Abstract
Cyclic voltammetric studies have been undertaken on highly insoluble decaphenylferrocene (DPFc), on substituted forms of the compound [methyl (Me 2 DPFc, Me 6 DPFc, and Me 1 0 DPFc), bromide (Br 2 DPFc), and ethynyl (Ethin 2 DPFc)], and on their more soluble one-electron-oxidized DPFc + forms. Studies with DPFc + and its derivatives dissolved in dichloromethane (DCM) enable the reversible potentials (E 0 ') of one-electron reduction processes, DPFc + (DCM) + e - ⇄ DPFc(DCM), to be established. E 0 ' values obtained from these measurements exhibit the expected substituent dependence. Voltammetric studies with arrays of insoluble DPFc microparticles adhered to an electrode surface in contact with DCM (0.1 M Bu 4 NPF 6 ) or ionic liquids are connected to the oxidized solid or dissolved forms of DPFc + via a range of pathways that are determined by the kinetics and thermodynamics of dissolution and reprecipitation processes. Comparative data obtained with more soluble ferrocene, ferri-cinium, and decamethylferrocene microparticles support the hypothesis that dissolution processes play an important role in determining the nature of the voltammetric response of adhered microparticles.
Published Version
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