- ISBN: 9781118394304 | 1118394305
- Cover: Hardcover
- Copyright: 10/28/2013
Aggregation-Induced Emission (AIE) is a novel photophysical phenomenon which offers a new platform for researchers to look into the light-emitting processes from luminogen aggregates, from which useful information on structure–property relationships may be collected and mechanistic insights may be gained. The discovery of the AIE effect opens a new avenue for the development of new luminogen materials in the aggregate or solid state. By enabling light emission in the practically useful solid state, AIE has the potential to expand significantly the technological applications of luminescent materials.
Aggregation-Induced Emission: Fundamentals is the first book to explore the fundamental issues of AIE, including the design, synthesis, and photophysical behavior of AIE-active molecules and polymers. The control of the morphological structures of the aggregates of AIE-active materials, and the experimental investigation and theoretical understanding of the AIE mechanism, are also covered in this volume.
Topics covered include:
- AIE in group 14 metalloles
- AIE in organic ion pairs
- Red light-emitting AIE materials
- Supramolecular structure and AIE
- AIE-active polymers
- Enhanced emission by restriction of molecular rotation
- Crystallization-induced emission enhancement
- Theoretical understanding of AIE phenomena
This book is essential reading for scientists and engineers who are designing optoelectronic materials and biomedical sensors, and will also be of interest to academic researchers in materials science and physical and synthetic organic chemistry, as well as physicists and biological chemists.
ANJUN QIN
Department of Polymer Science and Engineering, Zhejiang University, China
BEN ZHONG TANG
Department of Chemistry, The Hong Kong University of Science and Technology, China
List of Contributors xiii
Preface xvii
1 Synthesis of Siloles (and Germoles) that Exhibit the AIE Effect 1
Joyce Y. Corey
1.1 Introduction 1
1.2 Background 2
1.3 Synthesis of Siloles 4
1.3.1 Reductive dimerization of tolan 4
1.3.2 Intramolecular cyclization of dialkynylsilanes 7
1.3.3 Intramolecular cyclization of dialkynylsilanes utilizing
borane reagents 10
1.3.4 Synthesis of siloles using transition metal reagents 12
1.4 Modification of Preformed Siloles 14
1.4.1 Reactions at silicon centers 14
1.4.2 Reactions of a ring carbon center 15
1.5 Related Germole Methodology 15
1.5.1 Germoles produced by metathesis and exchange reactions 15
1.5.2 Germoles from other methods 16
1.5.3 Photoluminescence and AIE of germoles 18
1.6 Metallaindenes and Metallafluorenes of Si and Ge 19
1.6.1 Methods for the formation of silaindenes and germaindenes 19
1.6.2 Methods for the formation of metallafluorenes 21
1.7 Oligomers and Polymers of Metalloles and Benzene-Annulated
Metalloles 25
1.7.1 Oligomers that contain silole units connected at the 1,1-
and 2,5-positions 25
1.7.2 Polysiloles and silole polymers connected through 2,5-positions 26
1.7.3 Polymers with silole pendants and hyperbranched polymers 27
1.7.4 Polybenzosiloles and ladder polymers 28
1.7.5 Polymers that contain silafluorenes 29
1.7.6 Germoles in oligomers and polymers 30
1.8 Summary and Future Directions 31
References 33
2 Aggregation-Induced Emission in Group 14 Metalloles (Siloles, Germoles, and Stannoles):
Spectroscopic Considerations, Substituent Effects, and Applications 38
Jerome L. Mullin1 and Henry J. Tracy
2.1 Introduction 38
2.1.1 The group 14 metalloles 40
2.2 Characteristics of AIE in the Group 14 Metalloles 43
2.2.1 Aryl-substituted siloles 43
2.2.2 Aryl-substituted germoles and stannoles 46
2.3 Origins of AIE in Group 14 Metalloles: Restricted Intramolecular Rotation 47
2.3.1 Effect of solvent viscosity 47
2.3.2 Effect of temperature 47
2.3.3 Room-temperature glasses 48
2.3.4 Effect of pressure 48
2.3.5 Excited-state lifetimes 48
2.3.6 Molecular geometry 49
2.3.7 Aggregate nanoparticle morphology 49
2.3.8 Internal structural control of intramolecular rotations 49
2.4 Polymer Films and Polymerized Siloles 50
2.5 Applications of AIE-Active Metalloles 52
2.5.1 Electrooptical devices 52
2.5.2 Chemical sensors 52
References 53
3 Aggregation-Induced Emission of 9, 10-Distyrylanthracene Derivatives and
Their Applications 60
Bin Xu, Jibo Zhang, and Wenjing Tian
3.1 Introduction 60
3.2 AIE Molecules Based on 9,10-Distyrylanthracene 62
3.2.1 Small molecules 62
3.2.2 Macromolecules 63
3.3 AIE Mechanism of 9,10-Distyrylanthracene Molecule Systems 64
3.4 Application of AIE Luminogens Based on 9,10-Distyrylanthracene 66
3.4.1 Solid-state emitters 66
3.4.2 Piezochromism 71
3.4.3 Fluorescent sensors and probes 73
3.4.4 Bioimaging 74
3.5 Conclusion 79
Acknowledgments 79
References 79
4 Diaminobenzene-Cored Fluorophores Exhibiting Highly Efficient Solid-State
Luminescence 82
Masaki Shimizu
4.1 Introduction 82
4.2 1,4-Bis(alkenyl)-2,5-dipiperidinobenzenes 85
4.3 1,4-Diamino-2,5-bis(arylethenyl)benzenes 88
4.4 2,5-Diaminoterephthalates 92
4.5 2,5-Bis(diarylamino)-1,4-diaroylbenzenes 94
4.6 Applications 98
4.7 Conclusion 101
Acknowledgments 101
References 102
5 Aggregation-Induced Emission in Organic Ion Pairs 104
Suzanne Fery-Forgues
5.1 Introduction 104
5.2 Historical Background 105
5.3 Preparation and Control of the Fluorophore Arrangement 106
5.3.1 Type of interactions 106
5.3.2 Preparation 106
5.3.3 Influence of the nature of the counterion on the fluorophore arrangement 107
5.3.4 Influence of stoichiometry on the AIE effect 110
5.4 AIE-Active Organic Ion Pairs in Nano- and Microparticles 110
5.4.1 Controlled preparation of nanoparticles 111
5.4.2 Nanoparticles for biomedical imaging 113
5.4.3 Preparation of nanocrystals, nanofibers, and reticulated materials 113
5.5 Applications as Fluorescent Probes and Sensors for Analytical Purposes 114
5.5.1 Detection of small electrolytes 114
5.5.2 Detection of polyelectrolytes 115
5.6 Perspectives 121
Acknowledgments 121
References 122
6 Aggregation-Induced Emission Materials: the Art of Conjugation and Rotation 125
Jing Huang, Qianqian Li, and Zhen Li
6.1 Introduction 125
6.2 Rotation and Conjugation in AIE Molecules 126
6.3 Design of Functional Materials by Tuning the Conjugation Effect and
Restricting Rotations 132
6.3.1 Some AIE molecules with blue emission through modification of the
conjugation between the construction blocks 133
6.3.2 Some sensing systems by selectively controlling rotation 140
6.3.3 Some other systems utilizing the AIE concept 143
6.4 Outlook 149
References 150
7 Red-Emitting AIE Materials 152
Xiao Yuan Shen, Anjun Qin, and Jing Zhi Sun
7.1 Introduction 152
7.2 Basic Principles of Molecular Design for Red-Emitting Materials 153
7.3 Acquirement of Red-Emitting AIE Materials by Reconstruction of Traditional
Red-Emitting Molecules 155
7.4 Preparation of Red-Emitting Materials by Introduction of Electron Donors/Acceptors
into AIE-Active Molecules 159
7.5 Outlook 161
Acknowledgments 162
References 162
8 Properties of Triarylamine Derivatives with AIE and Large Two-Photon
Absorbing Cross-Sections 165
Jianli Hua, He Tian, and Hao Zhang
8.1 Introduction 165
8.2 Design and Synthesis of Triarylamine Derivatives with AIE and 2PA 166
8.3 AIE Properties of Triarylamine Derivatives 166
8.3.1 AIE properties of diketopyrrolopyrrole (DPP)-based triarylamine derivatives 166
8.3.2 AIE properties of starburst triarylamine derivatives based on
cyano-substituted diphenylaminestyrylbenzene 169
8.3.3 AIE properties of multibranched triarylamine end-capped triazines 170
8.4 One-Photon and Two-Photon Absorption Properties of Triarylamine
Derivatives with AIE 172
8.5 Application of Triarylamine Materials with AIE and 2PA 176
8.5.1 Fluorescence switching 176
8.5.2 Organic light-emitting diodes 176
8.5.3 Fluorescence probes for hg2þ
176
8.6 Conclusion 177
References 178
9 Photoisomerization and Light-Driven Fluorescence Enhancement
of Azobenzene Derivatives 181
Mina Han and Yasuo Norikane
9.1 Introduction 181
9.2 Photoisomerization and Fluorescence of Azobenzene Derivatives 182
9.2.1 Ground-state structure of azobenzene 182
9.2.2 Reversible isomerization of azobenzene 183
9.2.3 Sterically hindered azobenzene derivatives 184
9.2.4 Fluorescence from azobenzene derivatives 186
9.3 Aggregation-Induced Emission (AIE) 187
9.4 Fluorescence from Azobenzene-Based Aggregates 189
9.4.1 Light-driven self-assembly and fluorescence enhancement 190
9.4.2 Factors affecting fluorescence enhancement of azobenzenes 191
9.4.3 Modulation of fluorescence color 192
9.4.4 Fluorescent organic films 194
9.5 Conclusion 195
References 195
10 Supramolecular Structure and Aggregation-Induced Emission 201
Hongyu Zhang and Yue Wang
10.1 Introduction 201
10.2 Hydrogen Bonding-Based Molecular Dimer and AIE 202
10.2.1 The role of hydrogen bonds in AIE 202
10.2.2 AIE and single crystal structures 204
10.2.3 Relationship between supramolecualr structures and AIE 205
10.2.4 Amplified spontaneous emission (ASE) property 206
10.3 Quinacridine Derivatives with 1D Aggregation-Induced Red Emission 206
10.3.1 Contradiction between 1D self-assembly and AIE 206
10.3.2 Design of novel QAwith AIE and 1D self-assembly 207
10.3.3 AIE behavior 208
10.3.4 Morphology transition from 0D nanostructures to 1D microwires 210
10.3.5 1D self-assembly 210
10.3.6 Crystal Structure 211
10.4 Multi-Stimuli-Responsive Fluorescence Switching of AIE/AIEE Luminogens 213
10.4.1 Mechanism of stimuli-responsive fluorescence switching 213
10.4.2 Design strategy towards stimuli-responsive AIE/AIEE molecules 214
10.4.3 AIE phenomenon in neutral and acid states 214
10.4.4 Molecular and supramolecular structures in crystal 216
10.4.5 Multi-stimuli-responsive AIE switching 216
10.4.6 Multi-stimuli-responsive fluorescence of other AIE/AIEE molecules 217
10.5 Pt Pt Interaction-Induced Emissive and Conductive 1D Crystals 218
10.5.1 AIE of organometallic complexes 218
10.5.2 Pt Pt interaction-induced luminescent crystals 219
10.5.3 1D nano-/micro aggregation and photophysical properties 219
10.5.4 Vapor-responsive emission behavior of nanowires 221
10.5.5 Pt Pt interaction-induced 1D semiconductor 221
10.6 Conclusion 222
References 223
11 Aggregation-Induced Emission in Supramolecular p-Organogels 228
Pengchong Xue and Ran Lu
11.1 Introduction 228
11.2 Organogels Based on Discotic Molecules with AIE 229
11.2.1 Triphenylbenzene-cored discotic molecules 229
11.2.2 Other discotic gelators 232
11.3 Organogels Based on Rod-Like Molecules with AIE 233
11.3.1 Styrene derivatives 233
11.3.2 Other linear molecules 236
11.4 Organogels Based on Banana-Shaped Molecules with AIE 237
11.4.1 Salicylideneaniline derivatives 237
11.4.2 Other banana-shaped gelators 240
11.5 Organogels Based on Dendritic Molecules with AIE 241
11.6 Conclusion 244
References 245
12 AIE-Active Polymers 247
Rongrong Hu, Jacky W.Y. Lam, and Ben Zhong Tang
12.1 Introduction 247
12.2 Polyolefins 248
12.3 Polyacetylenes 252
12.4 Polydiynes 253
12.5 Polyarylenes 257
12.6 Polytriazoles 263
12.7 Polysilylenevinylenes 265
12.8 Poly(Vinylene Sulfide)s 266
12.9 Other Systems 271
12.10 Conclusion 274
References 274
13 Enhanced Emission by Restriction of Molecular Rotation 278
Jin-Long Hong
13.1 Background 278
13.2 Strategy to Restrict Molecular Rotation 279
13.2.1 Introduction of bulky substituents by chemical links 280
13.2.2 Introduction of bulky groups by complexation 283
13.2.3 Hindered molecular rotation by hydrogen bonding 285
13.2.4 Hindered molecular rotation by metal or metal ion chelation 289
13.3 Characterizations of Hindered Molecular Rotations 290
13.3.1 Solution fluorescence spectroscopy 290
13.3.2 1H NMR spectroscopy 291
13.4 Conclusion 295
References 296
14 Restricted Intramolecular Rotations: a Mechanism for Aggregation-Induced
Emission 299
Junwu Chen and Ben Zhong Tang
14.1 Introduction: 2,3,4,5-Tetraphenylsilole, the Prototype Molecule
of Aggregation-Induced Emission (AIE) 299
14.2 Crystal Structures of 2,3,4,5-Tetraphenylsiloles 302
14.2.1 Twisted arrangements of phenyl groups on the silole core 302
14.2.2 Enlarged distance between silole cores: far beyond p–p interactions 303
14.3 Restricted Intramolecular Rotation (RIR) 304
14.3.1 Thickening-enhanced emission of silole solutions (viscochromism) 305
14.3.2 Piezochromism 305
14.3.3 Cooling-enhanced emission (thermochromism) 306
14.3.4 On–off fluorescence switching of silole thin films: activation
of rotations in solvent vapors (vapochromism) 308
14.3.5 Fluorescence decay dynamics 309
14.3.6 Highly emissive silole solutions: restriction of rotation by internal
structural tuning 310
14.4 Conclusion 312
Acknowledgments 312
References 312
15 Crystallization-Induced Emission Enhancement 315
Yongqiang Dong
15.1 Introduction 315
15.2 Traditional Luminogens 316
15.3 Crystallization-Induced Emission Enhancement (CIEE) 316
15.3.1 CIEE luminogens 317
15.3.2 Potential applications 322
15.4 Conclusion 325
References 326
16 Time-Resolved Spectroscopic Study of the Aggregation-Induced Emission
Mechanism 328
Bing-rong Gao, Hai-yu Wang, Qi-dai Chen, and Hong-bo Sun
16.1 Introduction 328
16.2 Time-Resolved Spectroscopy 329
16.2.1 Femtosecond time-resolved fluorescence system 329
16.2.2 Femtosecond transient absorption system 330
16.2.3 Time-correlated single-photon counting (TCSPC) system 332
16.3 AIE Molecules Without Electron Donor–Acceptor Units 332
16.3.1 Time-resolved fluorescence study of HPS 332
16.3.2 Time-resolved fluorescence study of CNDPDSB 333
16.3.3 Transient absorption study of CNDPDSB 334
16.4 AIE Molecules with Electron Donor–Acceptor Units 335
16.4.1 Steady-state properties of CNDPASDB 335
16.4.2 Time-resolved fluorescence study of CNDPASDB 337
16.4.3 Transient absorption study of CNDPASDB 342
16.4.4 Discussion 344
16.5 Conclusion 344
Acknowledgments 345
References 345
17 Theoretical Understanding of AIE Phenomena Through Computational
Chemistry 347
Qian Peng, Yingli Niu, Qunyan Wu, Xing Gao, and Zhigang Shuai
17.1 Introduction 347
17.2 Fundamental Photophysics Relating to AIE Phenomena 348
17.2.1 Absorption and emission 348
17.2.2 Luminescence quantum efficiency 349
17.3 Computational Approaches to Investigate AIE molecules 350
17.3.1 Molecular optical spectra formalisms 350
17.3.2 Molecular radiative and nonradiative rate formalisms 355
17.3.3 Computational details 357
17.4 Computational Results 360
17.4.1 Optical spectra 360
17.4.2 Excited-state decay processes 366
17.4.3 A nonadiabatic dynamic simulation 375
17.5 Summary and Outlook 379
References 380
18 Recent Theoretical Advances in Understanding the Mechanism of Aggregation-Induced
Emission for Small Organic Molecules 389
Jun-Ling Jin, Yun Geng, and Zhong-Min Su
18.1 Introduction 389
18.2 Theoretical Methods 390
18.2.1 Main photophysical processes of organic molecules 390
18.2.2 Theoretical estimation of photophysical parameters 392
18.3 Recent Theoretical Advances in Understanding the Mechanism of
Aggregation-Induced Emission 396
18.3.1 Restriction of intramolecular rotation (RIR) 396
18.3.2 Influence of molecular packing and intermolecular interactions on the
photophysical properties and fluorescence efficiencies in the solid phase 401
18.4 Prospects 403
18.4.1 Other AIE mechanisms except for the conventional RIR mechanism 403
18.4.2 Design of multifunctional materials with AIE 403
Acknowledgments 404
References 404
Index
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