This thesis extends investigations into renewable amines for photochemical CO2 reduction by the Carpenter group. This work is motivated by a desire to provide solutions for green energy production. Modifications to the tricyclic amine, 20, were studied computationally using DFT calculations. These studies suggest that there are no simple modifications to this class of amines that will offer significantly improved properties for CO2 reduction. A second class of amines is then proposed in which radical stabilization groups can be introduced to promote the desired photochemistry. From this class of amines the phenyl derivative, 34, was identified as the best candidate. Rate calculations predict that distonic radical cation formation will not present a bottleneck in the reaction scheme. A synthesis of this class of amines is proposed and supporting DFT calculations indicate that it is a viable synthesis. Using the leads from computational studies synthetic work was undertaken to find a synthetic route to amines, 14+ 66. The routes developed are capable of producing the desired amines but need to be optimized for full_scale photochemical studies. The final chapter presents a tool named Quantum Chemistry Interface that is designed mainly as a teaching tool for computational chemistry. It facilitates rapid generation of libraries of substituted molecules. It also understands a simple language for describing reaction steps to automate calculations of reaction thermodynamic parameters. Its utility is shown with a small project with an undergraduate student.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:633565 |
| Date | January 2014 |
| Creators | Holland, Edward |
| Publisher | Cardiff University |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://orca.cf.ac.uk/68775/ |
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