Aggregation-Induced Emission : Fundamentals
[Book Description]
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.
[Table of Contents]
List of Contributors xiii
Preface xvii
1 Synthesis of Siloles (and Germoles) that 1 (38)
Exhibit the AIE Effect
Joyce Y. Corey
1.1 Introduction 1 (1)
1.2 Background 2 (2)
1.3 Synthesis of Siloles 4 (10)
1.3.1 Reductive dimerization of tolan 4 (3)
1.3.2 Intramolecular cyclization of 7 (3)
dialkynylsilanes
1.3.3 Intramolecular cyclization of 10 (2)
dialkynylsilanes utilizing borane
reagents
1.3.4 Synthesis of siloles using 12 (2)
transition metal reagents
1.4 Modification of Preformed Siloles 14 (1)
1.4.1 Reactions at silicon centers 14 (1)
1.4.2 Reactions of a ring carbon center 15 (1)
1.5 Related Germole Methodology 15 (4)
1.5.1 Germoles produced by metathesis 15 (1)
and exchange reactions
1.5.2 Germoles from other methods 16 (2)
1.5.3 Photoluminescence and AIE of 18 (1)
germoles
1.6 Metallaindenes and Metallafluorenes 19 (6)
of Si and Ge
1.6.1 Methods for the formation of 19 (2)
silaindenes and germaindenes
1.6.2 Methods for the formation of 21 (4)
metallafluorenes
1.7 Oligomers and Polymers of Metalloles 25 (6)
and Benzene-Annulated Metalloles
1.7.1 Oligomers that contain silole 25 (1)
units connected at the 1,1-and
2,5-positions
1.7.2 Polysiloles and silole polymers 26 (1)
connected through 2,5-positions
1.7.3 Polymers with silole pendants and 27 (1)
hyperbranched polymers
1.7.4 Polybenzosiloles and ladder 28 (1)
polymers
1.7.5 Polymers that contain 29 (1)
silafluorenes
1.7.6 Germoles in oligomers and polymers 30 (1)
1.8 Summary and Future Directions 31 (8)
References 33 (6)
2 Aggregation-Induced Emission in Group 14 39 (22)
Metalloles (Siloles, Germoles, and
Stannoles): Spectroscopic Considerations,
Substituent Effects, and Applications
Jerome L. Mullin
Henry J. Tracy
2.1 Introduction 39 (5)
2.1.1 The group 14 metalloles 41 (3)
2.2 Characteristics of AIE in the Group 44 (4)
14 Metalloles
2.2.1 Aryl-substituted siloles 44 (3)
2.2.2 Aryl-substituted germoles and 47 (1)
stannoles
2.3 Origins of AIE in Group 14 48 (3)
Metalloles: Restricted Intramolecular
Rotation
2.3.1 Effect of solvent viscosity 48 (1)
2.3.2 Effect of temperature 48 (1)
2.3.3 Room-temperature glasses 49 (1)
2.3.4 Effect of pressure 49 (1)
2.3.5 Excited-state lifetimes 49 (1)
2.3.6 Molecular geometry 50 (1)
2.3.7 Aggregate nanoparticle morphology 50 (1)
2.3.8 Internal structural control of 50 (1)
intramolecular rotations
2.4 Polymer Films and Polymerized Siloles 51 (2)
2.5 Applications of AIE-Active Metalloles 53 (8)
2.5.1 Electrooptical devices 53 (1)
2.5.2 Chemical sensors 53 (1)
References 54 (7)
3 Aggregation-Induced Emission of 61 (22)
9,10-Distyrylanthracene Derivatives and
Their Applications
Bin Xu
Jibo Zhang
Wenjing Tian
3.1 Introduction 61 (2)
3.2 AIE Molecules Based on 63 (2)
9,10-Distyrylanthracene
3.2.1 Small molecules 63 (1)
3.2.2 Macromolecules 64 (1)
3.3 AIE Mechanism of 65 (2)
9,10-Distyrylanthracene Molecule Systems
3.4 Application of AIE Luminogens Based 67 (13)
on 9,10-Distyrylanthracene
3.4.1 Solid-state emitters 67 (5)
3.4.2 Piezochromism 72 (2)
3.4.3 Fluorescent sensors and probes 74 (1)
3.4.4 Bioimaging 75 (5)
3.5 Conclusion 80 (3)
Acknowledgments 80 (1)
References 80 (3)
4 Diaminobenzene-Cored Fluorophores 83 (22)
Exhibiting Highly Efficient Solid-State
Luminescence
Masaki Shimizu
4.1 Introduction 83 (3)
4.2 86 (3)
1,4-Bis(alkenyl)-2,5-dipiperidinobenzenes
4.3 89 (4)
1,4-Diamino-2,5-bis(arylethenyl)benzenes
4.4 2,5-Diaminoterephthalates 93 (2)
4.5 95 (4)
2,5-Bis(diarylamino)-1,4-diaroylbenzenes
4.6 Applications 99 (3)
4.7 Conclusion 102 (3)
Acknowledgments 102 (1)
References 103 (2)
5 Aggregation-Induced Emission in Organic 105 (22)
Ion Pairs
Suzanne Fery-Forgues
5.1 Introduction 105 (1)
5.2 Historical Background 106 (1)
5.3 Preparation and Control of the 107 (4)
Fluorophore Arrangement
5.3.1 Type of interactions 107 (1)
5.3.2 Preparation 107 (1)
5.3.3 Influence of the nature of the 108 (3)
counterion on the fluorophore
arrangement
5.3.4 Influence of stoichiometry on the 111 (1)
AIE effect
5.4 AIE-Active Organic Ion Pairs in 111 (4)
Nano-and Microparticles
5.4.1 Controlled preparation of 112 (2)
nanoparticles
5.4.2 Nanoparticles for biomedical 114 (1)
imaging
5.4.3 Preparation of nanocrystals, 114 (1)
nanofibers, and reticulated materials
5.5 Applications as Fluorescent Probes 115 (7)
and Sensors for Analytical Purposes
5.5.1 Detection of small electrolytes 115 (1)
5.5.2 Detection of polyelectrolytes 116 (6)
5.6 Perspectives 122 (5)
Acknowledgments 122 (1)
References 123 (4)
6 Aggregation-Induced Emission Materials: 127 (28)
the Art of Conjugation and Rotation
Jing Huang
Qianqian Li
Zhen Li
6.1 Introduction 127 (1)
6.2 Rotation and Conjugation in AIE 128 (6)
Molecules
6.3 Design of Functional Materials by 134 (17)
Tuning the Conjugation Effect and
Restricting Rotations
6.3.1 Some AIE molecules with blue 135 (7)
emission through modification of the
conjugation between the construction
blocks
6.3.2 Some sensing systems by 142 (3)
selectively controlling rotation
6.3.3 Some other systems utilizing the 145 (6)
AIE concept
6.4 Outlook 151 (4)
References 152 (3)
7 Red-Emitting AIE Materials 155 (14)
Xiao Yuan Shen
Anjun Qin
Jing Zhi Sun
7.1 Introduction 155 (1)
7.2 Basic Principles of Molecular Design 156 (2)
for Red-Emitting Materials
7.3 Acquirement of Red-Emitting AIE 158 (4)
Materials by Reconstruction of
Traditional Red-Emitting Molecules
7.4 Preparation of Red-Emitting Materials 162 (2)
by Introduction of Electron
Donors/Acceptors into AIE-Active Molecules
7.5 Outlook 164 (5)
Acknowledgments 165 (1)
References 165 (4)
8 Properties of Triarylamine Derivatives 169 (16)
with AIE and Large Two-Photon Absorbing
Cross-Sections
Jianli Hua
He Tian
Hao Zhang
8.1 Introduction 169 (1)
8.2 Design and Synthesis of Triarylamine 170 (1)
Derivatives with AIE and 2PA
8.3 AIE Properties of Triarylamine 170 (6)
Derivatives
8.3.1 AIE properties of 170 (3)
diketopyrrolopyrrole (DPP)-based
triarylamine derivatives
8.3.2 AIE properties of starburst 173 (1)
triarylamine derivatives based on
cyano-substituted
diphenylaminestyrylbenzene
8.3.3 AIE properties of multibranched 174 (2)
triarylamine end-capped triazines
8.4 One-Photon and Two-Photon Absorption 176 (4)
Properties of Triarylamine Derivatives
with AIE
8.5 Application of Triarylamine Materials 180 (1)
with AIE and 2PA
8.5.1 Fluorescence switching 180 (1)
8.5.2 Organic light-emitting diodes 180 (1)
8.5.3 Fluorescence probes for Hg2+ 180 (1)
8.6 Conclusion 181 (4)
References 182 (3)
9 Photoisomerization and Light-Driven 185 (20)
Fluorescence Enhancement of Azobenzene
Derivatives
Mina Han
Yasuo Norikane
9.1 Introduction 185 (1)
9.2 Photoisomerization and Fluorescence 186 (5)
of Azobenzene Derivatives
9.2.1 Ground-state structure of 186 (1)
azobenzene
9.2.2 Reversible isomerization of 187 (1)
azobenzene
9.2.3 Sterically hindered azobenzene 188 (2)
derivatives
9.2.4 Fluorescence from azobenzene 190 (1)
derivatives
9.3 Aggregation-Induced Emission (AIE) 191 (2)
9.4 Fluorescence from Azobenzene-Based 193 (6)
Aggregates
9.4.1 Light-driven self-assembly and 194 (1)
fluorescence enhancement
9.4.2 Factors affecting fluorescence 195 (1)
enhancement of azobenzenes
9.4.3 Modulation of fluorescence color 196 (2)
9.4.4 Fluorescent organic films 198 (1)
9.5 Conclusion 199 (6)
References 199 (6)
10 Supramolecular Structure and 205 (28)
Aggregation-Induced Emission
Hongyu Zhang
Yue Wang
10.1 Introduction 205 (1)
10.2 Hydrogen Bonding-Based Molecular 206 (4)
Dimer and AIE
10.2.1 The role of hydrogen bonds in AIE 206 (2)
10.2.2 AIE and single crystal structures 208 (1)
10.2.3 Relationship between 209 (1)
supramolecualr structures and AIE
10.2.4 Amplified spontaneous emission 210 (1)
(ASE) property
10.3 Quinacridine Derivatives with 1D 210 (7)
Aggregation-Induced Red Emission
10.3.1 Contradiction between 1D 210 (1)
self-assembly and AIE
10.3.2 Design of novel QA with AIE and 211 (1)
1D self-assembly
10.3.3 AIE behavior 212 (2)
10.3.4 Morphology transition from 0D 214 (1)
nanostructures to 1D microwires
10.3.5 1D self-assembly 214 (1)
10.3.6 Crystal structure 215 (2)
10.4 Multi-Stimuli-Responsive 217 (5)
Fluorescence Switching of AIE/AIEE
Luminogens
10.4.1 Mechanism of stimuli-responsive 217 (1)
fluorescence switching
10.4.2 Design strategy towards 218 (1)
stimuli-responsive AIE/AIEE molecules
10.4.3 AIE phenomenon in neutral and 218 (2)
acid states
10.4.4 Molecular and supramolecular 220 (1)
structures in crystal
10.4.5 Multi-stimuli-responsive AIE 220 (1)
switching
10.4.6 Multi-stimuli-responsive 221 (1)
fluorescence of other AIE/AIEE molecules
10.5 Pt ... Pt Interaction-Induced 222 (4)
Emissive and Conductive 1D Crystals
10.5.1 AIE of organometallic complexes 222 (1)
10.5.2 Pt ... Pt interaction-induced 223 (1)
luminescent crystals
10.5.3 1D nano-/micro aggregation and 223 (2)
photophysical properties
10.5.4 Vapor-responsive emission 225 (1)
behavior of nanowires
10.5.5 Pt ... Pt interaction-induced 1D 225 (1)
semiconductor
10.6 Conclusion 226 (7)
References 227 (6)
11 Aggregation-Induced Emission in 233 (20)
Supramolecular π-Organogels
Pengchong Xue
Ran Lu
11.1 Introduction 233 (1)
11.2 Organogels Based on Discotic 234 (4)
Molecules with AIE
11.2.1 Triphenylbenzene-cored discotic 234 (3)
molecules
11.2.2 Other discotic gelators 237 (1)
11.3 Organogels Based on Rod-Like 238 (4)
Molecules with AIE
11.3.1 Styrene derivatives 238 (3)
11.3.2 Other linear molecules 241 (1)
11.4 Organogels Based on Banana-Shaped 242 (4)
Molecules with AIE
11.4.1 Salicylideneaniline derivatives 242 (3)
11.4.2 Other banana-shaped gelators 245 (1)
11.5 Organogels Based on Dendritic 246 (3)
Molecules with AIE
11.6 Conclusion 249 (4)
References 250 (3)
12 AIE-Active Polymers 253 (32)
Rongrong Hu
Jacky W. Y. Lam
Ben Zhong Tang
12.1 Introduction 253 (1)
12.2 Polyolefins 254 (4)
12.3 Polyacetylenes 258 (1)
12.4 Polydiynes 259 (4)
12.5 Polyarylenes 263 (6)
12.6 Polytriazoles 269 (2)
12.7 Polysilylenevinylenes 271 (1)
12.8 Poly(Vinylene Sulfide)s 272 (5)
12.9 Other Systems 277 (3)
12.10 Conclusion 280 (5)
References 280 (5)
13 Enhanced Emission by Restriction of 285 (22)
Molecular Rotation
Jin-Long Hong
13.1 Background 285 (1)
13.2 Strategy to Restrict Molecular 286 (11)
Rotation
13.2.1 Introduction of bulky 287 (3)
substituents by chemical links
13.2.2 Introduction of bulky groups by 290 (2)
complexation
13.2.3 Hindered molecular rotation by 292 (4)
hydrogen bonding
13.2.4 Hindered molecular rotation by 296 (1)
metal or metal ion chelation
13.3 Characterizations of Hindered 297 (5)
Molecular Rotations
13.3.1 Solution fluorescence 297 (1)
spectroscopy
13.3.2 1H NMR spectroscopy 298 (4)
13.4 Conclusion 302 (5)
References 303 (4)
14 Restricted Intramolecular Rotations: a 307 (16)
Mechanism for Aggregation-Induced Emission
Junwu Chen
Ben Zhong Tang
14.1 Introduction: 307 (3)
2,3,4,5-Tetraphenylsilole, the Prototype
Molecule of Aggregation-Induced Emission
(AIE)
14.2 Crystal Structures of 310 (2)
2,3,4,5-Tetraphenylsiloles
14.2.1 Twisted arrangements of phenyl 310 (1)
groups on the silole core
14.2.2 Enlarged distance between silole 311 (1)
cores: far beyond π-π interactions
14.3 Restricted Intramolecular Rotation 312 (8)
(RIR)
14.3.1 Thickening-enhanced emission of 313 (1)
silole solutions (viscochromism)
14.3.2 Piezochromism 313 (1)
14.3.3 Cooling-enhanced emission 314 (2)
(thermochromism)
14.3.4 On--off fluorescence switching 316 (1)
of silole thin films: activation of
rotations in solvent vapors
(vapochromism)
14.3.5 Fluorescence decay dynamics 317 (1)
14.3.6 Highly emissive silole 318 (2)
solutions: restriction of rotation by
internal structural tuning
14.4 Conclusion 320 (3)
Acknowledgments 320 (1)
References 320 (3)
15 Crystallization-Induced Emission 323 (14)
Enhancement
Yongqiang Dong
15.1 Introduction 323 (1)
15.2 Traditional Luminogens 324 (1)
15.3 Crystallization-Induced Emission 324 (9)
Enhancement (CIEE)
15.3.1 CIEE luminogens 325 (5)
15.3.2 Potential applications 330 (3)
15.4 Conclusion 333 (4)
References 334 (3)
16 Time-Resolved Spectroscopic Study of the 337 (20)
Aggregation-Induced Emission Mechanism
Bing-rong Gao
Hai-yu Wang
Qi-dai Chen
Hong-bo Sun
16.1 Introduction 337 (1)
16.2 Time-Resolved Spectroscopy 338 (3)
16.2.1 Femtosecond time-resolved 338 (1)
fluorescence system
16.2.2 Femtosecond transient absorption 339 (2)
system
16.2.3 Time-correlated single-photon 341 (1)
counting (TCSPC) system
16.3 AIE Molecules Without Electron 341 (3)
Donor--Acceptor Units
16.3.1 Time-resolved fluorescence study 341 (1)
of HPS
16.3.2 Time-resolved fluorescence study 342 (1)
of CNDPDSB
16.3.3 Transient absorption study of 343 (1)
CNDPDSB
16.4 AIE Molecules with Electron 344 (9)
Donor--Acceptor Units
16.4.1 Steady-state properties of 344 (2)
CNDPASDB
16.4.2 Time-resolved fluorescence study 346 (5)
of CNDPASDB
16.4.3 Transient absorption study of 351 (2)
CNDPASDB
16.4.4 Discussion 353 (1)
16.5 Conclusion 353 (4)
Acknowledgments 354 (1)
References 354 (3)
17 Theoretical Understanding of AIE 357 (42)
Phenomena Through Computational Chemistry
Qian Peng
Yingli Niu
Qunyan Wu
Xing Gao
Zhigang Shuai
17.1 Introduction 357 (1)
17.2 Fundamental Photophysics Relating to 358 (2)
AIE Phenomena
17.2.1 Absorption and emission 358 (1)
17.2.2 Luminescence quantum efficiency 359 (1)
17.3 Computational Approaches to 360 (10)
Investigate AIE Molecules
17.3.1 Molecular optical spectra 360 (5)
formalisms
17.3.2 Molecular radiative and 365 (2)
nonradiative rate formalisms
17.3.3 Computational details 367 (3)
17.4 Computational Results 370 (19)
17.4.1 Optical spectra 370 (6)
17.4.2 Excited-state decay processes 376 (9)
17.4.3 A nonadiabatic dynamic simulation 385 (4)
17.5 Summary and Outlook 389 (10)
References 390 (9)
18 Recent Theoretical Advances in 399 (20)
Understanding the Mechanism of
Aggregation-Induced Emission for Small
Organic Molecules
Jun-Ling Jin
Yun Geng
Zhong-Min Su
18.1 Introduction 399 (1)
18.2 Theoretical Methods 400 (6)
18.2.1 Main photophysical processes of 400 (2)
organic molecules
18.2.2 Theoretical estimation of 402 (4)
photophysical parameters
18.3 Recent Theoretical Advances in 406 (7)
Understanding the Mechanism of
Aggregation-Induced Emission
18.3.1 Restriction of intramolecular 406 (5)
rotation (RIR)
18.3.2 Influence of molecular packing 411 (2)
and intermolecular interactions on the
photophysical properties and
fluorescence efficiencies in the solid
phase
18.4 Prospects 413 (6)
18.4.1 Other AIE mechanisms except for 413 (1)
the conventional RIR mechanism
18.4.2 Design of multifunctional 413 (1)
materials with AIE
Acknowledgments 414 (1)
References 414 (5)
Index 419
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