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Organic Redox Systems

Synthesis, Properties, and Applications
1. Aufl.

von: Tohru Nishinaga
171,99 €
Verlag:	Wiley
Format:	PDF
Veröffentl.:	25.11.2015
ISBN/EAN:	9781118858851
Sprache:	englisch
Anzahl Seiten:	616

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Titelbeschreibung

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

Inhaltsverzeichnis

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 C??C 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 R2E?TER2 and Heavy Analogs of Alkynes R??E≡E??R, 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

Autorenportrait

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.

Back cover copy

Redox (reduction-oxidation) reactions include all chemical reactions in which atoms have their oxidation state changed — that is, redox reactions involve the transfer of electrons between species. The design of new redox active conjugated systems is essential for developing organic functional materials and has been the subject of intense research in recent years. Providing a thorough overview of leading research from internationally-recognized contributing authors, Organic Redox Systems offers a valuable guide for chemists whose work touches on design and synthesis of these conjugated systems. The book covers preparative methods, unique structural features, physical properties, material applications, and potential of redox active pi-conjugated systems. Such a fundamental understanding of the structure-property relationship of these systems is one of the important research fields in physical organic chemistry. It features coverage of bond formation and cleavage of radicals, supramolecular systems based on redox reactions, molecular design, synthesis and properties, and device applications that include transistors, photovoltaics, and batteries. Chemists relying on this book will find a valuable resource for research across organic and materials chemistry, with key chapters that include such topics as: <ul> <li>Bond formation and cleavage and supramolecular assembly of radicals</li> <li>Oxidant, mixed valence systems, and multi radicals</li> <li>Polycyclic aromatic hydrocarbons and heteroles</li> <li>Weakly coordinating anions and pi-systems of heavier group 14 and 15 elements</li> </ul>