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Issue 21, 2002
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Two new hexanuclear iron(III) complexes with S = 5 ground states

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The synthesis and magnetic properties of two new hexanuclear iron complexes [Fe6O2(OH)2(O2CR)10L2] (R = But (3), Me (4); LH = 2-(2-hydroxyethyl)pyridine (hepH) (3), 6-methyl-2-(hydroxymethyl)pyridine (Me-hmpH) (4)) are reported. Both compounds are prepared by treatment of [Fe3O(O2CR)6(H2O)3]+ with three equivalents of LH in MeCN. The X-ray crystal structure of 3·2CHCl3·2H2O is presented. It consists of a planar array of six Fe3+ ions comprising two [Fe33-O)] subunits that are related by an inversion centre and linked at two of their apices, each linkage consisting of one μ-hydroxo and two μ-carboxylato groups. DC magnetic susceptibility measurements at 1.0 and 0.10 Tesla in the 2.0–300 K range show an increase in the effective magnetic moment with decreasing temperature, corresponding to a high spin (S) ground state. The spin of the ground state was established by magnetization measurements in the 1.0–7.0 T field range and 1.7–4.0 K temperature range. Fitting of the reduced magnetization data by full matrix diagonalization, incorporating both axial and rhombic anisotropy, gave S = 5, g = 1.96, D = 0.46 cm−1 and |E| = 0.046 cm−1 for 3, and S = 5, g = 2.07, D = 0.27 cm−1 and |E| = 0 cm−1 for 4. Alternative fits with a negative ZFS were rejected based on their relative fitting error as well as on measurements of the magnetization relaxation behaviour of the complexes at very low temperature (≥0.04 K), where no hysteresis characteristic of a single-molecule magnet was observed.

Graphical abstract: Two new hexanuclear iron(iii) complexes with S = 5 ground states

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The article was received on 20 May 2002, accepted on 13 Aug 2002 and first published on 02 Oct 2002

Article type: Paper
DOI: 10.1039/B204903A
Citation: J. Chem. Soc., Dalton Trans., 2002,0, 4005-4010
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    Two new hexanuclear iron(III) complexes with S = 5 ground states

    C. Cañada-Vilalta, E. Rumberger, E. K. Brechin, W. Wernsdorfer, K. Folting, E. R. Davidson, D. N. Hendrickson and G. Christou, J. Chem. Soc., Dalton Trans., 2002, 0, 4005
    DOI: 10.1039/B204903A

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