Applications of Photoinduced Electron Transfer Chemistry: Photoremovable Protecting Groups and Carbon Dioxide Conversion

Traditional 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.

Between Nation and State: Albanian Associations from Ottoman Origins to a Communist Party, 1880 - 1945

This dissertation addresses the broader antecedents of the Communist Party of Albania (CPA) as one of a number of associations whose experience was central to Albanian political history. This long experience dates back to the informal national associations formed in the Ottoman Empire of the late nineteenth century. The dissertation examines the role of these associations which, pursuing language rights and political representation through imperial state reforms, set a pattern that struggled to connect nation and state, rather than asserting the territorial demands for a nation-state familiar across the region. Starting out in the Ottoman Empire, but then maturing in the Albanian diaspora in Romania, Bulgaria, Egypt and the United States, this dissertation shows politically significant processes of longer-term adaptation that created informal associations as institutional structures able to channel collective action. It then traces the reframing of these patterns through their destruction in the Balkan Wars and the First World War to the emergence of communist associations in the interwar period and beyond. This dissertation is a sustained study that traces long-term Ottoman imperial political legacies in the Albanian successor state. The story of the associations, based on hitherto unexamined archival documents, shows that the Albanians possessed a far greater capacity for political mobilization that previously acknowledged by historians. Moreover, the dissertation successfully challenges the conventional wisdom that portrays the Albanians as irreparably divided along sectarian and regional faultlines. It finds that Albanian national activism was civic in character rather than ethnic as elsewhere in the Balkans. The Albanians fought to remain within a multinational framework because this afforded them political security, social advancement and potential economic growth. In the late Ottoman period, this political objective was manifested in the acceptance of the supranational imperial order whereas during the Second World War, in the aspiration to become members of the Comintern internationalist movement. Another important find, is the newly-discovered evidence concerning the founding of the CPA and its wartime conduct as an organization created and led by the Albanians themselves, albeit with Yugoslav ideological assistance under the transnational umbrella of the Comintern.