Stepwise assembly of acceptor-sigma spacer-donor monolayers: preparation and electrochemical characterization

Abstract

Self-assembled monolayers comprising benzoquinone-methylene spacer-ferrocene molecules have been prepared on gold surfaces using a stepwise assembly procedure. A base monolayer of cystamine is formed on a gold surface. Benzoquinone is then attached to the amine end of the cystamine monolayer by a Michael's addition reaction. Subsequently, a diaminoalkane spacer of varying length is introduced. Finally, ferrocene is attached to the diamonoalkane spacer through an amide bond to complete the acceptor-sigma spacer-donor assembly. The distance between the two redox moieties has been varied systematically by altering the length of the alkyl chain spacer present between them. The quinone attachment to the cystamine monolayer leads to two different redox forms, a mono- and a diamino derivative. The pK_a values have been evaluated for both of the derivatives. The monomolecular layer assembly has been characterized extensively using electrochemical techniques and the electrochemical kinetic parameters have been evaluated at different stages of modification.