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Issue 72, 2014
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High nuclearity Ni(II) cages from hydroxamate ligands

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Abstract

The synthesis, structural and magnetic characterisation of a family of Ni(II) cages built from hydroxamate ligands is presented. Two pentanuclear 12-MCNi(II)-4 metallacrowns [Ni5(L1)4(MeOH)4](ClO4)2·2MeOH (1) and [Ni5(L1)4(py)5](ClO4)2·H2O (2) (where L1H2 = 2-(dimethylamino)phenylhydroxamic acid) share analogous, near-planar {Ni5(L1)4}2+ cores, but differ in the number and nature of the ligands located at the axial Ni(II) sites; the addition of pyridine converting square planar Ni(II) ions to square-based pyramidal and octahedral Ni(II) ions, introducing extra paramagnetic metal centres which ‘switch on’ additional magnetic superexchange pathways. Subtle variations in the reaction scheme used to produce complexes 1 and 2 result in both a change of topology and an increase in nuclearity, through isolation of the hepta- and nonametallic complexes [Ni7(L1H)8(L1)2(H2O)6](SO4)·15H2O (3), [Ni9(μ-H2O)2(L2)6(L2H)4(H2O)2](SO4)·29H2O (4) and [Ni9(μ-H2O)2(L2)6(L2H)4(H2O)2](ClO4)2·2MeOH·18H2O (5) (where L2H2 = 2-(amino)phenylhydroxamic acid). Complementary dc magnetic susceptibility studies and DFT analysis indicate dominant antiferromagnetic exchange interactions in 1, 2, 4 and 5, but competing ferro- and antiferromagnetic exchange in 3.

Graphical abstract: High nuclearity Ni(ii) cages from hydroxamate ligands

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Publication details

The article was received on 21 Jun 2014, accepted on 13 Aug 2014 and first published on 13 Aug 2014


Article type: Paper
DOI: 10.1039/C4RA06064D
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RSC Adv., 2014,4, 38182-38191

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    High nuclearity Ni(II) cages from hydroxamate ligands

    C. McDonald, S. Sanz, E. K. Brechin, M. K. Singh, G. Rajaraman, D. Gaynor and L. F. Jones, RSC Adv., 2014, 4, 38182
    DOI: 10.1039/C4RA06064D

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