Molecular Level Synthesis of InFeO₃ and InFeO₃/Fe₂O₃ Nanocomposites

New heterometallic In-Fe alkoxides [InFe(OBu)₄(PyTFP)₂] (1), [InFe₂(OPen)₉(Py)] (2), and [InFe₃(OPen)₁₂] (3) were synthesized and structurally characterized. The arrangement of metal centers in mixed-metal framework was governed by the In:Fe ratio and the coordination preferences of Fe(III) and In(III) centers to be in tetrahedral and octahedral environments, respectively. 3 displayed a star-shaped so-called "Mitsubishi" motif with the central In atom coordinated with three tetrahedral {Fe(OPen)₄}^- anionic units. The deterministic structural influence of the larger In atom was evident in 1 and 2 which displayed the coordination of neutral coligands to achieve the desired coordination number. Thermal decomposition studies of compounds 1-3 under inert conditions with subsequent powder diffraction studies revealed the formation of Fe₂O₃ and In₂O₃ in the case of 3 and 2, whereas 1 intriguingly produced elemental In and Fe. In contrary, the thermal decomposition of 1-3 under ambient conditions produced a ternary oxide, InFeO₃, with additional Fe₂O₃ present as a secondary phase in a different stoichiometric ratio predetermined through the In:Fe ratio in 2 and 3. The intimate mixing of different phases in InFeO₃/Fe₂O₃ nanocomposites was confirmed by transmission electron microscopy of solid residues obtained after the decomposition of 1 and 2. The pure InFeO₃ particles demonstrated ferromagnetic anomalies around 170 K as determined by temperature-dependent field-cooled and zero-field-cooled magnetization experiments. A first-order magnetic transition with an increase in the ZFC measurements was explained by temperature-induced reduction of the Fe-Fe distance and the corresponding increase in superexchange.