Synthesis, structures and magnetic properties of two hexanuclear complexes

Chen I. Yang, Kai Hung Cheng, Motohiro Nakano, Gene Hsiang Lee, Hui-Lien Tsai

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19 Citations (Scopus)

Abstract

The reaction of salicylaldoxime (H2salox) with Mn(ClO4)2 · 6H2O, NaN(CN)2 and NEt3 in MeOH affords a MnIII6 hexanuclear complex of [Mn6O2(salox)6(MeOH)6(NCNCONH2)2] (1), while reaction of H2salox with MnCl2 · 4H2O and NEt4OH in EtOH affords a MnIII6 hexanuclear complex of [Mn6O2(salox)6(EtOH)4(H2O)2Cl2] (2). Both complexes 1 and 2 contain a [MnIII63-O)2]14+ core, which is a known structural type in the family of Mn6 complexes. Variable temperature magnetic susceptibilities and magnetization measurement of complexes 1 and 2 have been carried out. Exchange interactions of metal centers for complexes 1 and 2 are fitted by a full diagonalization matrix method. The fitting results indicate that both complexes 1 and 2 have the ground-state spin value of S = 4, and the ground state of complex 1 has the much closer energy to low-lying spin states than that of complex 2. Magnetization measurements at 2.0-4.0 K and 10-70 kG confirm that the ground state is S = 4, with significant magnetoanisotropy as gauged by the D value of -0.82 cm-1 and -1.18 cm-1, for 1 and 2, respectively. The frequency dependence of the out-of-phase component in alternating current magnetic susceptibilities for both complexes 1 and 2 indicates the slow magnetic relaxation of superparamagnetic behaviour with a Ueff of 27.0(1) K and τ0 = 3.8(2) × 10-9 s for complex 1, and Ueff of 25.1(6) K and τ0 = 4.6(1) × 10-8 s for complex 2.

Original languageEnglish
Pages (from-to)1842-1851
Number of pages10
JournalPolyhedron
Volume28
Issue number9-10
DOIs
Publication statusPublished - 2009 Jun 22

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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