Homoleptic Alkynyl‐Protected Gold Nanoclusters: Au₄₄(PhC≡C)₂₈ and Au₃₆(PhC≡C)₂₄

For the first time total structure determination of homoleptic alkynyl‐protected gold nanoclusters is reported. The nanoclusters are synthesized by direct reduction of PhC≡CAu, to give Au 44 (PhC≡C) 28 and Au 36 (PhC≡C) 24 . The Au 44 and Au 36 nanoclusters have fcc‐type Au 36 and Au 28 kernels, respectively, as well as surrounding PhC≡C‐Au‐C 2 (Ph)Au‐C≡CPh dimeric “staples” and simple PhC≡C bridges. The structures of Au 44 (PhC≡C) 28 and Au 36 (PhC≡C) 24 are similar to Au 44 (SR) 28 and Au 36 (SR) 24 , but the UV/Vis spectra are different. The protecting ligands influence the electronic structures of nanoclusters significantly. The synthesis of these two alkynyl‐protected gold nanoclusters indicates that a series of gold nanoclusters in the general formula Au x (RC≡C) y as counterparts to Au x (SR) y can be expected.