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Table of Contents 1. Introduction 1.1. The Oxygen Evolving Complex ¨C The Site Where Water Is Oxidized 1.2. Artificial Photosynthesis ¨C Architectural Complexity 1.2.1. Light Absorption by a Chromophore ¨C The Photosensitizer 1.2.2. Reduction of Protons for the Generation of Solar Fuels ¨C The Reduction Catalyst 1.2.3. The Water Oxidation Catalyst ¨C Catalytic Complexity at the Frontier 1.3. Experimental Design for Evaluating Water Oxidation Catalysts 1.3.1. Commonly Used Chemical Oxidants 1.3.2. Light-Driven Water Oxidation 1.3.3. (Photo)electrochemical Water Oxidation 1.3.4. Homogeneous versus Heterogeneous Catalysis ¨C The Conversion of Molecular Entities to Heterogeneous Catalytically Active Species 1.4. Mechanistic Considerations Associated with Artifical Water Oxidation Catalysts 2. Molecular Ruthenium-Based Water Oxidation Catalysts 2.1. Dinuclear Ruthenium-Based Systems for Water Oxidation 2.2. Single-Site Ruthenium-Based Catalysts ¨C Simple and Efficient 2.2.1. Mononuclear Ruthenium Catalysts Comprising Neutral Ligand Frameworks 2.2.2. Mononuclear Ruthenium Catalysts Containing Anionic Ligand Backbones 3. Iridium-Based Systems for Water Oxidation 3.1. Cyclometalated Iridium Complexes 3.2. Iridium Catalysts Based on Cyclopentadiene-Type Ligands 3.3. Development of Iridium N-Heterocyclic Carbene and Other Iridium Catalysts 3.4. Decomposition of Homogeneous Iridium Catalysts ¨C Generation of Catalytically Active Heterogeneous Iridum Species 4. Artificial Catalysts Housing Earth-Abundant First-Row Transition Metals 4.1. Early Biomimetic Manganese-Based Photosynthetic Mimics 4.2. Manganese-Based Catalysts Capable of Generating Oxygen 4.3. Molecular Water Oxidation Catalysts Based on Iron 4.4. Oxygen Formation in Copper-Based Systems 4.5. Cobalt-Based Catalysts Capable of Oxidizing Water 5. Synthetic Metal¨COxo Mimics of the Oxygen Evolving Complex 5.1. Polyoxometalates ¨C The Molecular, Inorganic Alternative 5.1.1. Ruthenium-Based Polyoxometalates 5.1.2. Cobalt-Based Polyoxometalates ¨C The Ambiguity of Distinguishing between Homogeneous and Heterogeneous Catalysis 5.1.3. Other Metal-Based Polyoxometalates 5.2. Metal Cubanes Based on Earth-Abundant Metals as Water Oxidation Catalysts 5.2.1. The Self-Assembling Cobalt¨CPhosphate (Co¨CPi) Catalyst 5.2.2. Cobalt Cubanes and Related Cobalt Oxide Materials as Oxygen Evolving Catalysts 5.2.3. Manganese Cubanes as Water Oxidation Catalysts 6. Conclusions |
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