Supramolecular block and random copolymers in multifunctional assemblies
Burd, Caroline Glenn
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This thesis begins with a brief overview of supramolecular chemistry and selfassembly and simple examples derived from Nature that provide the motivation for the work presented here. The concept of a synthetic noncovalent toolbox is then introduced. The discussion then focuses more explicitly on side-chain and main-chain functionalized motifs and the methodologies employed in supramolecular polymer functionalization. The primary hypothesis of the thesis is that the combination of supramolecular strategies, ring-opening metathesis polymerization, and a well-understood toolbox of functionalities capable of noncovalent interactions, comprises a method for generating bioinspired materials. This hypothesis was tested by synthesizing unique functionalized supramolecular polymers that allowed for a detailed understanding of the orthogonality of noncovalent interactions and how such interactions can begin to mimic the complexity of functional biomaterials. The strategies and methods discussed in the synthesis of these bioinspired materials are divided into three chapters: (1) an exploration of the self-sorting phenomena between two non-complementary pairs of hydrogen bonds along polymer side-chains, (2) the extension of the self-sorting concept to include a metal coordination moiety, and (3) the side-chain functionalization strategies of chapters 2 and 3 in combination with the main-chain ROMP methodologies discussed in chapter 1 to form orthogonally self-assembled multifunctional block copolymers. The main results of this thesis include the results that multifunctional block copolymers can be fashioned via ROMP, functionalized in both the main- and side-chains, and self-assembled in an orthogonal fashion. In addition, these studies have found that self-sorting between pairs of non-complementary hydrogen bonding motifs can occur in supramolecular synthetic systems, that the interactions are extremely solvent dependent and that these interactions can result in unexpected phenomena. These results demonstrate the importance of a fully understood toolbox for the rapid development of supramolecular materials. The knowledge derived from this toolbox and presented in chapters 2, 3, and 4, allows for the careful selection of compounds for cleverly designed self-assembly materials inspired by Nature. Finally, conclusions are drawn to the success of the synthetic toolbox and the various strategies presented herein, and potential future directions are discussed.