Interfacial Electron-Transfer Kinetics of Ferrocene through Oligophenyleneethynylene Bridges Attached to Gold Electrodes as Constituents of Self-Assembled Monolayers:  Observation of a Nonmonotonic Distance Dependence

The standard heterogeneous electron-transfer rate constants (k n 0) between substrate gold electrodes and the ferrocene redox couple attached to the electrode surface by variable lengths of substituted or unsubstituted oligophenyleneethynylene (OPE) bridges as constituents of mixed self-assembled monolayers were measured as a function of temperature. The distance dependences of the unsubstituted OPE standard rate constants and of the preexponential factors (A n ) obtained from an Arrhenius analysis of the unsubstituted OPE k n 0 versus temperature data are not monotonic. This surprising result, together with the distance dependence of the substituted OPE preexponential factors, may be assessed in terms of the likely conformational variability of the OPE bridges (as a result of the low intrinsic barrier to rotation of the phenylene rings in these bridges) and the associated sensitivity of the rate of electron transfer (and, hence, the single-molecule conductance which may be estimated using A n ) through these bridges to the conformation of the bridge. Additionally, the measured standard rate constants were independent of the identity of the diluent component of the mixed monolayer, and using an unsaturated OPE diluent has no effect on the rate of electron transfer through a long-chain alkanethiol bridge. These observations indicate that the diluent does not participate in the electron-transfer event.