Investigation of the Photochemistry of Ruthenium Complexes Containing Unusual Acceptor Ligands

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ProQuest, 2006 - Chemistry, Inorganic - 122 pages
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Artificial photosynthesis is considered a key approach to harnessing the freely available energy from the sun for human consumption. Ruthenium based macrocyclic systems continue to play a significant role in the development of supramolecular photosystems for the advancement of this concept. This thesis focuses on the synthesis and examination of the photo- and electroreduction of a monomeric photocatalyst, [(bpy)2Ru(tatpp)] 2+. The complex has a tendency to form molecular aggregates in acetonitrile and these aggregates have important results on its photochemical and electrochemical activity. Aggregation was found to impact the kinetics of the photochemical reduction process, with increased aggregation enhancing the process. Photoirradiation of the complex in the presence of triethanolamine in both water and acetonitrile revealed that the complex is reduced by two electrons, along with concomitant protonation. To a large extent the first reduction process is thermally driven.

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