Evolution of catalytic activity driven by structural fusion of icosahedral gold cluster cores

Atomically precise gold cluster catalysts have emerged as a new frontier in catalysis science, owing to their unexpected catalytic properties. In this work, we explore the evolution of activity clusters formed by structural fusion icosahedral Au13 units, namely Au25(SR)18, Au38(SR)24, and Au25(PPh3)10(SC2H4Ph)5Cl2, oxidation pyrrolidine γ-butyrolactam. We demonstrate that forming vertex-fused (vf), face-fused (ff), body-fused (bf) clusters, can induce decrease following order: Aubf > Auff Auvf. The units does not distinguish adsorption modes over three from each other, but modulates chemical capacity electronic properties which is likely be key reason for observed changes reactivity. Our results are expected extendable study design atomically defined with elaborate patterns, order produce desired products.