Thesis advisor: Jeffery A. Byers / This dissertation discusses the development of a family of iron complexes and their role in the synthesis of degradable polymers. Chapter one will introduce the different areas of redox-switchable polymerization. In chapter two the synthesis of block copolymers containing a polyester and polyether block is presented. The application redox-switchable polymerization to form a copolymer with two fundamentally distinct backbone functionalities and their characterization is discussed. In chapter three the synthesis of a degradable cross-linked polymer through a novel redox-triggered cross linking event is summarized. In chapter four, a detailed mechanistic study of iron-complex catalyzed epoxide polymerization is examined and a unique mechanistic scheme is proposed. Lastly, in chapter five the synthesis and characterization of a formally iron(I) complex is presented. This complex shows remarkable catalytic activity towards ring-opening polymerization. / Thesis (PhD) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: Jeffery A. Byers / Thesis advisor: Petter Zhang / This thesis discusses the development of a surface-initiated N-carboxyanhydride (NCA) polymerization system from a redox-switchable catalyst for polyamide synthesis and further efforts towards the synthesis of polypeptide-based materials through the integration of NCA synthesis and its polymerization. In Chapter one, the most used methods to obtain polypeptide-based materials as well as their significant limitations are introduced. A new strategy is presented to access the polypeptide-based materials based on the integrated catalysis under spatial and temporal control. In Chapter two, a strategy to allow the attachment of a redox-switchable NCA polymerization catalyst on surface of titania for the synthesis of polyamide brushes will be demonstrated. Investigations about the kinetics of this surface-initiated ring-opening polymerization will be presented by carrying out the reaction in batch and under flow. Chapter three will discuss efforts towards achieving the integration of NCA synthesis and NCA polymerization, which includes an additional anchoring method to support polymerization catalyst and compatibility tests between the two separate reactions. / Thesis (MS) — Boston College, 2022. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.