Directed Assembly of Metal−Cyanide Cluster Magnets

Abstract

The simple, well-understood coordination chemistry of the cyanide ligand is of significant utility in the design of new single-molecule magnets. Its preference for bridging two transition metals in a linear M'-CN-M geometry permits the use of multidentate blocking ligands in directing the assembly of specific molecular architectures. This approach has been employed in the synthesis of numerous high-nuclearity constructs, including simple cubic M4M'4(CN)12 and face-centered cubic M8M'6(CN)24 coordination clusters, as well as some unexpected cluster geometries featuring as many as 27 metal centers. The ability to substitute a range of different transition metal ions into these structures enables adjustment of their magnetic properties, facilitating creation of high-spin ground states with axial magnetic anisotropy. To date, at least four different cyano-bridged single-molecule magnets have been characterized, exhibiting spin-reversal barriers as high as 25 cm(-1). Ultimately, it is envisioned that this strategy might lead to molecules possessing much larger barriers with the potential for storing information at more practical temperatures.

Surface Modification of a Six‐Capped Body‐Centered Cube Ni9W6 Cluster: Structure and Single‐Molecule Magnetism

“…[4] Alternatively, cyanides are frequently utilized for the construction of high-spin molecules because of their structural and magnetic predictability. [5] To attain SMMs with cyanides, it would be a rational approach to combine…”

Field-Induced Slow Magnetic Relaxation in Mn_9W_6 Cluster-Based Compound

“…Polynuclear clusters are studied widely by both chemists and physicists for their magnetic, optical and electronic properties [1][2][3][4]. High-nuclearity clusters based on magnetically coupled paramagnetic ions can often reveal a high-spin ground state.…”

Synthesis, crystal structure and properties of the cyano-bridged heteropolynuclear [Cu(meso)]3[Co(CN)6]2•9.5H2O compound

“…Therefore, controlling preparative methods is a key step in obtaining complexes with the desired structural and physical properties. 16,17 Our continuing interest in the tetradentate macrocyclic ligand meso = 5,5,7,12,12,14- …”