SYNTHESIS, STRUCTURE AND MAGNETISM OF A NEW IMIDAZOLATE-BRIDGED BINUCLEAR COMPLEX [Ni2(Im)(Phen)4]·(NO3)3·3H2O

Niu, Shu Yun; Jin, Jing; Yang, Guang; YE, LING

doi:10.1142/9789812776846_0040

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“…The crystal structure and the magnetic properties of two binuclear pentacoordinate Ni(II) complexes with an imidazolate bridge and nearly perfect spy geometry have been reported in the literature. 52,53 The exchange coupling parameters were reported to be anti-ferromagnetic and larger than 30 cm −1 in absolute value, and the effect of the ZFS was not taken into account. The exchange parameter in another binuclear complex with benzoimidazole bridging the Ni(II) ions was found equal to −5.8 cm −1 with D = 50 cm −1 , but the crystal structure was not reported.…”

Section: Inorganic Chemistrymentioning

confidence: 99%

Design of a Binuclear Ni(II) Complex with Large Ising-type Anisotropy and Weak Anti-Ferromagnetic Coupling

et al. 2017

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The preparation of a binuclear Ni(II) complex with a pentacoordinate environment using a cryptand organic ligand and the imidazolate bridge is reported. The coordination sphere is close to trigonal bipyramidal (tbp) for one Ni(II) and to square pyramidal (spy) for the other. The use of the imidazolate bridge that undergoes π-π stacking with two benzene rings of the chelating ligand induces steric hindrance that stabilizes the pentacoordinate environment. Magnetic measurements together with theoretical studies of the spin states energy levels allow fitting the data and reveal a large Ising-type anisotropy and a weak anti-ferromagnetic exchange coupling between the metal ions. The magnitude and the nature of the magnetic anisotropy and the difference in anisotropy between the two metal ions are rationalized using wave-function-based calculations. We show that a slight distortion of the coordination sphere of Ni(II) from spy to tbp leads to an Ising-type anisotropy. Broken-symmetry density functional calculations rationalize the weak anti-ferromagnetic exchange coupling through the imidazolate bridge.

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Section: Inorganic Chemistrymentioning

confidence: 99%