Han Bao-Liang, Wang Zhi, Gupta Rakesh Kumar, Feng Lei, Wang Suna, Kurmoo Mohamedally, Gao Zhi-Yong, Schein Stan, Tung Chen-Ho, Sun Di
School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Ji'nan 250100, People's Republic of China.
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, and School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252000, China.
ACS Nano. 2021 May 25;15(5):8733-8741. doi: 10.1021/acsnano.1c00942. Epub 2021 Apr 28.
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@CuS@Cu(dpph)]X (X = OH, and X = PF, ; = ), by use of an antigalvanic reaction between organometallic [PhC≡CCu] and PhCSH with elemental silver. Both compounds are formed by fitting an Archimedean Ag@Cu cuboctahedral cluster into a Platonic Cu(dpph) tetrahedral cage [dpph = bis(diphenylphosphino)hexane]. The Ag@Cu cluster is a hollow cuboctahedral Cu cage filled with a central Ag atom, and all eight triangular faces of the Ag@Cu cuboctahedron are triply capped by eight S ions, four of which in a tetrahedral array further internally pillar four Cu vertices of the outer Cu(dpph) 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 cluster is quite stable in CHCl 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-cage compound but also provides deep insights into the binding and geometry matching between clusters and cages in one entity.
在受限空间中精确加载纳米团簇，这在科学领域一直备受追捧，但仍存在一些关于“如何”“何时”以及“为何”的谜团。在此，我们通过有机金属[PhC≡CCu]与PhCSH和元素银之间的抗电偶反应，分离出了两种相似的笼中异金属簇化合物，[Ag@CuS@Cu(dpph)]X（X = OH， 以及X = PF，； = ）。这两种化合物都是通过将一个阿基米德Ag@Cu立方八面体簇装入一个柏拉图式Cu(dpph)四面体笼[dpph = 双（二苯基膦基）己烷]中形成的。Ag@Cu簇是一个空心的立方八面体Cu笼，内部填充有一个中心Ag原子，Ag@Cu立方八面体的所有八个三角形面都由八个S离子三重封顶，其中四个以四面体排列进一步在内部支撑外部Cu(dpph)四面体的四个Cu顶点，将簇固定在笼中。这两种化合物都可被视为从填充有离散纳米团簇的多孔纳米材料中切下的分子片段，从而为理解原子精确纳米团簇的受限生长提供了更多细节。电喷雾电离质谱（ESI-MS）表明，AgCu簇在CHCl中相当稳定，并且在增加的碰撞能量下能在气相中逐步失去dpph配体。这项工作不仅展示了金属原子在受限腔内精确聚集形成笼中簇化合物，还深入洞察了一个实体中簇与笼之间的结合和几何匹配。
