Tianjin Key Lab for Rare Earth Materials and Applications, State Key Laboratory of Elemento-Organic Chemistry, School of Materials Science and Engineering, Nankai University, Tianjin, 300350, China.
Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK.
Nat Commun. 2020 Jul 10;11(1):3477. doi: 10.1038/s41467-020-17187-4.
Gold nanoparticles have been used for centuries, both for decoration and in medical applications. More recently, many of the major advances in cluster chemistry have involved well-defined clusters containing tens or hundreds of atoms, either with or without a ligand shell. In this paper we report the synthesis of two gold/lead clusters, [AuPb] and [AuPb], both of which contain nido [Au@Pb] icosahedra surrounding a core of Au atoms. Analogues of these large clusters are not found in the corresponding Ag chemistry: instead, the Ag-centered nido icosahedron, [Ag@Pb], is the only isolated product. The structural chemistry, along with the mass spectrometry which shows the existence of [AuPb] but not [AgPb], leads us to propose that the former species is the key intermediate in the growth of the larger clusters. Density functional theory indicates that secondary π-type interactions between the [Au@Pb] ligands and the gold core play a significant part in stabilizing the larger clusters.
金纳米颗粒已经使用了几个世纪，既用于装饰，也用于医学应用。最近，簇化学的许多重大进展都涉及到含有数十个或数百个原子的、有或没有配体壳的、结构明确的团簇。在本文中，我们报告了两种金/铅团簇[AuPb]和[AuPb]的合成，它们都包含围绕金原子核心的 nido [Au@Pb] 二十面体。这些大团簇的类似物在相应的 Ag 化学中没有发现：相反，Ag 为中心的 nido 二十面体[Ag@Pb]是唯一的分离产物。结构化学，以及质谱，表明[AuPb]的存在而不是[AgPb]，这使我们提出前者是更大团簇生长的关键中间体。密度泛函理论表明，[Au@Pb]配体和金核之间的二次π型相互作用在稳定更大的团簇方面起着重要作用。
