Probing the limits: ultraslow diffusion and heterogeneous electron transfers in redox polyether hybrid cobalt...

This paper describes microelectrode voltammetry measurements of self-diffusion coefficients and of heterogeneous Co(II/III) electron-transfer rate constants (ko) in undiluted molten salts of three cobalt tris(bipyridine) perchlorate complexes in which the bipyridine ligands are "tailed" with poly(propylene oxide) and poly(ethylene oxide) oligomers. The self-diffusion coefficients are measured with potential step chronoamperometry and range from 10(-12) to 10(-17) cm2/s, while the quasi-reversible reaction rate constants are measured using cyclic voltammetry and small potential steps and range from 10(-7) to 10(-12) cm/s. The ko measurements are unusual in that when rate constants become smaller, the reaction remains quasi-reversible, because of concurrently decreasing self-diffusion rates. The measurements are, furthermore, accomplished in the face of uncompensated resistances that range from mega- to gigaohms, which is made possible by the combination of microelectrode properties and small diffusivities. The melt in which self-diffusion and ko values are smallest is at a temperature below its nominal glassing transition and in the regime of molecule-scale diffusion profiles.