Department of Chemistry, National Dong Hwa University, No.1, Sec. 2, Da Hsueh Rd. Shoufeng, Hualien, 97401, Taiwan R.O.C.
University of Rennes, CNRS, ISCR-UMR 6226, 35000, Rennes, France.
Chemistry. 2018 Sep 25;24(54):14352-14357. doi: 10.1002/chem.201802679. Epub 2018 Aug 31.
A templated galvanic exchange performed on [Ag {Se P(OiPr) } ] of C symmetry with three equiv Au yields a mixture of [Au Ag {Se P(OiPr) } ] (x=0-2) from which [Au@Ag {Se P(OiPr) } ] and [Au@Au Ag {Se P(OiPr) } ] are successfully characterized to have T and C symmetry, respectively. Crystal structural analyses combined with DFT calculations on the model compounds explicitly demonstrate that the central Ag of Ag being oxidized by Au migrates to the protecting atomic shell as a new capping Ag , and both second and third Au dopants prefer occupying non-adjacent icosahedron vertices. The differences in symmetry, T and C , are manifested in the spatial orientation of their protecting atomic shell composed of eight capping Ag atoms as well as re-construction upon the replacement of Ag atoms on the vertices of AuAg icosahedral core with second and third Au dopants. As a result, a unique pathway for substitutional-doped clusters with increased nuclearity is proposed.
采用 C 对称的 [Ag{Se P(OiPr) } ] 模板进行的电化交换反应，用三个等效的 Au 进行反应，得到了 [AuAg{Se P(OiPr) } ]（x=0-2）的混合物，从中成功地对 [Au@Ag{Se P(OiPr) } ] 和 [Au@AuAg{Se P(OiPr) } ] 进行了特征化，它们分别具有 T 和 C 对称性。晶体结构分析结合对模型化合物的 DFT 计算明确表明，Au 氧化 Ag 中心的 Ag 迁移到保护原子壳作为新的盖帽 Ag，并且第二和第三 Au 掺杂剂都更喜欢占据非相邻的二十面体顶点。在对称性方面的差异，即 T 和 C，表现在它们由八个盖帽 Ag 原子组成的保护原子壳的空间取向以及在顶点处用第二和第三 Au 掺杂剂取代 Ag 原子时的重建。因此，提出了一种具有增加核性的取代掺杂团簇的独特途径。
