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Magnetic Properties of a Dinuclear Nickel(II) Complex with
Hiroshi Sakiyama1, Yukako Chiba1, Katsuya Tone1
1Department of Material and Biological Chemistry, Faculty of Science, Yamagata University , 1-4-12 Kojirakawa, Yamagata 990-8560, Japan.
Abstract:
Magnetic properties of dinuclear nickel(II) complex [Ni2(sym-hmp)2](BPh4)2·3.5DMF·0.5(2-PrOH) (1), where (sym-hmp)- is 2,6-bis[(2-hydroxyethyl)methylaminomethyl]-4-methylphenolate anion and DMF indicates dimethylformamide, were investigated using high-frequency and -field electron paramagnetic resonance (HFEPR). To magnetically characterize the mononuclear nickel(II) species forming the dimer, its two dinuclear zinc(II) analogues, [Zn2(sym-hmp)2](BPh4)2·3.5DMF·0.5(2-PrOH) (2) and [Zn2(sym-hmp)2](BPh4)2·2acetone·2H2O (2'), were prepared. One of them (2') was structurally characterized by X-ray diffractometry and doped with 5% mol nickel(II) ions to prepare a mixed crystal 3. From the HFEPR results on complex 1 obtained at 40 K, the spin Hamiltonian parameters of the first excited spin state (S = 1) of the dimer were accurately determined as |D1| = 9.99(2) cm-1, |E1| = 1.62(1) cm-1, and g1 = [2.25(1), 2.19(2), 2.27(2)], and for the second excited spin state (S = 2) at 150 K estimated as |D2| ≈ 3.5 cm-1. From these numbers, the single-ion zero-field splitting (ZFS) parameter of the Ni(II) ions forming the dimer was estimated as |DNi| ≈ 10-10.5 cm-1. The HFEPR spectra of 3 yielded directly the single-ion parameters for DNi = +10.1 cm-1, |ENi| = 3.1 cm-1, and giso = 2.2. On the basis of the HFEPR results, the previously obtained magnetic data (Sakiyama, H.; Tone, K.; Yamasaki, M.; Mikuriya, M. Inorg. Chim. Acta 2011, 365, 183) were reanalyzed, and the isotropic interaction parameter between the Ni(II) ions was determined as J = -70 cm-1 (Hex = -J SA·SB). Finally, density functional theory calculations yielded the J value of -90 cm-1 in a qualitative agreement with the experiment.
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