Division of Interfacial Water and Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China.
Nanoscale. 2017 Jul 6;9(26):8990-8996. doi: 10.1039/c7nr03508j.
An understanding of the structural stability and formation mechanism of ligated gold nanoclusters with triply coordinated μ-sulfido (μ-S) motifs is important not only for gold chemistry but also for the design of more effective catalysts or drug carriers for various applications. In this article, a new elementary block Au(μ-S) with zero valence electrons [referred to as Au(μ-S)(0e)] has been identified, which describes all crystallized ligated gold clusters with μ-S motifs, in conjunction with the previously reported Au(2e) and Au(2e) elementary blocks, in a grand unified model (GUM). This Au(μ-S)(0e) elementary block has a tripod structure with the S atom bonding to three Au atoms in a μ bridging mode, and can be considered as a μ-S atom balancing out the 2e valence electrons of the Au(2e) block. Using Au(μ-S) as a building block, a special group of quasi-fullerene hollow-cage [Au(μ-S)] gold(i) μ-S clusters are designed, which exhibit high stabilities. In addition, a series of theoretical structures are predicted to be increasingly stable after introducing μ-S atoms, based on the crystallized clusters. Overall, the introduction of a Au(μ-S)(0e) elementary block can help with the understanding of diverse structures of ligated gold clusters with μ-S motifs, thereby assisting the rational design of new forms of gold nanoclusters.
理解具有三重配位 μ-硫基 (μ-S) 配体的键合金纳米簇的结构稳定性和形成机制不仅对金化学很重要，而且对设计用于各种应用的更有效的催化剂或药物载体也很重要。本文中，我们确定了一个新的零价电子的基本单元 Au(μ-S)(0e)[称为 Au(μ-S)(0e)]，它结合了之前报道的 Au(2e)和 Au(2e)基本单元，在一个大统一模型 (GUM) 中描述了所有具有 μ-S 配体的结晶键合金簇。这个 Au(μ-S)(0e)基本单元具有三脚架结构，其中 S 原子以 μ 桥接的方式与三个 Au 原子键合，可以被认为是一个 μ-S 原子，平衡了 Au(2e)单元的 2e 价电子。使用 Au(μ-S)作为构建块，设计了一组特殊的类富勒烯中空笼 [Au(μ-S)] 金(i) μ-S 簇，它们表现出很高的稳定性。此外，基于结晶簇，预测了一系列理论结构在引入 μ-S 原子后会变得越来越稳定。总的来说，引入 Au(μ-S)(0e)基本单元有助于理解具有 μ-S 配体的键合金纳米簇的各种结构，从而辅助新形式的金纳米簇的合理设计。
