Computational Comparative Study of the Binding of Americium with N-Donor Ligands

The accessibility of multiple valence states of americium (Am) inspired redox-based protocols aimed at efficient separation of trivalent Am (Am³⁺) from trivalent lanthanides (Ln³⁺) alternative to the traditional liquid-liquid extraction. This requires an extensive understanding of the coordination chemistry of Am in its various accessible valence states in the aqueous phase. In this work, by means of DFT calculations, the coordination of Am^III-VI with five typical N-donor ligands, i.e., terpyridine (tpy), bispyrazinylpyridine (dpp), bistriazinylpyridine (BTP), bistriazinyl bipyridine (BTBP), and bistrazinyl phenanthroline (BTPhen), was studied in terms of energy and topological analysis. The results show that the exchange of aqua ligands of hydrated ions by N-donor ligands is an entropy-driven process and enthalpically unfavorable. Topological analysis suggests a distinct mechanism of BTP to modulate the redox potential of Am(III) in that BTP can assist the relay of the leaving electron of Am^III, while the other N-donor ligands can detain the oxidation of Am by offering their electron instead. This comparative study enriches our understanding of the coordination chemistry of high-valent Am with N-donor ligands and recommends the ligand design toward the modulation of redox potentials of hydrated Am(III) ions.