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Issue 12, 2011
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Structures and magnetism of {Ni2Na2}, {Ni4} and {Ni6IINiIII} 2-hydroxy-3-alkoxy-benzaldehyde clusters

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Abstract

Three polynuclear complexes, [NiNa(μ1,1,1-N3)(μ-hmb)2(DMF)]2, (1), [Ni43-OMe)4(heb)4(MeOH)1.05(H2O)2.95], (2) and [NiIII(OH)6(hmb)6NiII6]·(ClO4)3 (3) (Hhmb = 2-hydroxy-3-methoxy-benzaldehyde; Hheb = 2-hydroxy-3-ethoxy-benzaldehyde), were prepared by reaction of the appropriate ligand with nickel(II) perchloride hexahydrate under solvothermal conditions. All compounds were characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Compound 1 exhibits a centrosymmetric heterotetranuclear cluster which represents the first nickel complex to possess two connected face-sharing cubes structure {Ni2Na2N2O4}. Compound 2 has a tetranuclear Ni cluster with a cubane topology in which the Ni(II) and the oxygen atoms from the methanol ligands occupying alternate vertices of the cube. Compound 3 consisits of a mixed-valence [NiIII(OH)6(hmb)6NiII6]3+ subunits and it represents the first nickel {NiII6NiIII} complex to possess a planar hexagonal disc-like structure. The results show that the minor ligand modifications or solvent change have a key role in the structural control of the self-assembly process. Magnetic properties of 1–3 in the 300–2 K have been discussed. The {Ni2Na2} (1) and {Ni4} (2) core display dominant ferromagnetic interactions from the nature of the binding modes through μ3-N3 or μ3-OCH3, while {NiII6NiIII} core (3) displays dominant anti-ferromagnetic interactions from the nature of the binding modes through μ3-OH.

Graphical abstract: Structures and magnetism of {Ni2Na2}, {Ni4} and {Ni6IINiIII} 2-hydroxy-3-alkoxy-benzaldehyde clusters

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Publication details

The article was received on 31 Oct 2010, accepted on 12 Jan 2011 and first published on 16 Feb 2011


Article type: Paper
DOI: 10.1039/C0DT01498B
Citation: Dalton Trans., 2011,40, 3000-3007
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    Structures and magnetism of {Ni2Na2}, {Ni4} and {Ni6IINiIII} 2-hydroxy-3-alkoxy-benzaldehyde clusters

    S. Zhang, N. Li, C. Ge, C. Feng and L. Ma, Dalton Trans., 2011, 40, 3000
    DOI: 10.1039/C0DT01498B

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