la7b03649_si_001.pdf (102.89 kB)
Effect of Large Electrolyte Anions on the Sequential Oxidations of Bis(fulvalene)diiron Attached to Glassy Carbon by an Ethynyl Linkage
journal contribution
posted on 2018-01-08, 00:00 authored by Matthew
V. Sheridan, Paul Gamm, Severin T. Schneebeli, Rochus Breuer, Michael Schmittel, William E. GeigerTwo ethynyl-derivatized
isomers of bis(fulvalene)diiron (BFD, 1,1′-biferrocenylene)
were prepared and covalently attached to glassy carbon electrodes
through their ethynyl group by three different electrode modification
methods. Cyclic voltammetry and square wave (SW) voltammetry were
used to characterize surface coverages of 1.4–5.5 × 10–10 mol cm–2, the higher of these
corresponding to roughly a monolayer, based on computation of an idealized
close-packing structure for ethynylbis(fulvalene)diiron (E-BFD) on
a solid surface. In a dichloromethane solution containing a smaller
electrolyte anion such as [PF6]− or [ClO4]−, the E-BFD-modified electrodes exhibited
two quasi-Nernstian one-electron oxidations. In contrast, the current
for the second oxidation process, [E-BFD]+/2+, was diminished
in electrolytes containing one of the large fluoroaryl borate anions,
[B(C6F5)4]− or
[B(C6H3(CF3)2)4]−. The effect was enhanced for electrodes having
higher surface coverages being probed at shorter voltammetric time
scales. SW voltammetry showed that the diminished currents for [E-BFD]+/2+ in large-anion electrolytes are not caused by slow electron
transfer. Rather, they are attributed to mixed diffusivity of the
counter-anions at the electrode/solution interface, as [E-BFD]+ and the anion form the optimum (lowest-energy) configuration
of a 1:1 ion pair. The interior transport of the anion required to
reach this configuration may be sterically encumbered, accounting
for the diminished charge transfer observed with electrolytes containing
large anions.