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Molecular Nanographenes
Synthesis, Properties, and Applications
Nazario Martin (Edited by), Colin P. Nuckolls (Edited by)
9783527353224, Wiley
Hardback, published 21 May 2025
544 pages
24.4 x 17 x 1.5 cm, 0.68 kg
Explore the world’s most powerful materials with nanographene research Graphene, comprised of a single layer of carbon atoms in a honeycomb nanostructural arrangement, is the thinnest and strongest material yet known to science. Despite that this pristine carbon allotrope exhibits a variety of outstanding properties, its zero bandgap prevents its use for some optoelectronic applications. Fragments of graphene, or nanographenes, have shown a great potential to obviate these problems, thus paving the way for the development of chiroptical and optoelectronic properties. Molecular Nanographenes constitutes a comprehensive overview on the synthesis of these materials and their properties. Covering their widely varying morphologies, their potential applications, and their valuable chiroptical and photophysical features, it also analyzes multiple approaches to obtain nanographene by using both top-down and bottom-up methodologies. The result is a one-stop shop for materials scientists and other researchers interested in these emergent and fascinating materials. Molecular Nanographenes readers will also find: Molecular Nanographenes is ideal for materials scientists, polymer chemists, solid state chemists, organic chemists, and any other researchers looking to work with shape and size-controlled flakes of graphenes.
Foreword xiii Preface xvii 1 Aromaticity and Antiaromaticity in Nanographenes: An Overview 1 1.1 Introduction 1 1.2 Global and Local Aromaticity 2 1.3 Methods to Quantify Aromaticity 6 1.3.1 Energetic Descriptors of Aromaticity 7 1.3.2 Electronic Descriptors of Aromaticity 9 1.3.3 Geometric Descriptors of Aromaticity 13 1.3.4 Magnetic Descriptors of Aromaticity 14 1.4 The Analysis of Aromaticity in Nanographene Systems 20 1.5 Concluding Remarks 23 Acknowledgments 24 References 24 2 Covalent Patterned Functionalization of Graphene 31 2.1 Introduction 31 2.2 Substrate-Mediated Chemical Patterning 33 2.3 Tip-Induced Patterned Functionalization 35 2.4 Lithography-assisted Molecular Engineering 37 2.5 Laser Writing 44 2.6 Conclusion 50 References 51 3 Nanographenes by Bottom-up Approach: The Scholl Reaction 55 3.1 Introduction 55 3.2 Planar Nanographenes 56 3.3 Heterocyclic Analogs of Planar Nanographenes 63 3.4 Nonplanar, Curved, and Twisted Nanographenes 66 3.5 Heterocyclic Analogs of Nonplanar Nanographenes 71 3.6 Surface-assisted (cyclo)Dehydration 74 3.7 Summary and Outlook 76 Acknowledgment 77 References 77 4 Racemization Barriers in Chiral Molecular Nanographenes 83 4.1 Introduction 83 4.2 Structural Motifs for Chirality in Nanographenes 84 4.2.1 Gaussian Curvature 85 4.2.2 Helicenes 85 4.2.3 Rolling 86 4.2.4 Strain 87 4.3 Classification of Chiral Molecular NGs According to Their Isomerization Barriers 87 4.4 Flexible Nanographenes ( 4.5 Nanographenes with Spectroscopically Detectable Chirality (5–20 kcal mol −1) 89 4.6 Isolable Nanographenes (20–35 kcal mol −1) 90 4.7 Rigid Nanographenes (>35 kcal mol −1) 93 4.8 Enantioselective Synthesis of Rigid Molecular Nanographenes 95 4.9 Conclusion 98 References 99 5 Synthesis of Helicenes 105 5.1 Introduction 105 5.2 Characteristics of Helicenes 106 5.3 Synthetic Methodologies 107 5.3.1 Photocyclodehydrogenation of 1,2-Diaryl Olefins or Arenes 107 5.3.2 Oxidative Aromatic Coupling: Scholl Reaction 111 5.3.3 Transition Metal-Catalyzed [2 + 2 + 2] Cycloisomerization of π-Electron Systems 111 5.3.4 Diels–Alder Cycloaddition of Aromatic Vinylethers with p-Benzoquinone 117 5.3.5 Transition Metal-Catalyzed Hydroarylation of Alkynes 119 5.3.6 Other Synthetic Approaches 120 5.4 Advanced Helicene Architectures 123 5.5 Summary and Outlook 137 Acknowledgment 137 References 137 6 Carbon Nanobelt History and Chemistry 149 6.1 Introduction 149 6.2 Synthetic Attempts to CNBs 151 6.2.1 Some Synthetic Attempts to Cyclacenes 151 6.2.2 CNBs Observed by Mass Spectroscopy 152 6.2.3 Top-Down Approach to CNBs 152 6.3 Synthesis of CNBs 153 6.4 Synthesis of Related Aromatic Nanobelts 154 6.5 Synthesis of Topological Aromatic Nanobelts 157 6.6 Conclusion 159 References 159 7 Negatively Curved Nanographenes 163 7.1 Introduction 163 7.2 Negatively Curved Nanographenes Containing Seven-Membered Rings 164 7.2.1 Incorporation of Seven-Membered Rings at an Early Stage of Synthesis 165 7.2.2 Formation of Seven-Membered Rings at a Late Stage of the Synthesis 168 7.3 Negatively Curved Nanographenes Containing Eight-Membered Rings 174 7.3.1 Incorporation of Eight-Membered Rings at an Early Synthetic Stage 175 7.3.2 Formation of Eight-Membered Rings at the Final Step of Synthesis 179 7.4 Structures and Stereochemical Dynamics and Properties 181 7.5 Negatively Curved Molecular Nanocarbons Beyond Nanographenes and Bottom-up Approaches to Carbon Schwarzites 184 7.6 Conclusion and Outlook 186 References 188 8 From PAH-based Cyclophanes to Nanographenophanes 193 8.1 Introduction 193 8.2 Synthetic Considerations 197 8.3 Pentacenophanes (C22) 199 8.4 Indeno[2,3-b]triphenylenophanes (C25) 201 8.5 Dibenzo[c,l]chrysenophanes (C26) 203 8.6 Dibenzo[f,j]picenophanes (C30) and Tetrabenz[a,c,h,j]anthracenes (c30) 205 8.7 Teropyrenophanes (C36) 207 8.8 A π-Extended Azacorannulenophane (C36 N) 211 8.9 Hexabenzocoronenophanes (C42) 213 8.10 hept-Hexabenzocoronenophanes (C43) 217 8.11 Summary and Outlook 218 References 219 9 Bilayer and Multilayer Nanographenes: Synthesis and Properties 223 9.1 Introduction 223 9.2 Van der Waals Molecular Nanographenes 225 9.3 Bilayers from Fused Radicals 230 9.4 Covalently Linked Bilayers 232 9.5 Conclusions 238 References 239 10 Large π-Extended Carbon Nanorings: From Syntheses to Properties 243 10.1 Introduction 243 10.1.1 Carbon Nanorings with Inserted Six-Membered Ring-Based PAHs 244 10.1.1.1 With Inserted Naphthalene(s) 244 10.1.1.2 With Inserted Anthracene(s) or Phenanthrene(s) 247 10.1.1.3 With Inserted Pyrene(s) or Perylene(s) 248 10.1.1.4 With Inserted Other PAHs 249 10.1.2 Carbon Nanorings Consisting Solely of PAHs 252 10.1.2.1 Consisting Solely of Naphthalenes 253 10.1.2.2 Consisting Solely of Anthracenes, Pyrenes, or Chrysenes 254 10.1.2.3 Consisting Solely of Other PAHs 255 10.1.3 CPP-based Oligomers and Polymers 258 10.1.4 Conclusions and Outlook 261 References 262 11 Nanographenes with Multiple Zigzag Edges 267 11.1 Introduction 267 11.2 Peri-Acenes 268 11.3 Triangular Nanographenes 275 11.4 Peri-acenoacenes 278 11.5 Circumarenes 279 11.6 Conclusion 283 References 285 12 Synthesis of Graphene Nanoribbons, Nanographenes, and Fused Aromatic Networks Through the Formation of Pyrazine Rings 289 12.1 Introduction 289 12.2 Graphene Nanoribbons and Nanographenes 289 12.3 Fused Aromatic Networks 293 12.4 Conclusions 300 References 300 13 Conjugated Nanohoops: Synthesis, Properties, and Applications 303 13.1 Introduction 303 13.2 Synthetic Strategies to Conjugated Nanohoops 303 13.2.1 Pt-, Ni-, or Au-Mediated Macrocyclizations in the Synthesis of Nanohoops 304 13.2.2 Synthesis of Conjugated Nanohoops via Kinked Precursors to π-System Panels 307 13.3 Properties of Conjugated Nanohoops 309 13.3.1 Optoelectronic Properties 309 13.3.2 Chirality 311 13.3.3 Host–Guest Chemistry 311 13.3.4 Solid-State Structures 313 13.4 Applications of Conjugated Nanohoops 314 13.4.1 Organic Electronics 314 13.4.2 Bottom-up Synthesis of Carbon Nanotubes 316 13.4.3 Biological Fluorophores 317 13.5 Conclusions 317 References 318 14 Chiral Polycyclic Aromatic Compounds with Monkey Saddle Topologies 323 14.1 Introduction 323 14.2 Saddle Mathematics 327 14.3 Synthesis 328 14.4 X-Ray Crystal Structures of Monkey Saddle PAHs 331 14.5 NICS and ACID Plots 333 14.6 Inversion Barriers and Chiroptical Properties 334 14.7 Other Monkey Saddle PAHs and Related Systems 337 14.8 Summary and Outlook 339 References 340 15 On-Surface Synthesis of π-Conjugated Polymers 345 15.1 Introduction 345 15.2 Content 345 15.3 Conclusions 358 References 360 16 Merging Organic Chemistry with Surface Science for the Preparation of Nanographenes 363 16.1 Introduction 363 16.2 Scanning Probe Microscopies for the Characterization of Nanographenes Obtained by Solution-Phase Chemistry 364 16.3 Combining Solution-Phase and On-Surface Chemistry for the Synthesis of Nanographenes 366 16.3.1 Surface-Assisted Cyclodehydrogenation Reaction 367 16.3.2 Surface-Assisted Ullmann-Type Reactions 369 16.3.3 Alternative Reactions Used for the On-Surface Preparation of Nanographenes 371 16.3.4 Combining On-Surface Reactions Toward the Preparation of Nanographenes 373 16.4 Concluding Remarks 373 References 375 17 Chiral Materials from Twistacenes and Helicenes 381 17.1 Introduction 381 17.1.1 Background 381 17.1.2 The Building Block 381 17.2 Twistacene-based Materials 382 17.2.1 Preparation 382 17.2.2 Properties 383 17.2.3 Organic Photovoltaics and Photodetectors 388 17.2.4 Electrochemical Storage Using hPDIs 389 17.3 Helicene-Based Materials 391 17.3.1 Preparation 391 17.3.2 Chiral Amplification 392 17.4 Future Directions 393 References 393 18 Nanographene Diradicals 397 18.1 Introduction 397 18.2 On the Origin of the Diradical State in Monocyclic Conjugated Hydrocarbons: The Case of Cyclobutadiene 400 18.3 Nanographene Diradical Made from Mixtures of Quinoidal Bonding States and Nonbonding States 403 18.3.1 The Zethrene Family 404 18.3.2 The Bisphenalenylene Family 406 18.3.3 On-Surface Diradicals 407 18.3.4 Graphene Nanoribbons and Their Diradical (i.e. Polyradical Character) 409 18.4 The Diradical State in All-Zig-zag Polycyclic Conjugated Hydrocarbons: On the Reversed Aromatic→Quinoidal Way to Open-Shell Nanographenes 410 18.4.1 The Acenoacene Family 411 18.4.2 The Oligorylene Family 413 18.5 The Diradical State as a Result of Zig-zag Versus Arm-chair Structures with “Mobile” Quinoidal Rings with Quinoidal → Aromatic Transformation in the Diradical State 415 18.5.1 The Peri-Acene Family 415 18.5.2 The Circumacene Family 417 18.5.3 The Unique Case of Rhombenes 419 18.6 Conclusions 420 Acknowledgments 420 References 420 19 Circularly Polarized Luminescence (CPL) in Nanographenes 425 19.1 Introduction 425 19.2 (1 × HBC)-Based Chiral Nanographenes 428 19.3 (1 × HBC)-Based Heteroatom-Doped Chiral Nanographenes 431 19.4 2 × HBC-Based Chiral Nanographenes 434 19.5 3 × HBC-based Chiral Nanographenes 436 19.6 4 × HBCs-based Chiral Nanographenes and Beyond 438 19.7 Summary Table and Outlook 439 Acknowledgments 445 References 445 20 Redox Properties of Nanographenes 449 20.1 Introduction 449 20.2 Planar Nanographene Fragments 452 20.3 Contorted Nanographenes with Positive and Negative Curvatures 456 20.3.1 Corannulene-based Nanographenes 457 20.3.2 Cyclooctatetraene-based Nanographenes 463 20.3.3 Bilayer Nanographene 468 Acknowledgments 470 References 470 21 Kekulé and Non-Kekulé Nanographenes: A Magnetic Perspective 483 21.1 Introduction 483 21.2 Stable Open-Shell Kekulé NGs (S = 0) as Quantum Units 485 21.3 Concealed Non-Kekulé Nanographenes (S = 0) 486 21.4 Obvious Non-Kekulé Nanographenes (S > 0) 488 21.4.1 Spin 1 / 2 Non-Kekulé Nanographenes (S = 1 / 2) 489 21.4.2 High-Spin Non-Kekulé Nanographenes (S ≥ 1) 492 21.5 Engineering of Magnetic Coupling in Non-Kekulé Nanographenes 498 21.5.1 Spin 1 / 2 Dimers 498 21.5.2 Triangulene (S = 1) Dimers and Trimers 501 21.5.3 [3]Triangulene (S = 1) Based Spin Chains 501 21.6 Summary and Outlook 504 Acknowledgments 505 References 505 Index 511
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Daniel T. Gryko, Wojciech D. Petrykowski, and Krzysztof J. Kochanowski
Jesús M. Fernández-García, Patricia Izquierdo-García, Salvatore Filippone, and Nazario Martín
Irena G. Stará and Ivo Starý
Hiroki Shudo, Daiki Imoto, Akiko Yagi, and Kenichiro Itami
Ka Man Cheung and Qian Miao
Parinaz Salari and Graham J. Bodwell
Patricia Izquierdo-García, Juan Lión-Villar, Jesús M. Fernández-García, and Nazario Martín
Jinyi Wang, Dapeng Lu, and Pingwu Du
Ya Zou and Jishan Wu
Felix Hernández-Culebras and Aurelio Mateo-Alonso
Birgit Esser, Philipp Seitz, Andrej Weber, and Jan S. Wössner
Tobias Kirschbaum and Michael Mastalerz
Nazario Martín and David Écija
Iago Pozo, Dolores Pérez, and Diego Peña
Si Tong Bao, Qifeng Jiang, Haoyu Jiang, Daniel Èavloviæ, and Colin Nuckolls
Fabrizia Negri and Juan Casado
Carlos M. Cruz, Sandra Míguez-Lago, Daniel Salvador-Gil, and Araceli G. Campaña
Yikun Zhu and Marina A. Petrukhina
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Subject Areas: Chemistry [PN]
