Variations of Diffusion Coefficients of Redox Active Molecules in Room Temperature Ionic Liquids upon Electron Transfer

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Abstract
In ionic liquids, the diffusion coefficients of a redox couple vary considerably between the neutral and radical ion forms of the molecule. For a reduction, the inequality of the diffusion coefficients is characterized by the ratio γ = Dred/Dox, where Dred and Dox are the diffusion coefficients of the electrogenerated radical anion and of the corresponding neutral molecule, respectively. In this work, measurements of γ have been performed by scanning electrochemical microscopy (SECM) in transient feedback mode, in three different room temperature ionic liquids (RTILs) sharing the same anion and with a series of nitro-derivative compounds taken as a test family. The smallest γ ratios were determined in an imidazolium-based RTIL and with the charge of the radical anion localized on the nitro group. Conversely, γ tends to unity when the radical anion is fully delocalized or when the nitro group is sterically protected by bulky substituents. The γ ratios, standard potentials of the redox couple measured in RTILs, and those observed in a classical organic solvent were compared for the investigated family of compounds. The stabilization energies approximately follow the γ ratios in a given RTIL but change considerably between ionic liquids with the nature of the cation.

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