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 [LaTi(μ-O)(μ-OEt)(μ-OEt)(OEt)(Cl)(HOEt)] (), [LaZr(μ-O)(μ-OEt)(μ-Cl)(OEt)(HOEt)(Cl)] (), [LaHf(μ-O)(μ-OEt)(μ-Cl)(OEt)(HOEt)(Cl)] (), [NdTi(μ-O)(μ-OEt)(μ-OEt)(OEt)(HOEt)(Cl)] (), [NdZr(μ-O)(μ-OEt)(μ-Cl)(OEt)(HOEt)(Cl)] (), and [NdHf(μ-O)(μ-OEt)(μ-Cl)(OEt)(HOEt)(Cl)] () were synthesized via the reaction of a metallocene dichloride, CpM'Cl (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 - were examined by analytical and spectroscopic techniques and single-crystal X-ray diffraction. The magnetic properties of and were investigated by using direct and alternating current (dc and ac) susceptibility measurements. The results indicated weak antiferromagnetic interactions between Nd ions and a field-supported slow magnetic relaxation. Lanthanum-titanium compound decomposed at 950 °C to give the perovskite compound LaTiO and small amounts of rutile TiO. Under the same conditions, decomposed to give a mixture of NdTiO and NdTiO. When was calcined at 1300 °C, decomposition of NdTiO to NdTiO and TiO was observed. Calcination of , , , and at 950-1500 °C led to the selective formation of heterometallic LaZrO, LaHfO, NdZrO, and NdHfO phases, respectively.