Edited byEli Zysman-Colman EaStCHEM School of Chemistry, University of St Andrews, UK

• List of Contributors xvForeword xviiPreface xixVOLUME 11 Archetypal Iridium(III) Compounds for Optoelectronic and Photonic Applications: Photophysical Properties and Synthetic Methods 1Joseph C. Deaton and Felix N. Castellano1.1 Introduction 11.2 Iridium Complex Ion Dopants in Silver Halide Photographic Materials 11.3 Overview of the Photophysical Properties of C^N and C^C: Cyclometalated Ir(III) Complexes 21.4 Importance of Ir—C Bonds in the Archetypal Ir(III) Complexes for Optoelectronic and Photonic Applications 91.5 Tuning Emission Color 141.6 Absorbance and Photoluminescence of C^N Cyclometalated Ir(III) Complexes 171.7 SOC Mechanism: Radiative Decay Rates and ZFS 231.8 Non-Radiative Decay Rates 391.9 Synthetic Methods Targeting C^N Cyclometalated Ir(III) Compounds 421.10 Synthetic Methods for Cyclometalated Ir(III) Compounds Containing Carbenes 471.11 Conclusions 482 Multinuclear Iridium Complexes 71J. A. Gareth Williams2.1 Introduction 712.2 Compounds Incorporating 'Single Atom Bridges': μ-Chloro, μ-Oxo and μ-Aza 722.3 Polyatomic Acyclic Bridges: Acetylides, Cyanides and Hydrazides 782.4 Compounds with Heterocyclic Bridges 822.5 Multinuclear Complexes Featuring Conjugated Bridges between Iridium-Bound Polypyridyl or Arylpyridyl Ligands 932.6 Concluding Remarks 1043 Soft Materials and Soft Salts Based on Iridium Complexes 111Etienne Baranoff and Yafei Wang3.1 Introduction 1113.2 Liquid Crystals 1123.3 Gels 1153.4 Micelles 1163.5 Langmuir–Blodgett Films 1183.6 Soft Salts 1183.7 Conclusion 1234 Porous Materials Based on Precious Metal Building Blocks for Solar Energy Applications 127Daniel Micheroni and Wenbin Lin4.1 Introduction 1274.2 The Luminescent Nature of MOFs and Their Use in Chemical Applications 1294.3 Energy Transfer in Porous Materials 1344.4 Porous Materials for Water Oxidation 1364.5 Porous Materials for Proton Reduction 1384.6 Porous Materials for CO2 Reduction 1404.7 Conclusions and Outlook 1415 Polymeric Architectures Containing Phosphorescent Iridium(III) Complexes 145Andreas Winter and Ulrich S. Schubert5.1 Introduction 1455.2 Ir(III)-Containing Polymers: Classification, Design Principles, and Syntheses 1465.3 Hyperbranched and Dendritic Architectures 1875.4 Concluding Remarks 1916 Iridium(III) Complexes for OLED Application 205Elena Longhi and Luisa De Cola6.1 Introduction 2056.2 Iridium Complexes 2066.3 Organic Light-Emitting Diodes 2166.4 Iridium(III) Complexes for PHOLED Application 2276.5 Conclusions and Perspectives 2627 A Comprehensive Review of Luminescent Iridium Complexes Used in Light-Emitting Electrochemical Cells (LEECs) 275Adam F. Henwood and Eli Zysman-Colman7.1 Introduction 2757.2 Device Fundamentals 2787.3 Green Emitters 2807.4 Blue Emitters 3017.5 Yellow Emitters 3237.6 Orange-Red Emitters 3347.7 Conclusions and Outlook 348VOLUME 28 Electrochemiluminescence of Iridium Complexes 359Sarah E. Laird and Conor F. Hogan8.1 Background and Overview of Electrochemiluminescence 3598.2 Iridium ECL 3639 Strategic Applications of Luminescent Iridium(III) Complexes as Biomolecular Probes, Cellular Imaging Reagents, and Photodynamic Therapeutics 415Karson Ka-Shun Tso and Kenneth Kam-Wing Lo9.1 Introduction 4159.2 General Cellular Staining Reagents 4169.3 Hypoxia Sensing Probes 4239.4 Molecular and Ion Intracellular Probes 4279.5 Organelle-Targeting Bioimaging Reagents 4419.6 Functionalized Polypeptides for Bioimaging 4509.7 Polymers and Nanoparticles for Bioimaging 4549.8 Photocytotoxic Reagents and Photodynamic Therapeutics 4589.9 Conclusion 46610 Iridium Complexes in the Development of Optical Sensors 479Teresa Ramón-Márquez, Marta Marín-Suárez, Alberto Fernández-Gutiérrez and J. F. Fernández-Sánchez10.1 Generalities of Optical Sensors 47910.2 Ir(III) Used as Optical Probes 48110.3 Ir(III) Used in the Development of Sensing Phases 50910.4 Conclusion and Future Challenges 52211 Photoredox Catalysis of Iridium(III)-Based Photosensitizers 541Timothy M. Monos and Corey R. J. Stephenson11.1 Introduction 54111.2 Iridium-Based Photoredox Catalysis in Organic Synthesis 54711.3 Conclusion 57412 Solar Fuel Generation: Structural and Functional Evolution of Iridium Photosensitizers 583Husain N. Kagalwala, Danielle N. Chirdon and Stefan Bernhard12.1 Introduction 58312.2 Fundamentals of [Ir(C^N)2(N^N)]+ Photosensitizers 58512.3 Application of [Ir(C^N)2(N^N)]+ in Photocatalytic Water Reduction 58912.4 Alternative Iridium Structures 60312.5 Outlook 60713 Iridium Complexes in Water Oxidation Catalysis 617Ilaria Corbucci, Alceo Macchioni and Martin Albrecht13.1 Introduction 61713.2 Sacrificial Oxidants 61913.3 Molecular Iridium Catalyst for Water Oxidation 62113.4 Conclusions 64714 Iridium Complexes as Photoactive Center for Light Harvesting and Solar Cell Applications 655Etienne Baranoff and Prashant Kumar14.1 Introduction 65514.2 Photoinduced Electron Transfer in Multicomponent Arrays 65614.3 Iridium Complexes as Photoactive Center for Solar Cell Applications 66514.4 Conclusions 676References 677Index 683

Edited byEli Zysman-Colman EaStCHEM School of Chemistry, University of St Andrews, UK

• List of Contributors xvForeword xviiPreface xixVOLUME 11 Archetypal Iridium(III) Compounds for Optoelectronic and Photonic Applications: Photophysical Properties and Synthetic Methods 1Joseph C. Deaton and Felix N. Castellano1.1 Introduction 11.2 Iridium Complex Ion Dopants in Silver Halide Photographic Materials 11.3 Overview of the Photophysical Properties of C^N and C^C: Cyclometalated Ir(III) Complexes 21.4 Importance of Ir—C Bonds in the Archetypal Ir(III) Complexes for Optoelectronic and Photonic Applications 91.5 Tuning Emission Color 141.6 Absorbance and Photoluminescence of C^N Cyclometalated Ir(III) Complexes 171.7 SOC Mechanism: Radiative Decay Rates and ZFS 231.8 Non-Radiative Decay Rates 391.9 Synthetic Methods Targeting C^N Cyclometalated Ir(III) Compounds 421.10 Synthetic Methods for Cyclometalated Ir(III) Compounds Containing Carbenes 471.11 Conclusions 482 Multinuclear Iridium Complexes 71J. A. Gareth Williams2.1 Introduction 712.2 Compounds Incorporating 'Single Atom Bridges': μ-Chloro, μ-Oxo and μ-Aza 722.3 Polyatomic Acyclic Bridges: Acetylides, Cyanides and Hydrazides 782.4 Compounds with Heterocyclic Bridges 822.5 Multinuclear Complexes Featuring Conjugated Bridges between Iridium-Bound Polypyridyl or Arylpyridyl Ligands 932.6 Concluding Remarks 1043 Soft Materials and Soft Salts Based on Iridium Complexes 111Etienne Baranoff and Yafei Wang3.1 Introduction 1113.2 Liquid Crystals 1123.3 Gels 1153.4 Micelles 1163.5 Langmuir–Blodgett Films 1183.6 Soft Salts 1183.7 Conclusion 1234 Porous Materials Based on Precious Metal Building Blocks for Solar Energy Applications 127Daniel Micheroni and Wenbin Lin4.1 Introduction 1274.2 The Luminescent Nature of MOFs and Their Use in Chemical Applications 1294.3 Energy Transfer in Porous Materials 1344.4 Porous Materials for Water Oxidation 1364.5 Porous Materials for Proton Reduction 1384.6 Porous Materials for CO2 Reduction 1404.7 Conclusions and Outlook 1415 Polymeric Architectures Containing Phosphorescent Iridium(III) Complexes 145Andreas Winter and Ulrich S. Schubert5.1 Introduction 1455.2 Ir(III)-Containing Polymers: Classification, Design Principles, and Syntheses 1465.3 Hyperbranched and Dendritic Architectures 1875.4 Concluding Remarks 1916 Iridium(III) Complexes for OLED Application 205Elena Longhi and Luisa De Cola6.1 Introduction 2056.2 Iridium Complexes 2066.3 Organic Light-Emitting Diodes 2166.4 Iridium(III) Complexes for PHOLED Application 2276.5 Conclusions and Perspectives 2627 A Comprehensive Review of Luminescent Iridium Complexes Used in Light-Emitting Electrochemical Cells (LEECs) 275Adam F. Henwood and Eli Zysman-Colman7.1 Introduction 2757.2 Device Fundamentals 2787.3 Green Emitters 2807.4 Blue Emitters 3017.5 Yellow Emitters 3237.6 Orange-Red Emitters 3347.7 Conclusions and Outlook 348VOLUME 28 Electrochemiluminescence of Iridium Complexes 359Sarah E. Laird and Conor F. Hogan8.1 Background and Overview of Electrochemiluminescence 3598.2 Iridium ECL 3639 Strategic Applications of Luminescent Iridium(III) Complexes as Biomolecular Probes, Cellular Imaging Reagents, and Photodynamic Therapeutics 415Karson Ka-Shun Tso and Kenneth Kam-Wing Lo9.1 Introduction 4159.2 General Cellular Staining Reagents 4169.3 Hypoxia Sensing Probes 4239.4 Molecular and Ion Intracellular Probes 4279.5 Organelle-Targeting Bioimaging Reagents 4419.6 Functionalized Polypeptides for Bioimaging 4509.7 Polymers and Nanoparticles for Bioimaging 4549.8 Photocytotoxic Reagents and Photodynamic Therapeutics 4589.9 Conclusion 46610 Iridium Complexes in the Development of Optical Sensors 479Teresa Ramón-Márquez, Marta Marín-Suárez, Alberto Fernández-Gutiérrez and J. F. Fernández-Sánchez10.1 Generalities of Optical Sensors 47910.2 Ir(III) Used as Optical Probes 48110.3 Ir(III) Used in the Development of Sensing Phases 50910.4 Conclusion and Future Challenges 52211 Photoredox Catalysis of Iridium(III)-Based Photosensitizers 541Timothy M. Monos and Corey R. J. Stephenson11.1 Introduction 54111.2 Iridium-Based Photoredox Catalysis in Organic Synthesis 54711.3 Conclusion 57412 Solar Fuel Generation: Structural and Functional Evolution of Iridium Photosensitizers 583Husain N. Kagalwala, Danielle N. Chirdon and Stefan Bernhard12.1 Introduction 58312.2 Fundamentals of [Ir(C^N)2(N^N)]+ Photosensitizers 58512.3 Application of [Ir(C^N)2(N^N)]+ in Photocatalytic Water Reduction 58912.4 Alternative Iridium Structures 60312.5 Outlook 60713 Iridium Complexes in Water Oxidation Catalysis 617Ilaria Corbucci, Alceo Macchioni and Martin Albrecht13.1 Introduction 61713.2 Sacrificial Oxidants 61913.3 Molecular Iridium Catalyst for Water Oxidation 62113.4 Conclusions 64714 Iridium Complexes as Photoactive Center for Light Harvesting and Solar Cell Applications 655Etienne Baranoff and Prashant Kumar14.1 Introduction 65514.2 Photoinduced Electron Transfer in Multicomponent Arrays 65614.3 Iridium Complexes as Photoactive Center for Solar Cell Applications 66514.4 Conclusions 676References 677Index 683

Edited byEli Zysman-Colman EaStCHEM School of Chemistry, University of St Andrews, UK

• List of Contributors xvForeword xviiPreface xixVOLUME 11 Archetypal Iridium(III) Compounds for Optoelectronic and Photonic Applications: Photophysical Properties and Synthetic Methods 1Joseph C. Deaton and Felix N. Castellano1.1 Introduction 11.2 Iridium Complex Ion Dopants in Silver Halide Photographic Materials 11.3 Overview of the Photophysical Properties of C^N and C^C: Cyclometalated Ir(III) Complexes 21.4 Importance of Ir—C Bonds in the Archetypal Ir(III) Complexes for Optoelectronic and Photonic Applications 91.5 Tuning Emission Color 141.6 Absorbance and Photoluminescence of C^N Cyclometalated Ir(III) Complexes 171.7 SOC Mechanism: Radiative Decay Rates and ZFS 231.8 Non-Radiative Decay Rates 391.9 Synthetic Methods Targeting C^N Cyclometalated Ir(III) Compounds 421.10 Synthetic Methods for Cyclometalated Ir(III) Compounds Containing Carbenes 471.11 Conclusions 482 Multinuclear Iridium Complexes 71J. A. Gareth Williams2.1 Introduction 712.2 Compounds Incorporating 'Single Atom Bridges': μ-Chloro, μ-Oxo and μ-Aza 722.3 Polyatomic Acyclic Bridges: Acetylides, Cyanides and Hydrazides 782.4 Compounds with Heterocyclic Bridges 822.5 Multinuclear Complexes Featuring Conjugated Bridges between Iridium-Bound Polypyridyl or Arylpyridyl Ligands 932.6 Concluding Remarks 1043 Soft Materials and Soft Salts Based on Iridium Complexes 111Etienne Baranoff and Yafei Wang3.1 Introduction 1113.2 Liquid Crystals 1123.3 Gels 1153.4 Micelles 1163.5 Langmuir–Blodgett Films 1183.6 Soft Salts 1183.7 Conclusion 1234 Porous Materials Based on Precious Metal Building Blocks for Solar Energy Applications 127Daniel Micheroni and Wenbin Lin4.1 Introduction 1274.2 The Luminescent Nature of MOFs and Their Use in Chemical Applications 1294.3 Energy Transfer in Porous Materials 1344.4 Porous Materials for Water Oxidation 1364.5 Porous Materials for Proton Reduction 1384.6 Porous Materials for CO2 Reduction 1404.7 Conclusions and Outlook 1415 Polymeric Architectures Containing Phosphorescent Iridium(III) Complexes 145Andreas Winter and Ulrich S. Schubert5.1 Introduction 1455.2 Ir(III)-Containing Polymers: Classification, Design Principles, and Syntheses 1465.3 Hyperbranched and Dendritic Architectures 1875.4 Concluding Remarks 1916 Iridium(III) Complexes for OLED Application 205Elena Longhi and Luisa De Cola6.1 Introduction 2056.2 Iridium Complexes 2066.3 Organic Light-Emitting Diodes 2166.4 Iridium(III) Complexes for PHOLED Application 2276.5 Conclusions and Perspectives 2627 A Comprehensive Review of Luminescent Iridium Complexes Used in Light-Emitting Electrochemical Cells (LEECs) 275Adam F. Henwood and Eli Zysman-Colman7.1 Introduction 2757.2 Device Fundamentals 2787.3 Green Emitters 2807.4 Blue Emitters 3017.5 Yellow Emitters 3237.6 Orange-Red Emitters 3347.7 Conclusions and Outlook 348VOLUME 28 Electrochemiluminescence of Iridium Complexes 359Sarah E. Laird and Conor F. Hogan8.1 Background and Overview of Electrochemiluminescence 3598.2 Iridium ECL 3639 Strategic Applications of Luminescent Iridium(III) Complexes as Biomolecular Probes, Cellular Imaging Reagents, and Photodynamic Therapeutics 415Karson Ka-Shun Tso and Kenneth Kam-Wing Lo9.1 Introduction 4159.2 General Cellular Staining Reagents 4169.3 Hypoxia Sensing Probes 4239.4 Molecular and Ion Intracellular Probes 4279.5 Organelle-Targeting Bioimaging Reagents 4419.6 Functionalized Polypeptides for Bioimaging 4509.7 Polymers and Nanoparticles for Bioimaging 4549.8 Photocytotoxic Reagents and Photodynamic Therapeutics 4589.9 Conclusion 46610 Iridium Complexes in the Development of Optical Sensors 479Teresa Ramón-Márquez, Marta Marín-Suárez, Alberto Fernández-Gutiérrez and J. F. Fernández-Sánchez10.1 Generalities of Optical Sensors 47910.2 Ir(III) Used as Optical Probes 48110.3 Ir(III) Used in the Development of Sensing Phases 50910.4 Conclusion and Future Challenges 52211 Photoredox Catalysis of Iridium(III)-Based Photosensitizers 541Timothy M. Monos and Corey R. J. Stephenson11.1 Introduction 54111.2 Iridium-Based Photoredox Catalysis in Organic Synthesis 54711.3 Conclusion 57412 Solar Fuel Generation: Structural and Functional Evolution of Iridium Photosensitizers 583Husain N. Kagalwala, Danielle N. Chirdon and Stefan Bernhard12.1 Introduction 58312.2 Fundamentals of [Ir(C^N)2(N^N)]+ Photosensitizers 58512.3 Application of [Ir(C^N)2(N^N)]+ in Photocatalytic Water Reduction 58912.4 Alternative Iridium Structures 60312.5 Outlook 60713 Iridium Complexes in Water Oxidation Catalysis 617Ilaria Corbucci, Alceo Macchioni and Martin Albrecht13.1 Introduction 61713.2 Sacrificial Oxidants 61913.3 Molecular Iridium Catalyst for Water Oxidation 62113.4 Conclusions 64714 Iridium Complexes as Photoactive Center for Light Harvesting and Solar Cell Applications 655Etienne Baranoff and Prashant Kumar14.1 Introduction 65514.2 Photoinduced Electron Transfer in Multicomponent Arrays 65614.3 Iridium Complexes as Photoactive Center for Solar Cell Applications 66514.4 Conclusions 676References 677Index 683