Ferromagnetic Exchange Coupling in a Family of Mn<sup>III</sup> Salen-Type Schiff-Base Out-of-Plane Dimers

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  • Chihiro Kachi-Terajima
    Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan
  • Rikako Ishii
    Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan
  • Yoshiaki Tojo
    Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan
  • Masato Fukuda
    Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan
  • Yasutaka Kitagawa
    Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan
  • Mizuki Asaoka
    Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan
  • Hitoshi Miyasaka
    Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan

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説明

A series of MnIII saltmen dimers, [Mn2(5-Rsaltmen)2(X)2](A)2n (saltmen2– = N,N′-(1,1,2,2-tetramethylethylene)bis(salicylideneiminate); R = H, Cl, Br, MeO, Me; X = H2O, ReO4–, NO3–, N3–, NCS–, A– = ClO4–, PF6–, CF3SO3– for X = H2O) were synthesized and structurally and magnetically investigated to understand the correlation between their intradimer ferromagnetic (FM) interaction and single-molecule magnet (SMM) behavior. All complexes had a similar di-μ-phenolate-bridged out-of-plane dimer structure but displayed different bridging Mn–Oph* distances depending on the R substituents of the saltmen ligand and axial X ligand. Magnetic susceptibility studies revealed intradimer FM coupling (JMn–Mn*), resulting in an ST = 4 ground state for all dimers. However, the magnitude of FM coupling strongly depended on R and X. JMn–Mn* increased with decreasing Mn–Oph* distance but decreased with decreasing Mn–X distance with a relation of H2O ≈ ReO4– > NO3– > N3– ≈ NCS– with a linear trend for R = H, Cl, Me but not for ...

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