Synthesis, Immobilization Strategies, and Mechanistic Analysis of Surface-Supported Molecular Palladium Cross-Coupling Catalysts for Single-Molecule Fluorescence Spectroscop

Single-molecule fluorescence spectroscopy is a compelling technique for studying the dynamics of catalytic reactions because heterogeneity in catalyst populations can be directly observed. Understanding the nature of diversity in catalyst behavior will lead to the design of better, more efficient catalysts. Synthetic challenges emerge when developing chemical systems for single-molecule spectroscopy techniques, because the molecules need to be fluorescently labeled and anchored to a surface for long-term imaging. A reliable attachment to the surface is critical for successful single-molecule spectroscopy investigations. Robust surface linkages play an important role in the stability and recyclability of surface-supported molecular catalysts as well.;This thesis focuses on the design and synthesis of suitable fluorescent chemical systems for single-molecule fluorescence spectroscopy investigations of catalyst transformations and highlights the challenges related to developing and implementing surface attachment strategies for surface-supported molecular catalysts.;A fluorescent Pd-PEPPSI precatalyst complex is designed and synthesized for single-molecule fluorescence spectroscopy experiments, and the mechanism of catalyst initiation is examined using both bulk NMR and single-molecule fluorescence spectroscopy. Various surface-attachment strategies are investigated for the immobilization of molecular Pd-PEPPSI complexes onto both polymers and metal oxides. Multiple characterization techniques are employed to analyze the nature of the surface linkage chemistries and gain insight into the stability and degradation mechanisms of surface-supported molecular palladium catalysts.