Same Magic Number but Different Arrangement: Alkynyl‐Protected Au25 with D3 Symmetry

Two homoleptic alkynyl‐protected gold clusters with compositions of NaAu₂₅(C≡CAr)₁₈] and (Ph₄P)Au₂₅(C≡CAr)₁₈] (Na? 1 and Ph₄P? 1 , Ar=3,5‐bis(trifluoromethyl)phenyl) were synthesized via a direct reduction method. 1 is a magic cluster analogous to Au₂₅(SR)₁₈]^? in terms of electron counts and metal‐to‐ligand ratio. Single‐crystal structure analysis reveals that 1 has an identical Au₁₃ kernel to Au₂₅(SR)₁₈]^?, but adopts a distinctly different arrangement of the six peripheral dimer staple motifs. The steric hindrance of alkynyl ligands is responsible for the D₃ arrangement of Au₂₅. The introduction of alkynyl also significantly changes the optical absorption features of the nanocluster as supported by DFT calculations. This magic cluster confirms that there is a similar but quite different parallel alkynyl‐protected metal cluster universe in comparison to the thiolated one.