Structural Design of Coordination Polymers Based on Manganese and Chromium Ions Bridged by Oxalate Ligands

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Abstract

Coordination polymers based on oxalate-bridged {[Mn<sup>II</sup>Cr<sup>III</sup>(oxalate)<sub>3</sub>]<sup>−</sup>}<sub>∞</sub> complexes of (DAT-2H<sup>2+</sup>)(DCH[18]crown-6)<sub>2</sub>[Mn<sup>II</sup>(CH<sub>3</sub>OH)Cr<sup>III</sup>(oxalate)<sub>3</sub>]<sup>−</sup><sub>2</sub>(CH<sub>3</sub>OH)<sub>3</sub> and (DABCO-H<sup>+</sup>)<sub>2</sub>(DABCO-2H<sup>2+</sup>)[Mn<sup>II</sup>(CH<sub>3</sub>OH)(Cl<sup>−</sup>)Cr<sup>III</sup>(oxalate)<sub>3</sub>]<sup>2−</sup><sub>2</sub>(CH<sub>3</sub>OH), where DAT, DABCO, and DCH[18]crown-6 denote 2,5-diaminotoluene, 1,4-diazabicyclo[2.2.2]octane, and <i>cis</i>-<i>syn</i>-<i>cis</i>-dicyclohexano[18]crown-6, respectively, were synthesized. The crystal structure of the former complex was composed of [Mn<sup>II</sup>(Λ)(CH<sub>3</sub>OH)Cr<sup>III</sup>(Λ)(oxalate)<sub>3</sub>]<sup>−</sup> units, whereas that of the latter crystal was composed of [Mn<sup>II</sup>(Λ)(CH<sub>3</sub>OH)(Cl<sup>−</sup>)Cr<sup>III</sup>(Δ)(oxalate)<sub>3</sub>]<sup>2−</sup> units. The large flexible supramolecular cation in the former provided the two-dimensional structure of [Mn<sup>II</sup>(Λ)(CH<sub>3</sub>OH)Cr<sup>III</sup>(Λ)(oxalate)<sub>3</sub>]<sup>−</sup>, although the two-dimensional honeycomb structure of the {[Mn<sup>II</sup>(Δ)Cr<sup>III</sup>(Λ)(oxalate)<sub>3</sub>]<sup>−</sup>}<sub>∞</sub> and {[Mn<sup>II</sup>(Λ)Cr<sup>III</sup>(Δ)(oxalate)<sub>3</sub>]<sup>−</sup>}<sub>∞</sub> networks are often observed for the oxalate complexes. The round-shaped DABCO molecule in the latter induced a one-dimensional chain structure of [Mn<sup>II</sup>(Λ)(CH<sub>3</sub>OH)Cr<sup>III</sup>(Δ)(oxalate)<sub>3</sub>]<sup>−</sup>. The former crystal showed a magnetic field dependence of magnetization typical for a spin-canting system.

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 89(3), 354-360, 2016

    The Chemical Society of Japan

Codes

  • NII Article ID (NAID)
    130005137575
  • NII NACSIS-CAT ID (NCID)
    AA00580132
  • Text Lang
    ENG
  • ISSN
    0009-2673
  • NDL Article ID
    027165363
  • NDL Call No.
    Z53-B35
  • Data Source
    NDL  J-STAGE 
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