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化学进展 2015, Vol. 27 Issue (12): 1743-1753 DOI: 10.7536/PC150529 前一篇   后一篇

• 综述与评论 •

硫醇保护金团簇的实验和理论研究现状

田志美1,2, 刘汪丹1, 程龙玖1*   

  1. 1. 安徽大学化学化工学院 合肥 230601;
    2. 阜阳师范学院化学与材料工程学院 阜阳 236037
  • 收稿日期:2015-05-01 修回日期:2015-06-01 出版日期:2015-12-15 发布日期:2015-09-17
  • 通讯作者: 程龙玖 E-mail:clj@ustc.edu
  • 基金资助:
    国家自然科学基金项目(No.21273008,21573001)资助
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Progress of the Experimental and Theoretical Studies on Aum(SR)n Clusters

Tian Zhimei1,2, Liu Wangdan1, Cheng Longjiu1*   

  1. 1. College of Chemistry & Chemical Engineering, Anhui University, Hefei 230601, China;
    2. School of Chemistry and Materials Engineering, Fuyang Teachers College, Fuyang 236037, China
  • Received:2015-05-01 Revised:2015-06-01 Online:2015-12-15 Published:2015-09-17
  • Supported by:
    The work was supported by the National Natural Science Foundation of China (No. 21273008, 21573001).
硫醇保护的金团簇(Aum(SR)n,m和n为Au和SR的数目)由于其特殊的光学、电学性质以及特别的物理/化学性质,在纳米催化、生物医学和光学设备中具有潜在的应用价值。Au102(SR)54和Au25(SR)18-团簇单晶结构的确定是Aum(SR)n团簇合成的两大突破,它们的结构揭示了Aum(SR)n团簇中Au-S键新的成键特征和新的原子堆积方式。本文总结了Aum(SR)n团簇实验合成单晶结构的研究成果,概述了有谱图无单晶结构的Aum(SR)n团簇的实验进展,介绍了密度泛函理论预测Aum(SR)n团簇的研究概况,并结合本课题组的研究课题归纳了解释团簇稳定性和化学成键方式的超原子复合物模型,超原子网络模型和超级共价键模型及其应用。最后,对Aum(SR)n团簇的研究趋势进行了展望。
关键词： Aum(SR)n团簇, 单晶结构, 质谱, 密度泛函理论方法, 超原子复合物模型, 超原子网络模型, 超级共价键模型
Due to the special optical, electronic properties, particular physical/chemical properties, thiolate protected gold nanoclusters (Aum(SR)n, in which m and n are the numbers of Au and SR) have potential applications in nanocatalysis, biomedicine and optical devices. Two breakthroughs in Aum(SR)n clusters are the crystal structure determinations of Au102(SR)54 and Au25(SR)18- clusters, which uncover the new Au-S chemical bonding features as well as the new atomic packing structures in Aum(SR)n clusters. In this paper, major advances of the Aum(SR)n clusters in the experimentally determined crystal structures are generalized. This is followed by the introduction of the progresses in the experimentally synthesized Aum(SR)n clusters with mass spectroscopy and the progresses made by the density functional theory predictions. We combine our study subject to generalize superatom complex model, superatom-network model and super valence bond model which are used to interpret the stability and chemical bonding patterns of Aum(SR)n clusters. Moreover, we take several Aum(SR)n clusters as examples to introduce the applications of the three models. Finally, we give future outlook of the Aum(SR)n clusters.

Contents
1 Introduction
2 Experiments and theoretical predictions of Aum(SR)n clusters
2.1 Aum(SR)n clusters with single crystal structures
2.2 Aum(SR)n clusters with mass spectroscopy
2.3 Aum(SR)n clusters by DFT structural predictions
3 Theoretical models for Aum(SR)n clusters
3.1 Superatom complex (SAC) model
3.2 Superatom-network (SAN) model
3.3 Super valence bond (SVB) model
4 Conclusion and outlook

Key words: Aum(SR)n cluster, single crystal structure, mass spectroscopy, density functional theory method, superatom complex model, superatom-network model, super valence bond model

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