Expanding the Structural Motif Landscape of Heterometallic β-Diketonates: Congruently Melting Ionic Solids.

The first example of ionic β-diketonates in which both the cation and anion are octahedral coordinatively saturated metal diketonate moieties are reported. Heterometallic tin-transition-metal heteroleptic diketonates were obtained through solid-state redox reactions and are formulated as {[Sn(thd)][M(hfac)]} (M = Mn (1), Fe (2), Co (3); thd = 2,2,6,6-tetramethyl-3,5-heptanedionate, hfac = hexafluoroacetylacetonate). X-ray single-crystal structural investigations along with DART mass spectrometry, multinuclear NMR, and magnetic susceptibility measurements have been used to confirm an assignment of metal oxidation states in compounds 1-3.

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.

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 MM'O 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(acac)][Co(hfac)] (1), [Co(hfac)][Fe(acac)][Co(hfac)] (2), and [Fe(hfac)][Fe(acac)][Co(hfac)] (3).

Mixed-Ligand Approach to Changing the Metal Ratio in Bismuth-Transition Metal Heterometallic Precursors.

A new series of heteroleptic bismuth-transition metal β-diketonates [BiM(hfac)3(thd)2] (M = Mn (1), Co (2), and Ni (3); hfac = hexafluoroacetylacetonate, thd = tetramethylheptanedionate) with Bi:M = 1:1 ratio have been synthesized by stoichiometric reactions between homometallic reagents [Bi(III)(hfac)3] and [M(II)(thd)2]. On the basis of analysis of the metal-ligand interactions in heterometallic structures, the title compounds were formulated as ion-pair {[Bi(III)(thd)2](+)[M(II)(hfac)3](-)} complexes. The direct reaction between homometallic reagents proceeds with a full ligand exchange between main group and transition metal centers, yielding dinuclear heterometallic molecules.

Mixed-valent, heteroleptic homometallic diketonates as templates for the design of volatile heterometallic precursors.

A novel series of mixed-valent, heteroleptic transition metal diketonates that can be utilized as prospective single-source precursors for the low-temperature preparation of oxide materials are reported. The first mixed-valent iron β-diketonates with different Fe/Fe ratios have been synthesized by applying the mixed-ligand approach. Based on nearly quantitative reaction yields and analysis of iron-oxygen bonds, these compounds were formulated as [Fe(acac)][Fe(hfac)] () and [Fe(hfac)][Fe(acac)][Fe(hfac)] ().

Mixed-ligand approach to design of heterometallic single-source precursors with discrete molecular structure.

Heterometallic single-source precursors for the Pb/Fe = 1:1 oxide materials, PbFe(β-dik)4 (β-dik = hexafluoroacetylacetonate (hfac, 1), acetylacetonate (acac, 2), and trifluoroacetylacetonate (tfac, 4)), have been isolated by three different solid-state synthetic methods. The crystal structures of heterometallic diketonates 1, 2, and 4 were found to contain polymeric chains built on alternating [Fe(β-dik)2] and [Pb(β-dik)2] units that are held together by bridging M-O interactions. Heterometallic precursors are highly volatile, but soluble only in coordinating solvents, in which they dissociate into solvated homometallic fragments.

Bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)tetrakis(μ4-1,1,1,5,5,5-hexafluoropentane-2,2,4,4-tetraolato)copper(II)octatin(II): a prospective precursor for Cu-doped SnO2 films.

The crystal structure of a tin-rich heterometallic supramolecular product, [CuSn8(C5HF6O2)2(C5H2F6O4)4] or [Sn4(hfpt)2-Cu(hfac)2-Sn4(hfpt)2], (I), is reported (hfpt is the tetraanion of 1,1,1,5,5,5-hexafluoropentane-2,2,4,4-tetraol and hfac is the anion of 1,1,1,5,5,5-hexafluoropentane-2,4-dione). Reaction between tin(II) tetraolate, [Sn4(hfpt)2], and copper(II) β-diketonate, [Cu(hfac)2], was utilized for the preparation of (I). The asymmetric unit consists of the whole [Sn4(hfpt)2] unit and half of a [Cu(hfac)2] unit, with the Cu atom lying on an inversion center.