Photochemistry allows chemists to harness the energy in specific wavelengths of light and use it to achieve new chemical transformations. These chemical transformations are often impossible or energetically demanding under traditional thermal conditions. My dissertation focuses broadly on different strategies to apply visible-light photochemistry and photocatalysis to the development of unique materials. Specifically, I synthesized new photoresponsive molecules that can manipulate and control the exchange of dynamic covalent bonds. Through a joint synthetic and computational approach, we explained how adjacent azobenzene photoswitches control boronic acid-ester exchange. Moreover, I have explored photoredox catalysis as an opportunity to access synthetically challenging polymer structures. I adapted a small-molecule photoredox Diels–Alder reaction to the synthesis of non-conjugated ladder polymers that have potential applications in gas and fluid membrane separation. I was able to identify multiple pathways of initiation for the polymerization and broaden the scope of the reaction to include myriad of photocatalysts, monomer structures, solvents, and oxidants. This approach allows us to access a unique fully saturated ladder polymer backbone. Throughout my thesis, I show opportunities to couple light with well-known chemistries to access new materials and address gaps in the application of photochemistry to materials synthesis.

Creator

• McClure, Emily Robin

DOI

• https://doi.org/10.21985/n2-nkth-t789

Subject

• Organic chemistry
• Polymer chemistry

Language

• en

Alternate Identifier

• http://dissertations.umi.com/northwestern:16785
• etdadmin_upload_1014485

Date created

• 2023-01-01

Resource type

• Dissertation

Rights statement

• In Copyright