Reactivity and Lability Modulated by a Valence Electron Weaving in and out of the 25‐Atom Gold Nanoclusters

The ability to pursue heterogeneous catalysis or nanocatalysis at a single-electron level has been largely unsuccessful. The emergence of atomically precise metal nanoclusters with unique electronic structures provides access to currently inaccessible issues. Here we investigate the catalytic behaviours by performing the incoming and outgoing of a free valence electron of Au 6s1 on the Au25(SR)18 nanoclusters. Our studies reveal the distinct performances: Au25(SR)18- from donating an electron to neutral Au25(SR)180 loses the reactivity and Au25(SR)18+ from dislodging an electron from neutral Au25(SR)180 loses the stability. The reactivity diversity of the three Au25(SR)18 clusters stems from the different affinities with reactants and different extents 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 established between the AuSR dissociation and polymerization influenced by one electron.