The impact of ligands upon topology and functionality of octacyanidometallate-based assemblies

Complete overview of octacyanidometallate polymetallic assemblies is presented from a novel viewpoint of the importance of incorporated ligands. The ligands are classified according to their structure and binding mode in metal-ligand-octacyanidometallate systems and their impact on topology and functionality is discussed. Monodentate ligands favour high-dimensionality structures and long-range magnetic ordering, apart from n-alcohols, which give exclusively pentadecanuclear high-spin clusters. Chelate ligands generally restrict dimensionality. Bridging ligands result in magnetically ordering hybrid networks, apart from compartmental ligands, which are used to construct discrete molecules. Intrinsic ligand functionalities, like chirality, can be successfully introduced into the resulting material. (C) 2012 Elsevier B.V. All rights reserved.