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Carboranealkynyl‐Protected Gold Nanoclusters: Size Conversion and UV/Vis–NIR Optical Properties
Author(s) -
Wang Jie,
Wang ZhaoYang,
Li ShiJun,
Zang ShuangQuan,
Mak Thomas C. W.
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202013027
Subject(s) - nanoclusters , tetrahydrothiophene , absorption spectroscopy , valence (chemistry) , metal , monolayer , absorption (acoustics) , valence electron , chemistry , photochemistry , materials science , crystallography , nanotechnology , electron , stereochemistry , physics , organic chemistry , quantum mechanics , composite material
Structure evolution has become an effective way to assemble novel monolayer‐protected metal nanomolecules. However, evolution with alkynyl‐stabilized metal clusters still remains rarely explored. Herein, we present a carboranealkynyl‐protected gold nanocluster [Au 28 (C 4 B 10 H 11 ) 12 (tht) 8 ] 3+ ( Au 28 , tht=tetrahydrothiophene) possessing an open‐shell electronic structure with 13 free electrons, which was isolated by a facile self‐reduction method with 9‐HC≡C‐ closo ‐1,2‐C 2 B 10 H 11 as the two‐in‐one reducing and protecting agent. Notably, Au 28 undergoes a complete transformation in methanol into a stable and smaller‐sized nanocluster [Au 23 (C 4 B 10 H 11 ) 9 (tht) 6 ] 2+ ( Au 23 ) bearing 12 valence electrons and crystal‐field‐like split superatomic 1D orbitals. The transformation process was systematically monitored with ESI‐MS and UV/Vis absorption spectra. Au 28 and Au 23 both display optical absorption covering the UV/Vis–NIR range and NIR emission, which facilitates their potential application in the biomedical and photocatalytic fields.