Comparative behavior of aromatic disulfide and diselenide monolayers on polycrystalline gold films using cyclic voltammetry, STM, and quartz crystal microbalance

Abstract

A comparative investigation of the self-assembled monolayers of diphenyl disulfide (DDS), diphenyl diselenide (DDSe), and naphthalene disulfide (NDS) on polycrystalline gold films using STM, QCM, and electrochemical techniques is presented. The geometric constraint imposed by the rigid naphthalene ring for NDS inhibits the cleavage of the S–S bond, thus adversely affecting the monolayer organization and stability relative to the monolayers formed with DDS and DDSe. A comparative analysis using techniques like cyclic voltammetry and quartz-crystal microbalance indicates that, for DDS, the facile cleavage of the S–S bond leads to strong binding of the adsorbate molecules at the preferred surface sites, resulting in a rather well-organized self-assembled structure. The STM pattern of NDS reveals a periodic domain (i.e., less than 10 nm in size) while no such small domains are seen in the case of DDS and DDSe due to the orientational flexibility of the rings.