No abstract

The acid-base equilibrium of ω-functionalized alkanethiol monolayers on Au(111) has been studied using the change in double-layer capacitance accompanied by the protonation-deprotonation of ω-terminals. The pK of ω-carboxyl alkanethiols on Au(111) increases by four pH units. The shift becomes greater as the alkyl chain length increases. The same magnitude of the pK shift to the acidic side occurs in the monolayers of aminoethane thiol. The surface pK varies little with the electrode potential, whereas the increase in the supporting electrolyte concentration slightly diminishes the pK shift. The drawn-out shape of the titration curves is consistent with the mean-field model taking account of the repulsive interaction between adsorbed molecules, indicating the significance of the strong electrostatic repulsion between adsorbed thiol molecules in its charged states. The magnitude of the pK shift is, more than that predicted by the mean-field model, however, and suggests the considerable contribution from other factors that stabilize the uncharged state, for example, hydrogen bonding and low dielectric constant in the vicinity of the self-assembled monolayer. The possibility of counterion binding when the degree of deprotonation is large has been suggested.

The reductive desorption process of self-assembled monolayers of 1-hexadecanethiol, 1-propanethiol, and 3-mercaptopropionic acid on Au(111) has been studied in 0.5 M KOH solution by in-situ scanning tunneling microscopy (STM) and cyclic voltammetry. In-situ STM images of the monolayers at the potentials between −0.2 V and the reduction potentials of each thiols show the pits that are commonly seen in STM images of thiol self-assembled monolayers. A drastic morphological change takes place in the STM image around the peak potential in a cyclic voltammogram for the reductive desorption of adsorbed thiols. The images indicate that 3-mercaptopropionic acid molecules diffuse away from the surface after the reduction because of its higher solubility, while 1-propanethiol and 1-hexadecanethiol molecules stay in the vicinity of the surface forming aggregates. The partial recovery of the 1-hexadecanethiol monolayer after the anodic scan, suggested by cyclic voltammograms, is confirmed by STM, whereas 1-propanethiol aggregates remain at the surface without being reoxidized. The difference in the reoxidation behavior reflects the different amphiphilic properties of the desorbed molecules and the resultant molecular organizations formed on the surface.

A new method for preparing phase-separated binary self-assembled monolayers (SAMs) of alkanethiols on gold is proposed. Binary SAMs of 3-mercaptopropionic acid (MPA) and hexadecanethiol (HDT) at various mixing ratios which exhibit phase separation in nanometer scale are used as starting substrates. Because the MPA domains in the binary SAMs have a less negative desorption potential, they can be selectively removed by controlling the potential of gold substrates in 0.5 M KOH. Other alkanethiols with various chain lengths and terminal groups can subsequently be adsorbed where MPA was originally adsorbed, resulting in phase-separated binary SAMs with different combinations of alkanethiols.