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Full-Text Articles in Physical Sciences and Mathematics
Approaches In Molecular Engineering To Optimize The Desired Properties Of Photoactive Molecules, Douglas Joseph Breen
Approaches In Molecular Engineering To Optimize The Desired Properties Of Photoactive Molecules, Douglas Joseph Breen
Chemistry and Chemical Biology ETDs
Within this dissertation, photochemical systems that bear significance to next-generation photonic materials and devices are explored. Notable advances in the design, synthesis, and characterization of three distinct groups of photoactive molecules are achieved through molecular design and spectroscopic analysis. First, novel ruthenium sulfoxide complexes bearing substituted phosphine ligands are found to provide extraordinary control over photoisomerization quantum yields. A comparison of these complexes reveals ground-state characteristics that are instrumental in this reactivity, while a novel spectroscopic technique provides rare structural evidence for an O-bonded metastable isomer. Ruthenium complexes bearing chelating carbene-sulfoxide ligands rapidly thermally revert from the O-bonded metastable isomer …
The Profound Photophysical Effects Of Organic Chromophore Connectivity And Coupling, David J. Walwark Jr
The Profound Photophysical Effects Of Organic Chromophore Connectivity And Coupling, David J. Walwark Jr
Nanoscience and Microsystems ETDs
Through-bond and through-space interactions between chromophores are shown to have wide-ranging effects on photophysical outcomes upon light absorption in organic molecules. In collapsed poly(3-hexylthiophene), through-space coupling creates hybrid chromophores that act as energy sinks for nearby excitons and favorable sites for molecular oxygen to dock. Upon excitation with visible light the highly-coupled chromophores react with the docked oxygen and subsequently do not quench nearby excitons as efficiently. In tetramer arrays of perylene diimide chromophores the central moiety through-bond connectivity is synthesized in two variants which exhibit vastly different single-molecule blinking behavior and theoretically-predicted electronic transition character. In the more-connected tetramer …