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dc.contributor.advisorFalvey, Danielen_US
dc.contributor.authorDenning, Derek Michaelen_US
dc.date.accessioned2016-09-03T05:37:39Z
dc.date.available2016-09-03T05:37:39Z
dc.date.issued2016en_US
dc.identifierhttps://doi.org/10.13016/M2750J
dc.identifier.urihttp://hdl.handle.net/1903/18565
dc.description.abstractTraditional organic chemistry has long been dominated by ground state thermal reactions. The alternative to this is excited state chemistry, which uses light to drive chemical transformations. There is considerable interest in using this clean renewable energy source due to concerns surrounding the combustion byproducts associated with the consumption of fossil fuels. The work presented in this text will focus on the use of light (both ultraviolet and visible) for the following quantitative chemical transformations: (1) the release of compounds containing carboxylic acid and alcohol functional groups and (2) the conversion of carbon dioxide into other useable chemicals. Chapters 1-3 will introduce and explore the use of photoremovable protecting groups (PPGs) for the spatiotemporal control of molecular concentrations. Two new PPGs are discussed, the 2,2,2-tribromoethoxy group for the protection of carboxylic acids and the 9-phenyl-9-tritylone group for the protection of alcohols. Fundamental interest in the factors that affect C–X bond breaking has driven the work presented in this text for the release of carboxylic acid substrates. Product analysis from the UV photolysis of 2,2,2-tribromoethyl-(2′-phenylacetate) in various solvents results in the formation of H–atom abstraction products as well as the release of phenylacetic acid. The deprotection of alcohols is realized through the use of UV or visible light photolysis of 9-phenyl-9-tritylone ethers. Central to this study is the use of photoinduced electron transfer chemistry for the generation of ion diradicals capable of undergoing bond-breaking chemistry leading to the release of the alcohol substrates. Chapters 4 and 5 will explore the use of N-heterocyclic carbenes (NHCs) as a catalyst for the photochemical reduction of carbon dioxide. Previous experiments have demonstrated that NHCs can add to CO2 to form stable zwitterionic species known as N-heterocylic-2-carboxylates (NHC–CO2). Work presented in this text illustrate that the stability of these species is highly dependent on solvent polarity, consistent with a lengthening of the imidazolium to carbon dioxide bond (CNHC–CCO2). Furthermore, these adducts interact with excited state electron donors resulting in the generation of ion diradicals capable of converting carbon dioxide into formic acid.en_US
dc.language.isoenen_US
dc.titleApplications of Photoinduced Electron Transfer Chemistry: Photoremovable Protecting Groups and Carbon Dioxide Conversionen_US
dc.typeDissertationen_US
dc.contributor.publisherDigital Repository at the University of Marylanden_US
dc.contributor.publisherUniversity of Maryland (College Park, Md.)en_US
dc.contributor.departmentChemistryen_US
dc.subject.pqcontrolledChemistryen_US
dc.subject.pqcontrolledOrganic chemistryen_US
dc.subject.pqcontrolledPhysical chemistryen_US
dc.subject.pquncontrolledCarbon Dioxideen_US
dc.subject.pquncontrolledOrganic Chemistryen_US
dc.subject.pquncontrolledPhotochemistryen_US
dc.subject.pquncontrolledPhotoinduced Electron Transferen_US
dc.subject.pquncontrolledProtecting Groupsen_US


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