Polycyclic Arenes and Heteroarenes Synthesis, Properties, and Applications

Preface XI

List of Contributors XIII

Part I Polycyclic Arenes 1

1 Open-Shell Benzenoid Polycyclic Hydrocarbons 3
Soumyajit Das and JishanWu

1.1 Introduction 3

1.2 Higher Order Acenes 6

1.3 Phenalenyl-Based Diradicaloids 9

1.3.1 Bis(phenalenyl)s 10

1.3.2 Zethrenes 14

1.4 Anthenes and Periacenes 21

1.5 π-Extended p-Quinodimethane 27

1.6 Triangulene-Based Triplet Biradicals 31

1.7 Potential Applications 32

1.8 Conclusion 33

References 33

2 Planar Cyclopenta-Fused Polycyclic Arenes 37
Gabriel E. Rudebusch andMichael M. Haley

2.1 Introduction 37

2.2 Acenaphthylenes 37

2.3 Dibenzopentalenes 43

2.4 Indenofluorenes 51

2.5 Conclusions 57

Acknowledgment 58

References 58

3 Growing Buckybowl Chemistry 61
Shuhei Higashibayashi and Hidehiro Sakurai

3.1 Introduction 61

3.2 π-Extended Buckybowls 62

3.3 Chiral Buckybowl 65

3.4 Heterobuckybowl 68

3.5 Columnar Crystal Packing of Buckybowls 75

3.6 Summary and Conclusions 80

References 80

4 Polycyclic Arenes Containing Seven-Membered Carbocycles 85
Kwan Yin Cheung and QianMiao

4.1 Introduction 85

4.2 Azulene, Oligo-azulenes, and Fused Azulenes 85

4.3 Polycyclic Arenes Containing 5H-Dibenzo[a,d]cycloheptene Units 92

4.4 Cyclohepta[de]naphthalene, dicyclohepta[de,ij]naphthalene, and Their Benzannulated Derivatives 97

4.5 Curved Polycyclic Arenes Containing Highly Fused Cycloheptatriene 101

4.6 Conclusions 107

Acknowledgment 107

References 107

5 Polycyclic Arenes Containing Eight-Membered Carbocycles 111
Chun-Lin Deng, Xiao-Shui Peng, and Henry N. C.Wong

5.1 Introduction 111

5.2 [8]Annulenes 112

5.2.1 Dehydro[8]annulenes 112

5.2.2 Benzo-Fused [8]annulenes 116

5.2.3 Biphenylene-Fused [8]annulenes 119

5.3 Tetraphenylenes 122

5.3.1 Synthesis 122

5.3.1.1 Ring Opening of the Strained Four-Membered Ring of Biphenylene Derivatives 123

5.3.1.2 Transition-Metal-Mediated Oxidative Coupling 123

5.3.1.3 Cycloaddition–Deoxygenation Protocol 124

5.3.1.4 Synthesis of Enantiopure Tetraphenylenes 125

5.3.2 Properties and Potential Applications 127

5.4 [8]Circulene 133

5.5 Concluding Remarks 138

References 138

6 Cycloparaphenylenes and Carbon Nanorings 143
Shigeru Yamago, Eiichi Kayahara, and Sigma Hashimoto

6.1 Introduction 143

6.2 Early Developments 144

6.3 Strain and HOMO/LUMO Energies of CPPs 146

6.4 Synthesis of CPPs 147

6.5 Properties of CPPs 154

6.5.1 Photophysical Properties 154

6.5.2 Redox Properties of CPPs 155

6.5.3 Host–Guest Chemistry 158

6.6 Summary and Conclusions 160

References 160

7 Advances in Chemistry of Dehydrobenzoannulenes 163
Shunpei Nobusue and Yoshito Tobe

7.1 Introduction 163

7.2 Synthesis and Properties of New DBAs 164

7.2.1 Single-Ring DBAs 164

7.2.2 Multiple-Ring DBAs 166

7.3 DBAs as Graphyne and Graphdiyne Motifs 169

7.3.1 Theoretical and Synthetic Studies on Graphyne and Graphdiyne 170

7.3.2 Synthesis of Graphyne and Graphdiyne Motifs and Related Multiple DBA Systems 171

7.4 DBAs as Supramolecular Building Blocks 171

7.4.1 Crystal Engineering 172

7.4.2 3D Assemblies: Gels, Fibers, Vesicles, and Liquid Crystals 174

7.4.3 2D Self-Assembly on Surfaces and Interfaces 175

7.5 DBAs in Optoelectronic Applications 180

7.6 DBAs as Synthetic Precursors 181

7.6.1 Transannular Bond Formation Leading to Unconventional Aromatic Molecules 181

7.6.2 Strain-Assisted Cycloaddition and Biological Applications 185

7.7 Summary and Conclusions 187

References 187

8 Tetraarylethenes and Aggregation-Induced Emission 193
Zujin Zhao and Ben Zhong Tang

8.1 Introduction 193

8.2 Fundamentals 194

8.2.1 Pristine Tetraphenylethene (TPE) 194

8.2.2 Rigidified TPE Derivatives 195

8.2.3 Adducts of TPE and Planar Chromophores 200

8.2.4 Emission Color Tuning of TPE Derivatives 202

8.2.5 Complex Tetraarylethenes 204

8.3 Applications 210

8.3.1 Chemosensors 210

8.3.2 Mechanochromic Luminescent Materials 211

8.3.3 Light-Emitting Materials 213

8.4 Outlook 218

References 219

Part II Polycyclic Heteroarenes 223

9 N-Containing Polycyclic Heteroarenes 225
Arun Naibi Lakshminarayana and Chunyan Chi

9.1 Introduction 225

9.2 Linear and Extended N-Heteroarenes 226

9.2.1 N-Heteroacenes 226

9.2.1.1 History and Synthesis 226

9.2.1.2 Properties and Applications 228

9.2.2 Extended N-Heteroarenes 232

9.2.2.1 Unconventional N-Heteroacenes 232

9.2.2.2 N-Annulated Perylenes 235

9.3 Nitrogen-Rich Macrocyclic Arenes 236

9.3.1 Porphyrin and Porphyrinoids 236

9.3.1.1 Synthesis 237

9.3.1.2 General Properties 237

9.3.1.3 Diversity of Porphyrinoids 239

9.3.1.4 Applications 241

9.3.2 Phthalocyanines 242

9.3.2.1 History and Synthesis 242

9.3.2.2 General Properties and Applications 243

9.4 Miscellaneous 244

9.5 Summary and Conclusion 246

References 247

10 Boron-Containing Polycyclic Aromatics 251
David R. Levine and John D. Tovar

10.1 Introduction 251

10.2 Historical Perspective and Representative Structures 251

10.3 General Synthetic Strategies 253

10.3.1 Metalation/Ring Closure 253

10.3.2 Element–Boron Exchange (Metathesis) 254

10.3.3 Intramolecular Cascade Cyclizations 255

10.3.4 Photoisomerization/Thermal Isomerization 256

10.3.5 Oxidative and Radical Cyclizations – Toward Two-Dimensional π-Systems 257

10.3.6 Functionalization at Boron: Hydroboration Chemistry 258

10.4 Recent Developments in B-PAH Structures and Properties 259

10.4.1 Linear Ladder-Type π-Systems 259

10.4.1.1 Borole-Based PAHs 259

10.4.1.2 Borepin-Based PAHs 261

10.4.1.3 Boraacenes andTheir Congeners 262

10.4.1.4 Tetravalent Boron: B–N Coordinated and Other Zwitterionic Systems 265

10.4.2 Two-Dimensionally Fused π-Systems 267

10.4.2.1 Fundamental Impacts of Enforced Planarity in Triarylboranes 267

10.4.2.2 Fully Conjugated Two-Dimensional Materials 270

10.5 Conclusions/Outlook 272

References 273

11 S-Containing Polycyclic Heteroarenes: Thiophene-Fused and Thiadiazole-Fused Arenes as Organic Semiconductors 277
Masashi Mamada and Yoshiro Yamashita

11.1 Introduction 277

11.2 Electronic Structures of FusedThiophenes andThiadiazoles 278

11.3 p-Type Semiconductors with Fused Thiophenes 282

11.3.1 Acenothiophenes (AcTs) and Acenodithiophenes (AcDTs) 282

11.3.1.1 Overview 282

11.3.1.2 AcT and AcDT Derivatives 284

11.3.1.3 AcT and AcDT Derivatives with Trialkylsilylethynyl Groups 284

11.3.2 [n]Thienoacenes ([n]TAcs) and Related Compounds 286

11.3.2.1 Overview 286

11.3.2.2 [n]TAc Derivatives 286

11.3.3 Alternating Rings of Fused Benzene and Thiophene Molecules (ABTs) 288

11.3.3.1 Overview 288

11.3.3.2 Isoelectronic Analogs of Dibenzo[a,h]anthracene 290

11.3.3.3 Isoelectronic Analogs of Pentaphene 290

11.3.3.4 Isoelectronic Analogs of Benzo[a]tetracene 290

11.3.4 Diacene-Fused Thienothiophenes (DAcTTs) 290

11.3.4.1 Overview 290

11.3.4.2 Symmetric DAcTTs 291

11.3.4.3 Asymmetric DAcTTs 291

11.3.5 Others (2-D π-Extended Fused Thiophenes) 293

11.3.5.1 Overview 293

11.3.5.2 2-D π-Extended Fused Thiophenes 293

11.4 n-Type Semiconductors with Fused Thiophenes 293

11.4.1 Overview 293

11.4.2 n-Type Semiconductors with Fused Thiophenes 295

11.5 Thiadiazole Derivatives 297

11.5.1 Overview 297

11.5.2 Thiadiazole Derivatives for p-Type Semiconductors 298

11.5.3 Thiadiazole Derivatives for Ambipolar Semiconductors 298

11.5.4 Thiadiazole Derivatives for n-Type Semiconductors 300

11.6 Summary and Conclusions 300

References 303

12 P-Containing Heteroarenes: Synthesis, Properties, Applications 309
Monika Stolar and Thomas Baumgartner

12.1 Introduction 309

12.2 Five-Membered Ring Systems 309

12.3 Six-Membered Ring Systems 321

12.4 Seven-Membered Ring Systems 323

12.5 Other Phosphorus-Containing Diketo-Ring Systems 325

12.6 Summary and Conclusions 326

Acknowledgments 327

References 327

Index 331

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