Extension of tetrathiafulvalene conjugation through pyrrollic-based dyes : ExTTF porphyrin and ExTTF BODIPY

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dc.contributor.advisorSessler, Jonathan L.
dc.creatorBill, Nathaniel Lloyden
dc.date.accessioned2014-03-17T20:18:21Zen
dc.date.accessioned2017-05-11T22:47:43Z
dc.date.available2017-05-11T22:47:43Z
dc.date.issued2013-12en
dc.date.submittedDecember 2013en
dc.date.updated2014-03-17T20:18:21Zen
dc.descriptiontexten
dc.description.abstractThe research and development of organic electron donors is essential in the discovery of photodynamic therapy photosensitizers and catalysts, as well as in the fabrication of organic-based electronic devices. Recently, [pi]-extended tetrathiafulvalenes (exTTFs) have emerged as important organic donors due to their superb electronic properties. However, in general, exTTFs lack significant absorption in the visible and near-infrared portions of the electromagnetic spectrum, thereby limiting their utility. This doctoral dissertation depicts the author's efforts to address this inherent drawback of exTTFs by extending the electronic conjugation of tetrathiafulvalene moieties through pyrrole-based chromophores. The reported findings describe the design, synthesis, properties and potential applications of exTTFs with greatly enhanced absorption profiles. The first Chapter provides a brief historical overview on the history and development of [pi]-extended tetrathiafulvalenes. The various conjugated linkers utilized in exTTF systems are reviewed. In the latter part of the Chapter, emphasis is given to the applications in which exTTFs find use. Chapter 2, as the major focus of the dissertation, details the synthesis and characteristics of a quinoidal porphyrin-bridged exTTF, termed MTTFP. Several metalated complexes, including the Zn, Co, Cu, and Ni derivatives of MTTFP are reported. Additionally, the electrochemical, photophysical, and structural properties of MTTFPs are discussed. We also detail our efforts to synthesize and characterize both the one- and two-electron oxidized forms of MTTFPs. Finally, we discuss our efforts to reversibly switch thermodynamic electron transfer from ZnTTFP to Li@Cā‚†ā‚€ through coordination of axial ligands. Chapter 3 describes the formation of a 2:1 supramolecular ionic porphyrin complex between the two-electron oxidized form of ZnTTFP and a tetranionic sulfonated porphyrin. The association constants and the X-ray crystal structure of the complex are reported. A brief discussion outlining the photophysical characteristics (performed in Prof. Shunichi Fukuzumi and Prof. Dongho Kim's group) of the porphyrin donor-acceptor complexes are included. Chapter 4 details the synthesis, photophysical properties, and spectroelectrochemistry of a difluoroboradiazaindacene (BODIPY) bridged exTTF. This compound is referred to as ex-BODIPY. A singlet oxygen generation study provides initial evidence that ex-BODIPY could potentially serve as a photosensitizer. All of the experimental procedures, characterization data, and X-ray crystallographic data tables are reported in Chapter 5.en
dc.description.departmentChemistryen
dc.embargo.lift12/1/2014en
dc.embargo.terms12/1/2014en
dc.format.mimetypeapplication/pdfen
dc.identifier.urihttp://hdl.handle.net/2152/23527en
dc.subjectSolar cellen
dc.subjectOrganic donoren
dc.subjectElectron donoren
dc.subjectTetrathiafulvaleneen
dc.subjectexTTFen
dc.subjectBODIPYen
dc.subjectPorphyrinen
dc.subjectNear infrareden
dc.subjectCharge transferen
dc.titleExtension of tetrathiafulvalene conjugation through pyrrollic-based dyes : ExTTF porphyrin and ExTTF BODIPYen
dc.typeThesisen

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