<p>Foreword<br /><i>by Dr Hamaguchi xiii</i></p> <p>Foreword<br /><i>by Dr Noyori xv</i></p> <p>Preface xvii</p> <p><b>1 Charge Transport Simulations for Organic Semiconductors 1<br /></b><i>Hiroyuki Ishii</i></p> <p>1.1 Introduction 1</p> <p>1.1.1 Historical Approach to Organic Semiconductors 1</p> <p>1.1.2 Recent Progress and Requirements to Computational “Molecular Technology” 4</p> <p>1.2 Theoretical Description of Charge Transport in Organic Semiconductors 4</p> <p>1.2.1 Incoherent Hopping Transport Model 6</p> <p>1.2.2 Coherent Band Transport Model 7</p> <p>1.2.3 Coherent Polaron Transport Model 9</p> <p>1.2.4 Trap Potentials 10</p> <p>1.2.5 Wave-packet Dynamics Approach Based on Density Functional Theory 11</p> <p>1.3 Charge Transport Properties of Organic Semiconductors 15</p> <p>1.3.1 Comparison of Polaron Formation Energy with Dynamic Disorder of Transfer Integrals due to Molecular Vibrations 15</p> <p>1.3.2 Temperature Dependence of Mobility 16</p> <p>1.3.3 Evaluation of Intrinsic Mobilities for Various Organic Semiconductors 17</p> <p>1.4 Summary 18</p> <p>1.4.1 Forthcoming Challenges in Theoretical Studies 19</p> <p>Acknowledgments 20</p> <p>References 20</p> <p><b>2 Liquid-Phase Interfacial Synthesis of Highly Oriented Crystalline Molecular Nanosheets 25<br /></b><i>Rie Makiura</i></p> <p>2.1 Introduction 25</p> <p>2.2 Molecular Nanosheet Formation with Traditional Surfactants at Air/Liquid Interfaces 26</p> <p>2.2.1 History of Langmuir–Blodgett Film 26</p> <p>2.2.2 Basics ofMolecular Nanosheet Formation at Air/Liquid Interfaces 27</p> <p>2.3 Application of Functional OrganicMolecules for Nanosheet Formation at Air/Liquid Interfaces 27</p> <p>2.3.1 Functional Organic Molecules with Long Alkyl Chains 27</p> <p>2.3.2 Functional Organic Molecules without Long Alkyl Chains 27</p> <p>2.3.3 Application of Functional Porphyrins on Metal Ion Solutions 28</p> <p>2.4 Porphyrin-Based Metal–Organic Framework (MOF) Nanosheet Crystals Assembled at Air/Liquid Interfaces 29</p> <p>2.4.1 Metal–Organic Frameworks 29</p> <p>2.4.2 Method of MOF Nanosheet Creation at Air/Liquid Interfaces 29</p> <p>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</p> <p>2.4.4 Application of a PostinjectionMethod Leading to Enlargement of the Uniform MOF Nanosheet Domain Size 35</p> <p>2.4.5 Layer-by-Layer Sequential Growth of Nanosheets – Toward Three-Dimensionally Stacked Crystalline MOFThin Films 38</p> <p>2.4.6 Manipulation of the Layer Stacking Motif in MOF Nanosheets 41</p> <p>2.4.7 Manipulation of In-Plane Molecular Arrangement in MOF Nanosheets 46</p> <p>References 51</p> <p><b>3 Molecular Technology for Organic Semiconductors Toward Printed and Flexible Electronics 57<br /></b><i>Toshihiro Okamoto</i></p> <p>3.1 Introduction 57</p> <p>3.2 Molecular Design and Favorable Aggregated Structure for Effective Charge Transport of Organic Semiconductors 58</p> <p>3.3 Molecular Design of Linearly Fused Acene-Type Molecules 59</p> <p>3.4 Molecular Technology of π-Conjugated Cores for p-Type Organic Semiconductors 61</p> <p>3.5 Molecular Technology of Substituents for Organic Semiconductors 64</p> <p>3.5.1 Bulky-Type Substituents 64</p> <p>3.5.2 Linear Alkyl Chain Substituents 65</p> <p>3.6 Molecular Technology of Conceptually-new Bent-shaped π-Conjugated Cores for p-Type Organic Semiconductors 66</p> <p>3.6.1 Bent-Shaped Heteroacenes 66</p> <p>3.7 Molecular Technology for n-Type Organic Semiconductors 71</p> <p>3.7.1 Naphthalene Diimide and Perylene Diimide 72</p> <p>References 77</p> <p><b>4 Design of Multiproton-Responsive Metal Complexes as Molecular Technology for Transformation of</b> <b>Small Molecules 81<br /></b><i>Shigeki Kuwata</i></p> <p>4.1 Introduction 81</p> <p>4.2 Cooperation of Metal and Functional Groups in Metalloenzymes 81</p> <p>4.2.1 [FeFe] Hydrogenase 82</p> <p>4.2.2 Peroxidase 82</p> <p>4.2.3 Nitrogenase 83</p> <p>4.3 Proton-Responsive Metal Complexes with Two Appended Protic Groups 84</p> <p>4.3.1 Pincer-Type Bis(azole) Complexes 84</p> <p>4.3.2 Bis(2-hydroxypyridine) Chelate Complexes 89</p> <p>4.4 Proton-Responsive Metal Complexes with Three Appended Protic Groups on Tripodal Scaffolds 94</p> <p>4.5 Summary and Outlook 98</p> <p>Acknowledgments 98</p> <p>References 98</p> <p><b>5 Photo-Control of Molecular Alignment for Photonic and Mechanical Applications 105<br /></b><i>Miho Aizawa, Christopher J. Barrett, and Atsushi Shishido</i></p> <p>5.1 Introduction 105</p> <p>5.2 Photo-Chemical Alignment 107</p> <p>5.3 Photo-Physical Alignment 112</p> <p>5.4 Photo-Physico-Chemical Alignment 115</p> <p>5.5 Application as Photo-Actuators 118</p> <p>5.6 Conclusions and Perspectives 123</p> <p>References 123</p> <p><b>6 Molecular Technology for Chirality Control: From Structure to Circular Polarization 129<br /></b><i>Yoshiaki Uchida, Tetsuya Narushima, and Junpei Yuasa</i></p> <p>6.1 Chiral Lanthanide(III) Complexes as Circularly Polarized Luminescence Materials 130</p> <p>6.1.1 Circularly Polarized Luminescence (CPL) 130</p> <p>6.1.2 Theoretical Explanation for Large CPL Activity of Chiral Lanthanide(III) Complexes 131</p> <p>6.1.3 Optical Activity of Chiral Lanthanide(III) Complexes 132</p> <p>6.1.4 CPL of Chiral Lanthanide(III) Complexes for Frontier Applications 135</p> <p>6.2 Magnetic Circular Dichroism and Magnetic Circularly Polarized Luminescence 135</p> <p>6.2.1 Magnetic–Field-induced Symmetry Breaking on Light Absorption and Emission 136</p> <p>6.2.2 Molecular Materials Showing MCD and MCPL and Applications 137</p> <p>6.3 Molecular Self-assembled Helical Structures as Source of Circularly Polarized Light 138</p> <p>6.3.1 Chiral Liquid Crystalline Phases with Self-assembled Helical Structures 139</p> <p>6.3.2 Strong CPL of CLC Laser Action 139</p> <p>6.4 Optical Activity Caused by Mesoscopic Chiral Structures and Microscopic Analysis of the Chiroptical Properties 140</p> <p>6.4.1 Microscopic CD Measurements via Far-field Detection 142</p> <p>6.4.2 Optical ActivityMeasurement Based on Improvement of a PEM Technique 143</p> <p>6.4.3 Discrete Illumination of Pure Circularly Polarized Light 143</p> <p>6.4.4 Complete Analysis of Contribution From All Polarization Components 145</p> <p>6.4.5 Near-field CD Imaging 145</p> <p>6.5 Conclusions 146</p> <p>References 147</p> <p><b>7 Molecular Technology of Excited Triplet State 155<br /></b><i>Yuki Kurashige, Nobuhiro Yanai, Yong-Jin Pu, and So Kawata</i></p> <p>7.1 Properties of the Triplet Exciton and Associated Phenomena for Molecular Technology 155</p> <p>7.1.1 Introduction: The Triplet Exciton 155</p> <p>7.1.2 Molecular Design for Long Diffusion Length 155</p> <p>7.1.3 Theoretical Analysis for the Electronic Transition Processes Associated with Triplet 158</p> <p>7.2 Near-infrared-to-visible Photon Upconversion: Chromophore Development and Triplet Energy Migration 162</p> <p>7.2.1 Introduction 162</p> <p>7.2.2 Evaluation of TTA-UC Properties 164</p> <p>7.2.3 NIR-to-visible TTA-UC Sensitized by Metalated Macrocyclic Molecules 165</p> <p>7.2.4 TTA-UC Sensitized by Metal Complexes with S–T Absorption 169</p> <p>7.2.5 Conclusion and Outlook 171</p> <p>7.3 Singlet Exciton Fission Molecules and Their Application to Organic Photovoltaics 171</p> <p>7.3.1 Introduction 171</p> <p>7.3.2 Polycyclic π-Conjugated Compounds 172</p> <p>7.3.2.1 Pentacene 172</p> <p>7.3.2.2 Tetracene 174</p> <p>7.3.2.3 Hexacene 175</p> <p>7.3.2.4 Heteroacene 175</p> <p>7.3.2.5 Perylene and Terrylene 175</p> <p>7.3.3 Nonpolycyclic π-Conjugated Compounds 177</p> <p>7.3.4 Polymers 178</p> <p>7.3.5 Perspectives 179</p> <p>References 180</p> <p><b>8 Material Transfer and Spontaneous Motion in Mesoscopic Scale with Molecular Technology 187<br /></b><i>Yoshiyuki Kageyama, Yoshiko Takenaka, and Kenji Higashiguchi</i></p> <p>8.1 Introduction 187</p> <p>8.1.1 Introduction of Chemical Actuators 187</p> <p>8.1.2 Composition of This Chapter 188</p> <p>8.2 Mechanism to Originate Mesoscale Motion 189</p> <p>8.2.1 Motion Generated by Molecular Power 189</p> <p>8.2.2 Gliding Motion of a Mesoscopic Object by the Gradient of Environmental Factors 189</p> <p>8.2.3 Mesoscopic Motion of an Object by Mechanical Motion of Molecules 191</p> <p>8.2.4 Toward the Implementation of a One-Dimensional Actuator: Artificial Muscle 191</p> <p>8.3 Generation of “Molecular Power” by a Stimuli-Responsive Molecule 193</p> <p>8.3.1 Structural Changes of Molecules and Supramolecular Structures 193</p> <p>8.3.2 Structural Changes of Photochromic Molecules 196</p> <p>8.3.3 Fundamentals of Kinetics of Photochromic Reaction 197</p> <p>8.3.4 Photoisomerization and Actuation 199</p> <p>8.4 Mesoscale Motion Generated by Cooperation of “Molecular Power” 199</p> <p>8.4.1 Motion in Gradient Fields 199</p> <p>8.4.2 Movement Triggered by Mobile Molecules 201</p> <p>8.4.3 Autonomous Motion with Self-Organization 203</p> <p>8.5 Summary and Outlook 204</p> <p>References 205</p> <p><b>9 Molecular Technologies for Photocatalytic CO2 Reduction 209<br /></b><i>Yusuke Tamaki, Hiroyuki Takeda, and Osamu Ishitani</i></p> <p>9.1 Introduction 209</p> <p>9.2 Photocatalytic Systems Consisting of Mononuclear Metal Complexes 213</p> <p>9.2.1 Rhenium(I) Complexes 213</p> <p>9.2.2 Reaction Mechanism 216</p> <p>9.2.3 Multicomponent Systems 218</p> <p>9.2.4 Photocatalytic CO2 Reduction Using Earth-Abundant Elements as the Central Metal ofMetal Complexes 220</p> <p>9.3 Supramolecular Photocatalysts: Multinuclear Complexes 223</p> <p>9.3.1 Ru(II)—Re(I) Systems 224</p> <p>9.3.2 Ru(II)—Ru(II) Systems 233</p> <p>9.3.3 Ir(III)—Re(I) and Os(II)—Re(I) Systems 234</p> <p>9.4 Photocatalytic Reduction of Low Concentration of CO2 236</p> <p>9.5 Hybrid Systems Consisting of the Supramolecular Photocatalyst and Semiconductor Photocatalysts 241</p> <p>9.6 Conclusion 245</p> <p>Acknowledgements 245</p> <p>References 245</p> <p><b>10 Molecular Design of PhotocathodeMaterials for Hydrogen Evolution and Carbon Dioxide Reduction</b> <b>251<br /></b><i>Christopher D.Windle, Soundarrajan Chandrasekaran, Hiromu Kumagai, Go Sahara, Keiji Nagai, Toshiyuki Abe, Murielle Chavarot-Kerlidou, Osamu Ishitani, and Vincent Artero</i></p> <p>10.1 Introduction 251</p> <p>10.2 Photocathode Materials for H2 Evolution 253</p> <p>10.2.1 Molecular Photocathodes for H2 Evolution Based on Low Bandgap Semiconductors 253</p> <p>10.2.1.1 Molecular Catalysts Physisorbed on a Semiconductor Surface 253</p> <p>10.2.1.2 Covalent Attachment of the Catalyst to the Surface of the Semiconductor 256</p> <p>10.2.1.3 Covalent Attachment of the CatalystWithin an Oligomeric or Polymeric Material Coating the Semiconductor Surface 258</p> <p>10.2.2 H2-evolving Photocathodes Based on Organic Semiconductors 260</p> <p>10.2.3 Dye-sensitised Photocathodes for H2 Production 263</p> <p>10.2.3.1 Dye-sensitised Photocathodes with Physisorbed or Diffusing Catalysts 266</p> <p>10.2.3.2 Dye-sensitised Photocathodes Based on Covalent or Supramolecular Dye–Catalyst Assemblies 268</p> <p>10.2.3.3 Dye-sensitised Photocathodes Based on Co-grafted Dyes and Catalysts 270</p> <p>10.3 Photocathodes for CO2 Reduction Based on Molecular Catalysts 273</p> <p>10.3.1 Photocatalytic Systems Consisting of a Molecular Catalyst and a Semiconductor Photoelectrode 274</p> <p>10.3.2 Dye-sensitised Photocathodes Based on Molecular Photocatalysts 278</p> <p>Acknowledgements 281</p> <p>References 281</p> <p><b>11 Molecular Design of Glucose Biofuel Cell Electrodes 287<br /></b><i>Michael Holzinger, Yuta Nishina, Alan Le Goff, Masato Tominaga, Serge Cosnier, and Seiya Tsujimura</i></p> <p>11.1 Introduction 287</p> <p>11.2 Molecular Approaches for Enzymatic Electrocatalytic Oxidation of Glucose 291</p> <p>11.3 Molecular Designs for Enhanced Electron Transfers with Oxygen-Reducing Enzymes 295</p> <p>11.4 Conclusion and Future Perspectives 297</p> <p>References 300</p> <p>Index 307</p>