Evolution from superatomic Au₂₄Ag₂₀ monomers into molecular-like Au₄₃Ag₃₈ dimeric nanoclusters

Hierarchical assembly of nanoparticles has been attracting wide interest, as advanced functionalities can be achieved. However, the ability to manipulate structural evolution of artificial nanoparticles into assemblies with atomic precision has been largely unsuccessful. Here we report the evolution from monomeric Au₂₄Au₂₀ into dimeric Au₄₃Ag₃₈ nanoclusters: Au₄₃Ag₃₈ inherits the kernel frameworks from parent Au₂₄Ag₂₀ but exhibits distinct surface motifs; Au₂₄Ag₂₀ is racemic, while Au₄₃Ag₃₈ is mesomeric. Importantly, the evolution from monomers to dimers opens up exciting opportunities exploring currently unknown properties of monomeric and dimeric alloy nanoclusters. The Au₂₄Ag₂₀ clusters show superatomic electronic configurations, while Au₄₃Ag₃₈ clusters have molecular-like characteristics. Furthermore, monomeric Au₂₄Ag₂₀ catalysts readily outperform dimeric Au₄₃Ag₃₈ catalysts in the catalytic reduction of CO₂.