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

• Published in: Chemistry : a European journal 2024-07, Vol.30 (42), p.e202401094-n/a
• Main Authors: Lei, Zhen, Zhao, Pei, Guan, Zong‐Jie, Nan, Zi‐Ang, Ehara, Masahiro, Wang, Quan‐Ming
• Format: Article
• Language: English
• Subjects: Alkynyl ligands; Cluster compounds; Clusters; Column chromatography; Columnar structure; Direct reduction; Gold; Molecular orbitals; Molecular structure; Nanoclusters; Precursors; Silica gel column chromatography; Structure determination
• ISSN: 0947-6539; 1521-3765; 1521-3765
• DOI: 10.1002/chem.202401094

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. We present here a ‘passivated precursor’ approach for all‐alkynyl‐protected gold nanoclusters, which consists of direct reduction and chromatography separation, and gives a series of clusters including Au22, Au36, Au44, Au130 and Au144. Notably, the overall yields are 40 %. In addition, total structure determination of Au130 has been achieved.