Edited by foremost leaders in chemical research together with a number of distinguished international authors, this fourth volume summarizes the most important and promising recent developments in synthesis, polymer chemistry and supramolecular chemistry.
Interdisciplinary and application-oriented, this ready reference focuses on innovative methods, covering new developments in catalysis, synthesis, polymers and more.
Table of Contents
1 Polymerization-Induced Self-assembly of Block Copolymer Nano-objects via Green RAFT Polymerization 1
Shinji Sugihara
1.1 Introduction 1
1.2 Block Copolymer Solution 1
1.3 Synthesis of Block Copolymers via RAFT Polymerization 4
1.4 Polymerization-Induced Self-assembly 6
1.4.1 PISA Using RAFT Process: Emulsion and Aqueous Dispersion Polymerization 6
1.4.2 Reagents for RAFT Aqueous Dispersion Polymerization 9
1.4.2.1 RAFT Agents 9
1.4.2.2 Steric Stabilizer (Macro-CTA, Shell) 9
1.4.2.3 Monomers (Core) 9
1.4.3 Representative RAFT Aqueous Dispersion Polymerization 11
1.5 Promising Polymerization Technology 17
References 21
2 Chemical Functionalization of Graphitic Nanocarbons 31
Yuta Nishina
2.1 Purpose of Functionalization 31
2.2 Edge Functionalization 34
2.3 Basal Plane Functionalization 37
2.3.1 Hydrogenation and Halogenation 37
2.3.2 Radical Addition 37
2.3.3 Cycloaddition 40
2.4 Miscellaneous 42
2.4.1 Oxidation 42
2.4.2 Covalent Bond Formation via Halogenation 42
2.4.3 Rearrangement 42
2.5 Non-covalent Functionalization 44
2.5.1 Functionalization with π-π Interactions 45
2.5.2 Functionalization with van der Waals, Ionic Interactions, and Hydrogen Bonding 45
2.5.3 Functionalization with Polymers 46
2.6 Future Perspective of Graphitic Nanocarbon Functionalization 48
References 48
3 Synthetic Methods Using Interactions Between Sustainable Iron Reagents and Functionalized Carbon-Carbon Multiple Bonds 51
Takeshi Hata
3.1 Cross-coupling Reactions 52
3.1.1 C(sp2)-X/C(sp3)-Metal 52
3.1.2 C(sp2)-X/C(sp2)-Metal 54
3.1.3 C(sp2)-X/C(sp)-Metal 55
3.1.4 C(sp)-X/C(sp2)-Metal 55
3.1.5 C(sp3)-X/C(sp2)-Metal 55
3.1.6 Mizoroki-Heck Reaction 56
3.2 Substitution Reactions 56
3.3 Carbometallation 58
3.4 Conjugate Addition 59
3.5 Cycloaddition 67
3.5.1 [2+2] Cycloadditions 67
3.5.2 [3+2] Cycloadditions 68
3.5.3 [4+1] Cycloadditions 68
3.5.4 [4+2] Cycloadditions 68
3.5.5 1,3-Dipolar Cycloadditions 70
3.6 Others 71
3.6.1 C - H Bond Activation 71
3.6.2 Nazarov Cyclization 72
3.6.3 Friedel-Crafts Reaction 72
3.7 Conclusion 73
References 73
4 Molecular Technology for Switch and Amplification of Chirality in Asymmetric Catalysis Using a Helically Dynamic Macromolecular Scaffold as a Source of Chirality 77
Michinori Suginome
4.1 Introduction 77
4.2 Molecular Design and Synthesis of PQX-Based Chiral Catalysts 79
4.3 Dynamic, Bidirectional Induction of Helical Chirality to PQX 81
4.4 PQX as Chirality-Switchable Chiral Catalysts in Catalytic Asymmetric Synthesis 82
4.4.1 Palladium-Catalyzed Asymmetric Reactions Using PQXphos Bearing Monophosphine Pendants on PQX 82
4.4.2 Copper-Catalyzed Asymmetric Reactions Using PQXbpy Bearing 2,2’-Bipyridin-6-yl Pendants on PQX 87
4.4.3 Organocatalytic Asymmetric Reactions Using PQXap Bearing 4-Aminopyridin-3-yl Pendants on PQX 88
4.5 Chirality Amplification in Asymmetric Catalysis 90
4.6 Closing Remarks 92
References 92
5 Cooperative Double Activation Metal/Metal and Metal/Organic Catalysis Enabling Challenging Organic Reactions 95
Yoshiaki Nakao
5.1 Introduction 95
5.2 C - H Functionalization by Cooperative Double Activation Catalysis 96
5.3 C - C Functionalization by Cooperative Double Activation Catalysis 106
5.4 Miscellaneous Reactions by Cooperative Double Activation Catalysis 109
5.5 Summary and Outlook 113
References 114
6 Siloxane-Based Building Blocks forMolecular Technology 119
Shohei Saito, Naoto Sato, Masashi Yoshikawa, Atsushi Shimojima, and Kazuyuki Kuroda
6.1 Introduction 119
6.2 Siloxane Bond Formation for Organization 120
6.2.1 Hydrolytic Reactions 120
6.2.2 Non-hydrolytic Reactions 121
6.3 Various Organosilane and Siloxane-Based Building Blocks 123
6.3.1 Organosilanes 123
6.3.2 Cyclic Siloxanes 126
6.3.3 Cage Siloxanes 127
6.3.4 Branched and Dendritic Siloxanes 131
6.4 Structure and Morphology of Assembled Building Blocks 133
6.4.1 Organization of Building Blocks 133
6.4.2 One-Dimensionally Structured Materials 134
6.4.3 Two-Dimensionally Structured Materials 137
6.4.4 Three-Dimensionally Structured Materials 144
6.5 Conclusions 150
References 151
7 Organic Molecular Catalysts in Radical Chemistry: Challenges Toward Selective Transformations 163
Daisuke Uraguchi, Kohsuke Ohmatsu, and Takashi Ooi
7.1 Background 163
7.2 Organic Photocatalysts 169
7.3 Selective Transformations Catalyzed or Mediated by Organic Molecular Radicals 181
7.4 Radical Reactions Combined with Asymmetric Organic Molecular Catalysis 184
7.5 Future Outlook 192
References 192
8 Coordination Molecular Technology 199
Nobuto Yoshinari and Takumi Konno
8.1 Introduction: Coordination Molecular Technology 199
8.2 Non-Coulombic Ionic Solid (NCIS) 200
8.3 Low-Packing Type NCIS 201
8.3.1 Porous Materials 201
8.3.2 Classical Molecular Design of Porous Ionic Solids 203
8.3.2.1 “Giant Ion Approach” for Porous Ionic Solids 205
8.3.2.2 “Low Coordination Number Approach” for Porous Ionic Solids 206
8.3.3 Prototype of Porous Low-Packing Type NCIS 207
8.3.4 pH-Controlled Formation of Porous Low-Packing Type NCIS 209
8.3.5 Short Summary of Low-Packing Type NCIS 211
8.4 Ion-Fluid Type NCIS 211
8.4.1 Ion-Conducting Ionic Solids 211
8.4.2 MOF-Based Ion-Conducting Materials 213
8.4.3 Design of Ion-Conducting Materials Based on Metal-Organic Clusters 214
8.4.4 Prototype of Ion-Fluid Type NCIS 215
8.4.5 Ion-Exchange Ability of Ion-Fluid Type NCIS 217
8.4.6 Short Summary of Ion-Fluid Type NCIS 218
8.5 Charge-Separation Type NCIS 218
8.5.1 Ionic Crystals with Non-alternate Arrangement of Cations and Anions 219
8.5.2 Prototype of Charge-Separation Type NCIS 220
8.5.3 Functionality of Charge-Separation Type NCIS 224
8.5.3.1 Catalase-Like Activity 224
8.5.3.2 Negative Electrostrictive Effect 225
8.5.4 Short Summary of Charge-Separation Type NCIS 226
8.6 Conclusion 226
References 227
9 Molecular Technology for Synthesis of Versatile Copolymers via Multiple Polymerization Mechanisms 231
Kotaro Satoh
9.1 Introduction 231
9.2 Transformation of Active Species in Chain-Growth Vinyl Polymerization 234
9.2.1 Controlled/Living Polymerization of Vinyl Monomers 234
9.2.2 Indirect Transformation Involving Terminal Conversion and Tandem Polymerization 236
9.2.3 Umpolung One-Pot Direct Polymerization 238
9.3 Mechanistic Transformation Through Carbon-Halogen Bond 238
9.3.1 Transformation of Anionic or Coordination Polymerization 238
9.3.2 Combination of Radical and Cationic Polymerizations 242
9.4 Mechanistic Transformation Through Carbon-Sulfur Bond 243
9.4.1 Transformation Using RAFT Polymerization 243
9.4.2 Reversible Umpolung Transformation During Polymerization 244
9.5 Combination Between Step- and Chain-Growth Polymerization 248
9.5.1 Indirect Transformation for Block Copolymer Synthesis 248
9.5.2 Simultaneous Step- and Chain-Growth Polymerization 250
9.6 Conclusion 251
References 251
10 Self-assembled Monolayers from Carbon-Based Ligands on Metal Surfaces 259
Christene A. Smith and Cathleen M. Crudden
10.1 Introduction 259
10.2 NHC Ligands on Two-Dimensional Surfaces 260
10.3 NHCs on Three-Dimensional Surfaces 272
10.3.1 NHC-Stabilized Au Metal Nanoparticles 273
10.3.1.1 NHC-Stabilized Au Metal Nanoparticles by Ligand Exchange 273
10.3.1.2 NHC-Stabilized Au Metal Nanoparticles by Bottom-Up Methods 275
10.3.1.3 NHC-Stabilized Au Metal Nanoparticles from Ionic Liquids 277
10.3.1.4 Water-Soluble NHC-Stabilized Au Nanoparticle Syntheses 278
10.3.2 NHC-Stabilized Au Metal Nanoparticles 280
10.3.2.1 NHC-Stabilized Reactive Metal Nanoparticles: Iridium 282
10.3.2.2 NHC-Stabilized Reactive Metal Nanoparticles: Ruthenium 282
10.3.2.3 NHC-Stabilized Reactive Metal Nanoparticles: Palladium 284
10.3.2.4 NHC-Stabilized Reactive Metal Nanoparticles: Platinum 287
10.3.2.5 NHC-Stabilized Reactive Metal Nanoparticles: Silver 287
10.4 Conclusions and Outlook 288
References 289
11 Supramolecular Web and Application for Chiroptical Functionalization of Polymer 297
Hirotaka Ihara, Makoto Takafuji, Yutaka Kuwahara, Yutaka Okazaki, Naoya Ryu, Takashi Sagawa, and Reiko Oda
11.1 Introduction 297
11.2 Supramolecular Gel for Molecular Web 298
11.2.1 What is Supramolecular Gel? 298
11.2.2 Low Molecular Weight Tool for Supramolecular Gel Formation 299
11.3 Chiroptical Properties of Glutamide-Based Supramolecular Gel 305
11.3.1 Colorless and Transparent Property 305
11.3.2 Fluorescent Property 306
11.3.3 Phosphorescent Property 308
11.3.4 Induction of Secondary Chirality 310
11.3.5 Induction of Circularly Polarized Luminescence 311
11.4 Functionalization of Polymer with Supramolecular Web 319
11.4.1 Polymerizing Supramolecular Gel 319
11.4.2 Introduction of Supramolecular Gel Function in the Polymer 321
11.4.2.1 Introduction Through Bulk Polymerization 321
11.4.2.2 Introduction of Supramolecular Web into Polymer Through Blend Method 322
11.4.3 Development of Optical Modulator 324
11.4.3.1 Wavelength Converter by High Storks Shift and Phosphorescence 324
11.4.3.2 Circularly Polarized Luminescent Material 328
11.5 Conclusions 329
References 330
12 Conformational Analysis of Organic Molecules with Single-Molecule Atomic-Resolution Real-Time Transmission Electron Microscopy (SMART-TEM) Imaging 339
Koji Harano and Eiichi Nakamura
12.1 Introduction 339
12.2 Conformational Analysis 340
12.2.1 Conformational Analysis of Single Molecules 342
12.2.2 Alkyl Chain Passing Through a Hole 346
12.2.3 Bond-by-Bond Analysis of the Conformation of a Perfluoroalkyl Chain 346
12.2.4 Determination of the Conformation of the PF Chain of 6 347
12.2.5 Orientation of Single Molecules of 1 in a CNT 350
12.2.6 3-D Structural Information on the Pyrene Amide Molecule 352
12.3 Images of Moving Biotin Triamide in a Vacuum 352
12.4 Control of Molecular Motions by the Acceleration Voltage 354
12.5 A More Complex Biotin Derivative 356
12.6 Cross-correlation Between Experimental and Simulated TEM Images 358
12.6.1 Stability of Single Molecules Under SMART-TEM Observation 361
12.7 Conclusion 364
Appendix 12.A Procedures for SMART-TEM Experiments 365
12.A.1 Synthesis of Biotinylated CNH 10 365
12.A.2 Sample Preparation for TEM Observation of CNH 11 366
12.A.3 Procedure for TEM Observation in Figure L.8 366
12.A.4 Cross-correlation Analysis of Overall Motion of Single Organic Molecules in TEM Movies 366
References 367
13 Designer Molecules Toward Sequence-Controlled Polymers via Chain-Growth Propagation Mechanism 369
Makoto Ouchi
13.1 Introduction 369
13.2 Cyclopolymerization 371
13.3 Iterative Single Unit Monomer Addition by Transformable Bulkiness 373
13.4 Iterative Cyclization 374
13.5 Conclusion 376
References 377
14 Hairy Particles Synthesized by Surface-Initiated Living Radical Polymerization 379
Kohji Ohno
14.1 Introduction 379
14.2 Surface-Initiated Living Radical Polymerization on the Surfaces of Various Particles 380
14.3 Precise Synthesis of Polymer-Brush-Decorated Particles 382
14.3.1 Monodisperse Hybrid Particles 382
14.3.2 Janus Particles Grafted with Polymer Brush 383
14.3.3 Polymer-Brush-Grafted Hollow Particles 385
14.3.4 Mixed Polymer Brushes on Particles 386
14.4 Structure of Polymer Brushes on the Particle Surface 387
14.5 Self-assembly of Hairy Particles 388
14.5.1 Two- and Three-Dimensional Ordered Arrays 388
14.5.2 Advantages of Semisoft Colloidal Crystals 391
14.5.3 Self-assembly of Hairy Anisotropic Particles 392
14.6 Conclusions 393
References 393
Index 399
