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

Bao-Liang Han; Zhi Wang; Rakesh Kumar Gupta; Lei Feng; Suna Wang; Mohamedally Kurmoo; Zhi-Yong Gao; Stan Schein; Chen-Ho Tung; Di Sun

doi:10.1021/acsnano.1c00942

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

ACS Nano. 2021 May 25;15(5):8733-8741. doi: 10.1021/acsnano.1c00942. Epub 2021 Apr 28.

Authors

Affiliations

¹ School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Ji'nan 250100, People's Republic of China.
² Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, and School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252000, China.
³ Institut de Chimie de Strasbourg, Université de Strasbourg, CNRS-UMR 7177, 4 rue Blaise Pascal, Strasbourg 67008 Cedex, France.
⁴ School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Normal University, Henan, Xinxiang 453007, People's Republic of China.
⁵ California NanoSystems Institute and Department of Psychology, University of California, Los Angeles, California 90095-1563, United States.

PMID: 33909407
DOI: 10.1021/acsnano.1c00942

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, SD/AgCu16a and X = PF₆, SD/AgCu16b; SD = SunDi), by use of an antigalvanic reaction between organometallic [PhC≡CCu]_n 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.

Keywords: antigalvanic reaction; atomic precision; cluster-in-cage compounds; electrospray ionization mass spectrometry; host−guest system.