Conjugated Polymers

[Book Description]

Conjugated polymers are gaining a lot of interest due to their inherent functional properties and applications in plastic electronics. Their characteristic charge transporting and conducting properties produces features including coloration, photoluminescence, electroluminescence, photoconductivity, and electrochromism. In order to develop new functional polymers, researchers need the background information on the synthesis of the different polymer systems. Conjugated Polymers focuses on the practical preparation of conjugated polymers with each chapter discussing a particular type of conjugated polymer including a general explanation of the polymer, experimental details for synthesis and characterization. Edited by world leading experts in the field of conjugated polymer synthesis, the book serves as a convenient guide for advanced undergraduate level and above.

[Table of Contents]

Chapter 1 Pi-Conjugated Polymers: The          1  (11)
    Importance of Polymer Synthesis
          John R. Reynolds
      1.1 Historical Perspective                   1  (2)
      1.2 Considerations in Polymerizations        3  (1)
      1.3 Side Chains, Processability and          4  (1)
      Molecular Weight
      1.4 Structural Control via Repeat Unit       5  (4)
      and Functionality
      1.5 Summary                                  9  (3)
        Acknowledgements                           10 (1)
        References                                 10 (2)
Chapter 2 Polyacetylenes 12 (25)
          Kazuo Akagi
      2.1 Introduction                             12 (17)
        2.1.1 Polyacetylene (PA)                   13 (5)
        2.1.2 Helical Polyacetylene (H-PA)         18 (6)
        2.1.3 H-PA with Bundle-Free Fibril         24 (4)
        Morphology
        2.1.4 Morphology-Retaining                 28 (1)
        Carbonization of H-PA
      2.2 Experimental Procedures                  29 (8)
        2.2.1 Synthesis of Shirakawa-Type PA       29 (1)
        2.2.2 Synthesis of Naarmann and            29 (1)
        Theophilou-Type PA
        2.2.3 Synthesis of Tsukamoto-Type PA       30 (1)
        2.2.4 Synthesis of High Mechanical         30 (1)
        Modulus and Strength PA
        2.2.5 Synthesis of Directly Aligned PA     31 (1)
        2.2.6 Synthesis of Helical PA              32 (1)
        2.2.7 Synthesis of Nematic Liquid          32 (1)
        Crystals and Chiral Dopants
        References                                 33 (4)
    Chapter 3 Substituted Polyacetylenes           37 (24)
          Fumio Sanda
          Masashi Shiotsuki
          Toshio Masuda
      3.1 Introduction                             37 (5)
        3.1.1 Polymers of Aromatic                 38 (1)
        Monosubstituted Acetylenes
        3.1.2 Polymers of Aliphatic                39 (1)
        Monosubstituted Acetylenes
        3.1.3 Polymers of Aromatic                 39 (1)
        Disubstituted Acetylenes
        3.1.4 Polymers of Aliphatic                40 (1)
        Disubstituted Acetylenes
        3.1.5 Functions of Substituted             41 (1)
        Polyacetylenes
      3.2 Experimental Procedures                  42 (19)
        3.2.1 Materials and General                42 (1)
        Polymerization Procedures
        3.2.2 Polymers of Aromatic                 43 (6)
        Monosubstituted Acetylenes
        3.2.3 Polymers of Aliphatic                49 (2)
        Monosubstituted Acetylenes
        3.2.4 Polymers of Aromatic                 51 (3)
        Disubstituted Acetylenes
        3.2.5 Polymers of Aliphatic                54 (2)
        Disubstituted Acetylenes
        3.2.6 Characterization and Remarks         56 (2)
        References                                 58 (3)
    Chapter 4 Polyphenylenes                       61 (26)
          Takakazu Yamamoto
      4.1 Introduction                             61 (5)
        4.1.1 Polyphenylenes without Side Chain    62 (3)
        4.1.2 Polyphenylenes with Side Chains      65 (1)
        or Side Rings
      4.2 Experimental Procedures                  66 (21)
        4.2.1 Materials and General                66 (1)
        Polymerization Procedures
        4.2.2 Polyphenylenes without Side Chain    67 (4)
        4.2.3 Polyphenylenes with Side Chains      71 (6)
        4.2.4 Polyphenylenes with -N=N- or -NR-    77 (2)
        Binding Units
        4.2.5 Polyphenylenes with Conjugated       79 (1)
        Side Rings
        4.2.6 Polyphenylenes with -SO3M or -NO2    80 (1)
        Side Chains Prepared via Ullmann
        Coupling
        4.2.7 Characterization and Remarks         81 (1)
        References                                 82 (5)
    Chapter 5 Polyfluorenes                        87 (26)
          Byung Jun Jung
          Hong-Ku Shim
          Do-Hoon Hwang
      5.1 Introduction                             87 (1)
      5.2 Experimental Procedures                  88 (11)
        5.2.1 Oxidative Polymerization             88 (1)
        5.2.2 Yamamoto Coupling Polymerization     89 (3)
        5.2.3 Suzuki Coupling Polymerization       92 (7)
      5.3 Developments in Polymerization           99 (2)
        5.3.1 Microwave-Assisted Polymerization    99 (1)
        5.3.2 Other Synthetic Techniques           99 (1)
        5.3.3 New Polymerization Methods           99 (1)
        5.3.4 Purification of Polymers             100(1)
      5.4 Various Applications of Polyfluorenes    101(6)
        5.4.1 Polymer Light-Emitting Diodes        101(4)
        (PLEDs)
        5.4.2 Sensing Applications                 105(1)
        5.4.3 Polymer Transistors and Solar        105(2)
        Cells
        5.4.4 Electron Injection Layers in         107(1)
        Organic Electronic Devices
      5.5 Remarks                                  107(6)
        References                                 108(5)
    Chapter 6 Poly(carbazolylene)s                 113(21)
          Sung Ju Cho
          Andrew C. Grimsdale
      6.1 Introduction                             113(8)
        6.1.1 Poly(3,6-carbazolylene)s             114(2)
        6.1.2 Poly(1,8-carbazolylene)s             116(1)
        6.1.3 Poly(2,7-carbazolylene)s             116(3)
        6.1.4 Poly(3,9-carbazolylene)s             119(1)
        6.1.5 Ladder-Type Polycarbazolylenes       120(1)
      6.2 Experimental Procedures                  121(13)
        6.2.1 Materials and General Procedures     121(1)
        6.2.2 Poly(3,6-carbazolylene)s             121(2)
        6.2.3 Poly(1,8-carbazolylene)s             123(1)
        6.2.4 Poly(2,7-carbazolylene)s             124(4)
        6.2.5 Poly(3,9-carbazolylene)s             128(1)
        6.2.6 Ladder-Type Poly(carbazolylene)s     129(3)
        References                                 132(2)
    Chapter 7 Poly(phenylenevinylene)s             134(22)
          Wallace W. H. Wong
          Helga Seyler
          Andrew B. Holmes
      7.1 Introduction                             134(1)
      7.2 Methods of Synthesis                     135(12)
        7.2.1 Precursor Routes via                 135(5)
        Radical/Anionic Polymerization Mechanism
        7.2.2 Direct Routes to PPVs:               140(4)
        Step-growth Polycondensation
        7.2.3 Ring-Opening Metathesis              144(1)
        Polymerization
        7.2.4 Alternative Routes                   145(1)
        7.2.5 Comparison of Syntheses and          146(1)
        Summary
      7.3 Experimental Procedures                  147(9)
        7.3.1 General Experimental Requirements    147(1)
        7.3.2 Example Procedures                   148(3)
        References                                 151(5)
    Chapter 8 Poly(p-phenyleneethynylene)s and     156(24)
    Poly(aryleneethynylene)s
          Uwe H. F. Bunz
      8.1 Introduction                             156(9)
        8.1.1 Alkyl-PPEs and PAEs by Alkyne        159(2)
        Metathesis
        8.1.2 Alkyl-PPEs by Pd Catalysis           161(1)
        8.1.3 Alkoxy-PPEs by Pd Catalysis          162(1)
        8.1.4 Poly(fluorenyleneethynylene)s by     163(1)
        Alkyne Metathesis
        8.1.5 Other PAEs by Pd Catalysis           164(1)
        8.1.6 Side-Chain Functionalized PPEs by    165(1)
        Pd-Catalyzed Coupling
      8.2 Experimental Procedures                  165(15)
        8.2.1 Materials and General                165(3)
        Polymerization Procedures
        8.2.2 Didodecyl-PPE 13b by Alkyne          168(1)
        Metathesis of 12b
        8.2.3 Sonogashira Reactions, General       168(3)
        Remarks
        8.2.4 Polyfluorenyleneethynylene by        171(1)
        ADIMET
        8.2.5 Quinoxaline-Containing PAEs          171(2)
        8.2.6 Benzothiadiazole-Containing PAE      173(1)
        8.2.7 Quinoline-Containing PAEs            173(1)
        8.2.8 Grafted PPEs                         174(2)
        8.2.9 Characterization and Concluding      176(1)
        Remarks
        References                                 177(3)
    Chapter 9 Polythiophenes                       180(21)
          Dahlia Haynes
          Richard McCullough
      9.1 Introduction                             180(7)
        9.1.1 Synthesis of Nonsubstituted          181(1)
        Polythiophenes (PT)s
        9.1.2 Synthesis of Regioirregular          182(2)
        Substituted Polythiophenes (PST)
        9.1.3 Synthesis of Regioregular            184(3)
        Poly(Substituted Thiophenes) (rr-P3STs)
      9.2 Experimental Procedures                  187(9)
        9.2.1 Nonsubsitiuted Polythiophenes        187(2)
        9.2.2 Syntheses of Regioirregular          189(2)
        Substituted Polythiophenes
        9.2.3 Syntheses of Regioregular            191(5)
        Substituted Polythiophenes
        9.2.4 General Procedures and               196(1)
        Characterization
      9.3 Conclusion and Outlook                   196(5)
        References                                 197(4)
    Chapter 10 Poly(oxythiophene)s                 201(23)
          Anil Kumar
          Sreelekha P. Gopinathan
          Rekha Singh
      10.1 Introduction                            201(3)
        10.1.1 Polymerization Processes            202(1)
        10.1.2 Poly(3-oxythiophene)s               202(1)
        10.1.3 Poly(3,4-dioxythiophene)s           203(1)
        10.1.4 Miscellaneous Poly(oxythiophene)s   204(1)
      10.2 Experimental Procedures                 204(14)
        10.2.1 Oxidative Polymerization            208(7)
        10.2.2 Transition-Metal-Assisted           215(3)
        Polymerization
      10.3 Concluding Remarks                      218(6)
        References                                 219(5)
    Chapter 11 Polypyrroles                        224(24)
          Pierre Audebert
          Fabien Miomandre
      11.1 Introduction                            224(1)
      11.2 Polypyrrole Electrosynthesis            225(9)
        11.2.1 Overview                            225(3)
        11.2.2 Experimental Procedures             228(6)
      11.3 Polypyrroles -- Chemical Syntheses      234(14)
        11.3.1 Overview                            234(1)
        11.3.2 Classical Polypyrrole Synthesis     235(3)
        through Pyrrole Oxidation
        11.3.3 Experimental Procedures             238(6)
        References                                 244(4)
    Chapter 12 Polyanilines                        248(17)
          Jacob Tarver
          Yueh-Lin Loo
      12.1 Introduction                            248(2)
        12.1.1 Synthesis Mechanism                 250(1)
      12.2 Experimental Procedures                 250(15)
        12.2.1 Chemical Polymerization of          251(5)
        Anilines
        12.2.2 Electrochemical Polymerization      256(1)
        of Anilines
        12.2.3 Template Polymerization of          257(3)
        Anilines
        12.2.4 Secondary Doping of Polyanilines    260(1)
        12.2.5 Characterization and Remarks        261(1)
        References                                 262(3)
    Chapter 13 Si--Si Bond Polymers, Oligomers,    265(31)
    Molecules, Surface, and Materials
          Michiya Fujiki
      13.1 Hierarchy of the Si--Si Bond Family:    265(1)
      From Gaseous SiH4 to Crystal Silicon
      13.2 Polymerization Techniques               266(4)
        13.2.1 Wurtz-Type Condensation -- The      266(1)
        Most Versatile Method
        13.2.2 Electrochemical Reduction           267(1)
        13.2.3 Ring-Opening Reactions with         267(1)
        Precursors
        13.2.4 Dehydrogenative Coupling with       268(1)
        Organometallic Catalysts
        13.2.5 Postpolymerization toward           268(1)
        Functionalization
        13.2.6 Chemical Modification of Si--H      268(1)
        Bonds at the Surface of Crystal Silicon
        13.2.7 Deintercalation from the Zintl      268(1)
        Phase -- An Ideal Two-Dimensional Si
        Skeleton
        13.2.8 Thermolysis                         269(1)
      13.3 Features of Si--Si Bond Family          270(15)
      Members
        13.3.1 Chain-Like Polysilanes and          270(8)
        Oligosilanes
        13.3.2 Cyclic Four-Membered                278(1)
        Oligosilanes and Ladder Oligosilanes
        13.3.3 Network-Like Organopolysilanes      278(1)
        (Organopolysilyne)
        13.3.4 Chemical Modification of Ideal      279(1)
        Two-Dimensional Si--Si Polymers with
        CaSi2
        13.3.5 Highly Strained Persila-Polyhedra   279(2)
        13.3.6 Exotic Unsaturated Multiple         281(2)
        Si--Si Bond Compounds
        13.3.7 Surface Modification of Si--C       283(2)
        Linkages from c-Si with Si--H Bond
      13.4 Experimental Procedures                 285(11)
        13.4.1 Poly(diarylsilane)s                 285(2)
        13.4.2 Fluoroalkylpolysilane Homo- and     287(1)
        Copolymers
        13.4.3 Poly(alkylarylsilane) Homo- and     288(2)
        Copolymers
        13.4.4 Poly(alkylsilyne)s and Vacuum       290(1)
        Pyrolysis
        References                                 291(5)
    Chapter 14 Alternating Polyheterocycles        296(23)
          Kazuo Tanaka
          Yoshiki Chujo
      14.1 Introduction                            296(9)
        14.1.1 Alternating Polymers of Boron       297(4)
        14.1.2 Alternating Polymers of Silicon     301(2)
        14.1.3 Alternating Polymers of Germanium   303(1)
        14.1.4 Alternating Polymers of             304(1)
        Phosphorus
        14.1.5 Alternating Polymers of             305(1)
        Transition Metals
      14.2 Experimental Procedures                 305(14)
        14.2.1 Materials and General               305(2)
        Polymerization Procedures
        14.2.2 Alternating Polymers of Boron       307(4)
        14.2.3 Alternating Polymers of Silicon     311(1)
        14.2.4 Alternating Polymers of Germanium   312(1)
        14.2.5 Alternating Polymers of             313(1)
        Phosphorus
        14.2.6 Alternating Polymers of             314(2)
        Transition Metals
        References                                 316(3)
    Chapter 15 Donor--Acceptor Alternating         319(24)
    Copolymers
          Wentao Li
          Wei You
      15.1 Introduction                            319(3)
        15.1.1 Inception of the Concept of D--A    320(1)
        Alternating Copolymers
        15.1.2 Advantages of D--A Alternating      320(2)
        Copolymers and the State-of-the-Art
      15.2 General Methods for D--A                322(6)
      Copolymerization
        15.2.1 Suzuki Reaction vs. Stille          322(1)
        Reaction
        15.2.2 Factors to Consider from the        323(1)
        Perspective of Stille Polymerization
        15.2.3 Factors to Consider from the        324(1)
        Perspective of Suzuki Polymerization
        15.2.4 Factors to Consider from the        325(2)
        Perspective of Step Growth
        15.2.5 New Development: Direct             327(1)
        Arylation and Chain-Growth
        Polymerization
      15.3 Synthesis of Selected Monomers and      328(15)
      Typical Polymerizations
        15.3.1 Synthesis of Donor Monomers         328(2)
        15.3.2 Synthesis of Acceptor Monomers      330(4)
        15.3.3 Purification of Reagents            334(1)
        15.3.4 Typical Procedure of                335(1)
        Polymerization and Purification of
        Product
        15.3.5 Representative Syntheses of D--A    336(2)
        Alternating Copolymers
        15.3.6 Characterization and Remarks        338(1)
        References                                 338(5)
    Chapter 16 Conjugated Polyelectrolytes         343(16)
          Anand Parthasarathy
          Xuzhi Zhu
          Kirk S. Schanze
      16.1 Introduction                            343(7)
        16.1.1 A Brief History of Conjugated       344(1)
        Polyelectrolytes
        16.1.2 Synthesis of Conjugated             345(1)
        Polyelectrolytes -- General
        Considerations
        16.1.3 Conjugated Polyelectrolyte          346(2)
        Synthesis by the Direct Approach
        16.1.4 Conjugated Polyelectrolyte          348(2)
        Synthesis by the Precursor Method
      16.2 Experimental Procedures                 350(9)
        16.2.1 Materials and General               350(1)
        Considerations
        16.2.2 Example Procedures                  351(6)
        References                                 357(2)
    Chapter 17 Self-Doped Polymers                 359(28)
          M. Ramesh Kumar
          Michael S. Freund
      17.1 Introduction                            359(4)
        17.1.1 Self-Doped Conducting Polymers      359(2)
        17.1.2 Types and Classes                   361(1)
        17.1.3 Doping Mechanisms and Properties    362(1)
      17.2 Experimental Procedures                 363(24)
        17.2.1 Common Synthetic Mechanisms and     363(3)
        Outcomes
        17.2.2 Common Methods of                   366(3)
        Characterization
        17.2.3 Polyanilines                        369(6)
        17.2.4 Polypyrroles                        375(1)
        17.2.5 Polythiophenes                      376(3)
        17.2.6 Polycarbazoles                      379(1)
        17.2.7 Poly(p-phenylene)s                  379(1)
        17.2.8 Poly(phenylenevinylene)s            380(1)
        17.2.9 Polyindoles                         381(1)
        17.2.10 Polyacetylenes                     382(1)
        References                                 383(4)
    Chapter 18 Fused Heterocycle Polymers          387(35)
          Sandeep Kaur
          Alexander L. Kanibolotsky
          Peter J. Skabara
      18.1 Introduction                            387(13)
        18.1.1 Dithiin-Based Polymers              389(2)
        18.1.2 Tetrathiafulvalene (TTF)-Based      391(1)
        Polymers
        18.1.3 Diketopyrrolopyrrole (DPP)-and      392(3)
        Thieno[3,4-c]pyrrole-4,6-dione
        (TDP)-Based Polymers
        18.1.4                                     395(2)
        4,4-Difluoro-4-boro-3a-4a-diaza-s-indace
        ne (BODIPY)- and Isoindigo (iI)-Based
        Polymers
        18.1.5 Azole- and Pyrazine-Based           397(3)
        Polymers
      18.2 Experimental Procedures                 400(22)
        18.2.1 Materials and General               400(1)
        Polymerization Procedures
        18.2.2 Dithiin-Based Polymers              401(2)
        18.2.3 TTF-Based Polymers                  403(3)
        18.2.4 DPP- and TDP-Based Polymers         406(4)
        18.2.5 BODIPY- and Isoindigo-Based         410(2)
        Polymers
        18.2.6 Azole- and Pyrazine-Based           412(6)
        Polymers
        18.2.7 Characterization and Remarks        418(1)
        References                                 419(3)
    Chapter 19 Direct Arylation/Heteroarylation    422(21)
    Polycondensation Reactions
          Lauren G. Mercier
          Agnieszka Pron
          Mario Leclerc
      19.1 Introduction                            422(1)
      19.2 Reaction Conditions                     423(7)
        19.2.1 General Comments                    423(1)
        19.2.2 Heck (Jeffery) Conditions           424(1)
        19.2.3 Carboxylic Acid Additives           425(2)
        19.2.4 Without Carboxylic Acid Additives   427(3)
      19.3 Mechanistic Investigations              430(3)
      19.4 Experimental Procedures                 433(6)
        19.4.1 Materials and General               433(1)
        Polymerization Procedures
        19.4.2 Polymerization Using Heck           434(1)
        (Jeffery) Conditions
        19.4.3 Polymerization with Carboxylic      434(3)
        Acid Additives
        19.4.4 Polymerization without              437(2)
        Carboxylic Acid Additives
      19.5 Conclusions                             439(4)
        References                                 440(3)
    Chapter 20 Chain-Growth Catalyst-Transfer      443(28)
    Polycondensations
          Anton Kiriy
          Volodymyr Senkovskyy
      20.1 Catalyst-Transfer Polycondensation:     443(9)
      Mechanism, Scope and Limitations
        20.1.1 Introduction                        443(1)
        20.1.2 Mechanism                           444(2)
        20.1.3 End-Functionalized Polymers and     446(1)
        Brushes
        20.1.4 Fully Conjugated Block Copolymers   447(2)
        20.1.5 Chain-Growth Polymerization of      449(1)
        Electron-Deficient Monomers
        20.1.6 Chain-Growth Suzuki                 449(2)
        Polycondensation
        20.1.7 Perspective                         451(1)
      20.2 Experimental Procedures                 452(19)
        20.2.1 Polythiophenes                      452(1)
        20.2.2 Polyfluorenes, Polycarbazoles,      453(2)
        Polyphenylenes and Alternating
        Copolymers
        20.2.3 End-Functionalized Polymers,        455(4)
        Stars and Brushes
        20.2.4 Rod--Coil Block Copolymers          459(2)
        20.2.5 All-Conjugated Block Copolymers     461(4)
        20.2.6 Suzuki Polymerization               465(2)
        References                                 467(4)
Subject Index                                      471