3 years ago

A Bis Binuclear Ni(II) complex with easy and hard axes of magnetization: complementary experimental and theoretical insights

Régis Guillot, Benjamin Cahier, Maurici Lopez-Jorda, Zeinab Saad, Fatima EL-Khatib, Talal Mallah, Eric Rivière, Hala Hafez, Nathalie Guihéry
The preparation of a tetranuclear Ni(II) complex, made of two binuclear species bridged by a nitrate anion, using a macrocyclic cryptand like ligand is reported. The metal ions within the binuclear species are hexacoordinate with different distorted environments. One nickel site, Ni1, has as a compressed octahedral geometry, while the other nickel site, Ni2, has a geometry closer to a square pyramid because of the presence of a one long metal-ligand bond distance. The magnetic properties show that the intra dimer exchange coupling is larger than the interdimer one due to the difference in the metal-ligand intra- and inter dimer bond lengths, as confirmed by broken symmetry Density Functional Theory calculations. Wave function based calculations allow analyzing both the nature and the magnitude of the magnetic anisotropy of the two Ni sites. The Ni1 and Ni2 sites have, respectively, easy and hard axis of magnetization that are almost orthogonal. Magneto-structural correlations show that the hard axis of magnetization on Ni2 is due to its geometry that is closer to square pyramidal despite the hexacoordination. On the other hand, the easy axis of magnetization of the Ni1 site is the result of the compressed octahedral geometry.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/ejic.201700977

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