Solution effect on diazonium-modified Au(111): reactions and structures.

Surface modifications of a Au(111) electrode with 4-bromobenzenediazonium tetrafluoroborate (BBD) in acetonitrile (ACN) and 0.1 M HClO4 have been characterized by scanning tunneling microscopy (STM). In ACN, STM results reveal the formation of disordered thin organic films. The involvement of the radical as an intermediate is evidenced by the negative effect of radical scavengers on organic thin film formation. In contrast, the 4,4'-dibromobiphenyl monolayer is observed when the aqueous solution is used as a medium to carry out the grafting experiment. The biphenyl compound is considered to be generated by a radical-radical coupling reaction.