Wydział Chemii

Rafał Petrus

Katarzyna Chomiak

Józef Utko

Magdalena Wilk-Kozubek

Tadeusz Lis

Joanna Cybińska

Piotr Sobota

2020

Inorganic Chemistry

59

8108-8120

10.1021/acs.inorgchem.0c00399

Naukowa

Angielski

Artykuł

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.

Zinc, Physical and chemical processes, Oxides, Materials, Ions

http://dx.doi.org/10.1021/acs.inorgchem.0c00399

https://www.acs.org/content/acs/en.html