Alkaline Earth Metal Zirconate Perovskites MZrO3 (M=Ba2+, Sr2+, Ca2+) Derived from Molecular Precursors and Doped with Eu3+ Ions

The effect of alkaline earth metal alkoxides on the protonation of zirconocene dichloride was investigated. This approach enabled the design of compounds with preset molecular structures for generating high‐purity binary metal oxide perovskites MZrO₃ (M=Ba²⁺, Sr²⁺, Ca²⁺). Single‐source molecular precursors [Ba₄Zr₂(μ₆‐O)(μ₃,η²‐OR)₈(OR)₂(η²‐HOR)₂(HOR)₂Cl₄], [Sr₄Zr₂(μ₆‐O)(μ₃,η²‐OR)₈(OR)₂(HOR)₄Cl₄], [Ca₄Zr₂(μ₆‐O)(μ₃,η²‐OR)₈(OR)₂Cl₄], and [Ca₆Zr₂(μ₂,η²‐OR)₁₂(μ‐Cl)₂(η²‐HOR)₄Cl₆] ? 8 CH₂Cl₂ were prepared via elimination of the cyclopentadienyl ring from Cp₂ZrCl₂ as CpH in the presence of M(OR)₂ and alcohol ROH (ROH=CH₃OCH₂CH₂OH) as a source of protons. The resulting complexes were characterized by elemental analysis, IR and NMR spectroscopy, and single‐crystal X‐ray diffraction. The compounds were then thermally decomposed to MCl₂/MZrO₃ mixtures. Leaching of MCl₂ from the raw powder with deionized water produced highly pure perovskite‐like oxide particles of 40–80 nm in size. Luminescence studies on Eu³⁺‐doped MZrO₃ revealed that the perovskites are attractive host lattices for potential applications in display technology.