<p>This thesis deals with the synthesis of new organicmaterials for electronic applications. Several new ring-formingmethods are employed to construct sulphur heterocycles: Tandemelectrophilic aromatic substitution and acid-catalyzedtransetherification of methoxythiophene, double electrophilicaromatic substitutions with ethane-1, 2-disulphenyl chloride,and also, the reaction of dienes with sulphur dichloride. Twonew condensed thiophenes have been incorporated in end-cappedoligothiophenes. An improvement of the synthesis of [3,2-b:2’, 3-d]thiophene is reported, with some attempts toincorporate it in oligomers. A synthesis of substitutednaphthalenes is also described. A new method of producingdisubstituted thiophenes from substituted butadienes anssulphur dichloride is employed in a new route to 3, 4-ethylenedioxythiophene, a very important monomer for conductingpolymers.</p><p><b>Keywords :</b>Organic Semiconductors, Thiophenes,Heterocyclic Synthesis, Dithienothiophene, Naphthalene,Ethylenedioxythiophene</p>

Thesis (Ph.D.)--University of Nebraska-Lincoln, 2007. / Title from title screen (site viewed Dec. 4, 2007). PDF text: x, 362 p. : ill. ; 13 Mb. UMI publication number: AAT 3271933 . Includes bibliographical references. Also available in microfilm and microfiche formats.

Thesis (Ph. D.)--Oregon State University, 2009. / Printout. Includes bibliographical references (leaves 142-148). Also available on the World Wide Web.

Thesis (Ph.D)--Chemical Engineering, Georgia Institute of Technology, 2009. / Committee Chair: J. Carson Meredith; Committee Member: Hang Lu; Committee Member: Joseph Schork; Committee Member: William Koros; Committee Member: Yadong Wang. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2009. / Committee Chair: Marder, Seth; Committee Member: Bredas, Jean-Luc; Committee Member: Collard, David; Committee Member: Kippelen, Bernard; Committee Member: Tolbert, Laren. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Thesis (Ph.D.(Chemistry))--University of Pretoria, 2000. / Includes abstract in English and Afrikaans. Includes bibliographical references. Also available online.

Thesis (Ph. D.)--Columbia University, 1922. / Vita. Bibliography: p. [29]-30.

Thesis (Ph. D.)--University of Washington, 2006. / Vita. Includes bibliographical references (leaves 118-129).

xxi, 294 p. ill. (some col.) A print copy of this title is available through the UO Libraries under the call number: SCIENCE QD403.O23 2008 / Highly conjugated carbon-rich systems have demonstrated many attractive applications for fundamental and materials science applications, including--but not limited to--probes for aromaticity, charge-transfer complexes, conducting/semi-conducting materials, linear/nonlinear optical materials, and solar cells. The bulk of this research has focused on carbon-rich fullerenes, conjugated polymers, or polycyclic aromatic hydrocarbons; however, with recent developments in cross-coupling chemistry, carbon rich chemistry, particularly dehydrobenzo[ n ]annulenes (DBAs), has grown to yield molecules of great diversity and utility. Concurrently, materials based on conjugated heterocycles have been developed and display similar and often enhanced properties to the aforementioned carbon rich systems. The lone pair of the heterocycle often adds additional stability and polarizablity, creating novel and tunable molecules. Assimilating techniques used to produce DBAs with heteroaromatic molecules, our work has afforded a novel class of conjugated macrocycles with the highly tunable optical-electronic properties of a DBA system. That in turn has led to the systematic study of the diverse structure-property relationships of the thiophene/DBA hybrids reported herein. Chapter I details the synthetic advances in the field of DBA chemistry. The first section discusses the methods of synthesis, inter- vs. intra- molecular approaches, while the remaining sections provide current examples of the DBAs reported. Chapter II briefly discuses conjugated thiophene chemistry, then describes the advantages of utilizing planarized thiophenes. Several examples of thiophene macrocycles are reviewed: both planar and nonplanar. Particular attention in the review focuses on synthesis, optical properties, and some redox properties. Chapters III and IV detail the synthesis and analysis of thiophenes locked into [14]- and [15]annulene scaffolds, respectively. The dehydrothieno[14]annulenes (DTAs) and DTA/DBA hybrids of chapter III serve as aromatic probes and show significant tunabilty with respect to the number and orientation of the thiophenes. Chapter IV's dehydrobenzo[15]annulenes, which are comprised of a cross-conjugated system, also display a structure-property relationship where the optical properties encompass a wider dispersion of wavelengths. Chapter IV also explores the incorporation of pyridines and the affects on conjugation. The electronic properties of the macrocycles were explored using NMR, UV-Vis absorption and fluorescence spectroscopy, and electrochemically (cyclic voltammetry). Chapter V is devoted to further functionalization of DTAs through alkylation and further cycliziation to yield planarized terthiophene units. This dissertation includes my previously published and co-authored material. / Adviser: Michael M. Haley

Two separate aspects involving the thiophenes of the Tageteae (Asteraceae) were investigated. The first concerned the distribution of four thiophenes in Tagetes patula L. which were examined by high pressure liquid chromatography (HPLC). The derivatives were found to be differentially distributed throughout hydroponically grown plants. The predominant thiophenes in roots were 5-(4-acetoxy-1-butenyl)-2,2'-bithienyl (BBT-OAc) and 5-(buten-3-ynyl)-2,2'-bithienyl (BBT). BBT-OAc was the main derivative in shoots, whereas 2,2':5',2''-terthienyl (alpha-T) was the major compound in flower petals. BBT and one unidentified compound were found to occur in leaf glands. The levels of BBT-OAc in shoots and BBT-OAc and BBT in roots increased over the life of the plant and reached a plateau following flowering. Alpha-T in roots and both alpha-T and BBT in shoots remained at low levels over the life of the plant while 5-(4-hydroxy-1-butenyl)-2,2'-bithienyl (BBT-OH) was found to be an minor component of roots or shoots. Fourteen species from four genera of the tribe Tageteae were also screened for the presence of thiophenes by HPLC. Representatives of Dyssodia, Porophyllum, and Tagetes all contained thiophenes, but none were detected in species of Pectis. The second part of this study concerned the photobiocidal effects of isolated thiophenes on Escherichia coli B which was used as a model biological system. Alpha-terthienyl (alpha-T), in the presence of UV-A irradiation (320nm-400nm), was found to be a Type II photosensitizer which required oxygen for the expression of biological activity. Scavenger studies with sodium azide and BHT suggested that both singlet oxygen and superoxide were generated by the photosensitized reaction. Cellular inactivation by alpha-T was sensitive to temperature and studies with recombination deficient mutants of E. coli K-12 did not indicate that damage to cellular DNA occurred. Proteins were found to be substantially affected by the photoactivated reaction. SDS-gel electrophoresis revealed that both cytoplasmic and membrane-associated proteins might be. crosslinked following treatment with alpha-T and UV-A. / Science, Faculty of / Botany, Department of / Graduate