The research work presented in this thesis investigates the mechanistic details of conventional as well as electrochemically directed self-assembly of alkylthiosulfates and explores the use of conjugated semiconducting polymers for organic electronic applications. Here, the significance of the use of conjugated polymers is twofold; first, to explore their applications in nanoelectronics and second, the possibility of using them as a top contact on the self-assembled monolayers (SAMs) for molecular electronic applications. Throughout this work, deposition of the organic materials was performed on prefabricated device structures that required no further lithographic or metal deposition steps after modification of the electrodes with the organic molecules. Self-assembly of alkylthiosulfates on gold are reported to form monolayers identical to those formed from the corresponding alkanethiols. However, these self-assembly processes follow more complex mechanisms of monolayer formation than originally recognized. Studies on the mechanism of alkylthiosulfate chemisorption on gold shows that the self-assembly process is influenced by electrolyte and solvent. Plausible mechanisms have been proposed for the role of trace water in the solvent on conventional as well as electrochemically assisted self-assembly of alkylthiosulfates on gold. Electroanalytical and spectroscopic techniques have been used to explore the mechanistic details of electrochemically directed self-assembly of alkylthiosulfates on gold. It has been found that the self-assembly process is dynamic under electrochemical conditions and the heterogeneous electron transfer process between the organosulfur compound and gold is mediated through gold surface oxide and accompanied by corrosion. Conducting polymers are serious candidates for organic electronic applications since their properties can be controlled by the manipulation of molecular architecture. Unique electronic properties of conjugated polypyrrole hybrid materials (PPy0DBS-Li+) with immobile dopant anions and mobile cations have been observed and explained on the basis of movement of the cations in an applied electric field. Based on this principle, functioning polymer resistive memory devices have been demonstrated which can be scalable to lower dimensions for nanoelectronics applications. Finally, proof of concept for using a conducting polymer as a top contact in molecular electronic devices created using electrochemically directed self-assembly is demonstrated.

The olefin metathesis reaction has become one of the most powerful carbon-carbon bond forming reaction in synthetic chemistry. This work has expanded the utility of olefin metathesis in metal coordination spheres in three major directions (1) the synthesis and characterization of trans-spanning bis(pyridine)PtCl2 complexes, (2) the developme-adducts of polyacetylene (PA), and (3) the development of regioregular -adducts of poly(phenylene-vinylene) (PPV). Chapter I gives a brief overview of olefin metathesis and previous applications to organometallic substrates. Chapter II details the synthesis of pyridine ligands containing alkenyl substituents, 2-NC5H4(CH2O(CH2)nCH=CH2) (n = 1, 2), 3-NC5H4(CH2O(CH2)nCH=CH2) (n = 1-5, 8, 9), and 3,5-NC5H3(p-C6H4O(CH2)7CH=CH2)2. Metalation of the new ligands with PtCl2 affords the corresponding trans-bis(pyridine)dichloroplatinum complexes, trans-PtCl2(2-NC5H4(CH2O(CH2)nCH=CH2))2 (n = 1, 2), trans-PtCl2(3-NC5H4(CH2O(CH2)nCH=CH2))2 (n = 1-5, 8, 9), and trans-PtCl2(3,5-NC5H3(p-C6H4O(CH2)7CH=CH2))2. Ring-closing metathesefirst generation catalyst followed by hydrogenations with Pd/C afford the title complexes trans-PtCl2-(NC5H4(CH2O(CH2)2n+2OCH2)H4C5N)] (n = 1, 2), trans-PtCl2-(NC5H4(CH2O(CH2)2n+2OCH2)H4C5N)] (n = 4, 8, 9), and trans-PtCl2-(NC5H3(p-C6H4O(CH2)12O-p-C6H4)2H3C5N)]. Reactions with methylmagnesium bromide afford trans-PtCl(CH3)(3-NC5H4(CH2O(CH2)nCH=CH2))2 (n = 2, 8) and trans-PtCl(CH3-(NC5H4(CH2O(CH2)nOCH2)H4C5N)] (n = 10, 18), which feature dipolar rotators. Low temperature NMR spectra in the latter remained facile on the NMR time scale in CDFCl2 at -120 degrees Celsius. Chapter III focuses on the application of ROMP with organometallic monomers to form metal pi-adducts of polyacetylene. The new complex (n4-benzene)Cp*Ir has been synthesized, crystallographically characterized, and evaluated in the ROMP reaction. Monomers (n4-benzene)CpIr, [(n6-COT)CpRu][PF6], and (n4-COT)Fe(CO)3 were also evaluated in the ROMP reaction. ROMP of (?4-benzene)CpIr with Grubbs' first generation catalyst afforded the conductive regioregular polymer CpIr-PA. Chapter IV focuses on the synthesis of the divinyl benzene complexes [Cp*Ir(C6H4(CH=CH2)2)][BF4]2 and [Cp*Ru(C6H4(CH=CH2)2)][OTf] and their polymerization via ADMET to afford PPV systems. Treatment of divinyl benzene ed the conductive regioregular polymers [Cp*Ir-PPV][BF4]2n and [Cp*Ru-PPV][OTf]n. The photophysical properties of the new -metal adducts of PPV exhibit blue-shifts relative to typical PPVs and retain strong UV absorption.

The ideas of Hideo Saito regarding conducting and conducting pedagogy are a valuable addition to the field, an addition that English-speaking people are likely to be unfamiliar with. Besides devising a unique collection of terms for talking about conducting, and assembling a set of exercises designed to facilitate the practice of a variety of gestures, Saito develops and operates from a framework which allows for the description and evaluation of almost any conceivable rhythmic gesture. While he pays attention to time, space, direction, size, and expectations, he often explores the ways velocity and changes in velocity can be employed to elicit desired sounds from players and singers. He is certainly not the first teacher to focus on the role of velocity in conducting gestures. However, the level of sophistication and thoroughness of his examination of velocity, and changes in velocity, is unique. His diagrams are noteworthy as well.Saito's conducting method is very popular in Japan. Seiji Ozawa, the Music Director/Conductor of the Boston Symphony Orchestra for more than 25 years, is just one of Saito's students who have had very successful conducting careers.This dissertation, in combination with accompanying videotaped examples of Morihiro Okabe teaching in the authentic Saito tradition, will provide the reader with an introduction to and an evaluation of the Saito conducting method. The reader will learn how to interpret Saito's diagrams of conducting motions, discover who the key people are, and view a Saito teacher instructing students. The reader will be introduced to the core teachings of Professor Saito, see what Saito's primary musical exercises are, and see how these exercises are used to promote musical and technical competence in conducting. This dissertation seeks to give the reader a foundation for further investigation of Saito's ideas and practices.This dissertation proposes, and employs English names for many gestures Saito labeled in Japanese. The Japanese terms are very descriptive of the motions. Providing equally descriptive English terms should be helpful to readers who are not fluent in Japanese. / School of Music

The research work presented in this thesis investigates the mechanistic details of conventional as well as electrochemically directed self-assembly of alkylthiosulfates and explores the use of conjugated semiconducting polymers for organic electronic applications. Here, the significance of the use of conjugated polymers is twofold; first, to explore their applications in nanoelectronics and second, the possibility of using them as a top contact on the self-assembled monolayers (SAMs) for molecular electronic applications. Throughout this work, deposition of the organic materials was performed on prefabricated device structures that required no further lithographic or metal deposition steps after modification of the electrodes with the organic molecules. Self-assembly of alkylthiosulfates on gold are reported to form monolayers identical to those formed from the corresponding alkanethiols. However, these self-assembly processes follow more complex mechanisms of monolayer formation than originally recognized. Studies on the mechanism of alkylthiosulfate chemisorption on gold shows that the self-assembly process is influenced by electrolyte and solvent. Plausible mechanisms have been proposed for the role of trace water in the solvent on conventional as well as electrochemically assisted self-assembly of alkylthiosulfates on gold. Electroanalytical and spectroscopic techniques have been used to explore the mechanistic details of electrochemically directed self-assembly of alkylthiosulfates on gold. It has been found that the self-assembly process is dynamic under electrochemical conditions and the heterogeneous electron transfer process between the organosulfur compound and gold is mediated through gold surface oxide and accompanied by corrosion. Conducting polymers are serious candidates for organic electronic applications since their properties can be controlled by the manipulation of molecular architecture. Unique electronic properties of conjugated polypyrrole hybrid materials (PPy0DBS-Li+) with immobile dopant anions and mobile cations have been observed and explained on the basis of movement of the cations in an applied electric field. Based on this principle, functioning polymer resistive memory devices have been demonstrated which can be scalable to lower dimensions for nanoelectronics applications. Finally, proof of concept for using a conducting polymer as a top contact in molecular electronic devices created using electrochemically directed self-assembly is demonstrated.

We investigate the newly discovered, superconducting metal-mixed polymers made by embedding a surface layer of metal (a tin-antimony alloy) into a plastic substrate (polyetheretherketone - PEEK). Focusing initially on pre-implanted systems, we show that while the substrate morphology does affect the distribution of metal deposited on the surface, the morphology has no affect on the film's electrical properties. We find that the metal content can be characterised via the film's optical absorption, which along with the conductivity, scales with thickness. By conducting low temperature resistivity measurements we observe that the superconducting critical temperature, $T_c$, remains at that of bulk Sn but the transition broadens with decreasing film thickness. Studying N-implanted metal-mixed polymers, we find that the implant temperature can influence the electrical properties of these systems, as higher implant temperatures result in greater disorder, which in turn causes higher residual resistances and broader superconducting transitions. We observe peaks in the magnetoresistance of superconducting/insulating systems, which we attribute to the competition between superconductivity and weak localisation in a granular network. We determine that the substrate morphology does not influence the electrical properties of implanted systems. We investigate the role sputtering plays by implanting heavier ions (Sn) and show that this technique can be used to overcome the issue of inhomogeneity inherent with using thinner initial films. We study the effect the fabrication parameters of implant dose, beam energy and film thickness have on Sn-implanted metal-mixed polymers and find that with only minor changes in the fabrication conditions, it is possible to tune the conductivities of these materials between a zero-resistance superconducting state, through a metal-insulator transition, to a severely insulating state ($R_s > 10^{10}~\Omega/\Box$). We find that the electrical properties can be further controlled by annealing the samples, and that it is possible to induce optical changes at temperatures approaching the glass transition temperature of PEEK. We demonstrate that metal-mixed polymers are suitable for use in resistance-based temperature sensors by comparing their performance directly against commercially available products and find that the metal-mixed polymers perform at least as well as the commercial models and, indeed, pass the highest industry standards.

Thesis (Ph.D.)--University of Wollongong, 2006. / Typescript. Includes bibliographical references.

Thesis (Ph.D.)--University of Wollongong, 2003. / Typescript. Includes bibliographical references.

Thesis (Ph.D.)--University of Wollongong, 2005. / Typescript. Includes bibliographical references.

Thesis (Ph. D.)--Ohio State University, 2008.

Thesis (M.M.)--University of Texas at El Paso, 2008. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.