Cyanide-bridged assemblies constructed from capped tetracyanometalate building blocks [MA(ligand)(CN)4]1−/2− (MA = Fe or Cr)

The design and synthesis of cyanide-bridged heterometallic molecular assemblies via self-assembly of capped tetracyanometalate [MA(L)(CN)4]n− (MA = FeIII/II, CrIII, L = bidentate ligand, n = 1, 2) and metal ions in the presence or absence of blocking ligands lead to a wide diversity of structures, ranging from di-, tri-, tetra-, hexanuclear compounds, to various one-dimensional (1D), two-dimensional (2D) and three-dimensional (3D) metal-cyanide architectures. Intensive research in this field resulted in the crystallographic and magnetochemical characterization of these metal-cyanide assemblies. The magnetic properties will be discussed in terms of the magnetic exchange coupling between MA and metal ions. Among these assemblies, ferromagnetically coupled 2,4-ribbon like chains which exhibit slow magnetic relaxation and hysteresis effects are the most appealing single-chain magnets (SCMs).

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► [MA(L)(CN)4]n− as capped tetracyanometalate precursors.
► Capped tetracyanometalate precursors result in clusters and nD assemblies (n = 1–3).
► Cyanide-bridged compounds with various structures and magnetic properties.