Symmetry Breaking of Atomically Precise Fullerene-like Metal Nanoclusters

Here we report a neutral fullerene-like core-shell homosilver Ag₁₃@Ag₂₀ nanocluster that is fully protected by an achiral bidentate thiolate ligand (9,12-dimercapto-1,2-closo-carborane, C₂B₁₀H₁₀S₂H₂), which crystallizes in centrosymmetric space group R3̅. Continuous Cu doping in the dodecahedral shell first induced symmetry breaking to generate chiral Ag₁₃@Ag_20-Cu (6 ≥ n ≥ 2) containing two acetonitrile ligands in space group P2₁2₁2₁, and then produced symmetric all-thiolated Ag₁₃@Ag_20-Cu (20 ≥ n ≥ 13) in the higher space group Im3̅. The selectively copper-doped Ag₁₃@Ag_20-Cu (6 ≥ n ≥ 2) cluster has its structure reorganized to a lower symmetry that shows chiroptical activity. Moreover, structural distortion of Ag₁₃@Ag_20-Cu (6 ≥ n ≥ 2) further expanded in chiral R-/S-propylene oxide, which induced a more prominent core-based CD response. This work revealed a novel mechanism of chirality generation at the atomic level through asymmetric shell-doping of metal nanoclusters, which provides new insight into the origin of chirality in inorganic nanostructures.