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

Lei, Zhen; Zhao, Pei; Guan, Zong‐Jie; Nan, Zi‐Ang; Ehara, Masahiro; Wang, Quan‐Ming

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 Au22(C≡CR)18 (R=−C6H4−2−F), Au36(C≡CR)24, Au44(C≡CR)28, Au130(C≡CR)50, and Au144(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 Au130(C≡CR)50 is revealed, which presents important information for understanding the structure of the mysterious Au130 nanoclusters. Theoretical calculations indicated Au130(C≡CR)50 has a smaller HOMO‐LUMO gap than Au130(S−C6H4−4−CH3)50. This facile and reliable synthetic approach will greatly accelerate further studies on all‐alkynyl‐protected gold nanoclusters.

GOLD clusters; MOLECULAR structure; COLUMN chromatography; NORMAL-phase chromatography

Chemistry - A European Journal, 2024, Vol 30, Issue 42, p1

0947-6539

Academic Journal

10.1002/chem.202401094