Isolation and Total Structure Determination of an All‐Alkynyl‐Protected Gold Nanocluster Au₁₄₄

Total structure determination of a ligand‐protected gold nanocluster, Au 144 , has been successfully carried out. The composition of title nanocluster is Au 144 (C≡CAr) 60 ( 1 ; Ar=2‐FC 6 H 4 ‐). The cluster 1 exhibits a quasi‐spherical Russian doll‐like architecture, comprising a Au 54 two‐shelled Mackay icosahedron (Au 12 @Au 42 ), which is further enclosed by a Au 60 anti‐Mackay icosahedral shell. The Au 114 kernel is enwrapped by thirty linear ArC≡C‐Au‐C≡CAr staple motifs. The absorption spectrum of 1 shows two bands at 560 and 620 nm. This spectrum is distinctly different from that of thiolated Au 144 , which was predicted to have an almost identical metal kernel and very similar ligands arrangement in 1 . These facts indicate the molecule‐like behavior of 1 and significant involvement of ligands in the electronic structure of 1 . The cluster 1 is hitherto the largest coinage metal nanocluster with atomically precise molecular structure in the alkynyl family. The work not only addresses the concern of structural information of Au 144 , which had been long‐pursued, but also provides an interesting example showing ligand effects on the optical properties of ligand protected metal nanoclusters.