List of Contributors xvii
Preface to Handbook of Aggregation-Induced Emission xxiii
Preface to Volume 2: Typical AIEgens Design xxv
1 Tetraphenylpyrazine-based AIEgens: Synthesis and Applications 1
Ming Chen, Anjun Qin, and Ben Zhong Tang
1.1 Introduction 1
1.2 Synthesis of TPP-based AIEgens 3
1.2.1 Cyclization Reaction 3
1.2.2 Suzuki-Miyaura Reaction 7
1.3 Functionalities of TPP-based AIEgens 8
1.3.1 Organic Light-emitting Diodes 8
1.3.2 Fluorescent Sensors 9
1.3.3 Chiral Cage for Self-assembly to Achieve White-light Emission 13
1.3.4 Metal-organic Framework 15
1.4 Conclusion 17
References 18
2 AIEgens Based on 9,10-Distyrylanthracene (DSA): From Small Molecules to Macromolecules 23
Leijing Liu, Bin Xu, and Wenjing Tian
2.1 Introduction 23
2.2 Application of AIE Luminogens Based on 9,10-Distyrylanthracene 24
2.2.1 Smart Materials with Stimulus Response 24
2.2.1.1 Piezofluorochromic Materials 24
2.2.1.2 Photochromic Materials 27
2.2.1.3 Thermochromic Materials 27
2.2.1.4 Acidichromic Materials 27
2.2.1.5 Multistimuli-responsive Materials 30
2.2.2 High Solid-state Luminescent Materials 30
2.2.3 Fluorescent Materials for Bioimaging 35
2.2.4 Fluorescent Probes for Chemical and Biological Sensing 41
2.2.4.1 Fluorescent Probes for Chemical Sensing 41
2.2.4.2 Fluorescent Probes for Biological Sensing 44
2.3 Conclusions and Outlook 46
Acknowledgments 47
References 47
3 Typical AIEgens Design: Salicylaldehyde Schiff Base 53
Yue Zheng and Aijun Tong
3.1 Introduction 53
3.1.1 AIE and ESIPT of Salicylaldehyde Schiff Base 53
3.1.2 Universal Design of SSB-based AIEgens 55
3.2 Fluorescent Probes 55
3.2.1 Metal Ion Detection and Imaging 55
3.2.2 Biologically and Environmentally Related Molecular Detection and Imaging 63
3.2.3 Ratiometric pH Probes 76
3.2.4 Bioimaging 76
3.3 Fluorescent Materials 81
3.3.1 Solid Fluorescence Emitting and Stimuli-Responsive Materials 81
3.3.2 Nanoparticles 88
3.4 Summary and Perspectives 91
References 92
4 Diaminodicyanoquinodimethanes: Fluorescence Emission Enhancement in Aggregates and Solids 97
N. Senthilnathan and T. P. Radhakrishnan
4.1 Introduction 97
4.1.1 Molecular Materials 97
4.1.2 'Push-Pull' Molecules 97
4.1.3 Diaminodicyanoquinodimethanes 98
4.2 Nonlinear Optical Materials based on DADQs 100
4.2.1 Molecular Hyperpolarizability 100
4.2.2 SHG Materials 100
4.2.3 Structure-Property Correlations 101
4.3 Enhanced Fluorescence in Aggregates and Solids Based on DADQs 102
4.3.1 Remote Functionalized Systems 102
4.3.2 Color Tuning, Nanocrystals, and Colloids 103
4.3.3 Ultrathin Films 105
4.3.4 New Directions 105
4.4 Mechanistic Insights into the Enhanced Fluorescence 106
4.4.1 Relevance of Intramolecular Effects 106
4.4.2 Role of Intermolecular Effects 106
4.5 Impact of Crystallinity on the Fluorescence Response 108
4.5.1 Amorphous-to-Crystalline Transformation: Fluorescence Switching and Tuning 108
4.5.2 Reversible Amorphous-Crystalline Transformations: Phase Change Materials 108
4.5.3 Impact of External Stimuli 110
4.6 Emergent and Potential Applications of DADQs 110
4.6.1 Electroluminescence and Nonlinear Optics 110
4.6.2 Bioimaging 110
4.6.3 Photoelectrochemical and Photobioelectrochemical Applications 112
4.6.4 Memory Devices 112
4.7 Concluding
Remarks 113
Acknowledgements 114
References 114
5 Aggregation-induced Emission from the Sixth Main Group 119
Jan Balszuweit, Bibhisan Roy, and Jens Voskuhl
5.1 Introduction 119
5.2 Oxygen 119
5.2.1 Oxygen-Containing Heterocycles 120
5.2.2 Oxo-ether Containing AIE-Active Luminogens 122
5.3 Sulfur 126
5.3.1 Luminogens Based on Thiophenes 126
5.3.2 Thioethers with Aggregation-Induced Emission Properties 129
5.3.3 Emissive Sulfones 131
5.4 Selenium and Tellurium 132
5.4.1 Selenium-Containing Luminophores 132
5.4.2 Tellurium-Containing Luminophores 134
5.5 Conclusion 138
Acknowledgment 138
References 138
6 Fluorescence Detection of Dynamic Aggregation Processes Using AIEgens: Hexaphenylsilole and Cyanostilbene 143
Fuyuki Ito
6.1 Introduction 143
6.2 Selective Detection of Phase Transformation During Evaporative Crystallization of Hexaphenylsilole 145
6.3 Observation of the Initial Stage of Organic Crystal Formation During Solvent Evaporation Using a Cyanostilbene Derivative 149
6.4 Chemometrix Analysis of the Aggregated Structure of Cyanostilbene in a Reprecipitation Solution Using Fluorescence Excitation Spectroscopy 152
6.5 UV-triggered Fluorescence Enhancement of a Dicyanostilbene Derivative Film Cast from an Ethanol Solution 158
6.6 Concluding Remarks 162
Acknowledgments 162
References 162
7 Cyclic Triimidazole Derivatives: An Intriguing Family of Multifaceted Emitters 165
Elena Cariati, Elena Lucenti, Andrea Previtali, and Alessandra Forni
7.1 Introduction 165
7.2 The Protoype: Cyclic Triimidazole 166
7.3 Halogenated Derivatives of Cyclic Triimidazole 175
7.3.1 Bromine Derivatives 176
7.3.2 Iodine Derivatives 179
7.4 Organic Derivatives 184
7.4.1 2-Fluoropyridine Derivative 185
7.4.2 Tribenzoimidazole Derivative 186
7.5 Hybrid Inorganic/Organic Derivatives 188
7.6 Conclusions 191
Acknowledgments 191
References 191
8 Synthesis of Multi-phenyl-substituted Pyrrole (MPP)-based AIE Materials and Their Applications 195
Zhengxu Cai, Yunxiang Lei, and Yuping Dong
8.1 Introduction 195
8.2 Modular Approach: Systematic Synthesis of MPPs 196
8.3 Structures and Photophysical Properties 198
8.4 Applications of MPP-based Materials 204
8.4.1 Chemical/Biological Sensing 204
8.4.2 Multi-stimulus Response Materials 208
8.4.3 Optoelectronic Systems 210
8.4.4 Biological Application 213
8.5 Conclusion and Outlook 216
References 216
9 Development of a New Class of AIEgens: Tetraarylpyrrolo [3,2-b] Pyrroles (TAPPs) 221
Vishal G. More, Ratan W. Jadhav, Mohammad Al Kobaisi, Lathe A. Jones, and Sheshanath V. Bhosale
9.1 Introduction 221
9.2 The Accidental Discovery of TAPP 223
9.3 Synthesis of TAPP 223
9.4 Possible Mechanism of TAPP Synthesis 227
9.5 Reactivity of TAPP 228
9.6 ¿-Expansion of TAPP 229
9.7 ¿-Expanded 1,4-dihydropyrrolo[3,2-b] pyrrole 231
9.8 Photophysical Optical Properties of TAPP 239
9.9 Conclusion and Outlook 245
Acknowledgments 247
References 247
10 Small Molecule Organogels from AIE Active ¿-Cyanostilbenes 255
Jagadish Katla, Beena Kumari, and Sriram Kanvah
10.1 Introduction 255
10.2 Organogels with Trifluoromethyl Substitution 256
10.3 Organogels with Chiral Units/Chiral Hosts 260
10.4 Stimuli-Responsive Organogels 262
10.5 Organogels with Sensing Applications 266
10.6 Concluding Remarks 271
Acknowledgments 271
References 271
11 Stimuli-responsive Pure Organic Luminescent Supramolecules 277
Siyu Sun and Xiang Ma
11.1 Introduction 277
11.2 Pure Organic Fluorescent Supramolecules 280
11.2.1 Pure Organic Fluorescent Supramolecules Containing Macrocycles 280
11.2.1.1 Pure Organic Fluorescent Supramolecules Containing Cyclodextrins 280
11.2.1.2 Pure Organic Fluorescent Supramolecules Containing Calixarenes 284
11.2.1.3 Pure Organic Fluorescent Supramolecules Containing Cucurbiturils 284
11.2.1.4 Pure Organic Fluorescent Supramolecules Containing Pillararene 288
11.2.1.5 Pure Organic Fluorescent Supramolecules Containing Crown Ether 290
11.2.2 Pure Organic Fluorescent Supramolecules Without Macrocycles 291
11.3 Pure Organic Phosphorescent Supramolecules 293
11.3.1 Pure Organic Phosphorescent Supramolecules Based on Macrocyclic Molecules 293
11.3.1.1 Pure Organic Phosphorescent Supramolecules Containing Cyclodextrin 293
11.3.1.2 Pure Organic Phosphorescent Supramolecules Containing Cucurbiturils 297
11.3.1.3 Pure Organic Phosphorescent Supramolecules Containing Calixarenes 297
11.3.1.4 Pure Organic Phosphorescent Supramolecules Containing Crown Ether 297
11.3.2 Pure Organic Phosphorescent Supramolecules Without Macrocyclic Molecules 299
11.3.2.1 Pure Organic Supramolecular Phosphorescence System With Doping-Based Host-Guest Interaction 299
11.3.2.2 Other Pure Organic Phosphorescent Supramolecules 301
11.4 Conclusions 306
Acknowledgments 306
References 307
12 AIE Fluorescent Polymersomes 311
Hui Chen and Min-Hui Li
12.1 Introduction 311
12.2 Structural Consideration of Block Copolymers for Polymersome Formation 314
12.3 Methods of Polymersome Preparation 315
12.4 Techniques of Polymersome Characterization 317
12.5 AIE Polymersomes Based on PEG-b-POSS 317
12.6 AIE Polymersomes Based on Amphiphilic Polypeptoids 319
12.7 AIE Polymersomes Based on PEG-b-Polycarbonate 321
12.8 AIE Polymersomes Based on Amphiphilic Polynorbornene 323
12.9 AIE Polymersomes Based on Amphiphilic Block Copolymers by RAFT Polymerization 326
12.10 Summary and Perspectives 330
References 334
13 Designs for AIE Molecules and Functional Luminescent Materials Based on Boron-containing Element-blocks 341
Kazuo Tanaka, Masayuki Gon, Shunichiro Ito, and Yoshiki Chujo
13.1 Introduction 341
13.1.1 Generals of Commodity Luminescent Boron Complexes 341
13.1.2 Trends in the Development of Advanced Organic Electronic Devices 342
13.1.3 Strategies for Obtaining Solid-state Luminescence and Stimuli-responsiveness 343
13.1.4 New Ideas for Material Design Based on "Element-blocks" 343
13.2 Solid-state Luminescence and Luminochromism of o-Carboranes 344
13.2.1 Emission Mechanism of Aryl-modified o-Carboranes 344
13.2.2 AIE Behavior of o-Carborane Materials 344
13.2.3 Formation of Twisted Intramolecular Charge Transfer (TICT) State in the Crystalline State of o-Carboranes 346
13.2.4 Thermochromic Luminescence of o-Carboranes 346
13.2.5 Intense Solid-state Luminescent Molecules 347
13.2.6 Solid-state Excimer Emission 348
13.3 Boron Complexes with ß-Ketimine and ß-Diketimine Ligands 349
13.3.1 Generals of Boron Ketiminates and Diketiminates 349
13.3.2 Unique Solid-state Luminescent Properties of Conjugated Boron Complexes 350
13.3.3 Thermally Stable Mechanochromic Luminescent Hybrid with the Siloxane Unit 350
13.3.4 Luminescent Properties of ß-Diketiminate Complexes 352
13.3.5 AIE-active Conjugated Polymers 352
13.3.6 Design for Film-type Sensors 353
13.3.7 Sensitive Luminochromic Sensors with Gallium Complexes 354
13.4 Rational Design for AIE-active Molecules Based on "Flexible" Boron Complexes 355
13.4.1 Concept for Rational Design 355
13.4.2 Ring-fused or Nonring-fused Molecules 355
13.4.3 Thermosalient-active Molecules 357
13.4.4 Solid-state Luminescent ¿-Conjugated Polymer 358
13.5 Conclusion 359
References 359
14 Aggregation-induced Emission (AIE) Active Metal-Organic Coordination Complexes 367
Xueliang Shi, Xuzhou Yan, and Hai-Bo Yang
14.1 Introduction 367
14.2 Conception and Design Strategy 368
14.3 AIE Active Metallacycles 371
14.3.1 AIE Active Simple Metallacycles 371
14.3.2 AIE Active Fused Metallacycles 378
14.3.3 AIE Active Metallacycle Polymers 382
14.4 AIE Active Metallacages 389
14.5 AIE Active Metal-organic Frameworks (MOFs) 397
14.6 Summary and Outlook 405
Acknowledgments 406
References 406
15 AIE-type Luminescent Metal Nanoclusters 411
Zhennan Wu, Qiaofeng Yao, and Jianping Xie
15.1 Introduction 411
15.2 In the "Single-cluster" Scenario 412
15.2.1 AIE-type Luminescent Metal NCs 412
15.2.2 Atomically Precise AIE-type Luminescent Metal NCs 416
15.2.3 Approaches to Luminescence Enhancement of Metal NCs in the Scheme of AIE 418
15.2.3.1 Surface Engineering 418
15.2.3.2 Roles of the Core 422
15.3 Beyond the "Single-cluster" Scenario 423
15.3.1 Poor-solvent-induced AIE of Metal NCs 423
15.3.2 Ion-induced AIE of Metal NCs 423
15.3.3 Supramolecular Interactions Induced AIE of Metal NCs 426
15.3.4 Spatial Confinement-induced AIE of Metal NCs 429
15.4 Application of the AIE-type Luminescent Metal NCs 433
15.4.1 Chemical Sensing 433
15.4.2 Biological Applications 434
15.4.3 Photosensitizer 434
15.4.4 Light-emitting Diodes (LEDs) 434
15.5 Conclusion and Outlook 436
References 437
16 Aggregation-induced Emission in Coinage Metal Clusters 443
Shuang-Quan Zang and Kai Li
16.1 Introduction 443
16.2 AIE-active Gold Cluster 444
16.3 AIE-active Silver Cluster 450
16.4 AIE-active Copper Cluster 454
16.5 AIE-active Bimetallic Cluster 462
16.6 Conclusions 465
References 466
17 Activated Alkynes in Metal-free Bioconjugation 471
Xianglong Hu and Ben Zhong Tang
17.1 Introduction 471
17.2 Alkyne-Azide-based Bioconjugation 472
17.3 Activated Alkyne-Amine-based Bioconjugation 473
17.4 Activated Alkyne-Thiol-based Bioconjugation 480
17.5 Activated Alkyne-Hydroxyl-based Bioconjugation 483
17.6 Activated Alkyne-based Bioconjugation and Polymerization in Living Cells and Pathogens 484
17.7 Conclusion 488
References 488
18 AIE-active BODIPY Derivatives 493
Yali Liu, Yuzhang Huang, Rongrong Hu, and Ben Zhong Tang
18.1 Introduction 493
18.2 Structures of BODIPY Derivatives 495
18.2.1 BODIPY Derivatives Without Other Chromophore 495
18.2.2 TPE-containing BODIPYs 496
18.2.3 TPA-containing BODIPYs 498
18.2.4 Benzodithiophene-containing BODIPYs 499
18.2.5 Chiral BODIPYs 500
18.2.6 Metal-containing BODIPYs 502
18.2.7 BODIPY-containing Polymers 503
18.2.8 Other BODIPY Derivatives 504
18.3 Structural-property Relationship 508
18.3.1 Conjugation Effect 508
18.3.2 Number and Position of Substitutes 508
18.3.3 Substitution Group 513
18.3.4 Alkyl Substitutes on BODIPY Core 516
18.3.5 AIEgens Attached Through Nonconjugated Spacers 518
18.3.6 Other Substitution Structures 519
18.4 Application 522
18.4.1 Chemosensor 522
18.4.2 Bioimaging 526
18.5 Conclusion 532
References 532
19 Photochemistry-regulated AIEgens and Their Applications 537
Xia Ling and Meng Gao
19.1 Introduction 537
19.2 Photocleavage Reaction 537
19.3 Photoreduction Reaction 539
19.4 Photocyclodehydrogenation Reaction 540
19.5 Photooxidative Dehydrogenation Reaction 543
19.6 Spiropyran-merocyanine Reversible Conversion 544
19.7 Dithienylethene-based Ring-open/-closing Reaction 545
19.8 Enol-Keto Isomerization Reaction 550
19.9 E/Z Isomerization Reaction 552
19.10 Photo-induced [2 + 2] Cycloaddition 554
19.11 Combinational Photoreactions 554
19.12 Conclusion and Outlook 556
References 556
20 Design and Development of Naphthalimide Luminogens 559
Niranjan Meher and Parameswar Krishnan Iyer
20.1 Introduction 559
20.2 Naphthalimides with N-Functionalization (I) 564
20.3 Naphthalimides Substituted at the 4th Position with Oxygen Atom (II) 567
20.4 Naphthalimides Substituted at the 4th Position with Nitrogen Atom (III) 570
20.5 Naphthalimides with C¿C Aromatic Substitution (IV) 571
20.6 Naphthalimides with C¿C Double-and Triple-Bond Substitutions (V and VI) 574
20.7 Naphthalimides with the Significant Role of Multifunctionalization (VII) 576
20.8 Conclusion and Outlooks 580
References 581
Index 587
