New Organic and Organometallic Platforms for Luminescence and Catalysis Applications
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Abstract
This dissertation describes the development of organometallic compounds, including cyclometalated platinum and iridium complexes and iridium pincer complexes, and organic chromophores, applied to dehydrogenation of alkanes, Lewis-acid-modulated luminescence, and ratiometric O2 sensing. Chapter 1 describes a series of cyclometalated platinum complexes with two different fluorinated β-diketiminate (NacNac) ligands, with the nuclearity of the product depending on the temperature of the reaction. The two types of complexes are characterized by X-ray crystallography, UV-vis absorption and emission spectroscopy, and by cyclic voltammetry, which shows a reversible reduction at mild potentials. All of these properties are suggested to involve NacNac-centered frontier orbitals. Chapter 2 describes two pyridyl-substituted BODIPY compounds and one aza-BODIPY, which can interact with the strong Lewis acid B(C6F5)3. The interactions of BODIPYs with borane Lewis acids induce significant changes in the photophysical properties of these chromophoric molecules. Chapter 3 introduces a new class of ratiometric O2 sensors for hypoxic environments. Two-component structures composed of phosphorescent cyclometalated Ir(III) complexes and the well-known organic fluorophore BODIPY exhibit dual emission, with significant phosphorescence from the iridium site and fluorescence from the BODIPY, and thus function as ratiometric oxygen sensors. Finally, Chapter 4 describes the synthesis of two type iridium pincer complexes (CCC- and CNC types) as precatalysts for the dehydrogenation of cyclooctane.