Electrochemical Study of Acetate Coordination to U(VI) within Monohalogenated Schiff‐Base Naphthylsalophen Ligands

Uranyl complexes of monohalogenated naphthylsalophen ligands (fluorinated ( H 2 L 1 ) , chlorinated ( H 2 L 2 ) , and brominated ( H 2 L 3 ) ) and their redox properties are described. Each complex demonstrates a unique effect upon the coordination of an anion. Acetate coordination, resulting in increased stabilization of the U(VI) oxidation state, was observed as a shift in the apparent uranium reduction potential to more negative values. Template synthesis with uranyl acetate enabled the synthesis of the complexes [Net 3 ][UO 2 (OAc)L 1 ]‐ [Net 3 ][UO 2 (OAc)L 3 ] . While the synthesis of UO 2 (Solvent)L 1 ‐ UO 2 (Solvent)L 3 requires the addition of uranyl nitrate to each ligand with heat, investigation of the electrochemical properties of the metal complexes through cyclic voltammetry displays redox features beyond ligand‐centered reductions, with halogen trends and U‐L substituents playing a role in the uranium redox behavior. Switching the acetate with solvent molecules reveals quasi and reversible waves attributable to U(V)/U(VI). Spectrochemical and X‐ray crystallographic studies allow for a closer look at inner‐sphere interactions.