Supramolecular block and random copolymers in multifunctional assemblies

Metal coordination;Hydrogen bonding;Side chain functionalized;Self-sorting;Supramolecular;Self-assembly;Telechelic polymers

Burd, Caroline Glenn ; Chemistry and Biochemistry

University:Georgia Institute of Technology

Department:Chemistry and Biochemistry

关键词: Metal coordination;    Hydrogen bonding;    Side chain functionalized;    Self-sorting;    Supramolecular;    Self-assembly;    Telechelic polymers;   

Others  :  https://smartech.gatech.edu/bitstream/1853/24627/1/Burd_Caroline_G_200808_phd.pdf

美国|英语

来源: SMARTech Repository

【 摘 要 】

This thesis begins with a brief overview of supramolecular chemistry and selfassemblyand simple examples derived from Nature that provide the motivation for thework presented here. The concept of a synthetic noncovalent toolbox is then introduced.The discussion then focuses more explicitly on side-chain and main-chain functionalizedmotifs 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 functionalitiescapable of noncovalent interactions, comprises a method for generating bioinspiredmaterials. This hypothesis was tested by synthesizing unique functionalizedsupramolecular polymers that allowed for a detailed understanding of the orthogonalityof noncovalent interactions and how such interactions can begin to mimic the complexityof functional biomaterials. The strategies and methods discussed in the synthesis of thesebioinspired materials are divided into three chapters: (1) an exploration of the self-sortingphenomena between two non-complementary pairs of hydrogen bonds along polymerside-chains, (2) the extension of the self-sorting concept to include a metal coordinationmoiety, and (3) the side-chain functionalization strategies of chapters 2 and 3 incombination with the main-chain ROMP methodologies discussed in chapter 1 to formorthogonally self-assembled multifunctional block copolymers. The main results of thisthesis include the results that multifunctional block copolymers can be fashioned viaROMP, functionalized in both the main- and side-chains, and self-assembled in anorthogonal fashion. In addition, these studies have found that self-sorting between pairs of non-complementary hydrogen bonding motifs can occur in supramolecular syntheticsystems, that the interactions are extremely solvent dependent and that these interactionscan result in unexpected phenomena. These results demonstrate the importance of a fullyunderstood toolbox for the rapid development of supramolecular materials. Theknowledge derived from this toolbox and presented in chapters 2, 3, and 4, allows for thecareful selection of compounds for cleverly designed self-assembly materials inspired byNature. Finally, conclusions are drawn to the success of the synthetic toolbox and thevarious strategies presented herein, and potential future directions are discussed.