Journal
INORGANICA CHIMICA ACTA
Volume 491, Issue -, Pages 138-146Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2019.04.005
Keywords
Ni(II) complexes; X-ray structure; Magnetic susceptibility; Zero-field splitting; Magnetostructural D-correlations
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Funding
- Slovak grant agencies [VEGA 1/0534/16, APVV-14-0073]
- UCM
- MSVVaS of the Slovak Republic within the Research and Development Operation Programme for the project University Science Park of STU Bratislava (ITMS project) [26240220084]
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Four novel Ni(II) complexes, [Ni(dppm(O,O))(2)(NCS)(2)](1), [Ni(dppm(O,O))(3)][NiCl4](2), [Ni(dmbpy)(H2O)(2)Br-2] 3 and [Ni (dppm(O,O))(3)][NiCl4]center dot[Ni(dppm)Cl-2] 4 (dppm = bis(diphenylphosphino)methane, dppm(O,O) = bis(diphenylphosphanoxido)methane, dmbpy = 4,4'-dimethyl-2,2'-bipyridine), have been synthesized and structurally and magnetically characterized. Complexes 1 and 3 are routinely pseudooctahedral, while 2 and 4 are unique due to the existence of hexa(-)or tetracoordination in two/three independent Ni(II) atoms. For hexacoordinated systems the magnetic data confirm small magnetic anisotropy expressed through the axial zero-field splitting parameter D/hc = -4.5 to + 4.4 cm(-1). For [NiCl4](2-) tetrahedral units (in complexes 2 and 4) the magnetic anisotropy is substantially larger. Experimental findings have been confirmed by ab initio calculations and forwarded to magnetostructural D-correlations.
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