A Guide to Nonaqueous Electrochemistry of f-Element Complexes.

Electrochemistry is a powerful tool for assessing and understanding the redox chemistry of molecular complexes. Cyclic voltammetry enables the f-element community to study molecules in unusually high or low oxidation states, which potentially pose important broad-scope questions of electronic structure. In the pursuit of boundary-pushing compounds, reactive air- and moisture-sensitive species are often encountered, which can be challenging to characterize, especially when they are chemically incompatible with certain solvents, electrolytes, or electrodes or when their potentials lie outside of common electrochemical windows. Nonaqueous solvents and pseudo reference electrodes complicate many of the standard practices in acquiring high-quality and reproducible electrochemical data. This guide presents a detailed discussion of selecting appropriate cell conditions and referencing and addresses metrics for evaluating electrochemical and chemical reversibility. These methodological approaches have been extended to best practices for the electrochemical analysis of radioactive transuranic complexes.