with different chain lengths between amide nitrogens; in addition, the corresponding 4,7-dichloro-substituted derivatives were prepared. Using a combination of quantum-chemical modeling, single-crystal X-ray diffraction, and nuclear magnetic resonance spectroscopy methods, the stereodynamics of such compounds was studied in detail. Solvent extraction tests of macrocyclic DAPhen's toward the Eu3+/Am3+ pair allowed to determine the most effective ligand in the series. It has been shown that 4,7-dichloro-substituted DAPhen's can exhibit much higher extraction efficiency for trivalent f-element cations under the same conditions compared to their unsubstituted analogs. These patterns were explained by using quantum-chemical modeling of the complexation of the synthesized macrocycles with lanthanide(III) nitrates.
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