Molecular Imaging of Viologen Adlayers and In Situ Monitoring Structural Transformations at Electrode-Electrolyte Interfaces.

The effects of temperature and molecular concentration on the ordering of two-dimensional (2D) nanostructures have been investigated at the well-defined Au(111)-electrolyte interface. In comparison to the assembly of thiolated alkanes or hydrogen-bonded nonthiolated molecules, fabricating large aromatic thiolated molecules into a highly ordered adlayer on a surface remained a challenge. In this study, we demonstrated the importance of controlling the assembly conditions and procedures for the formation of ordered adlayers of redox-active viologen derivatives. The assembly conditions that were explored include the variation of molar concentration of assembly solutions, assembly time, and thermal annealing. We report that the optimal assembly conditions for creating highly ordered thiolated viologen derivatives on a Au(111)-(1 × 1) electrode surface are to limit the time in which the electrode is immersed in a deoxygenated 0.05 mM ethanolic viologen solution (preheated to 70 °C) to 45 s, followed by thermal annealing in absolute ethanol for 12 h. Highly ordered molecular adlayers were imaged by electrochemical scanning tunneling microscopy (STM), revealing the molecular packing of low-coverage adlayers. Furthermore, in situ STM combined with cyclic voltammetry (CV) allowed for the exploration of the structural transformation and potential limit of reductive and "oxidative" desorption of adlayers within the electrochemical potential range of the sample potential () from -0.95 V to -0.10 V vs SCE.