Reactivity and Lability Modulated by a Valence Electron Moving in and out of 25-Atom Gold Nanoclusters

摘要

The emergence of atomically precise metal nanoclusters with unique electronic structures provides access to currently inaccessible catalytic challenges at the single-electron level. We investigate the catalytic behavior of gold Au-25(SR)(18)nanoclusters by monitoring an incoming and outgoing free valence electron of Au 6s(1). Distinct performances are revealed: Au-25(SR)(18)(-)is generated upon donation of an electron to neutral Au-25(SR)(18)(0)and this is associated with a loss in reactivity, whereas Au-25(SR)(18)(+)is generated from dislodgment of an electron from neutral Au-25(SR)(18)(0)with a loss in stability. The reactivity diversity of the three Au-25(SR)(18)clusters stems from different affinities with reactants and the extent of intramolecular charge migration during the reactions, which are closely associated with the valence occupancies of the clusters varied by one electron. The stability difference in the three clusters is attributed to their different equilibria, which are established between the AuSR dissociation and polymerization influenced by one electron.