Surface Menshutkin SN2 Reaction on Basic Gold Clusters Provides Novel Opportunities for the Cationization and Functionalization of Molecular Metal Clusters

Surface chemical reactions on atomically precise metal clusters have considerable attention for opening a new platform for cluster functionalization. In this study, basic Au25(4-PyET)18 (4-PyET = −SCH2CH2Py; Py = pyridyl) clusters were successfully transformed into cationized Au25(4-PyET-CH3 +) x (4-PyET)18‑x clusters, without altering their Au25 cores, through the Menshutkin SN2 reaction of their surface Py moieties. This study offers not only a simple cationization method but also a protocol for modifying the surface functionalities of molecular metal clusters via a synthetic reaction.