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List of Contributors ix 1 Stille Polycondensation: A Versatile Synthetic Approach to Functional Polymers 1 Tianyue Zheng, Alexander M. Schneider, and Luping Yu
1.1 Introduction 1
1.1.1 History of the Stille Reaction (and Polycondensation) 2
1.2 Reaction Mechanism 3
1.2.1 Simplified Mechanism 3
1.3 Reaction Conditions 6
1.3.1 Catalyst and Ligand 7
1.3.2 Solvent 9
1.3.3 Additive 10
1.3.4 Temperature 11
1.4 Examples of Functional Materials Synthesized by Stille Polycondensation 12
1.4.1 Nonlinear Optical (NLO) polymers 13
1.4.1.1 Background 13
1.4.1.2 Examples of NLO Polymers Synthesized by Stille Polycondensation 13
1.4.2 Organic Photovoltaic Polymers 16
1.4.2.1 Background 16
1.4.2.2 Examples of Donor Polymers 17
1.4.2.3 Examples of Acceptor Materials 23
1.4.3 Organic Field Effect Transistor (OFET) Polymers 28
1.4.3.1 Background 28
1.4.3.2 Examples of FET Polymers Synthesized by Stille Polycondensation 32
1.4.4 Organic Light-Emitting Diode (OLED) Polymers 35
1.4.4.1 Background 35
1.4.4.2 Examples of OLED Polymers Synthesized by Stille Polycondensation 36
1.4.5 Other Functional Materials 38
1.5 Challenge and Outlook 42
1.5.1 Advantages of the Stille Reaction 42
1.5.2 Disadvantages of Stille Reaction 44
1.6 Summary 47 References 48 2 Suzuki Polycondensation 59 Anurag Krishna, Andrey V. Lunchev, and Andrew C. Grimsdale
2.1 Introduction 59
2.2 Mechanism of Suzuki Coupling and Suzuki Polycondensation 60
2.3 Catalysts 62
2.4 Reaction Conditions for Suzuki Coupling 65
2.4.1 Bases, Water, Solvents 66
2.4.2 Microwave-Assisted Reactions 67
2.5 Side Reactions 67
2.6 AB versus AA/BB Suzuki Polycondensation 71
2.7 Monomer Purity, Stoichiometry, and Solvents 73
2.8 Monomers for SPC 75
2.8.1 Boron Monomers 75
2.8.2 Halide and Other Monomers 80
2.9 Chain Growth SPC 81
2.10 Scope and Applications of SPC 82
2.11 Conclusion 85 References 86 3 Controlled Synthesis of Conjugated Polymers and Block Copolymers 97 Tine Hardeman, Marie-Paule Van Den Eede, Lize Verheyen, and Guy Koeckelberghs
3.1 Introduction 97
3.2 Approaches to Controlled Polymerizations 97
3.2.1 Catalyst Transfer Polymerizations 97
3.2.1.1 Mechanism 97
3.2.1.2 Kumada Catalyst Transfer Polycondensation 99
3.2.1.3 Negishi Catalyst Transfer Polycondensation 102
3.2.1.4 CTP Based on Suzuki-Miyaura Couplings 102
3.2.1.5 CTP Based on Other Coupling Reactions 103
3.2.2 Controlled Polymerizations Based on Deactivation of the Monomer 103
3.2.2.1 Mechanism 103
3.2.2.2 Pd(RuPhos) Protocol 104
3.2.2.3 Miscellaneous 104
3.3 End-Functionalized Polymers 106
3.3.1 Introduction 106
3.3.2 External Functionalized Initiators 106
3.3.2.1 Principle 106
3.3.2.2 External Initiators with Ni as Catalyst 106
3.3.2.3 External Initiators with Pd as Catalyst 109
3.3.2.4 Grafting-from 110
3.3.3 End-Capping 111
3.3.3.1 Principle 111
3.3.3.2 End-Capping with Ni as Catalyst 111
3.3.3.3 End-Capping with Pd as Catalyst 112
3.3.4 Heterobifunctional Conjugated Polymers 112
3.4 Block Copolymers 112
3.4.1 Grafting-to Method 112
3.4.2 End-Functional Polymer Copolymerization Method 113
3.4.3 Grafting-from Method 114
3.4.4 Sequential Monomer Addition 114
3.5 Other Copolymers 117 References 117 4 Direct (Hetero)arylation Polymerization 131 Mario Leclerc and Serge Beaupré
4.1 Introduction 131
4.2 First Examples of Direct (Hetero) arylation Polymerization 134
4.3 Selectivity and Reactivity Problems 138
4.4 En Route to Defect-Free Conjugated Polymers 142
4.5 Outlook 150 References 150 5 Continuous Flow Synthesis of Conjugated Polymers and Carbon Materials 159 Valerie D. Mitchell and Wallace W. H. Wong
5.1 Introduction to Flow Chemistry 159
5.2 Conjugated Polymers 161
5.3 Carbon Materials 173
5.4 Material Processing 177
5.5 Summary 178 References 178 6 Synthesis of Structurally Defined Nanographene Materials through Oxidative Cyclodehydrogenation 183 Akimitsu Narita
6.1 Introduction 183
6.2 Synthesis of Nanographene Molecules through Oxidative Cyclodehydrogenation 186
6.2.1 Solution Synthesis of Extended Nanographene Molecules with FeCl3 and AlCl3 186
6.2.2 Complementary Cyclodehydrogenation Methods for the Solution Synthesis of Nanographene Molecules 188
6.2.3 Synthesis of Nanographene Molecules with Seven- and Eight-Membered Rings 195
6.2.4 Synthesis of Heteroatom-Doped Nanographene Molecules 198
6.2.5 Nanographene Molecules through Surface-Assisted Cyclodehydrogenation 202
6.3 Bottom-Up Synthesis of Graphene Nanoribbons 204
6.3.1 Graphene Nanoribbons from Solution-Mediated Cyclodehydrogenation 205
6.3.2 Graphene Nanoribbons from Surface-Assisted Cyclodehydrogenation 208
6.4 Conclusions 217 References 218 7 Photochemical and Direct C-H Arylation Routes toward Carbon Nanomaterials 229 Jean-Francois Morin, Maxime Daigle, and Maude Desroches
7.1 Introduction 229
7.2 Photochemical Routes toward PAHs and Carbon Nanomaterials 231
7.2.1 Photochemical Dehydrogenation 231
7.2.2 Photochemical Dehydrohalogenation (CDH) 237
7.2.3 Miscellaneous Photocyclization Reaction 242
7.3 Intramolecular Direct Arylation C-H 243
7.3.1 Conclusion and Perspective 249 References 250 8 Carbon-Rich Materials fromsp-Carbon Precursors 255 Dominik Prenzel and Rik R. Tykwinski
8.1 Introduction 255
8.2 Carbyne 256
8.3 Solid-State Reactions of Polyynes: Topochemical Polymerizations 261
8.4 Diyne Polymerization 261
8.5 Tubular Structures 264
8.6 Beyond Diynes - Topochemical Polymerization of Polyynes 268
8.7 Toward "Nanographene" 272
8.8 Pentalenes 274
8.9 Modification of sp-Precursors with Tetracyanoethylene (TCNE) 275
8.10 Thermal Dimerization of Cumulenes 278
8.11 Outlook: From Solution to Surface? 278
8.12 Summarizing Comments 282 Acknowledgments 286 References 286 Index 293