1,10-phenanthroline-2,9-dicarboxamides of various structure were synthesized and studied as ligands for separation and sensing of d-and f-metals. It was found that the extraction ability of dialkyl-diaryl-diamide to lanthanides decreases from La to Lu and extraction of Am is close to light lanthanides (La-Pr). Tetraalkyl-diamide are not selective to lanthanides, instead exhibiting moderate selectivity in Am/Ln separation. The diamide complexes with lanthanides and d-elements were synthesized and characterized by XRD analysis. All diamides have demonstrated good extraction ability to environmentally hazardous metals (cadmium, lead, copper). The synthesized compounds were also tested as ionophores in PVC-plasticized potentiometric sensor membranes. Such sensors displayed no perceptible response to lanthanides but exhibited high sensitivity towards copper, zinc, cadmium and lead. These compositions can be considered as promising cross-sensitive sensors for multisensor systems.
N,N'-Dialkyl-N,N'-diaryl-1,10-phenanthroline-2,9-dicarboxamides (IV) were predicted (DFT simulation) and then were proved experimentally to be efficient donor ligands with high and unusual selectivity for the extraction separation of lanthanides. Distribution coefficients D of lanthanide cations in two-phase aqueous solution-polar organic solvent decrease with increasing Ln(3+) atomic number. The selectivity factors SFLn1/Ln2 for adjacent lanthanide ions were found to be about 3.
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