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 |
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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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