Conformational disorder enhances electron transfer through alkyl monolayers: ferrocene on conductive diamond.

We have investigated the electron-transfer kinetics of ferrocene groups covalently tethered to surfaces of conductive diamond electrodes. Electrochemical measurements show that the rates are only weakly dependent on chain length but are strongly dependent on the surface coverage; these observations are contrary to what is commonly observed for self-assembled monolayers on gold, pointing to important mechanistic differences in electron transfer processes on covalently bonded materials. Molecular dynamics simulations show that dependence on chain length and molecular density can be readily explained in terms of dynamic crowding effects. At low coverage, conformational flexibility of surface-tethered alkyl chains allows the redox-active ferrocene group to dynamically approach the diamond surface, leading to facile electron transfer for all surface molecules. As the coverage is increased, steric crowding causes the average ferrocene-to-surface distance to increase, decreasing the electron transfer rate. Even at the most dense packings, the mismatch between the spacing of surface lattice sites and the optimum alkyl chain density leads to voids and inherent disorder that facilitates electron transfer. These results are significant in the design and optimization of electrocatalytically active surfaces on covalently bonded materials relevant for electro- and photocatalysis.