Handbook of Aggregation-Induced Emission, Volume 1 Tutorial Lectures and Mechanism Studies

The first volume of the ultimate reference on the science and applications of aggregation-induced emission 

The Handbook of Aggregation-Induced Emission explores foundational and advanced topics in aggregation-induced emission, as well as cutting-edge developments in the field, celebrating twenty years of progress and achievement in this important and interdisciplinary field. The three volumes combine to offer readers a comprehensive and insightful interpretation accessible to both new and experienced researchers working on aggregation-induced emission. 

In this first volume of three, the editors survey the subject of  aggregation-induced emission with a focus on the fundamentals of various branches of the discipline, such as crystallization-induced emission, room temperature phosphorescence, aggregation-induced delayed fluorescence, and more. This book covers the new properties of materials endowed by molecular aggregates. It also includes:  

• A thorough introduction to the mechanistic understanding of the importance of molecular motion to aggregation-induced emission 
• An exploration of the aggregation-induced emission mechanism at the molecular level 
• Practical discussions of aggregation-induced emission from the restriction of double bond rotation at the excited state, and clusterization-triggered emission 

Perfect for academic researchers working on aggregation-induced emission, this set of volumes is also ideal for professionals and students in the fields of photophysics, photochemistry, materials science, optoelectronic materials, synthetic organic chemistry, macromolecular chemistry, polymer science, and biological sciences. 

Youhong Tang is a Professor at Flinders University, Australia and actively works in aggregation-induced emission areas.

Ben Zhong Tang is a Chair Professor at the Chinese University of Hong Kong, Shenzhen. He is widely known as the pioneer of the study of aggregation-induced emission.

List of Contributors xv

Preface to Handbook of Aggregation-Induced Emission xxi

Preface to Volume 1: Fundamentals xxiii

1 The Mechanistic Understanding of the Importance of Molecular Motions to Aggregation-induced Emission 1
Junkai Liu and Ben Zhong Tang

1.1 Introduction 1

1.2 Restriction of Intramolecular Motion 2

1.2.1 Restriction of Intramolecular Rotation 3

1.2.2 Restriction of Intramolecular Vibration 4

1.2.3 Ultrafast Insights into Tetraphenylethylene Derivatives 6

1.2.4 Theoretical Insights into Restriction of Intramolecular Motion 8

1.3 Restricted Access to Conical Intersection 12

1.4 Restriction of Access to the Dark State 14

1.5 Suppression of Kasha’s Rule 15

1.6 Through Space Conjugation 17

1.6.1 Clusterization-Triggered Emission 18

1.6.2 Polymerization-induced Emission 19

1.6.3 Excited-state Through-space Conjugation 19

1.7 Perspective 21

References 23

2 Understanding the AIE Mechanism at the Molecular Level 27
Xiaoyan Zheng and Qian Peng

2.1 Introduction 27

2.2 Theoretical Methods 28

2.2.1 Radiative and Nonradiative Rate Constants 28

2.2.2 Computational Details 29

2.3 Revealed AIE Mechanism 31

2.3.1 Rotating Vibrations of Intramolecular Aromatic Ring 31

2.3.2 Stretching Vibrations of Bonds 33

2.3.3 Bending Vibration of Bonds 34

2.3.4 Flipping Vibrations of Molecular Skeletons 35

2.3.5 Twisting Vibration of Molecular Skeletons 36

2.4 Visualize Calculated Parameters in Experiments 37

2.4.1 Stokes Shift vs Reorganization Energy 37

2.4.2 Resonance Raman Spectroscopy (RSS) vs Reorganization Energy 38

2.4.3 Isotope Effect vs DRE 40

2.4.4 Linear Relationship between Fluorescence Intensity and Amorphous Aggregate Size 42

2.4.5 Pressure-induced Enhanced Emission (PIEE) 44

2.5 Molecular Design Based on AIE Mechanism 45

2.6 Summary and Outlook 46

Acknowledgments 48

References 48

3 Aggregation-induced Emission from the Restriction of Double Bond Rotation at the Excited State 55
Ming Hu and Yan-Song Zheng

3.1 Introduction 55

3.2 AIE Phenomena and Applications from RDBR Mechanism 58

3.2.1 Evolvement and Development of AIE Mechanisms 58

3.2.2 Investigation of RDBR AIE Mechanism by E/Z isomerization 64

3.2.3 Investigating of RDBR AIE Mechanism by Immobilization of TPE Propeller-like Conformation 69

3.2.4 Research of Theoretical Calculation on RDBR 78

3.2.5 Other AIEgens Involving RBDR Process 84

3.3 Conclusions 93

References 94

4 The Expansion of AIE Thought: From Single Molecule to Molecular Uniting 99
Qiuyan Liao, Qianqian Li, and Zhen Li

4.1 Aggregation-Induced Emission 99

4.2 Photoluminescence Materials Based on Molecular Set 101

4.3 Mechanoluminescence Materials Based on Molecular Set 106

4.3.1 Mechanoluminescence Materials with Fluorescence Emission 106

4.3.2 Mechanoluminescence Materials with Mechanical Induced Dual-or Tri-color Emission 115

4.3.3 Quantitative Research of Mechanoluminescence Property 121

4.4 Mechanochromism Materials 122

4.4.1 Mechanochromism Materials Based on Polymorphs 122

4.4.2 Mechanochromism Materials Based on Excimer Emission 125

4.4.3 Other Kinds of Mechanochromism Materials 128

4.5 Room Temperature Phosphorescence Materials Based on Molecular Uniting 131

4.5.1 Room Temperature Phosphorescence Materials with Aromatics 131

4.5.2 Room Temperature Phosphorescence Materials with Simple or Nonaromatic Structure 140

4.5.3 Room Temperature Phosphorescence Materials with Multiple Emission 142

4.5.4 Photoinduced Room Temperature Phosphorescence Materials 144

4.6 Conclusion and Perspectives 147

References 147

5 Clusterization-Triggered Emission 153
Haoke Zhang and Ben Zhong Tang

5.1 Introduction 153

5.2 Pure n-Electron Systems 156

5.3 Pure π-Electron Systems 160

5.4 (n, π)-Electrons Systems 164

5.5 Other Systems 166

5.6 Summary 167

References 168

6 Crystallization-induced Emission Enhancement 177
Yong Qiang Dong, Yingying Liu, Mengyang Liu, Qian Wang, and Kang Wang

6.1 Introduction 177

6.2 Tetraphenylethylene Derivatives 178

6.3 CIEE Active Luminogens with Bulky Conjugation Core 183

6.3.1 Dibenzofulvene (DBF) Derivatives (Chart 6.2) 183

6.3.2 9-([1,1′-Biphenyl]-4-ylphenylmethylene)-9H-xanthene 185

6.3.3 Dicyanomethylenated Acridones 186

6.3.4 Bis(diarylmethylene)dihydroanthracene [31] 187

6.4 Other High-contrast CIEE Luminogens 190

6.4.1 4-Dimethylamino-2-Benzylidene Malonic Acid Dimethyl Ester 190

6.4.2 Diphenyl Maleimide Derivatives [33] 191

6.4.3 3,4-Bisthienylmaleic Anhydride [34] 192

6.4.4 Boron-containing CIEE Luminogens 193

6.5 Potential Applications 196

6.5.1 Volatile Organic Compounds (VOCs) Sensor 196

6.5.2 OLED 196

6.5.3 High-density Data Storage 197

6.5.4 Mechanochromic (MC) Luminescent Sensor 198

6.6 Summary and Perspective 198

References 198

7 Surface-fixation Induced Emission 203
Yohei Ishida and Shinsuke Takagi

7.1 Introduction 203

7.2 What Happened to the Characteristics of Molecules on the Clay Mineral Nanosheets 205

7.3 Clay–Molecular Complexes 206

7.4 Absorption Spectra of Clay–Molecular Complexes 207

7.5 Emission Enhancement Phenomenon in Clay–Molecular Complexes: S-FIE 208

7.6 Mechanism of Surface-Fixation Induced Emission 211

7.7 Summary and Outlook 214

Acknowledgment 215

References 215

8 Aggregation-induced Delayed Fluorescence 221
Yan Fu, Hao Chen, Zujin Zhao, and Ben Zhong Tang

8.1 Introduction 221

8.2 Novel Aggregation-induced Delayed Fluorescence Luminogens 222

8.3 Conclusion and Outlook 247

References 247

9 Homogeneous Systems to Induce Emission of AIEgens 251
Kenta Kokado and Kazuki Sada

9.1 Introduction 251

9.2 Homogeneous Solution 252

9.2.1 Complexation with Anions 253

9.2.2 Complexation with Cations 254

9.2.3 Inclusion Complexes 256

9.2.4 Adhesion on Macromolecules 257

9.2.5 Steric Hindrance 258

9.2.6 Covalent Linkage 259

9.3 Liquid 260

9.4 Gels and Network Polymers 261

9.4.1 Chemically Crosslinked Gels 261

9.4.2 Physically Crosslinked Gels 262

9.5 Crystalline Materials 264

9.6 Outlook and Future Perspectives 266

References 266

10 Hetero-aggregation-induced Tunable Emission (HAITE) Through Cocrystal Strategy 273
Yinjuan Huang and Qichun Zhang

10.1 Introduction 273

10.2 Interactions Within Organic Cocrystals 274

10.3 Preparation of Organic Cocrystals 275

10.4 Molecular Stacking Modes Within Organic Cocrystals 276

10.5 Characterization of Organic Cocrystals 277

10.6 HAITE Through Cocrystal Strategy 277

10.6.1 HAITE with Tunable Color and Enhanced Emission 278

10.6.1.1 Insignificant Changed Intensity but Tuned Color 278

10.6.1.2 Enhanced Emission and Tuned Color 287

10.6.2 HAITE with Increased PLQY but Intrinsic Color 291

10.6.3 HAITE: Thermally Activated Delayed Fluorescence 297

10.6.4 HAITE-phosphorescence 300

10.7 Summary and Outlook 302

References 304

11 Anti-Kasha Emission from Organic Aggregates 311
Wenbin Huang and Zikai He

11.1 Introduction 311

11.2 Anti-Kasha Emission from Aromatic Carbonyl Compounds in Aggregates 312

11.3 Anti-Kasha Emission from Azulene Compounds in Aggregate 322

11.4 Anti-Kasha Emission from Other Unconventional Aromatic Compounds in Aggregates 324

11.5 Conclusions 327

References 327

12 Aggregation-enhanced Emission: From Flexible to Rigid Cores 333
Harnimarta Deol, Gurpreet Singh, Vandana Bhalla, and Manoj Kumar

12.1 Introduction 333

12.2 Freely Moving Rotors-induced Emission Enhancement 334

12.3 Guest-induced Emission Enhancement 344

12.4 Conclusion 366

Acknowledgment 367

References 367

13 Room-temperature Phosphorescence of Pure Organics 371
Tianwen Zhu, Zihao Zhao, Tianjia Yang, and Wang Zhang Yuan

13.1 Introduction 371

13.2 Fundamental Mechanism in Organic Phosphorescence 372

13.2.1 Photophysical Process for Phosphorescence 372

13.2.2 Theoretical Study on Phosphorescent Process 373

13.3 Recent Progress in Organic RTP Materials 375

13.3.1 Crystallization-induced RTP 375

13.3.1.1 Heavy Atom Effect 376

13.3.1.2 Molecular Interaction 380

13.3.1.3 H-aggregation 380

13.3.2 Doping in Rigid Matrix-induced RTP 382

13.3.2.1 Host–Guest System 385

13.3.2.2 Doping in Polymer Matrix 387

13.3.3 Clustering-triggered RTP 389

13.3.3.1 Natural Products 389

13.3.3.2 Synthetic Compounds 394

13.3.4 Other Systems 399

13.3.4.1 Amorphous Organics 399

13.3.4.2 Organic Framework 399

13.3.4.3 Supramolecular Organics 402

13.3.4.4 Hybrid Perovskites 403

13.3.5 Applications 405

13.4 Conclusions and Perspectives 405

References 407

14 A Global Potential Energy Surface Approach to the Photophysics of AIEgens: The Role of Conical Intersections 411
Rachel Crespo-Otero and Lluís Blancafort

14.1 Introduction 411

14.2 Methodological Aspects 412

14.2.1 Intramolecular Restriction Models and the FGR-based Approach 412

14.2.2 A PES-based Description of Photochemical Mechanisms 412

14.2.3 Computational Approaches for Excited States 416

14.2.3.1 Electronic Structure Methods for Excited States 416

14.2.3.2 Dynamics Simulations in the Context of AIE 420

14.2.4 Methods for Large Systems 420

14.3 CI-centered Global PES for AIEgens 424

14.3.1 Double-bond Torsion 424

14.3.2 Double-bond Torsion vs Cyclization in TPE Derivatives 428

14.3.3 Excited-state Intramolecular Proton Transfer (ESIPT) Compounds 431

14.3.4 Ring Puckering 432

14.3.5 Bond Stretching 435

14.3.6 A View of AIE Based on the RACI Model and the Global PES 436

14.4 Crystallization-induced Phosphorescence 436

14.5 Effect of Intermolecular and Intramolecular Interactions on the Photophysics of AIEgens 437

14.5.1 Excitonic Effects in AIE 437

14.5.2 Effect of Intramolecular and Intermolecular Interactions on Emission Color 439

14.6 New Challenges 439

14.6.1 The Role of Dark States in AIE 439

14.6.2 Pressure-induced Emission Enhancement 440

14.6.3 AIE in Transition Metal (TM) Compounds 442

14.7 Conclusions and Outlook 443

References 444

15 Multicomponent Reactions as Synthetic Design Tools of AIE and Emission Solvatochromic Quinoxalines 455
Lukas Biesen and Thomas J. J. Müller

15.1 Introduction 455

15.2 Synthetic Approaches to Quinoxalines via Multicomponent Reactions and One-Pot Processes 456

15.3 Photophysical Properties and Emission Solvatochromicity of Quinoxalines 462

15.4 AIE Characteristics and Effects of Quinoxalines 468

15.5 Conclusion 476

Acknowledgments 476

References 476

16 Aggregation-induced Emission Luminogens with Both High-luminescence Efficiency and Charge Mobility 485
Ying Yu, Zheng Zhao, and Ben Zhong Tang

16.1 Introduction 485

16.2 p-Type OSCs 487

16.3 n-Type OSCs 495

16.4 Ambipolar OSCs 500

16.5 Conclusion and Perspective 505

References 505

17 Morphology Modulation of Aggregation-induced Emission: From Thermodynamic Self-assembly to Kinetic Controlling 509
Kaizhi Gu, Chenxu Yan, Zhiqian Guo, and Wei-Hong Zhu

17.1 Introduction 509

17.2 Aggregation Modulation of AIE Bioprobes via Hydrophilicity Improvement 511

17.2.1 Molecular Modification 511

17.2.2 Polymerization with Hydrophilic Matrix 515

17.3 Thermodynamic Self-assembly of AIE Materials 519

17.4 Morphology Tuning of AIE Nanoaggregates 519

17.5 Kinetic-driven Preparation of AIE NPs 523

17.6 Conclusion and Outlook 527

References 527

18 AIE-active Polymer 531
Rong Hu, Anjun Qin, and Ben Zhong Tang

18.1 Introduction 531

18.2 Photophysical Properties 532

18.2.1 Quantum Yield 532

18.2.2 Photosensitization 536

18.2.3 Two-photon Absorption and Emission 538

18.2.4 Circularly Polarized Luminescence 540

18.3 Applications 541

18.3.1 Chem-sensor 541

18.3.2 Bioimaging 543

18.3.3 Therapy Applications 546

18.4 Conclusion and Perspective 549

Acknowledgments 550

References 550

19 Liquid-crystalline AIEgens: Materials and Applications 555
Kyohei Hisano, Supattra Panthai, and Osamu Tsutsumi

19.1 Introduction 555

19.2 Materials: Molecular Design 556

19.2.1 Discotic LC AIEgen 556

19.2.2 Calamitic LC AIEgens 561

19.2.3 Polymeric LC AIEgens 566

19.3 Applications of LC AIEgens 567

19.3.1 Linearly Polarized Luminescence 567

19.3.2 Circularly Polarized Luminescence 568

19.4 Conclusion 571

References 571

20 Push–Pull AIEgens 575
Andrea Nitti and Dario Pasini

20.1 Introduction 575

20.2 Basic Concept of Molecular Design 576

20.2.1 Photophysical Excited States in Aggregates 576

20.2.2 Fundamental Molecular Design to Achieve Push–Pull AIEgens 579

20.3 Push–Pull AIEgens from Rotor Structure 581

20.3.1 Double Bond Stator 582

20.3.2 Point-restricted Rotors from Atoms or Functional Groups 584

20.3.3 Aromatic Rotors 587

20.4 Push–Pull AIEgens from ACQ Chromophores 589

20.4.1 BT-based AIEgens 589

20.4.2 Cyanine and DCM-based AIEgens 594

20.4.3 QM-based AIEgens 595

20.4.4 DPP-based AIEgens 597

20.4.5 Rylene-based AIEgens 599

20.5 Concluding Remarks 602

References 602

Index 609

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