Molecular Level Synthesis of InFeO3 and InFeO3/Fe2O3 Nanocomposites

New heterometallic In-Fe alkoxides [InFe-((OBu)-Bu-t)(4)(PyTFP)(2)] (1), [InFe2(O(neo)Pen)(9)(Py)] (2), and [InFe3(O(neo)Pen)(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 socalled Mitsubishi motif with the central In atom coordinated with three tetrahedral {Fe(O(neo)Pen)(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.

Automated summary

New heterometallic In-Fe alkoxides were synthesized and characterized, showing different metal center arrangements and thermal decomposition behaviors. Transmission electron microscopy and magnetic measurements confirmed the properties of nanocomposites and ferromagnetic anomalies in pure InFeO3 particles.