For metal nanoclusters with the "cluster of clusters" intramolecular evolution pattern, most efforts have been made towards the vertical superposition of icosahedral nanobuilding blocks (e.g., from mono-icosahedral Au13 to bi-icosahedral… Click to show full abstract
For metal nanoclusters with the "cluster of clusters" intramolecular evolution pattern, most efforts have been made towards the vertical superposition of icosahedral nanobuilding blocks (e.g., from mono-icosahedral Au13 to bi-icosahedral Au25 and tri-icosahedral Au37), while the horizontal expansion of these rod-shaped multi-icosahedral aggregates was largely neglected. We herein report the horizontal expansion of the biicosahedral M25 cluster framework, yielding an [Au19Ag12(S-Adm)6(DPPM)6Cl7]2+ nanocluster that contains an Au13Ag12 kernel and six Au1(DPPM)1(S-Adm)1 peripheral wings. The structural determination of [Au19Ag12(S-Adm)6(DPPM)6Cl7]2+ resolved a decades-long question towards rod-shaped multi-icosahedral aggregates: how to load bidentate phosphine and bulky thiol ligands onto the nanocluster framework? The structural comparison between [Au19Ag12(S-Adm)6(DPPM)6Cl7]2+ and previously reported [Au13Ag12(PPh3)10Cl8]2+ or [Au13Ag12(SR)5(PPh3)10Cl2]2+ rationalized the unique packing of Au1(DPPM)1(S-Adm)1 motif structures on the surface of the former nanocluster. Overall, this work presents the horizontal expansion of rod-shaped multi-icosahedral nanoclusters, which provides new insights into the preparation of novel icosahedron-based aggregates with both vertically and horizontally growing extensions.
               
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