Pyridine N-oxides have long been investigated as efficacious chelating moieties of <i>f</i>-element ions and have found appreciable use in magnetic resonance imaging, luminescent labeling of biomolecules, and fluoroimmunoassays. With the goal of selectively complexing americium and curium over the lanthanides, a series of mixed S,N donor pyridine thiol complexes with lanthanides and americium have been prepared and fully characterized. The crystal chemistry, spectroscopy, and quantum mechanical analysis of bonding of this family of compounds is presented. In particular, the basis of a structural change from mononuclear to binuclear complexes across the <i>f</i>-block is explained. The presence of stronger bonding interactions in the binuclear americium compound are rationalized and compared to its isostructural Nd analogue.

Mixed N,S donor ligands for selective complexation of americium

ACS Spring 2022

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