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Organic Redox Systems: Synthesis, Properties, and Applications

ISBN: 978-1-118-85874-5
616 pages
December 2015
Organic Redox Systems: Synthesis, Properties, and Applications (1118858743) cover image

Description

Providing a thorough overview of leading research from internationally-recognized contributing authors, this book describes methods for the preparation and application of redox systems for organic electronic materials like transistors, photovoltaics, and batteries.

• Covers bond formation and cleavage, supramolecular systems, molecular design, and synthesis and properties
• Addresses preparative methods, unique structural features, physical properties, and material applications of redox active p-conjugated systems
• Offers a useful guide for both academic and industrial chemists involved with organic electronic materials
• Focuses on the transition-metal-free redox systems composed of organic and organo main group compounds

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Table of Contents

LIST OF CONTRIBUTO RS xv

PREFACE xix

1 Introduction: Basic Concepts and a Brief History of Organic Redox Systems 1
Tohru Nishinaga

1.1 Redox Reaction of Organic Molecules, 1

1.2 Redox Potential in Nonaqueous Solvents, 3

1.3 A Brief History of Organic Redox Compounds, 5

References, 10

2 Redox\Mediated Reversible 𝞂\Bond Formation/Cleavage 13
Takanori Suzuki, Hitomi Tamaoki, Jun\ichi Nishida, Hiroki Higuchi, Tomohiro Iwai, Yusuke Ishigaki, Keisuke Hanada, Ryo Katoono, Hidetoshi Kawai, Kenshu Fujiwara and Takanori Fukushima

2.1 Dynamic Redox (“Dyrex”) Systems, 13

2.1.1 π\Electron Systems Exhibiting Drastic Structural Changes upon Electron Transfer, 13

2.1.2 Redox Switching of a σ\Bond upon Electron Transfer, 16

2.1.3 Two Types of Dyrex Systems Exhibiting Redox Switching of a σ\Bond, 17

2.2 Advanced Electrochromic Response of “Endo”\Type Dyrex Systems Exhibiting Redox Switching of a σ\Bond, 19

2.2.1 Tetraaryldihydrophenanthrenes as Prototypes of “Endo”\Dyrex Systems, 19

2.2.2 Tricolor Electrochromism with Hysteretic Color Change in Non\C2\Symmetric “Endo”\Dyrex Pair, 20

2.2.3 Electrochromism with Chiroptical Output of Chiral “Endo”\Dyrex Pair, 21

2.2.4 Multi\Output Response System Based on Electrochromic “Endo”\Dyrex Pair, 24

2.3 Advanced Electrochromic Response of “Exo”\Type Dyrex Systems Exhibiting Redox Switching of a σ\Bond, 26

2.3.1 Bis(diarylethenyl)biphenyls as Prototypes of “Exo”\Dyrex Systems, 26

2.3.2 Electrochromism with Chiroptical Output of Chiral “Exo”\Dyrex Systems, 26

2.3.3 Electrochromism of “Exo”\Dyrex Systems in Aqueous Media, 28

2.4 Prospect: Redox Systems With Multiple Dyrex Units, 31

References, 33

3 Redox\Controlled Intramolecular Motions Triggered by π\Dimerization and Pimerization Processes 39
Christophe Kahlfuss, Eric Saint\Aman and Christophe Bucher

3.1 Introduction, 39

3.2 Oligothiophenes, 40

3.3 Phenothiazine, 44

3.4 Naphthalene and Perylene Bisimides, 45

3.5 para\Phenylenediamine, 47

3.6 Pyridinyl Radicals, 49

3.7 Viologen Derivatives, 50

3.8 Verdazyl, 60

3.9 Phenalenyl, 60

3.10 Porphyrins, 61

3.11 Benzenoid, 62

3.12 Cyclophane, 64

3.13 Tetrathiafulvalene, 68

3.14 Conclusion, 80

Acknowledgments, 80

References, 81

4 Tetrathiafulvalene: a Redox Unit for Functional Materials and a Building Block for Supramolecular Self\Assembly 89
Masashi Hasegawa and Masahiko Iyoda

4.1 Introduction: Past and Present of TTF Chemistry, 89

4.2 Basic Redox Properties of TTF and Stacked TTF, 90

4.2.1 Monomeric TTFs, 90

4.2.2 Interactions in Stacked TTF Dimer, 92

4.2.3 Interactions in Stacked TTF Oligomers, 97

4.2.4 Head\to\Tail TTF Dimer, 98

4.3 TTF as a Faithful Redox Active Unit in Functional Materials, 100

4.3.1 Electrochromic Materials, 100

4.3.2 Optically Active TTFs, 102

4.3.3 Uses as Positive Electrode Materials for Rechargeable Batteries, 108

4.4 Electroconducting Properties of TTF Derivatives Based on Supramolecular Self\Assembly, 112

4.4.1 Redox\Active Nanostructure Formation in the Solid State, 113

4.4.2 Conducting Nanostructure Formation, 115

4.4.3 Conducting Nanofibers by Iodine Doping, 116

4.4.4 Conducting Nanofibers Based on Cation Radicals, 120

4.4.5 Conducting Nanowires of Neutral TTF Derivatives, 123

4.5 Summary and Outlook, 124

References, 125

5 Robust Aromatic Cation Radicals as Redox Tunable Oxidants 131
Marat R. Talipov and Rajendra Rathore

5.1 Introduction, 131

5.2 Designing Molecules for the Formation of Stable Cation Radicals (Crs)—A Case Study, 135

5.2.1 Exploring the Cause of Exceptional Stability of The\Orange+·, 137

5.3 Methods of Preparative Isolation of Aromatic Cation Radicals, 142

5.3.1 Nitrosonium (NO+) Salts, 143

5.3.2 Antimony Pentachloride (SbCl5), 144

5.3.3 Triethyloxonium Hexachloroantimonate (Et3O+ SbCl6 –), 148

5.3.4 Ddq and HBF4\Ether Complex, 149

5.4 Q uantitative Oxidation of Electron Donors using THE-Orange+·SbCl6 – as One\Electron Oxidant, 150

5.4.1 Analysis of Two\Electron Oxidation Processes Using MF/D Plots, 157

5.5 Readily Available Electron Donors for the Redox\Tunable Aromatic Oxidants, 164

5.5.1 Triptycene Based Electron Donors, 164

5.5.2 Tetrabenzodifurans, 166

5.5.3 Polyaromatic Hydrocarbons, 168

5.5.4 Multi\Electron Redox Systems, 168

5.6 Conclusion, 171

References, 173

6 Air\Stable Redox\Active Neutral Radicals: Topological Symmetry Control of Electronic\Spin, Multicentered Chemical Bonding, and Organic Battery Application 177
Shinsuke Nishida and Yasushi Morita

6.1 Introduction, 177

6.2 Open\Shell Graphene Fragment : Design and Synthesis of Air\Stable Carbon\Centered Neutral Radicals Based on Fused\Polycyclic π\System, 179

6.3 Topological Symmetry Control of Electronic\Spin Density Distribution by Redox and other External Stimuli, 181

6.3.1 Redox\Based Spin Diversity of Oxophenalenoxyl Sytems, 181

6.3.2 Spin\Center Transfer and Solvato\/Thermochromism of Tetrathiafulvalene\Substituted 6\Oxophenalenoxyl Neutral Radical, 183

6.4 Control of Electronic\Spin Structure and Optical Properties of Multicentered CC Bonds, 184

6.4.1 Strong Somo–Somo Interaction within π\Dimeric Structure of Phenalenyl Derivatives, 184

6.4.2 Thermochromism Induced by Thermal Equilibrium of π\Dimeric Structure and σ\Dimeric Structure, 188

6.4.3 Weak Somo–Somo Interactions by Molecular Modification of Phenalenyl System, 190

6.4.4 Multidimensional Spin–Spin Interaction and π\Staked Radical Polymer, 193

6.5 Rechargeable Batteries Using Organic Electrode\Active Materials, 195

6.5.1 Closed\Shell Organic Molecules as Electrode\Active Materials, 196

6.5.2 Closed\Shell Organic Polymers, 214

6.5.3 Stable Organic Neutral Radicals, 218

6.5.4 Stable Organic Neutral Radical Polymers, 220

6.6 Molecular Spin Batteries : Design Criteria and Performance of High Capacity Organic Rechargeable Battery Materials, 223

6.6.1 Molecular Crystalline Secondary Batteries, 223

6.6.2 Trioxotriangulene Neutral Radical (Tot) Derivatives, 224

6.6.3 Molecular Spin Batteries, 227

6.7 Conclusion, 229

Acknowledgement, 231

References, 231

7 Triarylamine\Based Organic Mixed\Valence Compounds: The Role of the Bridge 245
Christoph Lambert

7.1 Introduction, 245

7.2 The Mv Concept, 246

7.3 The Redox Center, 250

7.4 The Bridge, 251

7.5 The Length of the Bridge, 254

7.6 Changing the Connectivity, 256

7.7 Twisting the Bridge, 258

7.8 Saturated vs Unsaturated Bridge, 258

7.9 Meta vs Para Conjugation, 260

7.10 Switching the Bridge, 262

7.11 Metal Atoms as the Bridge, 263

7.12 And Finally: Without a Bridge, 264

Acknowledgment, 265

References, 265

8 Magnetic Properties of Multiradicals Based on Triarylamine Radical Cations 269
Shuichi Suzuki and Keiji Okada

8.1 Introduction, 269

8.2 Triarylamine Radical Cations as Synthetic Reagents for Preparation of Donor Radical Cations with Various Counter Anions, 270

8.2.1 Syntheses of Tbpa +·Pf6− and Its Counteranion Analogues, 270

8.3 Stable Triarylamines without para\Substituents, 270

8.4 Models of Intermolecular Exchange Interaction in Heteroatomic Systems, 271

8.4.1 Dynamic Spin Polarization Model and Disjoint–Nondisjoint Model, 271

8.4.2 Dynamic Spin Polarization and Spin Delocalization, 272

8.4.3 Effect of Large Dihedral Angle between Spacer and Spin Source, 273

8.4.4 p\Phenylene Methodology or π\Conjugation Using Topologically Different Spin Sources, 275

8.5 Magnetic Susceptibility and Temperature Dependence, 275

8.6 Poly(Diarylamino benzene) Poly(Radical Cation)s, 276

8.7 Radical Substituted Triarylamines, 278

8.7.1 tbuno\Substituted Triarylamines, 278

8.7.2 Nn\Substituted Triarylamines, 279

8.8 Towards Further Developments, 282

References, 283

9 Open\Shell π\Conjugated Hydrocarbons 287
Takashi Kubo

9.1 Introduction, 287

9.2 Monoradicals, 288

9.2.1 Triphenylmethyl, 288

9.2.2 Phenalenyl, 289

9.2.3 Cyclopentadienyl, Indenyl, Fluorenyl, 291

9.2.4 Cycloheptatrienyl, 293

9.2.5 Bdpa , 294

9.2.6 Dinaphthofluorenyl, 294

9.3 Biradicals, 295

9.3.1 Triplet Biradicals, 295

9.3.2 Singlet Biradicals: Quinodimethanes, 296

9.3.3 Singlet Biradicals: Bisphenalenyl System, 298

9.3.4 Singlet Biradicals: Acences, 300

9.3.5 Singlet Biradicals: Anthenes, 301

9.3.6 Singlet Biradicals: Zethrenes, 303

9.3.7 Singlet Biradicals: Indenofluorenes, 304

9.4 Polyradicals, 304

References, 305

10 Indenofluorenes and Related Structures 311
Jonathan L. Marshall and Michael M. Haley

10.1 Introduction, 311

10.2 Indeno[1,2\a]fluorenes, 313

10.2.1 Indeno[1,2\a]fluorene\7,12\dione, 313

10.2.2 Truxenone, An Indeno[1,2\a]fluorene Related Structure, 314

10.3 Indeno[1,2\b]fluorenes, 320

10.3.1 Indeno[1,2\b]fluorene\6,12\diones, 320

10.3.2 Dicyanomethylene Indeno[1,2\b]fluorenes, 325

10.3.3 Fully Conjugated Indeno[1,2\b]fluorenes, 327

10.4 Indeno[2,1\a]fluorenes, 333

10.5 Indeno[2,1\b]fluorenes, 336

10.6 Indeno[2,1\c]fluorenes, 339

10.6.1 Indenofluorene-Related Structures, 341

10.7 Fluoreno[4,3\c]fluorene, 342

10.8 Indacenedithiophenes, 345

10.8.1 Indacenedithiophene Diones, 345

10.8.2 Tetrathiofulvalene and Dicyanomethylene Indacenedithiophenes, 347

10.8.3 Fully Conjugated Indacenedithiophenes, 349

10.9 Diindeno[n]thiophenes, 351

10.10 Conclusions, 354

Acknowledgment, 354

References, 354

11 Thienoacenes 359
Kazuo Takimiya

11.1 Introduction, 359

11.2 Synthesis of Thienoacenes via Thienannulation, 361

11.2.1 Bdt and Adt Derivatives, 361

11.2.2 Thienannulation to Construct Thienoacenes with Terminal Thiophene Ring(s), 362

11.2.3 Thienannulation to Construct Thienoacenes with Internal Thiophene Ring(s), 366

11.3 Molecular Electronic Structures, 370

11.4 Application to Electronic Devices, 373

11.4.1 Molecular Organic Semiconductors for p\Type OFET Devices, 373

11.4.2 Semiconducting Polymers for Pscs, 377

11.5 Summary, 379

References, 379

12 Cationic Oligothiophenes: p\Doped Polythiophene Models and Applications 383
Tohru Nishinaga

12.1 Introduction, 383

12.2 Design Principle and Synthetic Methods, 384

12.3 Electrochemistry, 390

12.4 Structural and Spectroscopic Properties as p\Doped Polythiophene Models, 397

12.5 Application to Supramolecular Systems, 403

12.6 Conclusion and Outlook, 406

References, 406

13 Electron\Deficient Conjugated Heteroaromatics 411
Yutaka Ie and Yoshio Aso

13.1 Introduction, 411

13.2 Hexafluorocyclopenta[c]thiophene and its Containing Oligothiiophenes, 412

13.3 Difluoromethylene\Bridged Bithiophene and its Containing Oligothiiophenes, 416

13.4 π\Conjugated Systems Having Thiazole\Based Carbonyl\Bridged Compounds, 419

13.5 Difluorodioxocyclopentene\Annelated Thiophene and its Containing Oligothiiophenes, 427

13.6 Dioxocycloalkene\Annelated Thiophene and its Containing Oligothiiophenes, 433

13.7 Dicyanomethylene\Substituted Cyclopenta[b]thiophene and its Containing π\Conjugated System, 434

13.8 Electron\Deficient π\Conjugated System Containing Dicyanomethylene\Substituted Cyclopenta[b]thiophene Toward Organic Photovoltaics, 437

13.9 Conclusion, 440

References, 441

14 Oligofurans 445
Ori Gidron

14.1 Background, 445

14.2 Synthesis and Reactivity, 446

14.3 Properties of Oligofurans in the Neutral State, 449

14.4 Properties of Cationic Oligofurans, 452

14.5 Polyfurans, 454

14.6 Devices with Furan\Containing Materials, 455

14.7 Summary and Outlook, 459

References, 459

15 Oligopyrroles and Related Compounds 463
Masayoshi Takase

15.1 Introduction, 463

15.2 Linear Oligopyrroles, 464

15.2.1 Synthesis, 464

15.2.2 Optical and Redox Properties, 465

15.2.3 π\Dimer of Oligopyrrole Radical Cations, 466

15.3 Cyclic Oligopyrroles, 467

15.3.1 Synthesis, 468

15.3.2 Optical and Redox Properties, 469

15.4 Pyrrole\Fused Azacoronenes, 469

15.4.1 Synthesis, 470

15.4.2 Optical and Redox Properties, 470

15.4.3 Aromaticity, 473

15.5 Conclusions, 474

References, 474

16 Phospholes and Related Compounds: Syntheses, Redox Properties, and Applications to Organic Electronic Devices 477
Yoshihiro Matano

16.1 Introduction, 477

16.2 Synthesis of π\Conjugated Phosphole Derivatives, 478

16.3 Redox Potentials of Phosphole Derivatives, 483

16.4 Electrochemical Behaviors of Phosphole Derivatives, 493

16.5 Applications of Phosphole\Based Materials to Organic Electronic Devices, 495

References, 497

17 Electrochemical Behavior and Redox Chemistry of Boroles 503
Holger Braunschweig and Ivo Krummenacher

17.1 Introduction, 503

17.2 Preparation, 505

17.3 Chemical Reactivity, 507

17.3.1 Lewis Acid–Base Adducts, 507

17.3.2 Cycloaddition Reactions, 508

17.3.3 σ\Bond Activation Reactions, 509

17.4 Redox Chemistry, 510

17.4.1 Electrochemistry, 510

17.4.2 Preparative Reduction Chemistry, 514

17.5 Conclusions and Outlook, 518

References, 519

18 Isolation and Crystallization of Radical Cations by Weakly Coordinating Anions 523
Xinping Wang

18.1 Introduction, 523

18.2 Radical Cations and Dications Based on Triarylamines, 524

18.3 Radical Cations Containing Phosphorus, 528

18.4 The Radical Cation Containing a Selenium–Selenium Three\Electron σ\Bond, 534

18.5 Radical Cations of Organic Oligomers (π\Dimerization), 536

18.6 σ\Dimerization of Radical Cations, 540

18.7 Conclusion, 541

References, 542

19 Heavier Group 14 Element Redox Systems 545
Vladimir Ya. Lee and Akira Sekiguchi

19.1 Introduction, 545

19.2 Redox Systems of the Heavier Group 14 Elements E (E = Si–Pb), 547

19.2.1 Interconversion between Cations R3E+, Radicals R3E ·, and Anions R3E−, 547

19.2.2 Anion and Cation\Radicals of the Heavy Analogs of Carbenes R2E:, 552

19.2.3 Anion\ and Cation\Radicals of the Heavy Analogs of Alkenes R2ETER2 and Heavy Analogs of Alkynes RE≡ER, 555

19.3 Summary, 559

References, 559

20 π\Electron Redox Systems of Heavier Group 15 Elements 563
Takahiro Sasamori, Norihiro Tokitoh and Rainer Streubel

20.1 Introduction, 563

20.2 The Redox Behavior of Dipnictenes, 564

20.3 The Redox Behavior of π\Conjugated Systems of Heavier Dipnictenes, 571

20.4 The Redox Behavior of d–π Electron Systems Containing Heavier Dipnictenes, 572

20.5 Conclusion, 575

References, 575

Index 579

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Author Information

Tohru Nishinaga, PhD, is an Associate Professor of Chemistry at Tokyo Metropolitan University. His current research interest is the design, synthesis and application of pi-electron systems with novel electronic properties. Dr. Nishinaga has published over 80 scientific papers and 10 book chapters.
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