The overarching goal of this work is to understand nanometer scale junctions and electron transport through molecules in these junctions. Calculations detailing quantum interference in the electron transport through molecules, and the control of these features, show great potential for use as discrete electronic elements. Concurrent work on the fabrication...
This thesis focuses on the design of hybrid organic materials comprising polymers and small molecules for biodiagnostic and electronic applications. Specifically, the electrochemical and fluorescent signaling properties of terthiophene-functionalized polymers are combined with the enhanced recognition properties of DNA hybrid materials, culminating in the development of a "loaded" probe for...
π-Conjugated oligomeric and polymeric semiconductors have been the focus of intense research over the past few decades as alternatives to inorganic semiconductors for low-cost electronic applications such as organic field-effect transistors (OFETs). These materials enable vapor- or solution-phase fabrication of large-area, light-weight electronic devices, and are compatible with plastic substrates...
This work is a research effort aimed at understanding the mechanisms of single-molecule surface-enhanced Raman spectroscopy (SMSERS). In the decade since its discovery in 1997, the role of resonance Raman (RR) enhancement, the origin of blinking, and the properties of the hot spot formed at the junction of two nanoparticles...
The utilization of hydrofluoric acid for the preparation of silver vanadium oxide fluorides has been advanced for the synthesis of Ag<sub>4</sub>V<sub>2</sub>O<sub>6</sub>F<sub>2</sub> and Ag<sub>3</sub>VO<sub>2</sub>F<sub>4</sub>. Silver-rich metal oxide fluorides are important battery cathode materials due to the high reduction potential of silver vs. Li, which is made even higher by the incorporation...
The new binuclear organo-zirconium and -titanium metal complexes {2,7-di-[(2,6diisopropylphenyl)imino]-1,8-naphthalenediolato group 4 metal complexes {1,8-(O)2C10H4-2,7[CH=N(2,6-iPr2C6H3)]2}Zr2Cl6(THF)2 (FI2-Zr2) and {1,8-(O)2C10H4-2,7-[CH=N(2,6-
i 2 t
Pr2C6H3)]2}Ti2Cl6(THF)2 (FI -Ti2) are compared to the mononuclear analogues {3- Bu-2(O)C6H3CH=N(2,6-iPr2C6H3)}ZrCl3(THF) (FI-Zr1) and {3-tBu-2-(O)C6H3CH=N(2,6-
i
Pr2C6H3)}TiCl3(THF) (FI-Ti1), respectively, in ethylene polymerization and ethylene + olefin copolymerization processes. The comonomers studied...
The safe and efficient storage of hydrogen is possibly the chief obstacle to its use as a fuel on a large scale. Metal-organic frameworks (MOFs) are well poised to provide unique solutions to hydrogen storage, and gas storage in general, a result of their crystalline, porous networks that present the...
Au nanoprisms are a new type of inorganic nanoparticle that is particularly interesting because these particles can be made in high yield, are composed of a metal with well known surface chemistry, exhibit strong, architecture and environment-sensitive optical features, and have well-defined crystallographic facets. All of these features make Au...
The promise of a clean, renewable, and abundant energy supply make the efficient conversion of solar energy to electricity a compelling scientific and societal goal. In the following chapters, I will describe my efforts to advance one class of photovoltaic technology, dye-sensitized solar cells, by demonstration and characterization of unexplored...
The biological antagonism between copper and molybdenum, first observed when cattle developed copper deficiencies after ingesting high levels of plant-born molybdenum, is currently being used in humans to treat two conditions: Wilson's Disease as well as several forms of metastatic cancer. There is surprisingly little known about the interaction of...