STM investigations of Au(1 1 1) electrodes coated with vitamin B12 derivatives

Vitamin B₁₂ derivatives immobilized at flame-annealed Au(1 1 1) electrode surfaces have been investigated in close correlation with their structural properties and spatial arrangement at the electrode substrate by scanning tunneling microscopy (STM) in air and in aqueous 0.1 M NaClO₄ solution. The investigated compounds were symmetrical (B₁₂C₁₀S-SC₁₀B₁₂) and nonsymmetrical (B₁₂C₁₀S-SC₁₀) dialkyl disulfide derivatives of vitamin B₁₂, attached to the electrode surfaces by the S-Au bond. The ex situ and in situ STM experiments show the formation of a surface layer, whose packing density and structure is presumably controlled by the spatial arrangement of the large cobyrinate head groups. In presence of the symmetrical B₁₂ compound, a disordered surface layer is observed. Voltammetric investigations show that, in 0.1 M NaClO₄, this layer becomes unstable at potentials approximately ? −1000 mV vs. MSE and is almost completely removed at more negative potentials. The STM imaging properties of the nonsymmetrical B₁₂ surface layer show a significant dependence on the tunneling distance. In particular, at small tunneling distances, a highly regular hexagonal surface pattern is observed that suggests strongly the presence of an ordered surface assembly. Modeling of the B₁₂ head group has been performed to provide information for a structure-related interpretation of the high-resolution STM images. The investigations are first STM results obtained at such B₁₂ modified electrodes.