The bridging azido ligand as a central “player” in high-nuclearity 3d-metal cluster chemistry

• Azido clusters for d-elements, with nuclearity equal to or larger than four, have been reviewed.
• Structural and synthetic features are described.
• Azide ligand plays a key role to promote ferromagnetic interactions and to generate systems with SMM response.

The chemistry of the azido-bridged coordination clusters continues to attract the intense interest of synthetic inorganic chemists and scientists working in the interdisciplinary field of Molecular Magnetism. In this review we have focused on describing aspects of synthesis, structures and magnetic properties of azido-bridged 3d- and d/d′-metal clusters with nuclearities equal to or higher than 4. Some of the clusters display slow magnetic relaxation at very low temperatures, mainly due to the ferromagnetic metal⋯metal exchange interactions propagated through the end-on azido ligand. The chemistry of polynuclear, azido-bridged 3d-metal complexes embedded in lacunary polyoxometalates is also discussed.

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