| The focus of this investigation was to develop a simple, high-yield synthetic approach to heterometallic diketonates using the same construction principles as for their polynuclear homometallic analogs. Several low-temperature solid-state synthetic routes were suggested that appear to be general for the preparation of heterometallic diketonates incorporating a wide range of s-, p-, d-, and f-metals. Using this investigative approach, two families of bimetallic homoleptic diketonates that contain heavy main group (BiIII, PbII) and the first row divalent transition metals (Mn, Fe, Co, Ni, Cu, and Zn) have been obtained. The heterometallic molecules that are held together by strong Lewis acid-base interactions have been shown to remain intact upon sublimation-deposition procedure as well as in solutions of non-coordinating solvents. Notably, compounds with different structures and metal ratios can be isolated in quantitative yield by using different starting materials.;For the first time, it has been demonstrated that heterometallic beta-diketonates can be utilized as single-source precursors for the synthesis of mixed-metal oxides. The composition and structure of precursors as well as thermolysis conditions have a profound influence on the resulting oxide products. Decomposition of heterometallic diketonates at different temperatures and annealing times affords a variety of main group -- transition metal oxides including those that cannot be obtained by conventional solid state methods.;A fluorinated tetraol, 1,1,1,5,5,5-hexafluoropentane-2,2,4,4-tetraol (H4hfpt), has been introduced as a controlled source of both oxo-groups and beta-diketonate ligands. The first bismuth oxo-diketonate, Bi9 O7(hfac)13, has been isolated and fully characterized. Its subsequent aggregation in solutions of coordinating solvents leads to the formation of a giant bismuth oxo-cluster, Bi38O45(hfac) 24. Preliminary studies on the use of hfpt4- as a tetradentate ligand have been carried out, resulting in a rational synthesis of a novel tetranuclear bismuth complex, Bi4(hfpt)2(hfac) 4(THF)5. |
