Title Details

Foreword
by Dr Hamaguchi xiii

Foreword
by Dr Noyori xv

Preface xvii

1 Charge Transport Simulations for Organic Semiconductors 1
Hiroyuki Ishii

1.1 Introduction 1

1.1.1 Historical Approach to Organic Semiconductors 1

1.1.2 Recent Progress and Requirements to Computational “Molecular Technology” 4

1.2 Theoretical Description of Charge Transport in Organic Semiconductors 4

1.2.1 Incoherent Hopping Transport Model 6

1.2.2 Coherent Band Transport Model 7

1.2.3 Coherent Polaron Transport Model 9

1.2.4 Trap Potentials 10

1.2.5 Wave-packet Dynamics Approach Based on Density Functional Theory 11

1.3 Charge Transport Properties of Organic Semiconductors 15

1.3.1 Comparison of Polaron Formation Energy with Dynamic Disorder of Transfer Integrals due to Molecular Vibrations 15

1.3.2 Temperature Dependence of Mobility 16

1.3.3 Evaluation of Intrinsic Mobilities for Various Organic Semiconductors 17

1.4 Summary 18

1.4.1 Forthcoming Challenges in Theoretical Studies 19

Acknowledgments 20

References 20

2 Liquid-Phase Interfacial Synthesis of Highly Oriented Crystalline Molecular Nanosheets 25
Rie Makiura

2.1 Introduction 25

2.2 Molecular Nanosheet Formation with Traditional Surfactants at Air/Liquid Interfaces 26

2.2.1 History of Langmuir–Blodgett Film 26

2.2.2 Basics ofMolecular Nanosheet Formation at Air/Liquid Interfaces 27

2.3 Application of Functional OrganicMolecules for Nanosheet Formation at Air/Liquid Interfaces 27

2.3.1 Functional Organic Molecules with Long Alkyl Chains 27

2.3.2 Functional Organic Molecules without Long Alkyl Chains 27

2.3.3 Application of Functional Porphyrins on Metal Ion Solutions 28

2.4 Porphyrin-Based Metal–Organic Framework (MOF) Nanosheet Crystals Assembled at Air/Liquid Interfaces 29

2.4.1 Metal–Organic Frameworks 29

2.4.2 Method of MOF Nanosheet Creation at Air/Liquid Interfaces 29

2.4.3 Study of the Formation Process of MOF Nanosheets by In Situ X-Ray Diffraction and Brewster Angle Microscopy at Air/Liquid Interfaces 32

2.4.4 Application of a PostinjectionMethod Leading to Enlargement of the Uniform MOF Nanosheet Domain Size 35

2.4.5 Layer-by-Layer Sequential Growth of Nanosheets – Toward Three-Dimensionally Stacked Crystalline MOFThin Films 38

2.4.6 Manipulation of the Layer Stacking Motif in MOF Nanosheets 41

2.4.7 Manipulation of In-Plane Molecular Arrangement in MOF Nanosheets 46

References 51

3 Molecular Technology for Organic Semiconductors Toward Printed and Flexible Electronics 57
Toshihiro Okamoto

3.1 Introduction 57

3.2 Molecular Design and Favorable Aggregated Structure for Effective Charge Transport of Organic Semiconductors 58

3.3 Molecular Design of Linearly Fused Acene-Type Molecules 59

3.4 Molecular Technology of π-Conjugated Cores for p-Type Organic Semiconductors 61

3.5 Molecular Technology of Substituents for Organic Semiconductors 64

3.5.1 Bulky-Type Substituents 64

3.5.2 Linear Alkyl Chain Substituents 65

3.6 Molecular Technology of Conceptually-new Bent-shaped π-Conjugated Cores for p-Type Organic Semiconductors 66

3.6.1 Bent-Shaped Heteroacenes 66

3.7 Molecular Technology for n-Type Organic Semiconductors 71

3.7.1 Naphthalene Diimide and Perylene Diimide 72

References 77

4 Design of Multiproton-Responsive Metal Complexes as Molecular Technology for Transformation ofSmall Molecules 81
Shigeki Kuwata

4.1 Introduction 81

4.2 Cooperation of Metal and Functional Groups in Metalloenzymes 81

4.2.1 [FeFe] Hydrogenase 82

4.2.2 Peroxidase 82

4.2.3 Nitrogenase 83

4.3 Proton-Responsive Metal Complexes with Two Appended Protic Groups 84

4.3.1 Pincer-Type Bis(azole) Complexes 84

4.3.2 Bis(2-hydroxypyridine) Chelate Complexes 89

4.4 Proton-Responsive Metal Complexes with Three Appended Protic Groups on Tripodal Scaffolds 94

4.5 Summary and Outlook 98

Acknowledgments 98

References 98

5 Photo-Control of Molecular Alignment for Photonic and Mechanical Applications 105
Miho Aizawa, Christopher J. Barrett, and Atsushi Shishido

5.1 Introduction 105

5.2 Photo-Chemical Alignment 107

5.3 Photo-Physical Alignment 112

5.4 Photo-Physico-Chemical Alignment 115

5.5 Application as Photo-Actuators 118

5.6 Conclusions and Perspectives 123

References 123

6 Molecular Technology for Chirality Control: From Structure to Circular Polarization 129
Yoshiaki Uchida, Tetsuya Narushima, and Junpei Yuasa

6.1 Chiral Lanthanide(III) Complexes as Circularly Polarized Luminescence Materials 130

6.1.1 Circularly Polarized Luminescence (CPL) 130

6.1.2 Theoretical Explanation for Large CPL Activity of Chiral Lanthanide(III) Complexes 131

6.1.3 Optical Activity of Chiral Lanthanide(III) Complexes 132

6.1.4 CPL of Chiral Lanthanide(III) Complexes for Frontier Applications 135

6.2 Magnetic Circular Dichroism and Magnetic Circularly Polarized Luminescence 135

6.2.1 Magnetic–Field-induced Symmetry Breaking on Light Absorption and Emission 136

6.2.2 Molecular Materials Showing MCD and MCPL and Applications 137

6.3 Molecular Self-assembled Helical Structures as Source of Circularly Polarized Light 138

6.3.1 Chiral Liquid Crystalline Phases with Self-assembled Helical Structures 139

6.3.2 Strong CPL of CLC Laser Action 139

6.4 Optical Activity Caused by Mesoscopic Chiral Structures and Microscopic Analysis of the Chiroptical Properties 140

6.4.1 Microscopic CD Measurements via Far-field Detection 142

6.4.2 Optical ActivityMeasurement Based on Improvement of a PEM Technique 143

6.4.3 Discrete Illumination of Pure Circularly Polarized Light 143

6.4.4 Complete Analysis of Contribution From All Polarization Components 145

6.4.5 Near-field CD Imaging 145

6.5 Conclusions 146

References 147

7 Molecular Technology of Excited Triplet State 155
Yuki Kurashige, Nobuhiro Yanai, Yong-Jin Pu, and So Kawata

7.1 Properties of the Triplet Exciton and Associated Phenomena for Molecular Technology 155

7.1.1 Introduction: The Triplet Exciton 155

7.1.2 Molecular Design for Long Diffusion Length 155

7.1.3 Theoretical Analysis for the Electronic Transition Processes Associated with Triplet 158

7.2 Near-infrared-to-visible Photon Upconversion: Chromophore Development and Triplet Energy Migration 162

7.2.1 Introduction 162

7.2.2 Evaluation of TTA-UC Properties 164

7.2.3 NIR-to-visible TTA-UC Sensitized by Metalated Macrocyclic Molecules 165

7.2.4 TTA-UC Sensitized by Metal Complexes with S–T Absorption 169

7.2.5 Conclusion and Outlook 171

7.3 Singlet Exciton Fission Molecules and Their Application to Organic Photovoltaics 171

7.3.1 Introduction 171

7.3.2 Polycyclic π-Conjugated Compounds 172

7.3.2.1 Pentacene 172

7.3.2.2 Tetracene 174

7.3.2.3 Hexacene 175

7.3.2.4 Heteroacene 175

7.3.2.5 Perylene and Terrylene 175

7.3.3 Nonpolycyclic π-Conjugated Compounds 177

7.3.4 Polymers 178

7.3.5 Perspectives 179

References 180

8 Material Transfer and Spontaneous Motion in Mesoscopic Scale with Molecular Technology 187
Yoshiyuki Kageyama, Yoshiko Takenaka, and Kenji Higashiguchi

8.1 Introduction 187

8.1.1 Introduction of Chemical Actuators 187

8.1.2 Composition of This Chapter 188

8.2 Mechanism to Originate Mesoscale Motion 189

8.2.1 Motion Generated by Molecular Power 189

8.2.2 Gliding Motion of a Mesoscopic Object by the Gradient of Environmental Factors 189

8.2.3 Mesoscopic Motion of an Object by Mechanical Motion of Molecules 191

8.2.4 Toward the Implementation of a One-Dimensional Actuator: Artificial Muscle 191

8.3 Generation of “Molecular Power” by a Stimuli-Responsive Molecule 193

8.3.1 Structural Changes of Molecules and Supramolecular Structures 193

8.3.2 Structural Changes of Photochromic Molecules 196

8.3.3 Fundamentals of Kinetics of Photochromic Reaction 197

8.3.4 Photoisomerization and Actuation 199

8.4 Mesoscale Motion Generated by Cooperation of “Molecular Power” 199

8.4.1 Motion in Gradient Fields 199

8.4.2 Movement Triggered by Mobile Molecules 201

8.4.3 Autonomous Motion with Self-Organization 203

8.5 Summary and Outlook 204

References 205

9 Molecular Technologies for Photocatalytic CO2 Reduction 209
Yusuke Tamaki, Hiroyuki Takeda, and Osamu Ishitani

9.1 Introduction 209

9.2 Photocatalytic Systems Consisting of Mononuclear Metal Complexes 213

9.2.1 Rhenium(I) Complexes 213

9.2.2 Reaction Mechanism 216

9.2.3 Multicomponent Systems 218

9.2.4 Photocatalytic CO2 Reduction Using Earth-Abundant Elements as the Central Metal ofMetal Complexes 220

9.3 Supramolecular Photocatalysts: Multinuclear Complexes 223

9.3.1 Ru(II)—Re(I) Systems 224

9.3.2 Ru(II)—Ru(II) Systems 233

9.3.3 Ir(III)—Re(I) and Os(II)—Re(I) Systems 234

9.4 Photocatalytic Reduction of Low Concentration of CO2 236

9.5 Hybrid Systems Consisting of the Supramolecular Photocatalyst and Semiconductor Photocatalysts 241

9.6 Conclusion 245

Acknowledgements 245

References 245

10 Molecular Design of PhotocathodeMaterials for Hydrogen Evolution and Carbon Dioxide Reduction251
Christopher D.Windle, Soundarrajan Chandrasekaran, Hiromu Kumagai, Go Sahara, Keiji Nagai, Toshiyuki Abe, Murielle Chavarot-Kerlidou, Osamu Ishitani, and Vincent Artero

10.1 Introduction 251

10.2 Photocathode Materials for H2 Evolution 253

10.2.1 Molecular Photocathodes for H2 Evolution Based on Low Bandgap Semiconductors 253

10.2.1.1 Molecular Catalysts Physisorbed on a Semiconductor Surface 253

10.2.1.2 Covalent Attachment of the Catalyst to the Surface of the Semiconductor 256

10.2.1.3 Covalent Attachment of the CatalystWithin an Oligomeric or Polymeric Material Coating the Semiconductor Surface 258

10.2.2 H2-evolving Photocathodes Based on Organic Semiconductors 260

10.2.3 Dye-sensitised Photocathodes for H2 Production 263

10.2.3.1 Dye-sensitised Photocathodes with Physisorbed or Diffusing Catalysts 266

10.2.3.2 Dye-sensitised Photocathodes Based on Covalent or Supramolecular Dye–Catalyst Assemblies 268

10.2.3.3 Dye-sensitised Photocathodes Based on Co-grafted Dyes and Catalysts 270

10.3 Photocathodes for CO2 Reduction Based on Molecular Catalysts 273

10.3.1 Photocatalytic Systems Consisting of a Molecular Catalyst and a Semiconductor Photoelectrode 274

10.3.2 Dye-sensitised Photocathodes Based on Molecular Photocatalysts 278

Acknowledgements 281

References 281

11 Molecular Design of Glucose Biofuel Cell Electrodes 287
Michael Holzinger, Yuta Nishina, Alan Le Goff, Masato Tominaga, Serge Cosnier, and Seiya Tsujimura

11.1 Introduction 287

11.2 Molecular Approaches for Enzymatic Electrocatalytic Oxidation of Glucose 291

11.3 Molecular Designs for Enhanced Electron Transfers with Oxygen-Reducing Enzymes 295

11.4 Conclusion and Future Perspectives 297

References 300

Index 307