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Synthesis, crystal structures, spectral, electrochemical and magnetic properties of di-µ-phenoxido-bridged dinuclear copper(II) complexes with N-salicylidene-2-hydroxybenzylamine derivatives: axial coordination effect of dimethyl sulphoxide molecule

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Abstract

The template reaction of salicylaldehyde and its substituted derivatives and 2-hydroxy-5-bromobenzylamine or 2-hydroxy-5-chlorobenzylamine with copper(II) acetate in dimethyl sulphoxide (dmso) afforded eight dinuclear Cu(II) complexes, [Cu2(L)2(dmso)2] (H2 L = N-salicylidene-2-hydroxy-5-bromobenzylamine, N-salicylidene-2-hydroxy-5-chlorobenzylamine and their 5-bromo, 5-nitro and 5-methyl-substituted salicylidene derivatives). These Cu(II) complexes were characterised by IR and UV-VIS-NIR spectroscopy, electric conductivity, cyclic voltammetry, and temperature dependence of magnetic susceptibilities (4.5–300 K). In the THF solution, the complexes are nonelectrolytes and exhibit a characteristic CT band due to phenoxido-bridging at 360–384 nm. In the cyclic voltammograms, an irreversible reduction process was observed at −1.18–1.54 V vs Fc/Fc+. Single-crystal X-ray crystallography revealed that two Cu(II) ions were bridged by the two phenoxido-oxygen atoms of the two Schiff-base ligands with axial coordination of dmso molecules forming a square pyramid with a Cu-Cu distance of 3.0628(8)–3.0931(6) °A. In accordance with the crystal structures, the magnetic interaction between the two Cu(II) ions is relatively anti-ferromagnetic with −2J value of 386–575 cm−1. The axial coordination effect of the dmso molecule was discussed in relation to the correlation between the Cu-O-Cu angle and the −2J value.

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Authors and Affiliations

  1. Department of Chemistry and Research Centre for Coordination Molecule-based Devices, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, 669-1337, Japan

    Yoshihisa Kakuta, Naoyuki Masuda, Michihiro Kurushima, Takashi Hashimoto, Daisuke Yoshioka & Masahiro Mikuriya

  2. Department of Material and Biological Chemistry, Faculty of Science, Yamagata University, 1-4-12 Kojirakawa, Yamagata, 990-8560, Japan

    Hiroshi Sakiyama

  3. Department of Chemistry, Interdisciplinary Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue, 690-8504, Japan

    Yuya Hiraoka & Makoto Handa

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  1. Yoshihisa Kakuta
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  2. Naoyuki Masuda
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  9. Masahiro Mikuriya
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Correspondence to Masahiro Mikuriya.

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Kakuta, Y., Masuda, N., Kurushima, M. et al. Synthesis, crystal structures, spectral, electrochemical and magnetic properties of di-µ-phenoxido-bridged dinuclear copper(II) complexes with N-salicylidene-2-hydroxybenzylamine derivatives: axial coordination effect of dimethyl sulphoxide molecule. Chem. Pap. 68, 923–931 (2014). https://doi.org/10.2478/s11696-013-0528-0

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