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Issue 17, 2014
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Triple-bridged ferromagnetic nickel(II) complexes: A combined experimental and theoretical DFT study on stabilization and magnetic coupling

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Abstract

Two dinuclear [Ni2L2(o-(NO2)C6H4COO)2(H2O)] (1), [Ni2L2(p-(NO2)C6H4COO)2(H2O)]·0.5CH3OH (2) complexes and one trinuclear [Ni3L2(p-(NO2)C6H4COO)4]·C2H5OH (3) Ni(II) complex have been synthesized using a tridentate Schiff base ligand, 1-[(3-dimethylamino-propylimino)-methyl]-naphthalen-2-ol (HL) along with ortho- and para-nitro benzoate as co-ligands. All these three (1–3) complexes have been characterized by spectral analysis, X-ray crystallography and variable temperature magnetic susceptibility measurements. The structural analyses reveal that complexes 1 and 2 are dinuclear in which two μ2-phenoxido and a water molecule bridge the two Ni(II) centers to make the complexes face sharing bioctahedra. Complex 3 is a linear triple bridged (phenoxido and carboxylato) trinuclear Ni(II) complex. Variable-temperature magnetic susceptibility studies indicate the presence of ferromagnetic exchange coupling in complexes 1–3 with J values of 25.4, 28.1 and 6.2 cm−1 respectively. Theoretically obtained J values of 21.4 cm−1 (for 1), 22.0 cm−1 (for 2) and 9.3 cm−1 (for 3) corroborate very well the experimental results. DFT calculation also shows that stronger H-bonding interactions present in the case of carboxylate based coligands stabilise the triple oxido-bridged complexes.

Graphical abstract: Triple-bridged ferromagnetic nickel(ii) complexes: A combined experimental and theoretical DFT study on stabilization and magnetic coupling

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Publication details

The article was received on 03 Oct 2013, accepted on 04 Feb 2014 and first published on 06 Feb 2014


Article type: Paper
DOI: 10.1039/C3DT52764F
Citation: Dalton Trans., 2014,43, 6455-6467
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    Triple-bridged ferromagnetic nickel(II) complexes: A combined experimental and theoretical DFT study on stabilization and magnetic coupling

    R. Biswas, C. Diaz, A. Bauzá, M. Barceló-Oliver, A. Frontera and A. Ghosh, Dalton Trans., 2014, 43, 6455
    DOI: 10.1039/C3DT52764F

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