Single-molecule magnet behavior in heterometallic MII-Mn III2-MII tetramers (MII = Cu, Ni) containing MnIII salen-type dinuclear core

Chihiro Kachi-Terajima, Hitoshi Miyasaka, Ayumi Saitoh, Naoki Shirakawa, Masahiro Yamashita, Rodolphe Clérac

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54 Citations (Scopus)


The linear-type heterometallic tetramers, [MnIII 2(5-MeOsaltmen)2MII2(L) 2](CF3SO3)2·2H2O (MII = Cu, 1a; Ni, 2a), where 5-MeOsaltmen2- = N,N′-(1,1,2,2-tetramethylethylene) bis(5-methoxysalicylideneiminate), and H2L = 3-{2[(2-hydroxy-benzylidene)-amino]-2-methyl-propylimino}- butan-2-one oxime, have been synthesized and characterized from structural and magnetic points of view. These two compounds are isostructural and crystallize in the same monoclinic P21/n space group. The structure has a [M II-NO-MnIII-(O)2-MnIII-ON-M II] skeleton, where -NO- is a linking oximato group derived from the non-symmetrical Schiff-base complex [MII(L)] and -(O)2- is a biphenolato bridge in the out-of-plane [Mn2(5-MeOsaltmen) 2]2+ dimer. The solvent-free compounds, 1b and 2b, have also been prepared by drying of the parent compounds, 1a and 2a, respectively, at 100°C under dried nitrogen. After this treatment, the crystallinity is preserved, and 1b and 2b crystallize in a monoclinic P21/c space group without significant changes in their structures in comparison to 1a and 2a. Magnetic measurements on 1a and 1b revealed antiferromagnetic Mn III⋯CuII interactions via the oximato group and weak ferromagnetic MnIII⋯MnIII interactions via the biphenolato bridge leading to an ST = 3 ground state. On the other hand, the diamagnetic nature of the square planar NiII center generates an ST = 4 ground state for 2a and 2b. At low temperature, these solvated (a) and desolvated (b) compounds display single-molecule magnet behavior modulated by their spin ground state.

Original languageEnglish
Pages (from-to)5861-5872
Number of pages12
JournalInorganic chemistry
Issue number15
Publication statusPublished - 2007 Jul 23

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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