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Ferromagnetic interactions through end-on azido bridges in a nickel(II) dimer: [Ni2(C15H11N3 )2(H2O)(N3)3]ClO4 .H2O

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5 Author(s)
Cortes, R. ; Dept. de Quimica Inorg., Pais Vasco Univ., Bilbao, Spain ; Lezama, L. ; Rojo, T. ; Karmele Urtiaga, M.
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The crystal structure of [Ni2(C15H11 N3)2-(H2O)(N3)3 ]ClO4.H2O, (C15H11N 3)=2,2':6', 2"-terpyride, has been solved: a=10.179(2), b=10.800(3), c=16.866(6) Å, α=85.54(2), β=78.49(2), γ=72.03(1)°, R=0.055, RW=0.061. It consists of dimeric cations where the two nickel(II) ions are linked through the nitrogen atoms of two azide bridging groups in end-on fashion and ClO 4-anions. Magnetic susceptibility measurements show the existence of ferromagnetic superexchange between the nickel ions. The exchange parameters determined are J=+13.6 cm-1, D=-19.2 cm(-1), Z'J'=0.03 cm-1 and g=2.12. Q-band EPR spectrum shows signals at 525 and 1100 mT values. A theoretical study, by using extended Huckel molecular orbital calculations, shows a minimum of the antiferromagnetic component of the exchange parameter for a bridging angle of 115°

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Magnetics, IEEE Transactions on  (Volume:30 ,  Issue: 6 )