Doubly phenoxide-bridged binuclear copper(II) complexes with ono tridentate schiff base ligand: Synthesis, structural, magnetic and theoretical studies

摘要

The tridentate ONO-donor Schiff base ligand H2L, derived from the condensation of 1-anisyl-1,3-butane-dione and 2-aminophenol, was generated in situ and reacted with Cu(NO3)(2)center dot 3H(2)O 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)(2)Cu2L2] (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 mu-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 (Delta H 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 aJ 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. (C) 2014 Elsevier Ltd. All rights reserved.