Controlling molecular weight, architecture, and comonomer incorporation in polymers is of paramount importance for the preparation of functional materials. This dissertation will highlight the development of three strategies that improve control in macromolecular synthesis, ranging from initial polymerization to macromolecular post-modification.

Controlled radical polymerization is a well-established platform for macromolecular engineering. However, many techniques require metal or sulfur additives and yield macromolecules with chain ends that are chemically reactive and thermally unstable. This dissertation presents a light-mediated method for the removal of such end groups, which is effective for a variety of chain ends as well as polymer families, both in solution and with spatial control on surfaces. Polymers with improved thermal and chemical stability can now be obtained under mild, metal-free conditions and with external regulation.

To circumvent the presence of such reactive chain ends altogether, triazine-based unimolecular initiators were developed. These metal- and sulfur-free mediators are shown to control the radical polymerization of several monomer classes.

Generally, the distribution of functional groups throughout the macromolecular backbone is important for numerous applications. An efficient and high-yielding strategy for the functionalization of well-defined polyethers is described herein. By controlling both the number and location of underwater adhesive catechol groups, these biomimetic macromolecules may facilitate future insights into the mechanics of mussel and underwater adhesion, and related antifouling materials.