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Efficient preparation of multimetallic ONO-based Schiff base complexes of nickel(II) and copper(II)

Abstract : A series of symmetrical D-π-D type complexes based on ONO tridentate Schiff base nickel(ii) and copper(ii) building blocks connected by a bidentate conjugated spacer [(R-ONO)M(μ-4,4′-bipy)M(R-ONO)] (M = NiII, R = An = anisyl (1), R = Fc = ferrocenyl (2); M = CuII, R = An (3), R = Fc (4); 4,4′-bipy = 4,4′-bipyridine) have been prepared in 70-85% yield. The four new compounds were characterized by elemental analysis, FT-IR and UV-vis spectroscopy, and by 1H-NMR spectroscopy in the case of the diamagnetic NiII derivatives 1 and 2. The molecular structures of complexes 1-3 were further confirmed by single-crystal X-ray diffraction methods, along with that of the doubly phenoxide-bridged derivative [Cu2(μ-Fc-ONO)2] 5, formed upon dissociation of the 4,4′-bipy spacer from 4. In 1, 2 and 5, the two four-coordinated nickel and copper atoms adopt a square planar geometry, whereas in 3 that forms a coordination polymer through apical Cu-O interactions (dCu-O = 2.411(5) Å) between dimers, the CuII metal ion is five-coordinated in a square pyramidal environment. The electrochemical behavior of compounds 1-4 has also been investigated by cyclic voltammetry. Variable temperature (2-300 K) magnetic susceptibility measurements reveal a weak antiferromagnetic coupling (J = -0.83 cm-1) in 3, and that there is no interaction between the two CuII spins carriers in 4. This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016.
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01367212
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Submitted on : Thursday, September 15, 2016 - 5:17:03 PM
Last modification on : Thursday, March 5, 2020 - 2:05:03 PM

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N. Novoa, T. Roisnel, V. Dorcet, O. Cador, C. Manzur, et al.. Efficient preparation of multimetallic ONO-based Schiff base complexes of nickel(II) and copper(II). New Journal of Chemistry, Royal Society of Chemistry, 2016, 40 (7), pp.5920--5929. ⟨10.1039/c6nj00932h⟩. ⟨hal-01367212⟩

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