硫醇保护金团簇的实验和理论研究现状

田志美; 刘汪丹; 程龙玖

doi:10.7536/PC150529

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

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硫醇保护金团簇的实验和理论研究现状

^1,2

^1*

作者信息 +

Progress of the Experimental and Theoretical Studies on Au_m(SR)_n Clusters

Tian Zhimei^1,2, Liu Wangdan¹, Cheng Longjiu^1*

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文章历史 +

摘要

硫醇保护的金团簇(Au_m(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Au_m(SR)_n团簇合成的两大突破,它们的结构揭示了Au_m(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Au_m(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Au_m(SR)_n团簇的实验进展,介绍了密度泛函理论预测Au_m(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Au_m(SR)_n团簇的研究趋势进行了展望。

Abstract

Due to the special optical, electronic properties, particular physical/chemical properties, thiolate protected gold nanoclusters (Au_m(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 Au_m(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 Au_m(SR)_n clusters. In this paper, major advances of the Au_m(SR)_n clusters in the experimentally determined crystal structures are generalized. This is followed by the introduction of the progresses in the experimentally synthesized Au_m(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 Au_m(SR)_n clusters. Moreover, we take several Au_m(SR)_n clusters as examples to introduce the applications of the three models. Finally, we give future outlook of the Au_m(SR)_n clusters.

Contents
1 Introduction
2 Experiments and theoretical predictions of Au_m(SR)_n clusters
2.1 Au_m(SR)_n clusters with single crystal structures
2.2 Au_m(SR)_n clusters with mass spectroscopy
2.3 Au_m(SR)_n clusters by DFT structural predictions
3 Theoretical models for Au_m(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

Graphical abstract

关键词

Au_m(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

Key words

Au_m(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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田志美, 刘汪丹, 程龙玖. 硫醇保护金团簇的实验和理论研究现状[J]. 化学进展, 2015, 27(12): 1743-1753 DOI:10.7536/PC150529

Tian Zhimei, Liu Wangdan, Cheng Longjiu. Progress of the Experimental and Theoretical Studies on Au_m(SR)_n Clusters[J]. Progress in Chemistry, 2015, 27(12): 1743-1753 DOI:10.7536/PC150529

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