Precise Implantation of an Archimedean Ag@Cu12 Cuboctahedron into a Platonic Cu4Bis(diphenylphosphino)hexane6 Tetrahedron

作者：Bao‐Liang Han, Zhi Wang, Rakesh Kumar Gupta, Lei Feng, Suna Wang, Mohamedally Kurmoo, Zhiyong Gao, Stan Schein, Chen‐Ho Tung, Di Sun · 发表于：ACS Nano · 年份：2021 · DOI：10.1021/acsnano.1c00942 · 被引用次数：45 · 研究领域：Nanocluster Synthesis and Applications、Molecular Sensors and Ion Detection、Supramolecular Self-Assembly in Materials

Precision loading of nanoclusters in confined spaces, which has been enthusiastically pursued in the scientific realm, is still associated with some mysteries of “how”, “when”, and “why”. Here, we isolated two similar heterometallic cluster-in-cage compounds, [Ag@Cu 12 S 8 @Cu 4 (dpph) 6 ]X (X = OH, SD/AgCu16a and X = PF 6, SD/AgCu16b; SD = SunDi ), by use of an antigalvanic reaction between organometallic [PhC≡CCu] n and Ph 3 CSH with elemental silver. Both compounds are formed by fitting an Archimedean Ag@Cu 12 cuboctahedral cluster into a Platonic Cu 4 (dpph) 6 tetrahedral cage [dpph = bis(diphenylphosphino)hexane]. The Ag@Cu 12 cluster is a hollow cuboctahedral Cu 12 cage filled with a central Ag I atom, and all eight triangular faces of the Ag@Cu 12 cuboctahedron are triply capped by eight S 2– ions, four of which in a tetrahedral array further internally pillar four Cu vertices of the outer Cu 4 (dpph) 6 tetrahedron, fixing the cluster in the cage. Both compounds can be deemed as molecular fragments excised from porous nanomaterials filled with discrete nanoclusters, thus providing more details for understanding the confined growth of atomically precise nanoclusters. Electrospray ionization mass spectrometry (ESI-MS) reveals that the AgCu 16 cluster is quite stable in CH 2 Cl 2 and can stepwise lose dpph ligand in the gas phase under increased collision energy. This work not only presents a precise aggregation of metal atoms in a confined cavity to form a cluster-in-cag...