Host−Guest Interaction at a Self-Assembled Monolayer/Solution Interface:  An Electrochemical Analysis of the Inclusion of 11-(Ferrocenylcarbonyloxy)undecanethiol by Cyclodextrins

A host−guest equilibrium involving the redox guest 11-(ferrocenylcarbonyloxy)undecanethiol (FcSH) in a self-assembled monolayer on gold electrode surfaces and a β-cyclodextrin (β-CD) host in solution is investigated. The effect of varying the ratio of FcSH to a diluent ( n -decanethiol) in the self-assembly solution on the electrochemical characteristics of the ferrocene/ferricenium redox process and the inclusion properties of FcSH self-assembled monolayers (FcSH-SAMs) is examined using cyclic voltammetry and chronoamperometry. α- and γ-cyclodextrin have a negligible effect on both the thermodynamics and kinetics of the redox reaction. The electrochemical and ion-pairing behavior of FcSH-SAMs in solutions containing β-CD suggests that an inclusion complex is formed and that the included form of the ferrocenyl group is electroinactive in the potential window investigated. Inclusion results in a decrease in cyclic voltammetric peak currents (surface coverage of electroactive FcSH) and a slight increase in the standard electron transfer rate constant for the ferrocene/ferricenium redox process. The decrease in surface coverage of electroactive FcSH upon addition of β-CD exhibits a response similar to that expected for a Langmuir adsorption isotherm. Stability constants for the inclusion complexes of β-CD and the ferrocenyl or ferricenium forms of an FcSH-SAMs, containing a FcSH surface coverage of 5.2 × 10 - 11 mol cm - 2, have been evaluated as 3.6 (0.4) × 10 4 and 3.2 (0.4) × 10 4, respectively. The stability constants thus evaluated were shown to be dependent on the surface coverage of FcSH in the FcSH-SAMs.