Synthesis of (NH₄)₂[X]La₁₋[X]SrX〔Fe(CN)₆〕・nH₂O from two heteronuclear complexes La〔Fe[Ⅲ](CN)₆〕・5H₂O and (NH₄)₂Sr-〔Fe[Ⅱ](CN)₆〕 by mechanochemical process

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  • AONO Hiromichi
    Materials Science and Biotechnology, Graduate School of Science and Engineering, Ehime University
  • KAN Tomoya
    Materials Science and Biotechnology, Graduate School of Science and Engineering, Ehime University
  • ITAGAKI Yoshiteru
    Materials Science and Biotechnology, Graduate School of Science and Engineering, Ehime University
  • YAMAGUCHI Ken-ichi
    Material and Biological Chemistry, Graduate School of Science and Engineering, Yamagata University
  • ITOH Shun
    Material and Biological Chemistry, Graduate School of Science and Engineering, Yamagata University
  • KURIHARA Masato
    Material and Biological Chemistry, Graduate School of Science and Engineering, Yamagata University
  • SAKAMOTO Masatomi
    Material and Biological Chemistry, Graduate School of Science and Engineering, Yamagata University

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  • Synthesis of (NH<sub>4</sub>)<sub>2X</sub>La<sub>1−X</sub>Sr<sub>X</sub>[Fe(CN)<sub>6</sub>]·nH<sub>2</sub>O from two heteronuclear complexes La[Fe<sup>III</sup>(CN)<sub>6</sub>]·5H<sub>2</sub>O and (NH<sub>4</sub>)<sub>2</sub>Sr[Fe<sup>II</sup>(CN)<sub>6</sub>] by mechanochemical process

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A heteronuclear (NH4)2Sr[FeII(CN)6] complex having a tetragonal phase was synthesized from Sr(NO3)2 and (NH4)4[FeII(CN)6]·nH2O. A single phase of the heteronuclear (NH4)2XLa1−XSrX[Fe(CN)6]·nH2O complex was synthesized by the coprecipitation for two heteronuclear hexacyano complexes of La[FeIII(CN)6]·5H2O and (NH4)2Sr[FeII(CN)6]. In this chemical method, the X value (Sr content) for the complex was lower than that of the starting material. This (NH4)2XLa1−XSrX[Fe(CN)6]·nH2O complex was also obtained by a mechanochemical reaction using a planetary ball-mill for two complexes (Total 0.01 mol = ca. 4 g) of (1 − X)La[FeIII(CN)6]·5H2O and X(NH4)2Sr[FeII(CN)6] with a small amount (5 ml) of methanol. The hydration number calculated from the elemental analysis agreed with the estimated values when a hexagonal single (NH4)0.8La0.6Sr0.4[Fe(CN)6]·4.2H2O phase formed for X = 0.4. This reaction for X = 0.4 was also possible for the dry process without methanol. In the case of X > 0.4, the peaks of the SrFe- complex were observed in the XRD pattern. The perovskite phase was directly formed by the thermal decomposition at a low temperature for the milled X = 0.4 complex.

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