Tricyanometalate molecular chemistry: A type of versatile building blocks for the construction of cyano-bridged molecular architectures

Cyano-bridged molecule-based magnetic materials with reduced dimensionality, such as single-molecule magnets (SMMs) and single-chain magnets (SCMs), have attracted great research interest during the last decade. Among the cyano-based molecular precursors with ample coordinating capability, we note the ability of the tricyanometalate to link various metal ions lead to a wide diversity of structural architectures ranging from discrete polynuclear complexes to various one-dimensional (1D) assemblies. Some of them are promising cyano-bridged SMMs and SCMs. The use of capping tridentate organic ligands results in a number of clusters containing di-, tri-, tetra-, penta-, hexa-, octa-, fourteen-nuclear and various 1D metal-cyanide molecular architectures. Here we review the structural topologies of these complexes and their related magnetic properties, highlight typical examples, and point out the main possible directions that remain to be developed in this field. From the crystal engineering point of view, the compounds reviewed here should provide useful information for further design and investigation on this elusive class of cyano-bridged SMMs and SCMs.

Research highlights
► fac- and mer-[LMA(CN)3]− as monoanionic tricyanometalate precursors.
► Tricyanometalate precursors result in clusters and 1D molecular architectures.
► Cyano-bridged compounds with various structures and magnetic properties and magnetic properties.
► The magnetic properties are related with the structural topologies.