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

Abstract

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@Cu₁₂S₈@Cu₄(dpph)₆]X (X = OH, <b>SD/AgCu16a</b> and X = PF₆, <b>SD/AgCu16b</b>; <b>SD</b> = <b>SunDi</b>), by use of an antigalvanic reaction between organometallic [PhC≡CCu]_<i>n</i> and Ph₃CSH with elemental silver. Both compounds are formed by fitting an Archimedean Ag@Cu₁₂ cuboctahedral cluster into a Platonic Cu₄(dpph)₆ tetrahedral cage [dpph = bis(diphenylphosphino)hexane]. The Ag@Cu₁₂ cluster is a hollow cuboctahedral Cu₁₂ cage filled with a central Ag^I atom, and all eight triangular faces of the Ag@Cu₁₂ 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 Cu₄(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 AgCu₁₆ cluster is quite stable in CH₂Cl₂ 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.