| Despite the fact that new dimensionally reduced hybrid organic-inorganic compounds have attracted considerable interest due to their unique optical and electronic properties, the rational synthesis of these new materials remains elusive. Here we studied the influence of the major synthetic parameters including temperature, ligand structure, and ligand to metal stoichiometry on the preparation of dimensionally reduced TiS2. One-dimensional TiS2 phases tend to form at high ligand to metal ratios and relatively lower temperatures, while the parent two-dimensional lattices form at higher temperature. The organic ligand structure dictates the temperature window at which a dimensionally reduced phase can be accessed. Although a small change in ligand structure, such as from ethylenediamine, en, to propylenediamine, pn, will significantly influence the stability of these phases, it will only subtly change the electronic structure. By developing a systematic understanding of the effects of various factors during the synthesis, we provide a pathway to rationally create new dimensionally reduced materials.;A second project in this dissertation focuses on the development of a solution phase route towards germanium carbide materials. We hypothesized metal germanium carbide materials could be created via the transmetallation of precursors that contain four C-B(OR)2 bonds with germanium-halogen (Ge-X) bond containing precursors to form networks containing Ge-C bonds. While this chemistry is an essential step in many well known organic reaction pathways, it has not been explored for the synthesis of germanium carbide materials in part due to the lack of commercial availability and the complicated synthesis of the C[B(OR)2]4 precursors. To these ends, we established the synthesis of the tetrasubstituted cyclic boronic ester, tetrakis (1,3 propanediolatoboronate) methane, which we denote as C(B pg)4. We have adapted and improved upon the previously reported route, which utilizes precursors that are not commercially available, and have been able to synthesize this material on the 20 g scale with an overall ~50% yield.;Upon establishing the large scale synthesis of C(Bpg) 4 precursors, we explored whether GeC can be created. GeC has attracted considerable theoretical interest, yet no such phase currently exists. In these experiments we describe the reactions between C(Bpg) 4 with many different germanium precursors across multiple different solvent and temperature conditions. These reactions and subsequent characterizations reveal that an analogous precursor, HC(Bpg)3, generates an amorphous GeCH phase while the C(Bpg)4 precursor does not immediately react and rather forms an oxidized Ge phase. The X-ray diffraction (XRD) of these materials showed no long-range crystallinity, and synchrotron X-ray Pair-distribution function (PDF) identified the presence of Ge-C bonds at 1.86 A in the amorphous GeCH phase in addition to Ge-O bonds at 1.74 A in the GeO2 phase. The Raman analysis showed no crystalline modes in the GeCH phase until annealing above 500 °C, at which point graphite and crystalline germanium modes appear. The lack of direct reactivity between C(Bpg)4 with tetrasubstituted Ge precursors merits the future exploration of base activation procedures.;In summary, the low-temperature solution-phase syntheses of TiS 2(en) and C(Bpg)4 and the progress towards carbides and small-molecule carbide analogues represent progress towards the wider use of solution-phase synthetic methods in order to generate advanced materials. |
