Does thiol-functionalized viologen monolayer memorize anion present when forming the monolayer?

We investigated the effect of the presence of an additive anion while forming a self-assembled monolayer of a thiol-functionalized redox active species upon the behavior in aqueous solutions. A bromide salt was added in an acetonitrile solution of a thiol-functionalized viologen (viologen-thiol: N-pentyl-N′-(11-mercapto)undecyl-4,4′-bipyridinium bishexafluorophosphate) in which the self-assembled monolayer was formed on a polycrystalline Au electrode. We examined the structure and electrochemical behavior of the resulting monolayer-modified electrode in three different aqueous electrolyte solutions. The viologen-thiol monolayer prepared in the presence of Br− exhibited obviously different behavior in both KBr and KF electrolyte solutions from that prepared in the absence of Br−. On the other hand, the difference was minor in KPF6 solution. The difference of the electrochemical behavior was represented by the coverage of the viologen-thiol and the formal potential of viologen dication/radical cation redox couple. The memory that the viologen-thiol monolayer was formed in the presence of Br− was retained in KF and KBr solutions, though it was erased in the electrolyte solution containing PF6−, which is a softer anion than Br−. However, no definitive difference of the film structure was deduced from the electroreflectance study in regard to the monomer content and the average orientation of the viologen moiety.