Selective Encapsulation and Separation of Dihalobenzene Isomers with Discrete Heterometallic Macrocages

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 RhIII/AgI 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.

Cavity-based applications of metallo-supramolecular coordination cages (MSCCs)

“…The guests within these isolated cavities are exposed to a completely different microenvironment and interactions with the host alone or with co-encapsulated guests. These reduced interactions alter the properties of bound guests and host complexes, leading to their applications in recognition and separation, [6][7][8][9][10] sensitive and reactive species stabilization, [11][12][13] catalysis, 2,14-16 biological processes for drug delivery, 4,[17][18][19] and as catalyst enhancers (increasing catalytic activity by encapsulation) 20 and nanoscale chemical vessels. 21 This review systematically describes the use of metal-ligand self-assembled nanocages for cavity-based applications.…”

Hydrophobic and Metal-Coordinated Confinement Effects Trigger Recognition and Selectivity

“…Finally, we applied the metallo-cavitand’s selective binding to the separation of halobenzene isomers . As these regioisomers have close boiling points, various difficulties are encountered in their separation .…”

pH‐Triggered Removal of Nitrogenous Organic Micropollutants from Water by Using Metal‐Organic Polyhedra

“…Researchers have recently begun to develop supramolecular strategies based on host‐guest chemistry to capture and separate substances of interest [9–12] . In these strategies, discrete molecular compounds can be used in solution to selectively recognise, adsorb, and entrap the substance of interest inside their cavities [13–16] . The resultant host‐guest complex is then isolated in solution by liquid/liquid extraction or phase transfer.…”

“…[9][10][11][12] In these strategies, discrete molecular compounds can be used in solution to selectively recognise, adsorb, and entrap the substance of interest inside their cavities. [13][14][15][16] The resultant host-guest complex is then isolated in solution by liquid/liquid extraction or phase transfer. Finally, the guest molecule is liberated from the host upon breakage of the host-guest interaction.…”