Title Details

1 Control of Electronic Property of C₆₀ Fullerene via Polymerization 1
Nobuyuki Aoki

1.1 Introduction 1

1.1.1 History of Polymerization of C₆₀ Fullerene 1

1.1.2 Electronic Property of Pristine C₆₀ and n-Type FET Action 4

1.2 Polymerization of C₆₀ Fullerene 5

1.2.1 Photo-irradiation 5

1.2.2 Doping Effect Using Alkali Metal and Superconductivity 8

1.2.3 High-Pressure and High-Temperature Application 9

1.2.4 Plasma and EB Irradiation 11

1.2.5 Low-Energy EB Irradiation 12

1.3 Summary 14

Acknowledgments 14

References 14

2 Flapping Molecules for Photofunctional Materials 17
Shohei Saito

2.1 Introduction 17

2.1.1 Motivation 17

2.1.1.1 Hybridization of Rigidity and Flexibility 17

2.1.2 Background 18

2.1.2.1 How to Change Photophysical Properties by Changing Conformation of Molecules 18

2.1.3 Flapping Fluorophore 19

2.2 Viscosity Imaging Technique 23

2.2.1 Molecular Design of Chemical Viscosity Probes 23

2.2.2 Flapping Viscosity Probe 24

2.2.2.1 Synthesis 24

2.2.2.2 Fluorescence and Excited-State Dynamics 27

2.2.2.3 Polarity-Independent Viscochromism 29

2.2.2.4 Monitoring the Epoxy Resin Curing 31

2.3 Light-Removable Adhesive 32

2.3.1 Polymer and Supramolecular Approach 33

2.3.2 Liquid Crystal Approach 33

2.3.3 Light-Melt Adhesive 36

2.3.3.1 Requirements for Applications 36

2.3.3.2 Materials Design 38

2.3.3.3 Adhesive Performance 38

2.3.3.4 Working Mechanism 42

2.4 Conclusion 44

References 44

3 Catechol-Containing Polymers: A Biomimetic Approach for Creating Novel Adhesive and ReducingPolymers 53
Hiroshi Yabu

3.1 Background 53

3.1.1 Adhesive Proteins of Mussels 53

3.1.2 Bio-Based Catechol-Containing Polymers 53

3.1.3 Synthetic Polymers Containing Catechol Moieties 56

3.1.4 Toward Biomimetic Molecular Technology 59

3.2 Advanced Adhesives and Surface Modification Agents 60

3.3 Reducing Agents for Creating Nanoscale Metallic Structures 62

3.4 Application as Proton-Conductive Thin Films 66

3.5 Templates for Carbon Materials 66

3.6 Summary 66

References 67

4 Development of Ultra-microfabricating Polymeric Materials and Its Self-assembly Technology 71
Teruaki Hayakawa

4.1 Introduction 71

4.2 Perpendicular Orientation of High-𝜒BCP Microphase-Separated Domains 72

4.2.1 Challenges in Perpendicular Orientation of High-𝜒BCP 72

4.2.2 Solvent Annealing Method 74

4.2.3 Top-Coat Method 75

4.2.4 Perpendicular Orientation by Molecular Structure Design 75

4.2.4.1 Development of Perpendicular Orientation High-𝜒BCP Using Silicon-Containing Polymer 75

4.2.4.2 Development of a Perpendicular Oriented High-𝜒BCP by Using a Polysiloxane Derivative 77

4.3 Conclusions 82

Acknowledgments 82

References 82

5 Molecular Simulations of Deformation and Fracture Processes of Crystalline Polymers 85
Yuji Higuchi

5.1 Introduction 85

5.2 Coarse-Grained Molecular Simulations 87

5.2.1 Deformation and Fracture Processes of Glass Polymers and Elastomers 87

5.2.2 Molecular Simulation of Polymer Crystallization 90

5.3 Deformation and Fracture Processes of Semicrystalline Polymers on the Molecular Scale 92

5.3.1 Deformation and Fracture Process 92

5.3.2 Discussion 97

5.3.2.1 Comparison of Simulation Results 98

5.3.2.2 Degradation and Mechanical Properties of Polymers 99

5.3.2.3 Future Work 100

5.4 Conclusions 101

References 101

6 A Tale of Chirality Transfer, Multistep Chirality Transfer from Molecules to Molecular Assemblies,Organic to Inorganic Materials, Then to Functional Materials 107
Reiko Oda, Emilie Pouget, Thierry Buffeteau, Sylvain Nlate, Hirotaka Ihara, Yutaka Okazaki, andNaoya Ryu

6.1 Introduction 107

6.2 Chirality Induction and Chirality Transfer 107

6.2.1 Notion and Examples of Chirality Induction and Chirality Transfer 108

6.2.2 From Molecule to Molecule 108

6.2.3 From Molecule to Self-assembled Systems 109

6.2.4 From Molecular Assemblies to Molecules 109

6.2.5 Inorganic Chiral Structures 110

6.2.6 Characterization Methods of Chiral Assemblies 111

6.2.7 Aim of This Chapter 112

6.3 Molecular and Supramolecular Chirality from Gemini-Tartrate Templates 112

6.3.1 Gemini-Tartrate Amphiphiles 112

6.3.1.1 Formation of Gels with Chiral Nanoribbon Structures 112

6.3.1.2 Specific Recognition Between Dication Amphiphiles and Tartrates 114

6.3.1.3 Conformation of Tartrate Ions in Solution, Micellar Aggregates, and Twisted Ribbons 115

6.3.1.4 Induction of Chiral Conformation in the Cationic Amphiphile 116

6.3.1.5 Effect of Enantiomeric Excess Studied by ECD, VCD, and XRD 118

6.3.2 Organic–Inorganic Nanohelices 122

6.3.2.1 Chirality of Silica Nanohelices Evidenced by VCD 123

6.3.3 Silica Nanohelices as Platform to Organize Non-chiral Objects 125

6.3.3.1 Induction of CD on Non-chiral Dye 125

6.3.3.2 Gold Nanoparticles Forming 3D Helical Superstructures with Controlled Morphology and Strong Chiroptical Property 127

6.4 Conclusion 128

References 130

7 Solution Plasma Reactions and Materials Synthesis 137
Gasidit Panomsuwan, Tomonaga Ueno, Hiroharu Yui, Jun Nakamura, and Nagahiro Saito

7.1 General Introduction 137

7.2 Solution Plasma 138

7.3 Materials Synthesis by Solution Plasma 139

7.3.1 Noble Metal Nanoparticles 141

7.3.2 Non-noble Metal Nanoparticles 144

7.3.3 Bimetallic and Alloy Nanoparticles 145

7.3.4 Metal Oxide 147

7.3.5 Metal Carbide, Boride, and Sulfide 150

7.3.6 Carbon Materials 152

7.3.7 Mesoporous Silica 158

7.3.8 Low Molecular Weight Biopolymer 158

7.3.9 Composite Materials 160

7.3.9.1 Noble Metal Nanoparticle/Carbon Composite 160

7.3.9.2 Metal Oxide/Carbon Composite 161

7.3.9.3 Metal Nanoparticle/Metal Oxide Composite 161

7.3.9.4 Metal Nanoparticle/Mesoporous Silica Composite 161

7.3.9.5 Metal Nanoparticle/Biopolymer Composite 163

7.3.9.6 Polymer/Carbon Composite 163

7.4 Summary and Future Challenge 163

7.4.1 Highly Controllable Synthesis of Materials 163

7.4.2 High-Precision Tools and Measurements 164

7.4.3 Computational Simulation 165

7.4.4 Large-Scale Synthesis 165

References 166

8 Global Reaction Route Mapping Strategy: A Tool for Finding New Chemistry in Computers 173
SatoshiMaeda, Yu Harabuchi, and Kenichiro Saita

8.1 Introduction 173

8.2 Methodology 174

8.2.1 Artificial Force Induced Reaction Method 174

8.2.2 Multicomponent Algorithm (MC-AFIR) 175

8.2.3 Single-Component Algorithm (SC-AFIR) 176

8.2.4 Search for Potential Crossing Points 177

8.3 Results and Discussion 178

8.3.1 Aldol Reaction 178

8.3.2 Passerini Reaction 179

8.3.3 Claisen Rearrangement 180

8.3.4 Co-catalyzed Hydroformylation 181

8.3.5 Lanthanide-Ion-Catalyzed Mukaiyama Aldol Reaction 184

8.3.6 Base-Mediated Borylation with a Silylborane 184

8.3.7 Search for Cluster Structures by AFIR 187

8.3.8 The Paternò–Büchi Reaction 188

8.3.9 Minimum Energy Conical Intersection Structures of 1,3-Butadiene and Benzene 189

8.3.10 Application of SMF/SC-AFIR for Medium-Sized Molecules 189

8.3.11 Ultrafast Nonradiative Decay in Organometallic Complex 191

8.3.12 Photochemical Ligand Substitution Reactions of fac-[ReI(bpy)(CO)3PR3]+ 192

8.4 Concluding Remarks 194

Acknowledgments 194

References 194

9 Computational Molecular Technology Toward Macroscopic Chemical Phenomena: Red MoonMethodology and Its Related Applications 201
Masataka Nagaoka, Masayoshi Takayanagi, Norio Takenaka, Yuichi Suzuki, Kentaro Matsumoto,Nobuaki Koga, Sandhya Karakkadparambil Sankaran, Purushotham Uppula, and Yukichi Kitamura

9.1 Introduction 201

9.2 Methodology 202

9.2.1 What Today’s Chemists Want and Need to Consider 202

9.2.2 Red Moon Methodology – A Recent Computational Molecular Technology 205

9.2.2.1 Molecular Description of Complex Chemical Reaction Systems 205

9.2.2.2 Red Moon Method – A Rare Event-Driving Methodology of Necessity (Red Moon) 206

9.2.2.3 Algorithmic Procedure of Red Moon Method 208

9.2.3 A Set-Up Using Conventional Computational Molecular Technology 209

9.2.3.1 Reaction Scheme – Quantum Chemistry (QC) and Experiment 209

9.2.3.2 Molecular Mechanical (MM) Force Fields 210

9.3 Applications 211

9.3.1 Ethylene Coordinative Chain Transfer Polymerization Mechanism on (Pyridylamide)Hf(IV) Catalyst 211

9.3.1.1 Active Site Opening Mechanism in Ion Pair of (Pyridylamide)Hf(IV) Catalyst: An Associative Mechanism 211

9.3.1.2 Ion Pair Structure and Its Molecular Mechanical (MM) Force Fields 211

9.3.1.3 Propagation Reaction on the Active Site of (Pyridylamide)Hf(IV) Catalyst 213

9.3.2 Propylene Polymerization Reaction Mechanism on C2 Symmetric [H₂Si(Ind)₂ZrCH₃]+ and [H₂Si(Ind)₂ZrCH₃]+[CH₃B(C₆F₅)₃]– 213

9.3.2.1 Energetics of Propylene Insertion into Active Catalyst H₂Si(Ind)₂ZrCH₃ + – Enantioselectivity and Regioselectivity 214

9.3.2.2 Reaction Mechanism of cis and trans Approach of Counter Anion [CH₃B(C₆F₅)₃]− on the Various Stereoisomers 215

9.3.2.3 Toward Propagation Reaction on the Active Site of the Catalyst Ion Pair [(CH₃)₂Si(Ind)₂ZrCH₃]+[CH₃B(C₆F₅)₃]− 217

9.3.3 Aromatic Polyamide Polymerization 220

9.3.3.1 Microscopic Clarification of the MPD/TMC Mixing Ratios for the Interfacial Polycondensation Reaction Process [20] 220

9.3.3.2 Water Permeability and Fidelity of the Membrane Model 224

9.3.3.3 Characteristics of Red Moon Method and Its Possibility 226

9.4 Lithium Ion and Sodium Ion Batteries 226

9.4.1 Strong Sensitivity to Small Structural Difference of Electrolyte Molecules on the Solid–Electrolyte Interphase (SEI) Film Formation 228

9.4.2 Microscopic Additive Effect on Solid–Electrolyte Interphase (SEI) Film Formation in Sodium Ion Batteries 228

9.5 Summary and Conclusions 231

Acknowledgments 232

References 232

10 Multi-timescale Measurements with Energetic Beams for Molecular Technology 235
Masaki Hada and Taiki Hoshino

10.1 Introduction 235

10.2 Time-Domain Measurements 236

10.2.1 Femtosecond Optical Pump–Probe Studies 236

10.2.2 Femtosecond X-ray and Electron Pulse Sources 238

10.2.3 Structural Dynamics Revealed by X-ray or Electron Probes 243

10.3 Time-Correlation Measurements 248

10.3.1 Introduction of X-ray Photon Correlation Spectroscopy 248

10.3.2 Principle of XPCS 249

10.3.3 Example 250

10.3.4 Particle Diffusion 251

10.3.5 Surface Fluctuation of Fluids 252

10.3.6 Summary and Perspective 255

References 257

11 Single Molecule Magnet for Quantum Information Process 263
Tadahiro Komeda, Keiichi Katoh, andMasahiro Yamashita

11.1 Introduction 263

11.2 Synthesis and Magnetic Properties of Double-Decker SMM 265

11.3 Device Applications of SMM for Spintronic Operations 269

11.4 Scanning Tunneling Microscopy (STM) and Spectroscopy (STS) Phthalocyaninato–Terbium(III)Multiple-Decker Complexes 273

11.4.1 Film Formation on Metal Substrates 274

11.4.2 Bonding Configuration of Pc Molecule 275

11.4.3 Molecule Films of Double-Decker Phthalocyaninato–Tb(III) Complexes: Bonding Configuration and Film Structure 276

11.4.4 Hetero-ligand Double-Decker Molecule 281

11.4.5 Triple-Decker Molecule 283

11.4.6 Double- and Triple-Decker Pc and Kondo Behavior 286

11.4.7 Ligand Effect on the Kondo Behavior 291

11.4.8 Molecular Ordering and Kondo Resonance 293

11.5 Summary and Future Scope 296

Acknowledgments 298

References 298

12 Molecular Technology for One- and Two-Dimensional Materials on Surfaces 305
Shigeki Kawai and Kazukuni Tahara

12.1 General Introduction 305

12.1.1 Scanning Tunneling Microscopy 305

12.1.2 Atomic Force Microscopy in Ultrahigh Vacuum Environment 306

12.1.3 High-Resolution Imaging with a Functionalized Tip Measurement at Low Temperature in Ultrahigh Vacuum Environment 310

12.1.4 Scanning Probe Microscopy at Liquid/Solid Interface 313

12.2 On-Surface Chemical Reaction 314

12.2.1 General Info About the On-Surface Chemical Reaction 314

12.2.2 Ultrahigh Vacuum Environment 314

12.2.3 Thermal-Assisted On-Surface Reaction in UHV 318

12.2.4 Local Probe-Assisted On-Surface Reaction in UHV 320

12.2.5 Chemical Reactions at the Liquid/Solid Interface 325

12.2.5.1 Carbon–Carbon Bond Formation Reactions 325

12.2.5.2 Dynamic Imine Formation Reactions 329

12.2.5.3 Condensation of Boronic Acids 333

12.3 Conclusion and Perspective 336

Acknowledgments 336

References 337

Index 343