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

Néstor Novoa, Thierry Roisnel, Vincent Dorcet, Olivier Cador, CECILIA CAROLINA MANZUR NAZAL, David Carrillo, Jean René Hamon

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

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.

Original languageEnglish
Pages (from-to)5920-5929
Number of pages10
JournalNew Journal of Chemistry
Volume40
Issue number7
DOIs
StatePublished - 2016
Externally publishedYes

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