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· 분류 : 외국도서 > 과학/수학/생태 > 과학 > 화학 > 무기화학
· ISBN : 9781119007142
· 쪽수 : 736쪽
· 출판일 : 2017-03-03
목차
List of Contributors xv
Foreword xvii
Preface xix
VOLUME 1
1 Archetypal Iridium(III) Compounds for Optoelectronic and Photonic Applications: Photophysical Properties and Synthetic Methods 1
Joseph C. Deaton and Felix N. Castellano
1.1 Introduction 1
1.2 Iridium Complex Ion Dopants in Silver Halide Photographic Materials 1
1.3 Overview of the Photophysical Properties of C^N and C^C: Cyclometalated Ir(III) Complexes 2
1.4 Importance of Ir─C Bonds in the Archetypal Ir(III) Complexes for Optoelectronic and Photonic Applications 9
1.5 Tuning Emission Color 14
1.6 Absorbance and Photoluminescence of C^N Cyclometalated Ir(III) Complexes 17
1.7 SOC Mechanism: Radiative Decay Rates and ZFS 23
1.8 Non-Radiative Decay Rates 39
1.9 Synthetic Methods Targeting C^N Cyclometalated Ir(III) Compounds 42
1.10 Synthetic Methods for Cyclometalated Ir(III) Compounds Containing Carbenes 47
1.11 Conclusions 48
Acknowledgements 49
Abbreviations for Ligands in Ir(III) Complexes 49
References 50
2 Multinuclear Iridium Complexes 71
J. A. Gareth Williams
2.1 Introduction 71
2.2 Compounds Incorporating ‘Single Atom Bridges’: μ-Chloro, μ-Oxo and μ-Aza 72
2.2.1 μ-Chloro-Bridged Complexes 72
2.2.2 μ-Aza-Bridged Complexes 74
2.2.3 μ-Hydroxo-Bridged Complexes 76
2.3 Polyatomic Acyclic Bridges: Acetylides, Cyanides and Hydrazides 78
2.4 Compounds with Heterocyclic Bridges 82
2.4.1 Bis-(N^N)-Coordinating Ligands and Related Systems Incorporating At Least One N^N Unit 83
2.4.2 Bis-(N^C)-Coordinating Ligands 89
2.5 Multinuclear Complexes Featuring Conjugated Bridges between Iridium-Bound Polypyridyl or Arylpyridyl Ligands 93
2.5.1 Systems Incorporating C≡C or N=N Bridges with One or More [Ir(N^C)2(N^N)]+ Units 95
2.5.2 Multinuclear Complexes Incorporating Phenyl and Polyphenylene Bridges between the Ligands: ‘Supramolecular Assemblies’ 96
2.6 Concluding Remarks 104
Acknowledgements 104
References 104
3 Soft Materials and Soft Salts Based on Iridium Complexes 111
Etienne Baranoff and Yafei Wang
3.1 Introduction 111
3.2 Liquid Crystals 112
3.3 Gels 115
3.4 Micelles 116
3.5 Langmuir–Blodgett Films 118
3.6 Soft Salts 118
3.7 Conclusion 123
Acknowledgements 123
References 123
4 Porous Materials Based on Precious Metal Building Blocks for Solar Energy Applications 127
Daniel Micheroni and Wenbin Lin
4.1 Introduction 127
4.2 The Luminescent Nature of MOFs and Their Use in Chemical Applications 129
4.3 Energy Transfer in Porous Materials 134
4.4 Porous Materials for Water Oxidation 136
4.5 Porous Materials for Proton Reduction 138
4.6 Porous Materials for CO2 Reduction 140
4.7 Conclusions and Outlook 141
References 141
5 Polymeric Architectures Containing Phosphorescent Iridium(III) Complexes 145
Andreas Winter and Ulrich S. Schubert
5.1 Introduction 145
5.2 Ir(III)-Containing Polymers: Classification, Design Principles, and Syntheses 146
5.2.1 Classification of Ir(III)-Containing Polymers 146
5.2.2 Design Principles for Metal-Containing Polymers 147
5.2.2.1 Decoration of Preformed Polymers with Ir(III) Complexes 149
5.2.2.2 Coordination of Ir(III) Precursor Complexes to Preformed Polymers 151
5.2.2.3 (Co)Polymerization of Ir(III)-Containing Monomers 157
5.2.2.4 Electropolymerization of Ir(III)-Containing Complexes 182
5.2.2.5 Synthetic Approaches Toward Ir(III)-Containing Polymers: The Roads Not Taken 186
5.3 Hyperbranched and Dendritic Architectures 187
5.3.1 Ir(III)-Containing Hyperbranched Polymers 187
5.3.2 Ir(III)-Containing Dendritic Systems 188
5.4 Concluding Remarks 191
References 192
6 Iridium(III) Complexes for OLED Application 205
Elena Longhi and Luisa De Cola
6.1 Introduction 205
6.2 Iridium Complexes 206
6.2.1 General Synthesis of Ir(III) Complexes 207
6.2.2 Luminescence of Iridium(III) Complexes 208
6.2.3 Emission Color Tuning in Iridium(III) Complexes 209
6.2.3.1 Influence of the (C^N) Ligand 210
6.2.3.2 Influence of the Ancillary Ligand 212
6.3 Organic Light-Emitting Diodes 216
6.3.1 Device Architecture and Fabrication 217
6.3.2 Device Lifetime 218
6.3.3 Device Efficiency 220
6.3.4 Phosphorescent Materials 221
6.3.5 Host Materials 222
6.4 Iridium(III) Complexes for PHOLED Application 227
6.4.1 Green Emitters 227
6.4.1.1 Role of the Ancillary Ligand 228
6.4.1.2 Modification of the Phenylpyridine Ring 229
6.4.1.3 Use of Different Tris-cyclometalated Motifs 230
6.4.2 Red Emitters 232
6.4.3 Blue Emitters 238
6.5 Conclusions and Perspectives 262
References 262
7 A Comprehensive Review of Luminescent Iridium Complexes Used in Light-Emitting Electrochemical Cells (LEECs) 275
Adam F. Henwood and Eli Zysman-Colman
7.1 Introduction 275
7.2 Device Fundamentals 278
7.3 Green Emitters 280
7.3.1 Archetypal Emitters 282
7.3.2 Pyrazoles 289
7.3.3 Imidazoles 292
7.3.4 Triazoles and Tetrazoles 293
7.3.5 Oxadiazoles 294
7.3.6 Thiophenes 296
7.3.7 Intramolecular π-Stacked Emitters 296
7.3.8 Supramolecular Emitters 300
7.4 Blue Emitters 301
7.4.1 [Ir(ppy)2(bpy)]+-Type Emitters 302
7.4.2 Pyrazoles 307
7.4.3 Imidazoles 312
7.4.4 Triazoles 313
7.4.5 Oxadiazoles 316
7.4.6 N-Heterocyclic Carbenes 320
7.4.7 Phosphines 322
7.5 Yellow Emitters 323
7.5.1 [Ir(ppy)2(bpy)]+-Type Emitters 324
7.5.2 Imidazole Emitters 327
7.5.3 Anionic Emitters 328
7.5.4 Intramolecularly π-Stacked Emitters 328
7.5.5 Multifunctional or Supramolecular Emitters 332
7.6 Orange-Red Emitters 334
7.6.1 [Ir(ppy)2(bpy)]+-Type Emitters 335
7.6.2 Emitters Bearing Five-Membered Heterocyclic Rings 340
7.6.3 Intramolecular π-Stacked Emitters 341
7.6.4 Multifunctional Emitters 345
7.7 Conclusions and Outlook 348
Acknowledgements 349
References 349
VOLUME 2
8 Electrochemiluminescence of Iridium Complexes 359
Sarah E. Laird and Conor F. Hogan
8.1 Background and Overview of Electrochemiluminescence 359
8.1.1 ECL from Metal Complexes 362
8.2 Iridium ECL 363
8.2.1 First Examples 363
8.2.2 Renewed Interest in Iridium ECL Stimulated by Progress in the Field of Light-Emitting Devices 364
8.2.3 Early Advances in Theoretical Understanding and Electrochemiluminophore Design 366
8.2.4 Modified Electrode Systems 370
8.2.5 ECL-Based Sensing Strategies 372
8.2.6 Issues Related to ECL of Iridium Complexes in Aqueous Media and Quenching by Oxygen 384
8.2.7 Tuning ECL Emission Colour and Redox Properties 386
8.2.8 Potential-Resolved Multicolour ECL 399
8.2.8.1 Miscellaneous ECL Systems Involving Iridium Complexes 405
8.2.9 Conclusion and Future Prospects 406
List of Ligand Abbreviations Used in Text 406
References 407
9 Strategic Applications of Luminescent Iridium(III) Complexes as Biomolecular Probes, Cellular Imaging Reagents, and Photodynamic Therapeutics 415
Karson Ka-Shun Tso and Kenneth Kam-Wing Lo
9.1 Introduction 415
9.2 General Cellular Staining Reagents 416
9.3 Hypoxia Sensing Probes 423
9.4 Molecular and Ion Intracellular Probes 427
9.4.1 Intracellular Probes for Sulfur-Containing Species 427
9.4.2 Intracellular Probes for Metal Ions 433
9.4.3 Intracellular Probes for Hypochlorous Acid and Hypochlorite 437
9.4.4 Intracellular Probes for Nitric Oxide 439
9.5 Organelle-Targeting Bioimaging Reagents 441
9.5.1 Nucleus 441
9.5.2 Nucleoli 443
9.5.3 Golgi Apparatus 445
9.5.4 Mitochondria 447
9.6 Functionalized Polypeptides for Bioimaging 450
9.7 Polymers and Nanoparticles for Bioimaging 454
9.8 Photocytotoxic Reagents and Photodynamic Therapeutics 458
9.9 Conclusion 466
Acknowledgements 466
Abbreviations 466
References 469
10 Iridium Complexes in the Development of Optical Sensors 479
Teresa Ramón-Márquez, Marta Marín-Suárez, Alberto Fernández-Gutiérrez and J. F. Fernández-Sánchez
10.1 Generalities of Optical Sensors 479
10.2 Ir(III) Used as Optical Probes 481
10.2.1 Optical Probes for the Detection of Gaseous Species 481
10.2.1.1 Oxygen 482
10.2.1.2 Other Gaseous Species 483
10.2.2 Optical Probes for the Detection of Ionic Species 485
10.2.2.1 Cations 485
10.2.2.2 pH 491
10.2.2.3 Anions 493
10.2.3 Optical Probes for the Detection of Biomolecules 498
10.2.3.1 Amino Acids and Proteins 498
10.2.3.2 Nucleotides and Nucleic Acids 506
10.2.4 Optical Probes for the Detection of Other Small Molecules 506
10.2.4.1 Explosives 506
10.2.4.2 Free Radicals 507
10.2.4.3 H2O2 508
10.2.4.4 Amines 508
10.2.4.5 Silver Salts 508
10.2.4.6 Hypochlorous Acid (HOCl) 508
10.3 Ir(III) Used in the Development of Sensing Phases 509
10.3.1 Sensing Phases for the Detection of Gases 509
10.3.1.1 Oxygen 509
10.3.1.2 Others Gases 516
10.3.2 Sensing Phases for the Detection of Ions 516
10.3.3 Sensing Phases for the Detection of Biomolecules 517
10.3.3.1 Glucose 518
10.3.3.2 BSA 520
10.3.3.3 Cysteine and Homocysteine 520
10.3.3.4 Heparin 520
10.3.3.5 Histone 521
10.3.4 Sensing Phases for Multiparametric Sensing 521
10.4 Conclusion and Future Challenges 522
Acronyms Used in the Names of the Complexes 525
References 528
11 Photoredox Catalysis of Iridium(III)-Based Photosensitizers 541
Timothy M. Monos and Corey R. J. Stephenson
11.1 Introduction 541
11.1.1 Photoredox Catalysis 541
11.1.2 Principles of Photoredox Catalysis 542
11.1.3 Iridium(III) Photocatalyst Design 542
11.1.4 Ir(III) Photocatalyst synthesis 545
11.2 Iridium-Based Photoredox Catalysis in Organic Synthesis 547
11.2.1 Net Oxidative Reactions 547
11.2.1.1 Amine Oxidation and Functionalization 547
11.2.1.2 Arene Oxidation 551
11.2.2 Net Reductive Reactions 551
11.2.2.1 Dehalogenation Reactions 551
11.2.2.2 Ketyl Radical Chemistry 553
11.2.3 Redox-Neutral Reactions 554
11.2.3.1 Atom Transfer Radical Addition 555
11.2.3.2 Radical-Based Arene Addition Reactions 561
11.2.3.3 Tandem Catalysis Methods 565
11.2.4 Amine Fragmentation 571
11.3 Conclusion 574
References 574
12 Solar Fuel Generation: Structural and Functional Evolution of Iridium Photosensitizers 583
Husain N. Kagalwala, Danielle N. Chirdon and Stefan Bernhard
12.1 Introduction 583
12.2 Fundamentals of [Ir(C^N)2(N^N)]+ Photosensitizers 585
12.2.1 Synthesis and Structure 585
12.2.2 Electronics: Photophysics and Electrochemistry 585
12.2.3 Complexes Made to Order 588
12.3 Application of [Ir(C^N)2(N^N)]+ in Photocatalytic Water Reduction 589
12.3.1 Initial Exploration 589
12.3.2 Systems with Non-precious Components 591
12.3.3 Strategies for Improved Efficiency 594
12.3.3.1 New C^N Ligands 594
12.3.3.2 New N^N Ligands 597
12.3.3.3 Orchestration 599
12.4 Alternative Iridium Structures 603
12.4.1 Tridentate Coordination 603
12.4.2 Tris-Cyclometalated Complexes 605
12.4.3 Dinuclear Iridium Complexes 606
12.5 Outlook 607
Acknowledgements 609
References 610
13 Iridium Complexes in Water Oxidation Catalysis 617
Ilaria Corbucci, Alceo Macchioni and Martin Albrecht
13.1 Introduction 617
13.2 Sacrificial Oxidants 619
13.2.1 Cerium(IV) Ammonium Nitrate 620
13.2.2 Sodium Periodate 620
13.3 Molecular Iridium Catalyst for Water Oxidation 621
13.3.1 Ir WOCs without Cp∗ 621
13.3.2 Ir WOCs with Cp∗ 624
13.3.3 Cp∗Ir WOCs Based on Carbene-Type Ligands 632
13.3.3.1 Cp∗Ir WOCs Bearing Normal Carbene-Type Ligands 633
13.3.3.2 Cp∗Ir WOCs Bearing Abnormal Carbene-Type Ligands 636
13.3.3.3 Comparison of Catalytic Activity of Cp∗Ir Bearing Mesoionic Imidazolylidene Ligand or the Mesoionic Triazolylidene Analogue 638
13.3.4 Heterogenized Molecular Iridium Catalyst for Water Oxidation 640
13.3.5 Iridium WOC as Photocatalyst for Water Oxidation under Visible Light Irradiation 645
13.4 Conclusions 647
Acknowledgements 648
Glossary of Terms and Abbreviations 648
References 649
14 Iridium Complexes as Photoactive Center for Light Harvesting and Solar Cell Applications 655
Etienne Baranoff and Prashant Kumar
14.1 Introduction 655
14.2 Photoinduced Electron Transfer in Multicomponent Arrays 656
14.2.1 Ir(tpy)2 Fragment (tpy = 2,2 :6 -2 -terpyridine) 656
14.2.2 Cyclometalated Iridium(III) 660
14.3 Iridium Complexes as Photoactive Center for Solar Cell Applications 665
14.3.1 Sensitizer for Dye-Sensitized Solar Cells 665
14.3.2 Iridium Complexes for Organic Photovoltaic Devices 673
14.4 Conclusions 676
References 677
Index 683
