NDLI: Slow Magnetic Relaxation from Hard-Axis Metal Ions in Tetranuclear Single-Molecule Magnets

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Slow Magnetic Relaxation from Hard-Axis Metal Ions in Tetranuclear Single-Molecule Magnets

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Sessoli, Roberta Rodriguez-douton, Maria Jesus Barra, Anne-laure Tancini, Erik Sorace, Lorenzo Cornia, Andrea
Description	Author Affiliation: Tancini E ( Department of Chemistry & INSTM research unit University of Modena and Reggio Emilia, Via G. Campi 183, 41100 Modena, Italy.)
Abstract	We report the synthesis of the novel heterometallic complex $[Fe_{3}Cr(L)_{2}(dpm)_{6}]⋅Et_{2}O$ $(Fe_{3}CrPh)$ (Hdpm=dipivaloylmethane, $H_{3}L=2-hydroxymethyl-2-phenylpropane-1,3-diol),$ obtained by replacing the central iron(III) atom by a chromium(III) ion in an $Fe_{4}$ propeller-like single-molecule magnet (SMM). Structural and analytical data, high-frequency EPR (HF-EPR) and magnetic studies indicate that the compound is a solid solution of chromium-centred $Fe_{3}Cr$ (S=6) and $Fe_{4}$ (S=5) species in an 84:16 ratio. Although SMM behaviour is retained, the \|D\| parameter is considerably reduced as compared with the corresponding tetra-iron(III) propeller (D=−0.179 vs. $−0.418 cm^{−1}),$ and results in a lower energy barrier for magnetisation reversal $(U_{eff}/k_{B}=7.0$ vs. 15.6 K). The origin of magnetic anisotropy in $Fe_{3}CrPh$ has been fully elucidated by preparing its Cr- and Fe-doped $Ga_{4}$ analogues, which contain chromium(III) in the central position (c) and iron(III) in two magnetically distinct peripheral sites (p1 and p2). According to HF-EPR spectra, the Cr and Fe dopants have hard-axis anisotropies with $D_{c}=0.470(5) cm^{−1},$ $E_{c}=0.029(1) cm^{−1},$ $D_{p1}=0.710(5) cm^{−1},$ $E_{p1}=0.077(3) cm^{−1},$ $D_{p2}=0.602(5) cm^{−1},$ and $E_{p2}=0.101(3) cm^{−1}.$ Inspection of projection coefficients shows that contributions from dipolar interactions and from the central chromium(III) ion cancel out almost exactly. As a consequence, the easy-axis anisotropy of $Fe_{3}CrPh$ is entirely due to the peripheral, hard-axis-type iron(III) ions, the anisotropy tensors of which are necessarily orthogonal to the threefold molecular axis. A similar contribution from peripheral ions is expected to rule the magnetic anisotropy in the tetra-iron(III) complexes currently under investigation in the field of molecular spintronics.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	34
Volume Number	16
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2010-09-10
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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