Metal–organic cages have demonstrated remarkable capabilities as functional materials in separations, sensing, and catalysis applications. However, the vast majority of cages are formed around mononuclear complexes at each vertex. This leaves the choice of organic components as the predominant source of diversity in new cage designs when seeking to access new properties or create new architecture types.

With a view to expanding beyond this, assemblies were synthesised using an organic subcomponent containing a 1,8-naphthyridine moiety. The non-converging coordination vectors of naphthyridine, assembled with a soft, cluster-forming metal such as silver, were intended to provide an enthalpic driving force for the formation of silver clusters at the vertices. This strategy has been previously demonstrated to form polynuclear vertices, including a disilver vertex in a trigonal prismatic cage, and Ag₄I or Ag₆(SO₄)₂ clusters in a series of helicates. In this work, this approach is extended to create novel cage architectures containing silver clusters.

The application of cages is also expanded. While the interior cavit which defines a metal–organic cage is frequently applied to the capture and separation (or detection) of a substrate, the inherent metal binding properties of the cage vertex have been underexplored. An organic cage, synthesised via a metal–organic cage, is used to bind cobalt out of an aqueous environment.