Investigation of Redox-Active Small Molecules and Organic Materials for Catalysis
Access to this document is restricted. Some items have been embargoed at the request of the author, but will be made publicly available after the "No Access Until" date.
During the embargo period, you may request access to the item by clicking the link to the restricted file(s) and completing the request form. If we have contact information for a Cornell author, we will contact the author and request permission to provide access. If we do not have contact information for a Cornell author, or the author denies or does not respond to our inquiry, we will not be able to provide access. For more information, review our policies for restricted content.
Redox-active organic materials, while ubiquitous in energy storage and photoredox catalysis, remain underexplored as heterogeneous electrocatalysts for organic synthesis. This dissertation first outlines the challenges and opportunities for using these materials as catalysts relevant to synthetic organic chemistry, then presents the first example of using redox-active organic polymers as scalable and recyclable catalyst platforms for heterogeneous electrophotocatalysis, which not only validates their use as heterogeneous catalysts, but also uncover key structural design principles that can overcome the traditional limitations of photoredox catalysis. Building upon these findings, more reducing electrophotocatalysts have been successfully developed to achieve more challenging reductive transformations. Besides catalysis, the effect of immobilizing redox-active moieties within extended solids has been systematically examined, wherein immobilization has been found to impart the materials with unique redox-activity not observed in solution, which has the potential to be translated into unique reactivity patterns in the solid state. These findings open the door for using heterogeneous redox-active organic materials for synthetic organic electrochemistry.