Evidence for stereoelectronic effects in ligand exchange reactions on Au₂₅ nanoclusters

Ligand exchange reaction (LER) is an important post-synthesis strategy and has been studied widely. The mechanism of this dynamic process for gold nanoclusters proved to be associative (SN2). Many factors affect the LER of clusters, including stability, solubility, chirality, electronic properties and so on. Some of these factors are not well understood and need further exploration. Here, we use a chiral fluoro-substituted ligand (R)-5,5',6,6',7,7',8,8'-octafluoro-[1,1'-binaphthalene]-2,2'-dithiol (8F-R-BINAS) to investigate the stereoelectronic and stereospecific effects during LER on achiral Au₂₅ cluster. It is demonstrated that the fluorine-substituted BINAS significantly decreases the LER reactivity both at the molecule and the related cluster level. The stereoelectronic effect is global and can be transmitted to the cluster surface. In contrast, the stereospecific effect is marginal.