Cationic assembly of metal complex aggregates: structural diversity, solution stability, and magnetic properties

Lin, X., Doble, D. M.J., Blake, A. J., Harrison, A., Wilson, C. and Schroder, M. (2003) Cationic assembly of metal complex aggregates: structural diversity, solution stability, and magnetic properties. Journal of the American Chemical Society, 125(31), pp. 9476-9483. (doi:10.1021/ja0341438) (PMID:12889978)

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Abstract

The tetradentate imino-carboxylate ligand [L]2- chelates the equatorial sites of NiII to give the complex [Ni(L)(MeOH)2] in which a NiII center is bound in an octahedral coordination environment with MeOH ligands occupying the axial sites. Lanthanide (Ln) and Group II metal ions (M) template the aggregation of six [Ni(L)] fragments into the octahedral cage aggregates {M[Ni(L)]6}x+ (1:  M = SrII; x = 2, 2:  M = BaII; x = 2, 3:  M = LaIII; x = 3, 4:  M = CeIII; x = 3, 5:  M = PrIII; x = 3, and 6:  M = NdIII; x = 3). In the presence of Group I cations, however, aggregates composed of the alkali metal-oxide cations template various cage compounds. Thus, Na+ forms the trigonal bipyramidal [Na5O]3+ core within a tricapped trigonal prismatic [Ni(L)]9 aggregate to give {(Na5O)⊂[Ni(L)]9(MeOH)3}(BF4)2·OH·CH3OH, 7. Li+ and Na+ together form a mixed Li+/Na+ core comprising distorted trigonal bipyramidal [Na3Li2O]3+ within an approximately anti-square prismatic [Ni(L)]8 cage in {(Na3Li2O)⊂[Ni(L)]8(CH3OH)1.3(BF4)0.7}(BF4)2.3·(CH3OH)2.75·(C4H10O)0.5, 8, while in the presence of Li+, a tetrahedral [Li4O]2+ core within a hexanuclear open cage [Ni(L)]6 in {(Li4O)⊂[Ni(L)]6(CH3OH)3}2ClO4·1.85CH3OH, 9, is produced. In the presence of H2O, the Cs+ cation induces the aggregation of the [Ni(L)(H2O)2] monomer to give the cluster Cs2[Ni(L)(H2O)2]6·2I·4CH3OH·5.25H2O, 10. Analysis by electronic spectroscopy and mass spectrometry indicates that in solution the trend in stability follows the order 1−6 > 7 > 8 ∼ 9. Magnetic susceptibility data indicate that there is net antiferromagnetic exchange between magnetic centers within the cages.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Wilson, Dr Claire
Authors: Lin, X., Doble, D. M.J., Blake, A. J., Harrison, A., Wilson, C., and Schroder, M.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the American Chemical Society
Publisher:American Chemical Society
ISSN:0002-7863
ISSN (Online):1520-5126

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