Heterometallic Group 4-Lanthanide Oxo-alkoxide Precursors for Synthesis of Binary Oxide Nanomaterials

In this study, an efficient procedure for the synthesis of uncommon group 4-lanthanide oxo-alkoxide derivatives was developed. Heterometallic clusters with the structures [La₂Ti₄(μ₄-O)₂(μ₃-OEt)₂(μ-OEt)₈(OEt)₆(Cl)₂(HOEt)₂] (1), [La₂Zr₂(μ₃-O)(μ-OEt)₅(μ-Cl)(OEt)₂(HOEt)₄(Cl)₄] (2), [La₂Hf₂(μ₃-O)(μ-OEt)₅(μ-Cl)(OEt)₂(HOEt)₄(Cl)₄] (3), [Nd₂Ti₄(μ₄-O)₂(μ₃-OEt)₂(μ-OEt)₈(OEt)₆(HOEt)₂(Cl)₂] (4), [Nd₄Zr₄(μ₃-O)₂(μ-OEt)₁₀(μ-Cl)₄(OEt)₈(HOEt)₁₀(Cl)₂] (5), and [Nd₄Hf₄(μ₃-O)₂(μ-OEt)₁₀(μ-Cl)₄(OEt)₈(HOEt)₁₀(Cl)₂] (6) were synthesized via the reaction of a metallocene dichloride, Cp₂M'Cl₂ (where M' = Ti, Zr, and Hf), and metallic lanthanum or neodymium in the presence of excess ethanol. This procedure gave crystalline precursors with molecular stoichiometries suitable for obtaining group 4-lanthanide oxide materials. Compounds 1-6 were examined by analytical and spectroscopic techniques and single-crystal X-ray diffraction. The magnetic properties of 5 and 6 were investigated by using direct and alternating current (dc and ac) susceptibility measurements. The results indicated weak antiferromagnetic interactions between Nd^III ions and a field-supported slow magnetic relaxation. Lanthanum-titanium compound 1 decomposed at 950 °C to give the perovskite compound La_0.66TiO₃ and small amounts of rutile TiO₂. Under the same conditions, 4 decomposed to give a mixture of Nd₄Ti₉O₂₄ and Nd_0.66TiO₃. When 4 was calcined at 1300 °C, decomposition of Nd₄Ti₉O₂₄ to Nd_0.66TiO₃ and TiO₂ was observed. Calcination of 2, 3, 5, and 6 at 950-1500 °C led to the selective formation of heterometallic La₂Zr₂O₇, La₂Hf₂O₇, Nd₂Zr₂O₇, and Nd₂Hf₂O₇ phases, respectively.