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Two W–Mn bimetallic assemblies built by octacyanotungstate(v) and Mn Schiff bases: Molecular structures and a spin-flop transition

Journal of the Chemical Society. Dalton Transactions, ISSN: 1477-9226, Issue: 20, Page: 2070-2076
2007
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  • Citations
    29
    • Citation Indexes
      29
  • Captures
    10

Article Description

Two W–Mn bimetallic compounds, [Mn(Cl-salmen)(HO)]([Mn(5-Clsalmen)(HO)][W(CN)]·2HO (1·2HO) [5-Clsalmen = N, N′-(1-methylethylene)bis(5-chlorosalicylideneiminato) dianion], which contains trinuclear MnW and isolated Mn moieties, and [Mn(3-MeOsalcy)(HO)][W(CN)]·2HO (2·2HO) [3-MeOsalcy = N, N′-(trans-1,2-cyclohexanediylethylene)bis(3-methoxysalicylideneiminato) dianion] molecules were prepared in redox processes and characterized using X-ray analysis and magnetic measurements. Compound 1 is composed of the ([Mn(5-Clsalmen)(HO)][W(CN)]) trimer, in which two CN groups among eight in [W(CN)] bridge W and two Mn ions and the remaining CN ligands are hydrogen-bonded to water molecules or unbound, and the [Mn(Cl-salmen)(HO)] cation. Subsequently, two water molecules of the isolated cation are subject to hydrogen bonds. For 2, there are no covalent bonds among the subunits and six serial stacks of [Mn(3-MeOsalcy)(HO)] units are all hydrogen-bonded. The many hydrogen bonds found in both complexes eventually lead to three-dimensional networks. The magnetic studies for 1 reveal that antiferromagnetic interactions (J = −5.4 cm) between W and Mn centers within the trimer are transmitted via the bridging CN groups. Intermolecular antiferromagnetic couplings (zJ′ = −0.2 cm) are also observed. The static and dynamic magnetic data of 1 demonstrate the existence of a field-induced spin-flop transition occurring among the clusters and monomeric molecules. © 2007 The Royal Society of Chemistry.

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