Steric hindrance of phenanthroline diamides enables a hundredfold increase in Am(iii) extraction efficiency

Abstract

Three novel 1,10-phenanthroline-2,9-dicarboxamides (DAPhen) were prepared and investigated in detail. The presence of alkyl groups in the ortho-positions of the aryl substituent in the ligand amide functions results in completely inhibited rotation around the N–Ar bond and complicated conformational behavior. A very significant effect of ligand steric hindrance on the solvent extraction of lanthanides(III) and Am(III) from nitric acid solution was demonstrated. Extraction tests indicated that all three ligands L1–L3 extract Am better than all lanthanides. Very high separation factors of Am from early lanthanides (La and Ce) SF_Am/La,Ce > 40 were observed. For all three ligands, the separation factors from all lanthanides are also high (SF_Am/Ln > 10), which makes them suitable for practical applications in spent nuclear fuel (SNF) reprocessing. The extraction efficiency (distribution ratio) increases by almost two orders of magnitude for all tested f-elements while maintaining an overall extraction trend. Since the solvent extraction of Ln(III) and/or Am(III) involves the formation of corresponding complex compounds, a detailed investigation of the coordination chemistry of novel sterically hindered DAPhen ligands toward lanthanides and americium nitrates was performed. A combination of single-crystal X-ray analysis, spectral techniques and quantum-chemical calculations allowed us to explain the nearly hundredfold increase in Am(III) extraction efficiency when moving from ortho-methyl substituents toward more bulky ortho-isopropyl groups.