Molecular Technology

Molecular Technology

Energy Innovation
1. Aufl.

von: Hisashi Yamamoto, Takashi Kato

124,99 €

Verlag: Wiley-VCH
Format: PDF
Veröffentl.: 11.06.2018
ISBN/EAN: 9783527802791
Sprache: englisch
Anzahl Seiten: 400

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Edited by foremost leaders in chemical research together with a number of distinguished international authors, this first of four volumes summarizes the most important and promising recent chemical developments in energy science all in one book. Interdisciplinary and application-oriented, this ready reference focuses on chemical methods that deliver practical solutions for energy problems, covering new developments in advanced materials for energy conversion, semiconductors and much more besides.Of great interest to chemists as well as researchers in the fields of energy science in academia and industry.
Forewordby Dr Hamaguchi xiii Forewordby Dr Noyori xv Preface xvii 1 Charge Transport Simulations for Organic Semiconductors 1Hiroyuki 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 25Rie 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 57Toshihiro 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 ?-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 ?-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 of Small Molecules 81Shigeki 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 105Miho 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 129Yoshiaki 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 155Yuki 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 ?-Conjugated Compounds 172 Pentacene 172 Tetracene 174 Hexacene 175 Heteroacene 175 Perylene and Terrylene 175 7.3.3 Nonpolycyclic ?-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 187Yoshiyuki 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 209Yusuke 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 Reduction 251Christopher 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 Molecular Catalysts Physisorbed on a Semiconductor Surface 253 Covalent Attachment of the Catalyst to the Surface of the Semiconductor 256 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 Dye-sensitised Photocathodes with Physisorbed or Diffusing Catalysts 266 Dye-sensitised Photocathodes Based on Covalent or Supramolecular Dye–Catalyst Assemblies 268 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 287Michael 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
Hisashi Yamamoto is Professor at the University of Chicago. He received his Ph.D. from Harvard under the mentorship of Professor E. J. Corey. His first academic position was as Assistant Professor and lecturer at Kyoto University, and in 1977 he was appointed Associate Professor of Chemistry at the University of Hawaii. In 1980 he moved to Nagoya University where he became Professor in 1983. In 2002, he moved to United States as Professor at the University of Chicago. He has been honored to receive the Prelog Medal in 1993, the Chemical Society of Japan Award in 1995, the National Prize of Purple Medal (Japan) in 2002, Yamada Prize in 2004, and Tetrahedron Prize in 2006 and the ACS Award for Creative Work in Synthetic Organic Chemistry to name a few. He authored more than 500 papers, 130 reviews and books (h-index ~90). Takashi Kato is a Professor at the Department of Chemistry and Biotechnology at the University of Tokyo since 2000. After his postdoctoral research at Cornell University, Department of Chemistry with Professor Jean M. J. Frechet, he joined the University of Tokyo. He is the recipient of The Chemical Society of Japan Award for Young Chemists (1993), The Wiley Polymer Science Award (Chemistry), the 17th IBM Japan Science Award (Chemistry), the 1st JSPS (Japan Society for the Promotion of Science) Prize and the Award of Japanese Liquid Crystal Society (2008). He is the editor in chief of the "Polymer Journal", and member of the editorial board of "New Journal of Chemistry".

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