Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged ZnII2LnIII2 complexes [(μ4-CO3)2{ZnIIL N ′-Bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato)

Kiyomi Ehama, Yusuke Ohmichi, Soichiro Sakamoto, Takeshi Fujinami, Naohide Matsumoto, Naotaka Mochida, Takayuki Ishida, Yukinari Sunatsuki, Masanobu Tsuchimoto, Nazzareno Re

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Carbonato-bridged ZnII2LnIII2 complexes [(μ4-CO3)2{ZnIIL nLnIII(NO3)}2]·solvent were synthesized through atmospheric CO2 fixation reaction of [Zn IILn(H2O)2]·xH2O, LnIII(NO3)3·6H2O, and triethylamine, where LnIII = GdIII, TbIII, by a spin Hamiltonian including the crystal field effect on the Ln III ions and the LnIII-LnIII magnetic interaction. The Stark splitting of the ground state was so evaluated, and the energy pattern indicates a strong easy axis (Ising type) anisotropy. Luminescence spectra of ZnII2TbIII2 complexes were observed, while those of ZnII2Dy III2 were not detected. The fine structure assignable to the 5D47F6 transition of ZnTb1 and ZnTb2 is in good accord with the energy pattern from the magnetic analysis. The ZnII2LnIII2 complexes (LnIII = TbIII, DyIII) showed an out-of-phase signal with frequency-dependence in alternating current susceptibility, indicative of single molecule magnet. Under a dc bias field of 1000 Oe, the signals become significantly more intense and the energy barrier, Δ/k B, for the magnetic relaxation was estimated from the Arrhenius plot to be 39(1) and 42(8) K for ZnTb1 and ZnTb2, and 52(2) and 67(2) K for ZnDy1 and ZnDy2, respectively.

Original languageEnglish
Pages (from-to)12828-12841
Number of pages14
JournalInorganic Chemistry
Issue number21
Publication statusPublished - Nov 4 2013

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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