Horizontal expansion of biicosahedral M₁₃-based nanoclusters: resolving decades-long questions

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.