P. Audebert et al., ELECTROCHEMICAL OXIDATION OF 5-UNIT HETEROCYCLES - A DISCUSSION ON THE POSSIBLE DIMERIZATION MECHANISMS, Journal of physical chemistry, 99(31), 1995, pp. 11923-11929
Several five-ringed heterocyclic oligomers (containing thiophene and p
yrrole units) have been studied by cyclic voltammetry and double-step
chronoamperometry in dichloromethane. The variation of the redox poten
tials with the substitution has been correlated with both electronic a
nd steric effects. Most of the compounds studied have been found to el
ectrodimerize by a cation radical-cation radical dimerization mechanis
m, and the corresponding rate constants have been extracted. In additi
on, it has been thoroughly discussed whether a possible slow deprotona
tion step following the irreversible dimerization step would affect th
e determination of the rate constants and also its possible effects on
the apparent number of electrons exchanged per oligomer.