Title: A 'Toolkit' of Small Molecules for Polymer Assembly and Post-Synthetic Modification Using 'Click' and Photoactive Chemistries
Description: Small molecules have been synthesized toward the goals of constructing and modifying polymeric materials according to simple, generalizeable, and universal processes. The prepared compounds rely upon a combination of photochemistry and the 'click' philosophy to alter the architecture, bulk properties, or surface chemistry of polymers. In Chapter 1, a review is presented that details the many implementations of the 'click' philosophy to polymer chemistry. The influence of 'click' and photochemistry upon macromolecules is discussed using a topological approach to polymer architecture. Chapter 2 details the synthesis of several second-generation homobifunctional exogenous photocrosslinkers that extend upon previous work from our group. Additionally, a first-generation crosslinker is used to core-crosslink micellar aggregates of block copolymers. Chapter 3 describes the design, synthesis, and implementation of a photoactive 'click' activator for polymer surfaces. This chapter extends the notion of a material-specific anchor from hard substrates to a range of soft polymer substrates.

Chapter 4 is an inquiry into the nature of the photoreaction of a standard photoactive moiety - benzophenone - with model compounds that represent polymers in which the crosslinkers of Chapter 2 are embedded. Comparison of competitive rates of abstraction gives insight into the reactive preferences of the crosslinkers and anchors of the previous chapters. In Chapter 5 small molecules and macromonomers are described that build upon the compounds described in previous chapters which collectively form the basis of a 'toolkit' approach to polymer assembly and modification. Variations and extensions upon the 'toolkit' are detailed in order to give a sense of the future possibilities of this approach.