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Part I: A novel series of bridging ligands and their RuII photosensitizer-catalyst dyads have been prepared and characterized by NMR and electronic absorption spectroscopy as well as cyclic voltammetry. The presence of asymmetry in the ligands facilitated selective metal coordination, which greatly enhanced the ease of the preparation of the dyads. The photophysical properties of the photosensitizers and the photosensitizer-catalyst dyads were also studied. All the photosensitizers were found to be strong fluorescent emitters while the extremely weak emission of the dyads suggested quenching by either energy or electron transfer. The water oxidation activities of the dyads have been evaluated under both light and CeIV activated conditions. The dyads were found to be active under CeIV activated conditions. Electrochemical studies also suggest that these systems may be used as catalysts for photoelectrochemical water oxidation. Part II: A novel dinuclear RuII water oxidation catalyst has been prepared. Its properties and catalytic activity have been evaluated and compared with an analogous system previously reported by our group. These catalysts are active under both light and CeIV activated conditions. A mononuclear analog of the new dinuclear catalyst has also been prepared and evaluated for its activity in order to examine the role of the RuII centers in the dinuclear catalyst. Incorporation of the second RuII center was found to greatly enhance the catalytic activity with respect to the mononuclear system.
A series of 3,3'-polymethylene-bridged 2,2'-biquinoline and 2,6-di-(quinolin-2'-yl)pyridines (dqp) brominated at 6- or 7-position were synthesized utilizing the Friedlander reaction. The NMR and UV spectra of these compounds varied as a function of the dihedral angle between adjacent aromatic rings and the different positions of the bromo substituents. Ru(II) complexes of the dqp derivatives were prepared. The chemical shift changes upon complexation for certain protons are very diagnostic of their spatial environment. Electronic absorptions and redox potentials for the dqp complexes did not differ dramatically for the 6-bromo and 7-bromo derivatives.
The handbook comprehensively covers the field of inorganic photochemistry from the fundamentals to the main applications. The first section of the book describes the historical development of inorganic photochemistry, along with the fundamentals related to this multidisciplinary scientific field. The main experimental techniques employed in state-of-art studies are described in detail in the second section followed by a third section including theoretical investigations in the field. In the next three sections, the photophysical and photochemical properties of coordination compounds, supramolecular systems and inorganic semiconductors are summarized by experts on these materials. Finally, the application of photoactive inorganic compounds in key sectors of our society is highlighted. The sections cover applications in bioimaging and sensing, drug delivery and cancer therapy, solar energy conversion to electricity and fuels, organic synthesis, environmental remediation and optoelectronics among others. The chapters provide a concise overview of the main achievements in the recent years and highlight the challenges for future research. This handbook offers a unique compilation for practitioners of inorganic photochemistry in both industry and academia.
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Photocatalytic water splitting is a promising strategy for capturing energy from the sun by coupling light harvesting and the oxidation of water, in order to create clean hydrogen fuel. Thus a deep knowledge of the water oxidation catalysis field is essential to be able to come up with useful energy conversion devices based on sunlight and water splitting. Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes presents a comprehensive and state-of-the-art overview of water oxidation catalysis in homogeneous phase, describing in detail the most important catalysts discovered today based on first and second row transition metals. A strong emphasis is placed on the description of their performance, as well as how they work from a mechanistic perspective. In addition, a theoretical description of some of the most relevant catalysts based on DFT are presented, as well as a description of related natural systems, such as the oxygen evolving system of photosystem II and the heme chlorite-dismutase. This book is a valuable resource for researchers working on water oxidation catalysis, solar energy conversion and artificial photosynthesis, as well as for chemists and materials scientists with a broad interest in new sustainable energy conversion schemes.