Metal nanoclusters with molecular compositions have attracted significant attention from fundamental scientific perspectives and technological applications in energy and biomedical fields. Proper design and synthesis of Au nanoclusters stabilized by multidentate dithiolates exhibit novel physicochemical properties distinct from their monothiolate counterparts. Furthermore, surprising stability and redox activities are frequently observed in recent reports of Au, Ag, and bimetallic nanoclusters. Limited mechanistic insights have been gained regarding how the newly-developed synthetic routes and the materials nature being adopted generate the novel nanoclusters that display fascinating properties. Herein, we will discuss the redox activities of reaction intermediates and final metal nanoclusters, composed of gold and/or silver as metal core stabilized by monothiolates and/or dithiolates as ligand monolayer. The voltammetry features directly reveal their energetics and shine light on the synthesis mechanism and the redox activities. The discussion will be focused on multi-dentate dithiolate systems established by our group that is proven effective to tailor the electrochemical and some optical properties. The distinct electrochemical features of reaction intermediates and final nanoclusters explain the advantages and limitations of multidentate and monodentate approaches respectively. The factors that could further improve fundamental properties will be addressed aiming at bioimaging, cellular transport and delivery, and energy and catalysis applications.

Stability and electrochemical activities of di- and mono- thiolates stabilized metal nanoclusters and their precursors

247th National Meeting (2014)

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