Selective Encapsulation and Separation of Dihalobenzene Isomers with Discrete Heterometallic Macrocages

Abstract

Abstract A series of metallosupramolecular architectures have been prepared, including rectangles, prisms and cages, that feature half‐sandwich rhodium(III) fragments at the vertices. Remarkably, a stable cage‐like heteropolymetallic complex possessing eight rhodium(III) and two silver(I) metal ions ( 3 ) has been obtained following a multistep procedure. The Rh III /Ag I mixed macrocage enables the separation of dihalogenated benzene derivatives with high selectivity. Furthermore, a detailed X‐ray crystallographic study confirmed that the discriminative encapsulation of para ‐dihalobenzene (dichlorobenzene, dibromobenzene and diiodobenzene) is favored by Ag‐π interactions and steric effects.