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

Abstract

Four bridged-azido Cu(II) complexes were synthesized and structurally characterized: [Cu2(Et3en)2(1,1-N3)2(N3)2] (1), [Cu2(ip2en)2(μ1,1-N3)2(N3)2] (2), catena-[Cu2(Et2Meen)2(1,3-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; ambza = 2-aminobenzylamine. Single crystal X-ray crystallography showed that complexes 1 and 2 are dinuclear with doubly bridged 1,1-N3, whereas 3 and 4 complexes constitute polymeric species with alternative sequence of single and double 1,3-N3 bridges for 3 with 1D chain, and triple 1,1,3-briding azide in 4 with 2D extended structure. Variable temperature magnetic susceptibility over the temperature range 2-298 K revealed weak antiferromagnetic coupling (J = -1.8 cm-1) for 1, and 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)(Cu(1’)]-(-[Cu(2’)(Cu(2’’)]-(-[Cu(1)(Cu(1’)]-… The three different coupling constants have been obtained through fitting procedure and by DFT calculations.

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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, Accepted Manuscript
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    Structure, magnetic properties and DFT calculations of azido copper(II)-diamine complexes with different azido-bonding modes, nuclearity and dimensionality

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

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