Browsing by Subject "BODIPY"
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Item Electrochemical and electrogenerated chemiluminescence studies of the BODIPY dyes(2011-08) Nepomnyashchii, Alexander Borisovich; Bard, Allen J.; Crooks, Richard M.; Stevenson, Keith J.; Mullins, Buddie C.; Korgel, Brian A.Electrochemical and electrogenerated chemiluminescence properties of the BODIPY (boron dipyrromethene) dyes are presented. Some specific features of the BODIPY dyes are obtained and described in the current dissertation. Separation of around 1.0-1.2 V is noticed between two oxidation and reduction waves for one center which is very different from 0.5 V seen for the polycyclic hydrocarbons. Cathodic and anodic stability is shown to depend upon absence or presence of certain degree of substitution. Different ways of electrochemical dimerization are explored and compared with the chemical dimerization. Photophysical and electrochemical properties of monomer, chemically synthesized dimer, trimer and polymer are described and the characteristic features determined.Item Extension of tetrathiafulvalene conjugation through pyrrollic-based dyes : ExTTF porphyrin and ExTTF BODIPY(2013-12) Bill, Nathaniel Lloyd; Sessler, Jonathan L.The 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@C₆₀ 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.Item Water-soluble bodipys: syntheses, derivatization and photophysical studies(2009-05-15) Li, LinglingA set of water-soluble 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) derivatives, has been prepared and their spectroscopic properties examined. These dyes can be used as either donor or acceptor in synthesis of through-bond energy transfer cassettes. Sulfonation conditions were developed for several BODIPY dyes to give the mono-sulfonated and di-sulfonated products. Compounds with an aryl iodide could be used for organometallic couplings. Similarly, BODIPYs with an aromatic bromide, but also two chlorine atoms could be replaced via SNAr reactions. The amine sulfonated BODIPY is amenable to couple to biomolecules via acylation reactions. A diazotization/azide reaction sequence was used to convert the amines into azides; the latter may be functionalized via click reactions. Spectral data for these materials indicates they are highly fluorescent probes in aqueous environments. We have also prepared some lipophilic BODIPY derivatives, which can be used for SNAr reactions and make some through-bond, energy transfer cassettes. DichloroBODIPYs can also be used for labeling proteins successfully.