Guiding the High-Yield Synthesis of NHC-Ligated Gold Nanoclusters by 19F NMR Spectroscopy

IF 4.8 Q2 NANOSCIENCE & NANOTECHNOLOGY ACS Nanoscience Au Pub Date : 2022-08-09 DOI:10.1021/acsnanoscienceau.2c00026
Hui Shen, Xiongkai Tang, Qingyuan Wu, Yuhao Zhang, Chuxin Ma, Zhen Xu, Boon K. Teo and Nanfeng Zheng*, 
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引用次数: 2

Abstract

Optimizing the synthesis of atomically precise metal nanoclusters by virtue of molecular tools is highly desirable but quite challenging. Herein we report how 19F NMR spectroscopy can be used to guide the high-yield synthesis of N-heterocyclic carbene (NHC)-stabilized gold nanoclusters. In spite of little difference, 19F NMR signals of fluoro-incorporated NHCs (FNHC) are highly sensitive to the tiny change in their surrounding chemical environments with different N-substituents, metals, or anions, thus providing a convenient strategy to discriminate species in reaction mixtures. By using 19F NMR, we first disclosed that the one-pot reduction of FNHC-Au-X (X is halide) yields multiple compounds, including cluster compounds and also a large amount of highly stable [Au(FNHC)2]+ byproduct. The detailed quantitative 19F NMR analyses over the reductive synthesis of NHC-stabilized Au nanoclusters reveal that the formation of the di-NHC complex is deleterious to the high-yield synthesis of NHC-stabilized Au nanoclusters. With the understanding, the reaction kinetic was then slowed by controlling the reduction rate to achieve the high yield of a [Au24(FNHC)14X2H3]3+ nanocluster with a unique structure. The strategy demonstrated in this work is expected to provide an effective tool to guide the high-yield synthesis of organic ligand-stabilized metal nanoclusters.

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用19F NMR光谱指导高产率合成NHC连接的金纳米团簇
借助分子工具优化原子级精确金属纳米团簇的合成是非常理想的,但相当具有挑战性。在此,我们报道了如何使用19F NMR光谱来指导N-杂环卡宾(NHC)稳定的金纳米团簇的高产率合成。尽管差异很小,但掺氟NHCs(FNHC)的19F NMR信号对其周围具有不同N-取代基、金属或阴离子的化学环境的微小变化高度敏感,从而提供了区分反应混合物中物种的方便策略。通过使用19F NMR,我们首先公开了FNHC-Au-X(X是卤化物)的一锅还原产生多种化合物,包括簇合物和大量高度稳定的[Au(FNHC)2]+副产物。对NHC稳定的Au纳米团簇的还原合成进行的详细的定量19F NMR分析表明,二-NHC络合物的形成对NHC稳定性Au纳米簇的高产率合成是有害的。有了理解,然后通过控制还原速率来减缓反应动力学,以实现具有独特结构的[Au24(FNHC)14X2H3]3+纳米团簇的高产率。这项工作中展示的策略有望为指导有机配体稳定的金属纳米团簇的高产率合成提供一个有效的工具。
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来源期刊
ACS Nanoscience Au
ACS Nanoscience Au 材料科学、纳米科学-
CiteScore
4.20
自引率
0.00%
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0
期刊介绍: ACS Nanoscience Au is an open access journal that publishes original fundamental and applied research on nanoscience and nanotechnology research at the interfaces of chemistry biology medicine materials science physics and engineering.The journal publishes short letters comprehensive articles reviews and perspectives on all aspects of nanoscience and nanotechnology:synthesis assembly characterization theory modeling and simulation of nanostructures nanomaterials and nanoscale devicesdesign fabrication and applications of organic inorganic polymer hybrid and biological nanostructuresexperimental and theoretical studies of nanoscale chemical physical and biological phenomenamethods and tools for nanoscience and nanotechnologyself- and directed-assemblyzero- one- and two-dimensional materialsnanostructures and nano-engineered devices with advanced performancenanobiotechnologynanomedicine and nanotoxicologyACS Nanoscience Au also publishes original experimental and theoretical research of an applied nature that integrates knowledge in the areas of materials engineering physics bioscience and chemistry into important applications of nanomaterials.
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