Doubly phenoxide-bridged binuclear copper(II) complexes with ono tridentate schiff base ligand: Synthesis, structural, magnetic and theoretical studies Dedicated to Dr. Claude Lapinte for his outstanding contribution to organometallic molecular wires.

Néstor Novoa, Frédéric Justaud, Paul Hamon, Thierry Roisnel, Olivier Cador, Boris Le Guennic, Carolina Manzur, David Carrillo, Jean René Hamon

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26 Scopus citations

Abstract

The tridentate ONO-donor Schiff base ligand H2L, derived from the condensation of 1-anisyl-1,3-butanedione and 2-aminophenol, was generated in situ and reacted with Cu(NO3)2·3H2O to yield two doubly phenoxo bridged di-copper(II) complexes depending on the nitrogenous base used. [Cu2L2] (1) is obtained in 85% and 75% yield in the presence of pyridine or 4-picoline, respectively, and [(py-tBu)2Cu2L2] (2) is isolated in 75% yield in the presence of 4-tert-butylpyridine. Compounds 1 and 2 were characterized in the solid-state by elemental analysis and FT-IR spectroscopy. Single crystal X-ray diffraction study reveals that in 1 the two four-coordinated copper atoms adopt a square planar geometry, whereas in 2 each Cu(II) metal ion shows a five coordinate square pyramidal (ONO,N + O) geometry. In each dimer, two μ-phenolic oxygen atoms bridge the two half-units forming a planar Cu2O2 core. EPR studies in fluid solutions indicate that the dimeric structure of 1 and 2 is destroyed upon dissolution. In the solid-state, 1 is EPR silent, whereas 2 presents an unresolved broad resonance (ΔH peak-to-peak = 71.5 G) with g = 2.071 at 298 K, along with the triplet state (S = 1) signature at g = 4.181. Variable temperature (2-300 K) magnetic susceptibility measurements exhibit strong antiferromagnetic interactions between the Cu(II) centers with a J value of -397 cm-1 for 1, while no interaction operates between the two spins localized on Cu(II) metal ions in 2. Ab initio calculations were also performed to supplement the experimental results.

Original languageEnglish
Pages (from-to)81-88
Number of pages8
JournalPolyhedron
Volume86
DOIs
StatePublished - 28 Jan 2015
Externally publishedYes

Keywords

  • Ab initio calculation
  • Copper(II)
  • Magnetic properties
  • ONO
  • Schiff base ligand
  • Structure determination
  • Tridentate

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