‘Passivated Precursor’ Approach to All‐Alkynyl‐Protected Gold Nanoclusters and Total Structure Determination of Au130

Abstract A ‘passivated precursor’ approach is developed for the efficient synthesis and isolation of all‐alkynyl‐protected gold nanoclusters. Direct reduction of dpa‐passivated precursor Au‐dpa (Hdpa=2,2’‐dipyridylamine) in one‐pot under ambient conditions gives a series of clusters including Au 22 (C≡CR) 18 (R=−C 6 H 4 −2−F), Au 36 (C≡CR) 24 , Au 44 (C≡CR) 28 , Au 130 (C≡CR) 50 , and Au 144 (C≡CR) 60 . These clusters can be well separated via column chromatography. The overall isolation yield of this series of clusters is 40 % (based on gold), which is much improved in comparison with previous approaches. It is notable that the molecular structure of the giant cluster Au 130 (C≡CR) 50 is revealed, which presents important information for understanding the structure of the mysterious Au 130 nanoclusters. Theoretical calculations indicated Au 130 (C≡CR) 50 has a smaller HOMO‐LUMO gap than Au 130 (S−C 6 H 4 −4−CH 3 ) 50 . This facile and reliable synthetic approach will greatly accelerate further studies on all‐alkynyl‐protected gold nanoclusters.