Inorganic-organic hybrid materials: Main group halometallate materials and coordination polymers

The field of inorganic-organic hybrid materials has been a rapidly growing field over the past few decades, and many classes of hybrid materials have been synthesized and characterized. Generally, these materials exhibit different chemical or physical properties than the inorganic constituent or the organic constituent alone; and consequently hybrid materials often exhibit new and interesting properties not achievable in strictly inorganic or strictly organic systems. This Thesis concerns the synthesis and physical property measurement of two different classes of inorganic-organic hybrid materials: main group halometallate materials and coordination polymers.; Main group halometallate materials are materials which contain a main group metal halide anionic component ([MnXp] m-, M = main group metal; X = Cl, Br, I) and a charge balancing counter-cation. To date, numerous main group halometallate materials based on diverse main group metals have been synthesized and structurally characterized; and these materials have interested chemists and materials scientists due to their interesting optoelectronic properties and wide structural diversity. With respect to the optical/electronic properties, behavior such as semiconductivity, luminescence, and nonlinear optical activity has been observed. Additionally, with respect to the structural diversity, metal halide anions of various sizes and dimensionalities have been reported. Because of the variation in anion size and dimensionality, dimensionality dependent optical properties (i.e., quantum confinement effects) may be observed in these systems. We have been interested in the synthesis and characterization of main group halometallate materials containing iodobismuthate anions of various sizes and dimensionalities, and we have been successful in the synthesis and structural characterization of a large number of these compounds, which contain either inorganic coordination cations (Chapter 2) or simple organic cations (Chapter 3, Appendix 1) as the charge-balancing species. The room temperature diffuse reflectance UV-visible absorption spectra of several of the new compounds were collected and compared to the spectrum of the starting material, BiI3, in an effort to correlate features of the UV-visible spectra to the size and dimensionality of the inorganic metal halide anion.; Chapters 4-7 of this Thesis concern the synthesis, structural characterization, and physical property measurement of several new 1-, 2-, and 3-dimensional coordination polymers. (Abstract shortened by UMI.)...