Why is the association of supramolecular assemblies different under homogeneous and heterogeneous conditions?

The origin of the change of the thermodynamic properties of association between homogeneous and heterogeneous systems is highlighted by numerical experiments.

Free energy calculations in electroactive self-assembled monolayers (SAMs): impact of the chain length on the redox reaction.

The free energy approach is used to study the effect of the relative chain length of the two constituents of electroactive self-assembled monolayers (SAMs) on gold. In this study, the ferrocene groups are exposed to the electrolyte solution. This situation is achieved by using shorter diluent alkanethiol chains. To this end, the mixed monolayers formed by the self-assembly of 11-ferrocenylundecanethiol and butanethiol FcC(11)S/C(4)S and of 6-ferrocenylhexanethiol and butanethiol FcC(6)S/C(4)S onto a gold surface are studied. Calculation of enthalpy and entropy differences are also performed using molecular simulations. Additionally, the electrochemical signatures of these systems are determined to allow a direct comparison with our calculations. The thermodynamic properties are discussed in terms of enthalpy and entropy changes. Two effects account for the thermodynamic behavior. The first one involves the ion pairing between the ferrocenium group and the perchlorate anion. The second one concerns the desolvation of the first hydration shell of the anions. Finally, this work is also completed with a microscopic description associated with an energy characterization of these SAMs as a function of the surface coverage under conditions close to experiments.

Toward a prediction of the redox properties of electroactive SAMs: a free energy calculation by molecular simulation.

We report free energy calculations of FcC(6)S-/C(4)S-Au and FcC(6)S-/C(12)S-Au binary self-assembled monolayers (SAMs) formed by one ferrocenylhexanethiolate chain and alkylthiolate chains. We demonstrate that the free energy perturbation methods are able to reproduce the positive shift of the redox potential when the coadsorbed butanethiolate C(4)S chains are replaced by dodecanethiolate C(12)S chains. The different contributions to the Ewald summation involved in the perturbation process are thoroughly described. We complete the study by a microscopic description of the binary SAMs before and after oxidation. The molecular dynamics (MD) simulations evidence that the formation of the ion-pair between the ferricinium and a single perchlorate anion of the supporting electrolyte is more favored in FcC(6)S-/C(12)S-Au SAM.