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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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