Tang Li, Deng Shiyao, Wang Shuxin, Pei Yong, Zhu Manzhou
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, AnHui Province, Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University, Hefei, Anhui 230601, P. R. China.
Department of Chemistry, Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University, Hunan Province, China, 411105, P. R. China.
Chem Commun (Camb). 2021 Feb 25;57(16):2017-2020. doi: 10.1039/d0cc07482a.
Thiolated-alloy nanocluster Au15.37Cu16.63(S-Adm)20 ((AuCu)32 for short) has been synthesized. Single crystal X-ray crystallography (SC-XRD) proved that this cluster contains a Au14Cu6 core, which is composed of double superatom chains, two M4(SR)5 (M = Au/Cu) motifs, four Cu(SR)2 monomer staples and two SR molecules at the waist. The composition of this nanocluster is confirmed by SC-XRD and further verified by XPS, EDX and 2H-NMR. Surprisingly, double superatom chains connect to each other only via two Au-Au bonds, which makes the kernel resemble a tunnel. Combined with DFT calculation and electronic structure analysis, it is further proved that the (AuCu)32 nanocluster contains six 2e alloy superatomic Au3Cu2+ units. This work is the first report showing that superatom units (CuAu32+) self-assembling to a hollow kernel maintain the superatom characteristic of metal nanoclusters, which enriches the fundamental knowledge of metal superatom clusters. The stable electronic structure of the nanocluster provides an experimental basis for theoretical analysis in the future. In addition, the hollow structure may be promising in catalytic applications.
已合成硫醇化合金纳米团簇Au15.37Cu16.63(S-Adm)20（简称为(AuCu)32）。单晶X射线晶体学（SC-XRD）证明该团簇包含一个Au14Cu6核，它由双超原子链、两个M4(SR)5（M = Au/Cu）基序、四个Cu(SR)2单体钉和腰部的两个SR分子组成。该纳米团簇的组成通过SC-XRD得到证实，并通过XPS、EDX和2H-NMR进一步验证。令人惊讶的是，双超原子链仅通过两个Au-Au键相互连接，这使得内核类似于一个隧道。结合密度泛函理论（DFT）计算和电子结构分析，进一步证明(AuCu)32纳米团簇包含六个2e合金超原子Au3Cu2+单元。这项工作是首次报道表明超原子单元（CuAu32+）自组装成中空内核仍保持金属纳米团簇的超原子特性，这丰富了金属超原子团簇的基础知识。纳米团簇稳定的电子结构为未来的理论分析提供了实验依据。此外，这种中空结构在催化应用中可能具有前景。
