Morgan Harry W T, Shu Cong-Cong, Sun Zhong-Ming, McGrady John E
Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K.
State Key Laboratory of Elemento-Organic Chemistry, Tianjin Key Lab of Rare Earth Materials and Applications, School of Material Science and Engineering, Nankai University, Tianjin 300350, China.
J Am Chem Soc. 2022 May 11;144(18):8007-8017. doi: 10.1021/jacs.1c10106. Epub 2022 Apr 22.
We report here the structure of an endohedral plumbaspherene, [CuPb], the gold analogue of which was previously postulated to be a "missing link" in the growth of larger clusters containing three and four icosahedral subunits. The cluster contains two [CuPb] subunits linked through a CuPb trigonal antiprism. Density functional theory reveals that the striking ability of mixed Pb/coinage metal Zintl clusters to oligomerize and, in the case of Au, to act as a site of nucleation for additional metal atoms, is a direct consequence of their d( + 1)s configuration, which generates both a low-lying ( + 1)s-based LUMO and also a high-lying Pb-centered HOMO. Cluster growth and nucleation is then driven by this amphoteric character, allowing the clusters to form donor-acceptor interactions between adjacent icosahedral units or to additional metal atoms.
我们在此报告一种内包式铅球烯[CuPb]的结构，其金类似物先前被假定为包含三个和四个二十面体亚基的较大团簇生长过程中的“缺失环节”。该团簇包含通过一个铜铅三角反棱柱连接的两个[CuPb]亚基。密度泛函理论表明，混合的铅/货币金属津特耳团簇显著的低聚能力，以及在金的情况下作为额外金属原子成核位点的能力，是其d( + 1)s构型的直接结果，这种构型既产生了一个基于低能( + 1)s的最低未占分子轨道，也产生了一个高能的以铅为中心的最高已占分子轨道。团簇的生长和成核随后由这种两性特征驱动，使得团簇能够在相邻的二十面体单元之间或与额外的金属原子形成供体-受体相互作用。
