Polynuclear coordination cages

Abstract

Reaction of simple bis-bidentate ligands, containing two chelating pyrazolyl-pyridine units connected to a central aromatic spacer, with six-coordinate transition metal dications results in self-assembly of an extensive series of polyhedral cage complexes. These include M(4)L(6) tetrahedra, M(8)L(12) cubes, M(12)L(18) truncated tetrahedra and M(16)L(24) tetra-capped truncated tetrahedra. In all cases the metal : ligand ratio is 2 : 3, reflecting the combination of six-coordinate metal ions with tetradentate ligands. The resulting structures are based on those polyhedra which have a 2 : 3 ratio of vertices to faces, with a metal ion at each vertex and bridging ligand spanning each edge. The cages display a range of interesting properties such as an anion-based template effect in the smaller examples; host-guest chemistry associated with the central cavity; aromatic stacking around the periphery between electron-poor and electron-rich ligand fragments which appears to contribute substantially to their stability; and modified fluorescence properties arising from the aromatic stacking of fluorophores such as naphthyl and anthracenyl groups built into the ligand backbone. Even more complex structural types are available using a mixture of face-capping (tris-bidentate) and edge-bridging (bis-bidentate) ligands, such as examples of M(12) cuboctahedra which select a combination of two types of ligand during the self-assembly process.