A Double‐Walled Tetrahedron with Ag^I₄ Vertices Binds Different Guests in Distinct Sites**

Abstract

A double-walled tetrahedral metal-organic cage assembled in solution from silver(I), 2-formyl-1,8naphthyridine, halide, and a threefold-symmetric triamine. The Ag I 4 X clusters at its vertices each bring together six naphthyridine-imine moieties, leading to a structure in which eight tritopic ligands bridge four clusters in an (Ag I 4 X) 4 L 8 arrangement. Four ligands form an inner set of tetrahedron walls that are surrounded by the outer four. The cage has significant interior volume, and was observed to bind anionic guests. The structure also possesses external binding clefts, located at the edges of the cage, which bound small aromatic guests. Halide ions bound to the silver clusters were observed to exchange in a well-defined hierarchy, allowing modulation of the cavity volume. The principles uncovered here may allow for increasingly more sophisticated cages with silver-cluster vertex architectures, with post-assembly tuning of the interior cavity volume enabling targeted binding behavior.

Constructing Ultrastable Metallo-Cages via In Situ Deprotonation/Oxidation of Dynamic Supramolecular Assemblies

“…3D metallo-supramolecules with confined inner spaces for guest molecules are highly attractive, on account of their diverse host–guest chemistry and potential applications in selective extraction, recognition, delivery, and stabilization of reactive species. , To construct 3D metallo-supramolecular cages with a precise and robust structure, we designed a series of hexatopic building blocks ( H 12 LA , H 12 LB , and H 12 LC ) for self-assembly, ligand exchange, and host–guest studies, with a hexaphenylbenzene core and 6 H 2 DAP moieties as the metal receptors. The theoretical modeling suggested that these building blocks would form metallo-supramolecular tetrahedra (Scheme ).…”