2D-3D Transformation of Layered Perovskites through Metathesis: Synthesis of New Quadruple Perovskites A2La2CuTi3O 12 (A = Sr, Ca)

T. Sivakumar, K. Ramesha, S. E. Lofland, K. V. Ramanujachary, G. N. Subbanna, J. Gopalakrishnan

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We describe the synthesis of two new quadruple perovskites, Sr 2La2CuTi3O12 (I) and Ca 2La2CuTi3O12 (II), by solid-state metathesis reaction between K2La2Ti3O 10 and A2CuO2Cl2 (A = Sr, Ca). I is formed at 920 °C/12 h, and II, at 750 °C/24 h. Both the oxides crystallize in a tetragonal (P4/mmm) quadruple perovskite structure (a = 3.9098- (2) and c = 15.794(1) Å for I; a = 3.8729(5) and c = 15.689(2) Å for II). We have determined the structures of I and II by Rietveld refinement of powder XRD data. The structure consists of perovskite-like octahedral CuO4/2O2/2 sheets alternating with triple octahedral Ti3O18/2 sheets along the c-direction. The refinement shows La/A disorder but no Cu/Ti disorder in the structure. The new cuprates show low magnetization (0.0065 μB for I and 0.0033 μ B for II) suggesting that the Cu(II) spins are in an antiferromagnetically ordered state. Both I and II transform at high temperatures to 3D perovskites where La/Sr and Cu/Ti are disordered, suggesting that I and II are metastable phases having been formed in the low-temperature metathesis reaction. Interestingly, the reaction between K2-La 2Ti3O10 and Ca2CuO 2Cl2 follows a different route at 650 °C, K 2La2Ti3O10 + Ca2CuO 2Cl2 → CaLa2Ti3O10 + CaCuO2 + 2KCl, revealing multiple reaction pathways for metathesis reactions.

Original languageEnglish (US)
Pages (from-to)1857-1864
Number of pages8
JournalInorganic Chemistry
Issue number6
StatePublished - Mar 22 2004

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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