A Silver Nanocluster Containing Interstitial Sulfur and Unprecedented Chemical Bonds
A Silver Nanocluster Containing Interstitial Sulfur and Unprecedented Chemical Bonds
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含有间隙硫和前所未有的化学键的银纳米团簇
DOI：
10.1002/anie.201805594
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
Wu Zhikun
中科院分区：
文献类型：
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作者：
Liu Xu;Chen Jishi;Yuan Jinyun;Li Yizhi;Li Jin;Zhou Shiming;Yao Chuanhao;Liao Lingwen;Zhuang Shengli;Zhao Yan;Deng Haiteng;Yang Jinlong;Wu Zhikun
硫醇化金属纳米团簇的出现为识别重大和前所未有的现象提供了机会，因为它们具有量子尺寸并且可以用X射线晶体学表征。近年来，银纳米团簇由于其成本低、性质丰富等优点受到了广泛的关注。本文成功合成了具有面心立方（fcc）结构的硫醇化银纳米团簇[Ag 46 S7（SPhMe 2）24]NO3（简称Ag 46），并通过X射线分析对其结构进行了解析。最重要的是，在Ag 46的晶格空隙中发现了间隙硫，而没有晶格畸变或膨胀，表明经典的间隙金属固溶体理论在量子尺寸下可能不适用。此外，在Ag 46中发现了前所未有的化学键和独特的结构特征（如不对称配位的μ4-S），可能与间隙硫有关，这得到了自然群体分析的支持。
The emergence of thiolated metal nanoclusters provides opportunities to identify significant and unprecedented phenomena because they are at quantum sizes and can be characterized with X‐ray crystallography. Recently silver nanoclusters have received extensive interest owing to their merits, such as low‐cost and rich properties. Herein, a thiolated silver nanocluster [Ag46S7(SPhMe2)24]NO3(Ag46for short) with a face‐centered cubic (fcc) structure was successfully synthesized and structurally resolved by X‐ray analysis. Most importantly, interstitial sulfur was found in the lattice void of Ag46without lattice distortion or expansion, indicating that the classic theory of interstitial metal solid solutions might be not applicable at quantum size. Furthermore, unprecedented chemical bonds and unique structural features (such as asymmetrically coordinated μ4‐S) were found in Ag46and might be related to the interstitial sulfur, which is supported by natural population analyses.