A Polyoxometalate Containing the {Ni2N3} Fragment: Ferromagnetic Coupling in a NiII μ‐1,1 Azido Complex with a Large Bridging Angle

Better by degrees: Insertion of an azido ligand in a polyoxometalate led to the complex KRb5[(PW10O37){Ni(H2O)2}(μ-N3)]⋅19 H2O, in which the NiII centers are ferromagnetically coupled (see picture). The {Ni(μ-1,1-N3)Ni} core constitutes the first monobridged azido NiII complex obtained. The Ni-N-Ni angle is the largest ever observed (129.3°), and suggests that μ-1,1-azido complexes are ferromagnetically coupled whatever the bridge angle.