List of Contributors xv
Preface xix
1 Incorporation of Boron into π-Conjugated Scaffolds to Produce Electron-Accepting π-Electron Systems 1
Atsushi Wakamiya
1.1 Introduction 1
1.2 Boron-Containing Five-Membered Rings: Boroles and Dibenzoboroles 2
1.3 Annulated Boroles 8
1.4 Boron-Containing Seven-Membered Rings: Borepins 11
1.5 Boron-Containing Six-Membered Rings: Diborins 14
1.6 Planarized Triphenylboranes and Boron-Doped Nanographenes 17
1.7 Conclusion and Outlook 21
References 22
2 Organoborane Donor–Acceptor Materials 27
Sanjoy Mukherjee and Pakkirisamy Thilagar
2.1 Organoboranes: Form and Functions 27
2.2 Linear D-A Systems 29
2.3 Non-conjugated D-A Organoboranes 32
2.4 Conjugated Nonlinear D-A Systems 33
2.5 Polymeric Systems 36
2.6 Cyclic D-A Systems: Macrocycles and Fused-Rings 39
2.7 Conclusions and Outlook 43
References 43
3 Photoresponsive Organoboron Systems 47
Soren K. Mellerup and Suning Wang
3.1 Introduction 47
3.1.1 Four-Coordinate Organoboron Compounds for OLEDs 47
3.1.2 Photochromism 49
3.2 Photoreactivity of (ppy)BMes2 and Related Compounds 50
3.2.1 Photochromism of (ppy)BMes2 50
3.2.2 Mechanism 51
3.2.3 Derivatizing (ppy)BMes2: Impact of Steric and Electronic Factors on Photochromism 52
3.2.3.1 Substituents on the ppy Backbone 52
3.2.3.2 Aryl Groups on Boron: Steric versus Electronic Effect 54
3.2.3.3 π-Conjugation and Heterocyclic Backbones 56
3.2.3.4 Impact of Different Donors 58
3.2.3.5 Polyboryl Species 60
3.3 Photoreactivity of BN-Heterocycles 62
3.3.1 BN-Isosterism and BN-Doped Polycyclic Aromatic Hydrocarbons (PAHs) 62
3.3.2 Photoelimination of (2-Benzylpyridyl)BMes2 62
3.3.3 Mechanism 64
3.3.4 Scope of Photoelimination: The Chelate Backbone 65
3.3.5 Strategies of Enhancing ΦPE: Metalation and Substituents on Boron 66
3.4 New Photochromism of BN-Heterocycles 68
3.4.1 Photochromism of (2-Benzylpyridyl)BMesF 2 and Related Compounds 68
3.4.2 Mechanism 70
3.5 Exciton Driven Elimination (EDE): In situ Fabrication of OLEDs 70
3.6 Summary and Future Prospects 73
References 74
4 Incorporation of Group 13 Elements into Polymers 79
Yi Ren and Frieder Jakle
4.1 Introduction 79
4.2 Tricoordinate Boron in Conjugated Polymers 80
4.3 Tetracoordinate Boron Chelate Complexes in Polymeric Materials 87
4.3.1 N-N Boron Chelates 88
4.3.2 N-O Boron Chelates 91
4.3.3 N-C Boron Chelates 92
4.4 Polymeric Materials with B-P and B-N in the Backbone 92
4.5 Polymeric Materials Containing Borane and Carborane Clusters 97
4.6 Polymeric Materials Containing Higher Group 13 Elements 101
4.7 Conclusions 105
Acknowledgements 106
References 106
5 Tetracoordinate Boron Materials for Biological Imaging 111
Christopher A. DeRosa and Cassandra L. Fraser
5.1 Introduction 111
5.1.1 Introduction to Luminescence 111
5.1.2 Tetracoordinate Boron Dye Scaffolds 113
5.2 Small Molecule Fluorescence Imaging Agents 114
5.2.1 Bright Fluorophores 116
5.2.2 Solvatochromophores 117
5.2.3 Molecular Motions of Boron Dyes 118
5.2.3.1 Molecular Rotors 121
5.2.3.2 Turn-On Probes 121
5.3 Polymer Conjugated Materials 124
5.3.1 Dye–Polymer Systems 124
5.3.2 Oxygen-Sensing Polymers 126
5.3.3 Energy Transfer in Polymers 129
5.3.4 Conjugated Polymers 130
5.3.5 Aggregation-Induced Emission Polymers 130
5.4 Conclusion and Future Outlook 133
References 133
6 Advances and Properties of Silanol-Based Materials 141
Rudolf Pietschnig
6.1 Introduction 141
6.2 Preparation 141
6.3 Reactivity 143
6.3.1 Adduct Formation 143
6.3.2 Metallation 145
6.3.3 Condensation 146
6.4 Properties and Application 148
6.4.1 Surface Modification 148
6.4.2 Catalysis 154
6.4.3 Bioactivity 155
6.4.3.1 Monosilanols 155
6.4.3.2 Silanediols 156
6.4.3.3 Silanetriols 157
6.4.4 Supramolecular Assembly 158
References 159
7 Silole-Based Materials in Optoelectronics and Sensing 163
Masaki Shimizu
7.1 Introduction 163
7.2 Basic Aspects of Silole-Based Materials 164
7.3 Silole-Based Electron-Transporting Materials 167
7.4 Silole-Based Host and Hole-Blocking Materials for OLEDs 170
7.5 Silole-Based Light-Emitting Materials 171
7.6 Silole-Based Semiconducting Materials 175
7.7 Silole-Based Light-Harvesting Materials for Solar Cells 179
7.8 Silole-Based Sensing Materials 185
7.9 Conclusion 189
References 190
8 Materials Containing Homocatenated Polysilanes 197
Takanobu Sanji
8.1 Introduction 197
8.2 Synthesis 197
8.3 Functional Modification of Polysilanes 198
8.4 Control of the Stereochemistry of Polysilanes 199
8.5 Control of the Secondary Structure of Polysilanes 200
8.6 Polysilanes with 3D Architectures 202
8.7 Applications 203
8.8 Summary 205
References 205
9 Catenated Germanium and Tin Oligomers and Polymers 209
Daniel Foucher
9.1 Introduction 209
9.2 Oligogermanes and Oligostannanes 209
9.3 Preparation of Polygermanes 212
9.3.1 Wurtz Coupling 212
9.3.2 Reductive coupling of Dihalogermylenes 214
9.3.3 Electrochemical Reduction of Dihalodiorganogermanes and Trihaloorganogermanes 215
9.3.4 Transition Metal-Catalyzed Polymerizations of Germanes 215
9.3.4.1 Demethanative Coupling of Germanes 216
9.3.5 Photodecomposition of Germanes 218
9.3.6 Properties and Characterization of Polygermanes 218
9.3.6.1 Thermal Properties of Polygermanes 218
9.3.6.2 Electronic Properties of Polygermanes 219
9.4 Preparation of Polystannanes 220
9.4.1 Wurtz Coupling 220
9.4.2 Electrochemical Synthesis 221
9.4.3 Dehydropolymerization 224
9.4.4 Alternating Polystannanes 227
9.4.5 Properties and Characterization of Polystannanes 227
9.4.5.1 Sn NMR 227
9.4.5.2 Thermal and Photostability 228
9.4.5.3 Electronic Properties 230
9.4.5.4 Conductivity 231
9.4.6 Molecular Modeling of Oligostannanes and Comparison of Group 14 Polymetallanes 231
9.5 Conclusions and Outlook 233
Acknowledgements 233
References 234
10 Germanium and Tin in Conjugated Organic Materials 237
Yohei Adachi and Joji Ohshita
10.1 Introduction 237
10.2 Germanium and Tin-Linked Conjugated Polymers 238
10.2.1 Germylene-Ethynylene Polymers 238
10.2.2 Fluorene- and Carbazole-Containing Germylene Polymers 240
10.2.3 Germanium- and Tin-Linked Ferrocenes and Related Compounds 241
10.3 Germanium- and Tin-Containing Conjugated Cyclic Systems 242
10.3.1 Non-fused Germoles and Stannoles 242
10.3.2 Dibenzogermoles and Dibenzostannoles 248
10.3.3 Dithienogermole and Dithienostannole 253
10.3.4 Other Fused Germoles 258
10.3.5 Germacycloheptatriene and Digermacyclohexadiene 259
10.4 Summary and Outlook 260
References 260
11 Phosphorus-Based Porphyrins 265
Yoshihiro Matano
11.1 Introduction 265
11.2 Porphyrins Bearing Phosphorus-Based Functional Groups at their Periphery 266
11.2.1 Porphyrins Bearing meso/β-Diphenylphosphino Groups 266
11.2.2 Porphyrins Bearing meso/β-Triphenylphosphonio Groups 269
11.2.3 Porphyrins Bearing meso/β-Diphenylphosphoryl Groups 273
11.2.4 Porphyrins Bearing meso/β-Dialkoxyphosphoryl Groups 276
11.2.5 Phthalocyanines Bearing Phosphorus-Based Functional Groups 280
11.3 Porphyrins and Related Macrocycles Containing Phosphorus Atoms at their Core 283
11.3.1 Core-Modified Phosphaporphyrins 284
11.3.2 Core-Modified Phosphacalixpyrroles 287
11.3.3 Core-Modified Phosphacalixphyrins 289
11.4 Conclusions 290
Acknowledgements 292
References 292
12 Applications of Phosphorus-Based Materials in Optoelectronics 295
Matthew P. Duffy, Pierre-Antoine Bouit, and Muriel Hissler
12.1 Introduction 295
12.2 Phosphines 296
12.2.1 Application as Charge-Transport Layer 296
12.2.2 Application as Host for Phosphorescent Complexes 299
12.2.3 Application as Emitting Materials 303
12.3 Four-Membered P-Heterocyclic Rings 306
12.3.1 Diphosphacyclobutanediyls 306
12.3.2 Phosphetes 307
12.4 Five-Membered P-Heterocyclic Rings: Phospholes 307
12.4.1 Application as Charge-Transport Layers 308
12.4.2 Application as Host for Phosphorescent Complexes 309
12.4.3 Application as Emitter in OLEDs 309
12.4.4 Dyes for Dye-Sensitized Solar Cells (DSSCs) 316
12.4.5 Donors in Organic Solar Cells (OSCs) 316
12.4.6 Application in Electrochromic Cells 317
12.4.7 Application in Memory Devices 318
12.5 Six-Membered P-Heterocyclic Rings 319
12.5.1 Phosphazenes 319
12.5.1.1 Application as Electrolyte for Solar Cells 319
12.5.1.2 Application as Host for Triplet Emitters in PhOLEDs 320
12.5.1.3 Application as Emitter for OLEDs 321
12.6 Conclusion 321
Abbreviations 322
References 324
13 Main-Chain, Phosphorus-Based Polymers 329
Klaus Duck and Derek P. Gates
13.1 Introduction 329
13.2 Polyphosphazenes 330
13.3 Poly(phosphole)s 333
13.4 Poly(methylenephosphine)s 336
13.5 Poly(arylene-/vinylene-/ethynylene-phosphine)s 341
13.6 Phospha-PPVs 343
13.7 Poly(phosphinoborane)s 345
13.8 Metal-Containing Phosphorus Polymers 347
13.9 Additional P-Containing Polymers 349
13.10 Summary 350
Acknowledgements 351
References 351
14 Synthons for the Development of New Organophosphorus Functional Materials 357
Robert J. Gilliard, Jr., Jerod M. Kieser, and John D. Protasiewicz
14.1 General Introduction 357
14.1.1 Phosphorus-Based Functional Materials 357
14.1.2 Phosphorus Allotropes 359
14.2 Phosphorus Transfer Reagents as Emerging Synthetic Approaches to Materials 360
14.2.1 Introduction to Phosphorus Transfer Reagents 360
14.2.2 Phosphaethynolate Salts 360
14.2.3 Phospha-Wittig Reagents 367
14.2.4 Phospha-Wittig–Horner Reagents 371
14.2.5 Phosphadibenzonorbornadiene Derivatives 373
14.3 Carbene-Stabilized Molecules as Phosphorus Reagents 375
14.3.1 Introduction to Carbene Phosphorus Complexes 375
14.3.2 N-Heterocyclic Carbene-Stabilized Phosphorus Complexes 375
14.3.3 Cyclic (Alkyl)(Amino) Carbene-Stabilized Phosphorus Compounds 376
14.3.4 Reactions of N-Heterocyclic Carbenes with Phosphaalkenes 377
14.4 Conclusions and Outlook 378
References 379
15 Arsenic-Containing Oligomers and Polymers 383
Hiroaki Imoto and Kensuke Naka
15.1 Introduction 383
15.2 Chemistry of Organoarsenic Compounds 384
15.3 Arsenic Homocycles 384
15.4 Development of C–As Bond Formation for Organoarsenic
15.4.1 Classical Methodologies 386
15.4.2 In Situ-Generated Organoarsenic Electrophiles from Arsenic Homocycles 387
15.4.3 In Situ-Generated Organoarsenic Nucleophiles from Arsenic Homocycles 388
15.4.4 Bismetallation Based on Arsenic Homocycles 388
15.5 Properties of Poly(vinylene-arsine)s 391
15.6 Properties of 1,4-Dihydro-1,4-diarsinines 391
15.7 Properties of Arsole Derivatives 394
15.8 Arsole-Containing Polymers 396
15.9 Conclusions 399
References 400
16 Antimony-and Bismuth-Based Materials and Applications 405
Anna M. Christianson and François P. Gabbaï
16.1 Introduction 405
16.2 Anion Binding and Sensing Applications 406
16.3 Small-Molecule Binding 418
16.4 Antimony and Bismuth Chromophores 426
16.5 Conclusion 430
References 430
17 High Sulfur Content Organic/Inorganic Hybrid Polymeric Materials 433
Jeffrey Pyun, Richard S. Glass, Michael M. Mackay, Robert Norwood, and Kookheon Char
17.1 Introduction 433
17.2 The Chemistry of Liquid Sulfur 434
17.2.1 Ring-Opening Polymerization of Elemental Sulfur 434
17.2.2 Synthesis of Inorganic Nanoparticles in Liquid Sulfur 435
17.2.3 Inverse Vulcanization of Elemental Sulfur 437
17.2.4 Transformation Polymerizations with Elemental Sulfur: Combining Inverse Vulcanization with Electropolymerization 441
17.3 Waterborne Reactions of Polysulfides 442
17.4 Controlled Polymerization with High Sulfur-Content Monomers 442
17.5 Modern Applications of High Sulfur-Content Copolymers 444
17.5.1 High Sulfur-Content Polymers as Cathode Materials for Li-S Batteries 444
17.5.2 High Sulfur-Content Polymers as Transmissive Materials for IR Thermal Imaging 445
17.6 Conclusion and Outlook 448
Acknowledgements 448
References 449
18 Selenium and Tellurium Containing Conjugated Polymers 451
Zhen Zhang, Wenhan He, and Yang Qin
18.1 Introduction 451
18.2 Selenium-Containing Conjugated Polymers 452
18.2.1 Background 452
18.2.2 Electron-Rich Homopolymers 453
18.2.3 Donor–Acceptor (D-A) Copolymers 457
18.2.3.1 Selenium-Containing Benzodithiophene-Benzothiadiazole (BDT-BT) Copolymer Derivatives 460
18.2.3.2 Selenium-Containing Benzodithiophene-Thienothiophene (BDT-TT) Copolymer Derivatives 462
18.2.3.3 Selenium-Containing Benzodithiophene-Diketopyrrolopyrrole (BDT-DPP) and Benzodithiophene-Thienopyrrole-4,6-dione (BDT-TPD) Copolymers 465
18.3 Tellurium-Containing Conjugated Polymers 467
18.3.1 Background 467
18.3.2 Synthesis of Tellurium-Containing Polymers 467
18.3.2.1 Early Examples of Insoluble Polymers 467
18.3.2.2 Tellurium-Bridge Polymers 469
18.3.2.3 Soluble Tellurophene-Containing Conjugated Polymers 469
18.3.2.4 Regio-Regular Poly(3-alkyltellurophene) 472
18.3.2.5 Other Tellurium-Containing Conjugated Polymers 473
18.3.3 Application of Tellurium-Containing Conjugated Polymers 473
18.4 Conclusions and Outlook 476
References 476
19 Hypervalent Iodine Compounds in Polymer Science and Technology 483
Avichal Vaish and Nicolay V. Tsarevsky
19.1 Introduction 483
19.1.1 Historical 483
19.1.2 Bonding in Hypervalent Iodine Compounds 484
19.1.3 Patterns of Reactivity Relevant to Applications in Polymer Science and Technology 486
19.2 Applications of Hypervalent Iodine Compounds in Polymer Science and Technology 487
19.2.1 HV Iodine Compounds as Initiators for Polymerization 487
19.2.1.1 Direct Application of HV Iodine Compounds 487
19.2.1.2 Functional Radical Initiators Generated as a result of Ligand-Exchange followed by Homolysis 493
19.2.2 Post-Polymerization Modifications using HV Iodine Compounds 495
19.2.3 HV Iodine Groups as Structural Elements in Polymers 496
19.2.3.1 Polymers with HV Iodine-Based Pendant Groups 496
19.2.3.2 HV Iodine Groups as part of the Polymer Backbone 505
19.3 Conclusions 508
Acknowledgements 508
References 508
Index
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