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Conjugated Polymer Synthesis: Methods and Reactions

Yoshiki Chujo (Editor)
ISBN: 978-3-527-63268-8
318 pages
August 2011
Conjugated Polymer Synthesis: Methods and Reactions (3527632689) cover image
Edited and authored by top international experts, this first book on conjugated polymers with a focus on synthesis provides a detailed overview of all modern synthetic methods for these highly interesting compounds. As such, it describes every important compound class, including polysilanes, organoboron compounds, and ferrocene-containing conjugated polymers. An indispensable source for every synthetic polymer chemist.
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Preface XI

List of Contributors XIII

1 Organometallic Polycondensation for Conjugated Polymers 1
Takakazu Yamamoto

1.1 Basic Organometallic C–C Coupling 1

1.2 Syntheses of p-Conjugated Polymers 4

1.3 Optical Properties 12

1.3.1 UV–Vis Data 12

1.3.2 Photoluminescence 14

1.3.3 Other Optical Properties 16

1.4 Redox Behavior and Electrical Conductivity 16

1.5 Linear Structure and Alignment on the Surface of Substrates 19

1.6 Stacking in the Solid and Colloid 21

1.7 Chemical Reactivity and Catalysis 22

1.7.1 Metal Complexes and Modification of Nitrogen 22

1.8 Electronic and Optical Devices (ECD, Battery, EL, Diode, Transistor, Nonlinear Optical Device, etc.) 24

1.8.1 Redox Functions 24

1.8.2 Electronic and Optical Devices 25

1.9 Conclusions 25

References 26

2 Catalyst-Transfer Condensation Polymerization for Precision Synthesis of p-Conjugated Polymers 35
Tsutomu Yokozawa

2.1 Introduction 35

2.2 Kumada–Tamao Coupling Polymerization with Ni Catalyst 36

2.2.1 Polythiophene 36

2.2.1.1 Discovery and Mechanism of Catalyst-Transfer Condensation Polymerization 36

2.2.1.2 A Variety of Monomers 39

2.2.1.3 Block Polythiophenes 40

2.2.1.4 Block Copolymers of Polythiophene and Other Polymers 42

2.2.1.5 Graft Copolymers 45

2.2.2 Polyphenylenes 48

2.2.3 Polypyrroles 50

2.2.4 Polyfluorenes and Polycarbazoles 51

2.3 Suzuki–Miyaura Coupling Polymerization with Pd Catalyst 53

2.3.1 Polyfluorenes 53

2.3.2 Polyphenylenes 54

2.4 Conclusion 55

References 55

3 Regioregular and Regiosymmetric Polythiophenes 59
Itaru Osaka and Richard D. McCullough

3.1 Introduction 59

3.2 Synthesis of Polythiophene and Regioirregular Polythiophenes 59

3.3 Head-to-Tail Coupled Regioregular Poly(3-Alkylthiophene)s 61

3.3.1 Design and Synthesis of rrP3ATs 61

3.3.1.1 McCullough Method 62

3.3.1.2 Rieke Method 64

3.3.1.3 GRIM Method 64

3.3.1.4 Palladium-Catalyzed Polymerization Methods 64

3.3.2 Mechanism of the Nickel-Catalyzed Polymerization 65

3.4 Side Chain Functionalized HT Regioregular Polythiophenes 66

3.4.1 Heteroatom-Containing Groups 68

3.4.2 Aromatic-Containing Group 69

3.4.3 Chiral Groups 69

3.4.4 c-Functionalized Groups 70

3.5 End Group Functionalized HT Regioregular Polythiophenes 70

3.5.1 Postpolymerization End Group Functionalization 70

3.5.2 In Situ End Group Functionalization 71

3.6 Block Copolymers Derived from HT Regioregular Polythiophenes 72

3.6.1 All-Conjugated Block Copolymers 73

3.6.2 Conjugated–Non-Conjugated Block Copolymers 76

3.7 Universal Use of the GRIM Method 80

3.8 Regiosymmetric Polythiophenes 85

3.9 Summary 86

References 87

4 Functional Hyperbranched Polymers Constructed from Acetylenic An-Type Building Blocks 91
Jianzhao Liu, Jacky W.Y. Lam, and Ben Zhong Tang

4.1 Introduction 91

4.2 Hyperbranched Polymers Constructed from Acetylenic An-Type Building Blocks 94

4.2.1 Hyperbranched Poly(Alkylenephenylene)s (hb-PAPs) 94

4.2.1.1 Synthesis 94

4.2.1.2 Structures 96

4.2.1.3 Properties 98

4.2.2 Hyperbranched Poly(Arylenephenylene)s (hb-PArPs) 100

4.2.2.1 Synthesis 100

4.2.2.2 Structures 102

4.2.2.3 Properties 103

4.2.3 Hyperbranched Poly(Aroylphenylene)s (hb-PAkPs) and Poly(Aroxycarbonylphenylene)s (hb-PAePs) 106

4.2.3.1 Synthesis 108

4.2.3.2 Structures 110

4.2.3.3 Properties 112

4.2.4 Hyperbranched Polytriazoles (hb-PTAs) 114

4.2.4.1 Synthesis 114

4.2.4.2 Structures 115

4.2.4.3 Properties 116

4.2.5 Hyperbranched Poly(Aryleneethynylene)s (hb-PAEs) 117

4.2.5.1 Synthesis 117

4.2.5.2 Properties 117

4.2.6 Hyperbranched Polydiynes (hb-PDYs) 119

4.2.6.1 Synthesis 119

4.2.6.2 Thermal Curing 121

4.2.6.3 Micropattern Formation 122

4.2.6.4 Metal Complexation 123

4.2.6.5 Magnetic Ceramization 125

4.3 Conclusions 127

References 128

5 Through-Space Conjugated Polymers 133
Yasuhiro Morisaki and Yoshiki Chujo

5.1 Introduction 133

5.2 Through-Space Conjugated Polymers with the Layered p-Electron Systems in the Side Chain 134

5.2.1 Polyacenaphthylene 134

5.2.2 Polydibenzofulvene 134

5.2.3 Polybenzofulvene 135

5.2.4 Polystyrene-graft-Poly(4-Phenylquinoline) 137

5.2.5 [3.2]Paracyclophane-Containing Polymer 138

5.2.6 Polymethylene with [2.2]Paracyclophane 139

5.3 Through-Space Conjugated Polymers with the Layered p-Electron Systems in the Main Chain 143

5.3.1 Phenylene-Layered Polymer Based on a Norbornane Scaffold 143

5.3.2 Aromatic Ring-Layered Polymers Based on a Xanthene Scaffold 144

5.3.2.1 [2.2]Paracyclophane-Layered Polymer 144

5.3.2.2 Oligophenylene-Layered Polymers 148

5.3.2.3 Ferrocene-Layered Polymers Based on a Naphthalene Scaffold 148

5.3.3 Cyclophane-Containing Through-Space Conjugated Polymers 149

5.3.3.1 [2.2]Metacyclophane-Containing Through-Space Conjugated Polymers 149

5.3.3.2 [2.2]Paracyclophane-Containing Through-Space Conjugated Polymers 151

5.4 Conclusion 159

References 160

6 Fully Conjugated Nano-Sized Macrocycles: Syntheses and Versatile Properties 165
Masayoshi Takase and Masahiko Iyoda

6.1 Introduction 165

6.2 Synthesis of p-Conjugated Macrocycles 166

6.2.1 One-Pot Synthesis of Phenylacetylene Macrocycles 166

6.2.2 Template Synthesis of Macrocycles 170

6.2.3 Synthesis of Conjugated Thiophene, Porphyrin, and Heteroarylene Macrocycles 170

6.3 Isolation and Self-Association in Solution and in the Solid State 183

6.4 Versatile Properties of Giant p-Conjugated Macrocycles 185

6.5 Conclusion 188

References 190

7 Organoboron Conjugated Polymers 195
Atsushi Nagai and Yoshiki Chujo

7.1 Introduction 195

7.2 Tricoordinate Boron p-Conjugated Polymers 196

7.2.1 Hydroboration Polymerization of Diyne Monomers 196

7.2.2 Tin–Boron Exchange Polymerization of Bis(Trimethylsilyl) Monomer 198

7.2.3 Haloboration–Phenylboration Polymerization of Diyne Monomers 199

7.2.4 Polycondensation of Aryldimethoxyborane Using Grignard and Organolithium Reagents 199

7.2.5 Stepwise Reaction from Boraanthracene 200

7.3 Tetracoordinate Boron p-Conjugated Polymers 201

7.3.1 p-Conjugated Poly(Cyclodiborazane)s 201

7.3.2 Poly(Pyrazabole)s 203

7.3.3 p-Conjugated Organoboron Quinolate Polymers 204

7.3.4 p-Conjugated Organoboron Diketonate Polymer 206

7.3.5 p-Conjugated BODIPY-Based Polymers 207

7.4 p-Conjugated Carborane-Based Polymers 209

7.5 Conclusions 210

References 211

8 Recent Developments in p-Conjugated Macromolecules with Phosphorus Atoms in the Main Chain 215
Paul W. Siu and Derek P. Gates

8.1 Introduction 215

8.2 Poly(Phosphole) and Related Polymers 215

8.3 Poly(p-Phenylenephosphine) and Related Polymers 221

8.4 Poly(Vinylenephosphine)s and Related Polymers 222

8.5 Poly(p-Phenylenephosphaalkene)s and Related Polymers 223

8.6 Poly(p-Phenylenediphosphene)s and Related Polymers 225

8.7 Summary 226

References 226

9 Organo-Arsenic, Phosphorus, and Antimony Conjugated Polymers 229
Kensuke Naka and Yoshiki Chujo

9.1 Introduction 229

9.2 Survey of Group 15 Element-Containing Polymers 230

9.3 Carbon–Main Group Element Bond Formation Via Bismetallation 230

9.4 Homocyclic Compounds of Group 15 Elements 231

9.5 Poly(Vinylene-Arsine)s 234

9.6 Poly(Vinylene-Phosphine)s 237

9.7 Poly(Vinylene-Stibine)s 238

9.8 Periodic Terpolymerization of Cyclooligoarsine, Cyclooligostibine, and an Acetylenic Compound 239

9.9 Stability 240

9.10 Optical Properties 241

9.11 Coordination Ability of Poly(Vinylene-Arsine)s Towards Transition Metal Ions 242

9.12 Cross-Linked Poly(Vinylene-Arsine)s 244

9.13 Conclusion 246

References 247

10 Synthetic Strategies to Conjugated Main-Chain Metallopolymers 251
Andreas Wild, Andreas Winter, Martin D. Hager, and Ulrich S. Schubert

10.1 Introduction 251

10.2 p-Conjugated Polymers with Terpyridine Units and Other Tridentate Ligands as Part of the Main Chain 254

10.3 p-Conjugated Polymers with Porphyrin Units as Part of the Main Chain 259

10.4 Rigid-Rod Polymetallaynes 268

10.5 Conclusion and Outlook 273

References 274

11 Helical Polyacetylene Prepared in a Liquid Crystal Field 289
Kazuo Akagi

11.1 Introduction 289

11.2 Chiral Dopants and Chiral Nematic LCs 290

11.3 Acetylene Polymerization in Chiral Nematic LC 292

11.4 Characterization of Helical Polyacetylene Film 293

11.5 Summary 298

References 299

Index 303

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Yoshiki Chujo completed his PhD at Kyoto University in 1980 and then joined Nagoya University as an assistant professor in 1981. In 1983, he joined the group of Prof. J. E. McGrath at Virginia Tech in the U.S.A. as a postdoctoral research fellow. He returned to Kyoto University as a lecturer in 1986 and has been Professor of Polymer Chemistry there since 1994. His research interests focus on polymer synthesis, inorganic polymers, and polymeric hybrid materials. He has published more than 400 papers.
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"The book is quite readable. A knowledgeable synthetic chemist can appreciate the detail and the examples that have been highlighted to emphasize the importance of each methodology. . . Overall, however, the book is very good and a worthwhile addition to the libraries of those who appreciate synthetic chemistry in conjugated polymers." (Journal of the American Chemical Society, 23 March 2011)

"An indispensable source for every synthetic polymer chemist." (Robotics Technology, 15 February 2011)

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