Investigation of the Photochemistry of Ruthenium Complexes Containing Unusual Acceptor Ligands
ProQuest, 2006 - Chemistry, Inorganic - 122 pages
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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1.0 equiv cobaltocene 1.0 equiv TFA 100 W tungsten 1H NMR 3MLCT Absorption spectra acetonitrile Ag/AgCl aqueous Artificial photosynthesis bpy)2Ru(tatpp bridging ligand bulb light source CD3CN chemical shift chromophores cobaltocene and 1.0 complex 12 cutoff filter 360 cuvettes cyclic dadppz dimer doubly reduced electrochemistry electroreduction energy ethanol excited exposure to air filter 360 nm hydrogen lifetime mixture MLCT molecular molecule mono-reduced monometallic monometallic complex multielectron N N N N N N N N,N-dimethylaniline observed one-electron one-electron reductant oxidation photocatalyst photochemical Photochemistry Photochemistry of 18 photoproducts Photosystem potential scan prior to irradiation pyrazine redox and protonation redox processes reduction of 12 reduction process ruthenium sacrificial donor shown in Figure shown in reaction shows solvent source and sample spectra of 12 Spectroelectrochemistry tatpp ligand tatpq TEOA TEOA in degassed thermal reduction triethanolamine triethylamine trifluoroacetic acid tungsten bulb light UV cutoff filter UV-vis visible region water-splitting