Effect of explicit cationic size and valence constraints on the phase stability of 1:2 B-site-ordered perovskite ruthenates

Job T. Rijssenbeek, Takashi Saito, Sylvie Malo, Masaki Azuma, Mikio Takano, Kenneth R. Poeppelmeier

Research output: Contribution to journalArticle

14 Citations (Scopus)


The related parameters of cation size and valence that control the crystallization of Sr3CaRu2O9 into a 1:2 B-site-ordered perovskite structure were explored by cationic substitution at the strontium and calcium sites and by the application of high pressure. At ambient pressures, Sr3MRu2O9 stoichiometries yield multiphasic mixtures for M = Ni2+, Mg2+, and Y 3+, whereas pseudocubic perovskites result for M = Cu2+ and Zn2+. For A-site substitutions, an ordered perovskite structure results for Sr3-xCaxCaRu2O9, with 0 ≤ x ≤ 1.5. In contrast, Ba2+ substitution for Sr2+ is accompanied by a phase change to a hexagonal BaTiO3 structure type. At high pressures and temperatures, a 1:2 B-site-ordered perovskite structure is stabilized for Sr3-xBaxCaRu2O 9, with 0 ≤ x ≤ 3. The scarcity of B-site-ordered perovskite ruthenates at ambient pressure and the metastable nature of the high-pressure phases underscore the strict size and valence requirements that must be met by the constituent cations to achieve these uncommon ordered structures.

Original languageEnglish
Pages (from-to)675-681
Number of pages7
JournalJournal of the American Chemical Society
Issue number2
Publication statusPublished - Jan 19 2005


ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this