Electrochemical and Spectroelectrochemical Studies of -Extended Porphyrins, Corroles and Bodipys
Ke, Xiangyi 1990-
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One part of this dissertation describes the electrochemistry and spectroelectrochemistry of π-extended and/or highly electron-withdrawing substituted porphyrins and corroles in non-aqueous media and another part is dedicated to a study of boron-dipyrromethenes (BODIPYs). In-situ electrogenerated -bonded cobalt porphyrins were also studied as to their electrochemical and spectral properties in their neutral and electroreduced states. The first examples for the facile, reversible, and stepwise electrogeneration of triply ring-reduced porphyrin macrocycles are presented and characterized by thin-layer UV-vis spectroelectrochemistry. The generation of multianionic porphyrins is interpreted as being due to an extensive stabilization of the LUMOs resulting from the electron-withdrawing and/or π extending substituents on the beta-pyrrole positions of the porphyrin macrocycle. The corroles whose electrochemistry and spectroelectrochemistry are described in this dissertation contained a copper center metal ion while the BODIPYs contained a BF2 center. All of the BODIPYs with nitrophenyl substituents on the BODIPYs were shown to undergo well-defined and reversible reductions under most solution condition.