Synthetic Methods for Conjugated Polymers and Carbon Materials (E-Book) von Mario Leclerc

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 SuzukiMiyaura 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 CH 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 CH 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

A concise and practical overview of the most important modern synthetic aspects of conjugated polymers and carbon materials, including their properties and applications.

Well structured, this book summarizes recent achievements, outlines the current state and reviews research trends. As such, a wide variety of polymerization techniques are included on both a strategic as well as a practical level, including Stille, Suzuki , and direct (hetero)arylation polymerizations. Furthermore, it covers various carbon-rich materials, such as graphene and carbon nanotubes, followed by a look at how the different synthetic pathways and strategies influence their final properties, for example, for use in organic electronic devices. The whole is rounded off with a discussion of future technology advances.

An essential reference for newcomers as well as experienced researchers in the field.

Mario Leclerc obtained a PhD in chemistry from the Universite Laval, Quebec City, Canada, in 1987. After a short post-doctoral stay at INRS-Energie et Materiaux near Montreal, he joined the Max-Planck-Institute for Polymer Research in Mainz, Germany, as a post-doctoral fellow in the research group of Prof. Dr. G. Wegner. In 1989, he accepted a position of professor at the department of chemistry of Universite de Montreal. In 1998, he moved to Universite Laval to join the Centre de Recherche sur les Materiaux Avances (CERMA). Since 2001, he is the recipient of the Canada Research Chair (Tier 1) on Electroactive and Photoactive Polymers. His current research activities include the synthesis and characterization of new conjugated oligomers and polymers for applications in the areas of micro-electronics, electro-optics, energy and genomics.
Prof. Leclerc has authored more than 250 scientific publications and 10 book chapters and has 10 patents.

Jean-Francois Morin obtained a PhD in chemistry from the Universite Laval, Quebec City, Canada, in 2004, under the supervision of Professor Mario Leclerc. His work focused on the design, synthesis and characterization of oligo- and poly(2,7-carbazole)s for organic electronic. He joined Professor James M. Tour's group at Rice University (Houston, USA) as a postdoctoral research associate where he worked on the development of self-propelled nanomachines on surfaces. In 2006, he moved back to the Universite Laval, Department of Chemistry, as an Assistant Professor. His current research activities include the synthesis and characterization of carbon nanomaterials, dendrimers for bio-related applications and organic semiconductors.
Prof. Morin has authored more than 60 scientific publications and several book chapters and has 4 patents.