Convenient Route to Heterometallic Group 4-Zinc Precursors for Binary Oxide Nanomaterials

In this study, simple and efficient synthetic routes to a family of uncommon group 4-zinc heterometallic alkoxides were developed. Single-source molecular precursors with the structures [Cp₂TiZn(μ,η-OR)(THF)Cl₂] (1), [Zr₃Zn₇(μ₃-O)(μ₃,η²-OR)₃(μ-OH)₃(μ,η²-OR)₆(μ,η-OR)₆Cl₆] (2), and [Hf₃Zn₇(μ₃-O)(μ₃,η²-OR)₃(μ-OH)₃(μ,η²-OR)₆(μ,η-OR)₆Cl₆] (3) were prepared via reduction of Cp₂TiCl₂ with metallic zinc or protonolysis of the metal-cyclopentadienyl bond in Cp₂M'Cl₂ (M' = Zr or Hf) in the presence of 2-methoxyethanol (ROH) and Zn(OR)₂. This synthetic route enables the creation of compounds with well-defined molecular structures and therefore provides precursors suitable for obtaining group 4-zinc oxides. Precursors 1-3 were characterized by elemental analysis, nuclear magnetic resonance and infrared spectroscopies, and single-crystal X-ray diffraction. Compound 1 decomposed at 800-900 °C to give a mixture of binary metal oxides (i.e., Zn₂Ti₃O₈, ZnTiO₃, or Zn₂TiO₄) and common polymorphs of TiO₂ and ZnO. After calcination at 1000 °C, only TiO₂ and the high-temperature-stable phase Zn₂TiO₄ were observed. Thermolysis of compounds 2 and 3 gave mixtures of ZnO and ZrO₂ or HfO₂, respectively. The obtained ZnO-ZrO₂ and ZnO-HfO₂ mixed oxide materials have constant phase compositions across a broad temperature range and therefore are attractive host lattices for Eu³⁺ for applications as yellow/red double-light-emitting phosphors. It was established that Eu³⁺ ions were successfully introduced into the ZnO and ZrO₂/HfO₂ lattices. It was revealed that Eu³⁺ ions prefer to occupy low-symmetry sites in ZrO₂/HfO₂ rather than in ZnO.