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Issue 4, 2018
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Structure, magnetic properties and DFT calculations of azido-copper(II) complexes with different azido-bonding, nuclearity and dimensionality

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Abstract

Four bridged-azido Cu(II) complexes were synthesized and structurally characterized: [Cu2(Et3en)21,1-N3)2(N3)2] (1), [Cu2(ip2en)21,1-N3)2(N3)2] (2), catena-[Cu2(Et2Meen)21,3-N3)3]ClO4 (3) and catena-[Cu(ambza)(μ1,1,3-N3)2] (4), where Et3en = N,N,N′-triethyl-1,2-diaminoethane; ip2en = N,N′-diisopropyl-1,2-diaminoethane; Et2Meen = N,N-diethyl-N′-methyl-1,2-diaminoethane; and ambza = 2-aminobenzylamine. Single crystal X-ray crystallography revealed that complexes 1 and 2 are dinuclear with doubly bridged μ1,1-N3, whereas complexes 3 and 4 constitute polymeric species with an alternative sequence of single and double μ1,3-N3 bridges for 3 with a 1D chain, and triple μ1,1,3-bridging azide in 4 with a 2D extended structure. Variable temperature magnetic susceptibilities over the temperature range of 2–298 K revealed a weak antiferromagnetic coupling (J = −1.8 cm−1) for 1, and a ferromagnetic coupling with J values of 7.0 and 7.7 cm−1, respectively, for complexes 2 and 4, respectively. Compound 3 shows a new topology for Cu(II) alternating chains [Cu(1)(μ1,3-N3)2Cu(1′)]-(μ1,3-N3)-[Cu(2′)(μ1,3-N3)2Cu(2′′)]-(μ1,3-N3)-[Cu(1)(μ1,3-N3)2Cu(1′)]-… Three different coupling constants were obtained through a fitting procedure and by DFT calculations.

Graphical abstract: Structure, magnetic properties and DFT calculations of azido-copper(ii) complexes with different azido-bonding, nuclearity and dimensionality

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Publication details

The article was received on 26 Oct 2017, accepted on 06 Jan 2018 and first published on 08 Jan 2018


Article type: Paper
DOI: 10.1039/C7NJ04150K
Citation: New J. Chem., 2018,42, 2627-2639
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    Structure, magnetic properties and DFT calculations of azido-copper(II) complexes with different azido-bonding, nuclearity and dimensionality

    S. S. Massoud, M. M. Henary, L. Maxwell, A. Martín, E. Ruiz, R. Vicente, R. C. Fischer and F. A. Mautner, New J. Chem., 2018, 42, 2627
    DOI: 10.1039/C7NJ04150K

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