Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Synthesis, Structure and Magnetic Properties of Mn12 Single Molecule Magnet Containing 4-(Methylthio)benzoate as Peripheral Ligands

  • Lim, Jin-Mook (Department of Chemistry, School of Molecular Science BK-21 and Center for Molecular Design and Synthesis, KAIST) ;
  • Do, Young-Kyu (Department of Chemistry, School of Molecular Science BK-21 and Center for Molecular Design and Synthesis, KAIST) ;
  • Kim, Jin-Kwon (Department of Chemistry, Kongju National University)
  • Published : 2005.07.20
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Abstract

$[Mn_{12}O_{12}(O_2CPh-4-SMe)_{16}(H_2O)_4]{\cdot}7CH_2Cl_2$ (1), a new single-molecule magnet complex has been successfully synthesized by substitution of acetate ligand of Mn12ac with 4-(methylthio)benzoic acid. Complex 1 crystallizes into triclinic P$\overline{1}$ with a = 18.321(3) $\AA$, b = 19.011(3) $\AA$, c = 27.230(4) $\AA$, $\alpha$ = 86.973(3)$^{\circ}$, $\beta$ = 76.919(3)$^{\circ}$, $\gamma$ = 87.613(3)$^{\circ}$, and Z = 2. In complex 1, one Mn(III) ion has an abnormal Jahn-Teller elongation axis oriented at an oxide ion. Complex 1 has two out-of-phase ac susceptibility peaks in the 2-4 K and 4-7 K regions. Effective anisotropy energy barrier and pre-exponential factor are $U_{eff}$ = 45.95 K, 1/$\tau$0 = 8.6 ${\times}\;10^9s^{-1}\;for\;{\chi}_M$'' peaks in the lower temperature region and $U_{eff}$ = 59.45 K, 1/$\tau_0$ = 2.2 ${\times}\;10^8\;s^{-1}$ for $\chi_M$'' peaks in the higher temperature region. The parameters of S = 10, g = 1.87, D = -0.40 $cm^{-1}$, and E = 0.00034 $cm^{-1}$ were obtained from the M/N${\mu}_B$ vs. H/T plot of complex 1.

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