Multicavity Metallosupramolecular Architectures

Abstract

Discrete metallosupramolecular systems are often macrocyclic or cage-like architectures with an accessible internal cavity. Guest molecules can reside within these cavities and much of the interest in these systems is derived from these fascinating host-guest interactions. A range of potential applications stem from the ability of these metallosupramolecular architectures to encapsulate guests. These applications include catalysis or acting as molecular reaction flasks, the molecular scavenging of pollutants, storage of reactive species, and drug delivery. Multicavity metallosupramolecular architectures combine the ability of large hollow assemblies to bind multiple guests concurrently with the binding specificity associated with small cages. A variety of different approaches to generating separate compartments within a single metallosupramolecular assembly have emerged. These include interpenetrated cages, cages with polytopic ligands that have a long backbone, and molecules that have two or more clefts. This review examines these approaches, and highlights key contributions to the field.

Backbone‐Bridging Promotes Diversity in Heteroleptic Cages

“…So far, two major strategies can be distinguished. [16] The first one makes use of multitopic ligands, e.g. tris-or even tetrakis-monodentate bridges, assembling with suitable metal nodes, e.g.…”

Rationalizing the “Diels-Alderase” Activity of Pd2L4 Self-Assembled Metallocages: Enabling the Efficient Prediction of Catalytic Scaffolds

“…topology is one of the most simple and versatile architectures. 30,32 To date, several homo-and heteroleptic variants (consisting of one or different types of ligand, respectively) have been reported by Hooley, 35 Shionoya, 36 Clever, [37][38][39][40] Crowley, 41,42 and others, [43][44][45] with applications in molecular recognition, 45 drug delivery, 29 stabilization of reactive species, 46 and recently catalysis. 47 Despite their promising applications and scope for redesign, no computational investigation has been carried out to explore their catalytic power.…”

“…7,27,28 In this work, we focus on the [Pd2L4] 4+ architecture, which occupies a prominent place in supramolecular chemistry. [29][30][31][32][33] Originally reported by Steel and co-workers, 34…”

A Peanut‐Shaped Polyaromatic Capsule: Solvent‐Dependent Transformation and Electronic Properties of a Non‐Contacted Fullerene Dimer

“…1nmi no uter diameter), the synthesis of host compounds capable of selectively binding two or more fullerene guests in the cavity still remains challenging, [6, 7] even though several host structures possess cavities whose sizes are larger than those of ac ouple of fullerenes. [8] Nitschke and co-workers succeeded recently in the preparation of fullerene (C 60 ) n assemblies (n = 2-4, Figure 1b), in which the fullerenes tightly contact each other,u tilizing porphyrin-based coordination cages. [9] However,t he detailed electrochemical characters of fullerene assemblies are still obscure and the redox properties of non-contacted, discrete fullerene assemblies, which are expected to display unique electronic communication, have not been recorded to date.H ere we present as traightforward synthesis of ap eanut-shaped polyaromatic capsule,b yt he self-assembly of metal ions and W-shaped bispyridine ligands (1)w ith embedded polyaromatic panels, and it allows the selective incorporation of two fullerene C 60 molecules with an intermolecular separation of 6.4 (Figure 1c).…”