The assembly of atomically precise metal nanoclusters offers exciting opportunities to gain fundamental insights into the hierarchical assembly of nanoparticles.H owever,itisstill challenging to control the assembly of individual nanoclusters at amolecular or atomic level. Herein, we report the dimeric assembly of Au 25 (PET) 18 (PET = 2-phenylethanethiol), where two Au 25 (PET) 18 monomers are bridged together by two Ag atoms to form the Ag 2 Au 50 (PET) 36 dimer.T he Ag 2 Au 50 (PET) 36 dimer is au nique mesomer,w hich has not been found in any other chiral metal nanoclusters.F urthermore,t he Ag 2 Au 50 (PET) 36 dimer is distinct from the Au 25-(PET) 18 monomer in its optical, electronic, and catalytic properties.This study is expected to provide afeasible strategy to precisely modulate the assembly of metal nanoclusters with controllable structures and properties.

With dual modifications of the surface and electronic structure, Au38Cd4(DMBT)30 exhibits distinct excitonic behaviors and photocatalytic performances compared to Au44(DMBT)28.

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 Au25(SR)18 nanoclusters by monitoring an incoming and outgoing free valence electron of Au 6s1. Distinct performances are revealed: Au25(SR)18− is generated upon donation of an electron to neutral Au25(SR)180 and this is associated with a loss in reactivity, whereas Au25(SR)18+ is generated from dislodgment of an electron from neutral Au25(SR)180 with a loss in stability. The reactivity diversity of the three Au25(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.

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Au28(SPh‐tBu)20 and Au28(S‐c‐C6H11)20, which have the same Au20 kernel but different surface atom packing structure, serve as mode catalysts to investigate the influence of isomerism in catalysts on catalytic properties. Au28(SPh‐tBu)20 exhibited more efficient activity for the oxidation of cyclohexane and benzyl alcohol than Au28(S‐c‐C6H11)20.