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Tuning the Magic Sizes and Optical Properties of Atomically Precise Bidentate N‐Heterocyclic Carbene‐Protected Gold Nanoclusters via Subtle Change of N‐Substituents
Author(s) -
Luo Peng,
Bai Sha,
Wang Xin,
Zhao Jing,
Yan ZhenNing,
Han YingFeng,
Zang ShuangQuan,
Mak Thomas C. W.
Publication year - 2021
Publication title -
advanced optical materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.89
H-Index - 91
ISSN - 2195-1071
DOI - 10.1002/adom.202001936
Subject(s) - nanoclusters , carbene , homoleptic , denticity , cluster (spacecraft) , crystallography , materials science , luminescence , substituent , electrospray ionization , crystal structure , mass spectrometry , metal , chemistry , stereochemistry , nanotechnology , organic chemistry , catalysis , programming language , optoelectronics , chromatography , computer science , metallurgy
Owing to the atomically precise structures, metal nanoclusters (NCs) have always served as model molecular tools to analyze NC surface chemistry and to investigate structure−property correlations. Herein, a series of bis‐N‐heterocyclic carbene (NHC)‐protected NCs of type [Au 11 (bis‐NHC) 5 ] 3+ and [Au 13 (bis‐NHC) 5 Br 2 ] 3+ obtained from direct reduction of Au−bis‐NHC complexes are described. The NCs type obtained depends on the N‐wingtip substituents of the Au−bis‐NHC complexes. Subtle changes in the lengths of the N‐wingtip substituents enable the fine‐tuning of the kernel with either Au 11 or Au 13 clusters. Among them, [Au 11 (bis‐NHC) 5 ] 3+ cluster is the first homoleptic NHC‐stabilized Au NC. The composition and structures of these NCs are unequivocally determined by single crystal X‐ray crystallography and electrospray ionization mass spectrometry. Contrary to the non‐emissive Au 11 cluster, the Au 13 NC exhibits high emission in solution and the luminescence properties are severely dependent onto the substituent effects. Additionally, peculiar Au⋯HC interactions are present in NHC‐protected clusters.