Multicomponent halide templating: The effect of structure-directing agents on the assembly of molecular and extended coordination compounds

Abstract

This account covers template effects that lead to the formation of polynuclear coordination compounds, with a focus on how the interplay of the structure-directing effects of multiple agents (including inorganic anions and organic ligands) combine to influence the geometry and nuclearity of metal-containing assemblies. Simple anions and ligands impart defined geometric shapes (triangles, squares, hexagons) onto oligonuclear assemblies, and these shapes can combine to produce a range of more sophisticated metallo-supramolecular architectures (including Platonic and Archimedean solids). An understanding of the structure-directing effects of simple templates is therefore necessary to predict or rationalise such polynuclear architectures, which may have wide-ranging applications in catalysis, in magnetism, as sensors, etc. This article primarily focuses on halide-templated assemblies of first row transition metal ions (particularly manganese coordination clusters and vanadates), but the principles discussed herein are applicable to a much wider range of coordination compounds.