Alkaline Earth Metal Zirconate Perovskites MZrO 3 (M=Ba 2+ , Sr 2+ , Ca 2+ ) Derived from Molecular Precursors and Doped with Eu 3+ Ions

• Published in: Chemistry : a European journal 2016-03, Vol.22 (14), p.4780-4788
• Main Authors: Drąg‐Jarząbek, Anna, John, Łukasz, Petrus, Rafał, Kosińska‐Klähn, Magdalena, Sobota, Piotr
• Format: Article
• Language: English
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201504846

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 MZrO 3 (M=Ba 2+ , Sr 2+ , Ca 2+ ). Single‐source molecular precursors [Ba 4 Zr 2 (μ 6 ‐O)(μ 3 ,η 2 ‐OR) 8 (OR) 2 (η 2 ‐HOR) 2 (HOR) 2 Cl 4 ], [Sr 4 Zr 2 (μ 6 ‐O)(μ 3 ,η 2 ‐OR) 8 (OR) 2 (HOR) 4 Cl 4 ], [Ca 4 Zr 2 (μ 6 ‐O)(μ 3 ,η 2 ‐OR) 8 (OR) 2 Cl 4 ], and [Ca 6 Zr 2 (μ 2 ,η 2 ‐OR) 12 (μ‐Cl) 2 (η 2 ‐HOR) 4 Cl 6 ] ⋅ 8 CH 2 Cl 2 were prepared via elimination of the cyclopentadienyl ring from Cp 2 ZrCl 2 as CpH in the presence of M(OR) 2 and alcohol ROH (ROH=CH 3 OCH 2 CH 2 OH) 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 MCl 2 /MZrO 3 mixtures. Leaching of MCl 2 from the raw powder with deionized water produced highly pure perovskite‐like oxide particles of 40–80 nm in size. Luminescence studies on Eu 3+ ‐doped MZrO 3 revealed that the perovskites are attractive host lattices for potential applications in display technology.