Position Assignment and Oxidation State Recognition of Fe and Co Centers in Heterometallic Mixed-Valent Molecular Precursors for the Low-Temperature Preparation of Target Spinel Oxide Materials

Abstract

A series of mixed-valent, heterometallic (mixed-transition metal) diketonates that can be utilized as prospective volatile single-source precursors for the low-temperature preparation of M_xM'_3-xO₄ spinel oxide materials is reported. Three iron-cobalt complexes with Fe/Co ratios of 1:1, 1:2, and 2:1 were synthesized by several methods using both solid-state and solution reactions. On the basis of nearly quantitative reaction yields, elemental analyses, and comparison of metal-oxygen bonds with those in homometallic analogues, heterometallic compounds were formulated as [Fe^III(acac)₃][Co^II(hfac)₂] (1), [Co^II(hfac)₂][Fe^III(acac)₃][Co^II(hfac)₂] (2), and [Fe^II(hfac)₂][Fe^III(acac)₃][Co^II(hfac)₂] (3). In the above heteroleptic complexes, the Lewis acidic, coordinatively unsaturated Co^II/Fe^II centers chelated by two hexafluoroacetylacetonate (hfac) ligands maintain bridging interactions with oxygen atoms of acetylacetonate (acac) groups that chelate the neighboring Fe^III metal ion. Preliminary assignment of Fe and Co positions/oxidation states in 1-3 drawn from X-ray structural investigation was corroborated by a number of complementary techniques. Single-crystal resonant synchrotron diffraction and neutron diffraction experiments unambiguously confirmed the location of Fe and Co sites in the molecules of dinuclear (1) and trinuclear (2) complexes, respectively. Direct analysis in real time mass spectrometry revealed the presence of Fe^III- and Co^II-based fragments in the gas phase upon evaporation of precursors 1 and 2 as well as of Fe^III, Fe^II, and Co^II species for complex 3. Theoretical investigation of two possible "valent isomers", [Fe^III(acac)₃][Co^II(hfac)₂] (1) and [Co^III(acac)₃][Fe^II(hfac)₂] (1'), provided an additional support for the metal site/oxidation state assignment giving a preference of 6.48 kcal/mol for the experimentally observed molecule 1. Magnetic susceptibility measurements data are in agreement with the presence of high-spin Fe^III and Co^II magnetic centers with weak anti-ferromagnetic coupling between those in molecules of 1 and 2. Highly volatile heterometallic complexes 1-3 were found to act as effective single-source precursors for the low-temperature preparation of iron-cobalt spinel oxides Fe_xCo_3-xO₄ known as important materials for diverse energy-related applications.