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Handbook of Aggregation-Induced Emission
Handbook of Aggregation-Induced Emission
Volume 2 Typical AIEgens Design
Edited by
Youhong Tang
Flinders University
Adelaide, Australia
Ben Zhong Tang

The Chinese University of Hong Kong
Shenzhen, China
This edition first published 2022
© 2022 John Wiley & Sons Ltd. Published 2022 by John Wiley & Sons Ltd.
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Library of Congress Cataloging-in-Publication data applied for
Hardback (Volume 2): 9781119642985
Cover Design: Wiley

Cover Image: © Chad Baker/Getty Images
Set in 9.5/12.5pt STIXTwoText by Straive, Pondicherry, India
10 9 8 7 6 5 4 3 2 1
ay our great respects to all the researchers who have contributed and are contributing to the study
P
of Aggregation Induced Emission (AIE).
vii
Contents
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
viii Contents
2.2.4.1 Fluorescent Probes for Chemical Sensing 41

2.2.4.2 Fluorescent Probes for Biological Sensing 44
2.3 onclusions and Outlook 46
C
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
Contents ix
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
6.2 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
Acknowledgments 162
References 162
7 Cyclic Triimidazole Derivatives: An Intriguing Family of Multifaceted

Emitters 165
Elena Cariati, Elena Lucenti, Andrea Previtali, and Alessandra Forni
7.2 The Protoype: Cyclic Triimidazole 166
x Contents
7.3 alogenated Derivatives of Cyclic Triimidazole 175

H
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
8.2 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
9.2 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 π-Expansion of TAPP 229
9.7 π-Expanded 1,4-dihydropyrrolo[3,2-b]pyrrole 231
9.8 Photophysical Optical Properties of TAPP 239
Acknowledgments 247
References 247
10 Small Molecule Organogels from AIE Active α-Cyanostilbenes 255

Jagadish Katla, Beena Kumari, and Sriram Kanvah
10.2 Organogels with Trifluoromethyl Substitution 256
10.3 Organogels with Chiral Units/Chiral Hosts 260
Contents xi
10.4 timuli–Responsive Organogels 262

S
10.5 Organogels with Sensing Applications 266
Acknowledgments 271
References 271
11 Stimuli-responsive Pure Organic Luminescent Supramolecules 277

Siyu Sun and Xiang Ma
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
12.2 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
xii Contents
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
13.1.1 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 β-Ketimine and β-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 β-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 π-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
14.2 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
Contents xiii
15 AIE-type Luminescent Metal Nanoclusters 411

Zhennan Wu, Qiaofeng Yao, and Jianping Xie
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
References 437
16 Aggregation-induced Emission in Coinage Metal Clusters 443

Shuang-Quan Zang and Kai Li
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
17.2 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
xiv Contents
18 AIE-active BODIPY Derivatives 493

Yali Liu, Yuzhang Huang, Rongrong Hu, and Ben Zhong Tang
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
19.2 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
References 556
20 Design and Development of Naphthalimide Luminogens 559

Niranjan Meher and Parameswar Krishnan Iyer
20.2 Naphthalimides with N-Functionalization (I) 564
Contents xv
20.3 aphthalimides Substituted at the 4th Position with Oxygen Atom (II) 567
N
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
xvii
List of Contributors
Jan Balszuweit Yoshiki Chujo

Faculty of Chemistry (Organic Chemistry) Department of Polymer Chemistry
University of Duisburg-Essen Graduate School of Engineering
Essen, Germany Kyoto University
Katsura, Kyoto, Japan
Sheshanath V. Bhosale
School of Chemical Sciences Yuping Dong
Goa University, Taleigao Plateau Beijing Key Laboratory of Construction
Goa, India Tailorable Advanced Functional Materials and
Green Applications
School of Materials Science & Engineering
Zhengxu Cai
Beijing Institute of Technology
Beijing Key Laboratory of
Beijing, PR China
Construction Tailorable Advanced
Functional Materials and Green
Alessandra Forni
Applications, School of Materials Science &
Institute of Sciences and Chemical
Engineering
Technologies “Giulio Natta” (SCITEC) of CNR
Beijing Institute of Technology
Milan, Italy
Beijing, PR China
Meng Gao
Elena Cariati
National Engineering Research Center for
Department of Chemistry
Tissue Restoration and Reconstruction
Università degli Studi di Milano
Key Laboratory of Biomedical Engineering of
Milan, Italy
Guangdong Province
Key Laboratory of Biomedical Materials and
Hui Chen Engineering of the Ministry of Education
Chimie ParisTech Innovation Center for Tissue Restoration and
PSL University Reconstruction
CNRS South China University of Technology
Institut de Recherche de Chimie Paris Guangzhou, China
Paris, France
Masayuki Gon
Ming Chen Department of Polymer Chemistry
College of Chemistry and Materials Science Graduate School of Engineering
Jinan University Kyoto University
Guangzhou, China Katsura, Kyoto, Japan
xviii List of Contributors
Rongrong Hu Lathe A. Jones

State Key Laboratory of Luminescent CAMIC
Materials and Devices School of Science
Guangdong Provincial Key Laboratory of RMIT University, Melbourne
Luminescence from Molecular Aggregates VIC, Australia
Center for Aggregation-Induced Emission
South China University of Technology Sriram Kanvah
Guangzhou, China Department of Chemistry
Indian Institute of Technology
Xianglong Hu Gandhinagar
Ministry of Education Key Laboratory of Palaj, Gandhinagar, India
Laser Life Science and Guangdong Provincial
Key Laboratory of Laser Life Science Jagadish Katla
College of Biophotonics Department of Chemistry
South China Normal University Indian Institute of Technology
Guangzhou, China Gandhinagar
Palaj, Gandhinagar, India
Yuzhang Huang
State Key Laboratory of Luminescent Mohammad Al Kobaisi
Materials and Devices School of Science
Guangdong Provincial Key Laboratory of Faculty of Science, Engineering and
Luminescence from Molecular Aggregates Technology
Center for Aggregation-Induced Emission Swinburne University of Technology
South China University of Technology Hawthorn, Australia
Guangzhou, China
Beena Kumari
Fuyuki Ito Department of Chemistry
Department of Chemistry Indian Institute of Technology Gandhinagar,
Institute of Education Palaj, Gandhinagar, India
Shinshu University
Nagano, Japan Yunxiang Lei
Beijing Key Laboratory of
Shunichiro Ito Construction Tailorable Advanced
Department of Polymer Chemistry Functional Materials and Green
Graduate School of Engineering Applications
Kyoto University School of Materials Science & Engineering
Katsura, Kyoto, Japan Beijing Institute of Technology
Beijing, China
Parameswar Krishnan Iyer
Department of Chemistry Kai Li
Centre for Nanotechnology Henan Key Laboratory of
Indian Institute of Technology Guwahati Crystalline Molecular Functional Materials
Guwahati, Assam, India Henan International Joint Laboratory of
Tumor Theranostical Cluster Materials
Ratan W. Jadhav Green Catalysis Center
School of Chemical Sciences College of Chemistry, Zhengzhou University
Goa University, Taleigao Plateau Zhengzhou, China
Goa, India
List of Contributors xix
Min-Hui Li East China University of Science &

Chimie ParisTech Technology
PSL University Shanghai, China
CNRS
Institut de Recherche de Chimie Paris Niranjan Meher
Paris, France Department of Chemistry
Indian Institute of Technology Guwahati,
Beijing Advanced Innovation Center for Soft Guwahati, Assam, India
Matter Science and Engineering
Beijing University of Chemical Technology Vishal G. More
Beijing, China School of Chemical Sciences
Goa University, Taleigao Plateau
Xia Ling Goa, India
National Engineering Research Center for
Tissue Restoration and Reconstruction Andrea Previtali
Key Laboratory of Biomedical Engineering of Department of Chemistry
Guangdong Province Università degli Studi di Milano
Key Laboratory of Biomedical Materials and Milan, Italy
Engineering of the Ministry of Education
Anjun Qin
Innovation Center for Tissue Restoration and
State Key Laboratory of Luminescent
Reconstruction
Materials and Devices
South China University of Technology
Guangdong Provincial Key Laboratory of
Guangzhou, China
Luminescence from Molecular Aggregates
Leijing Liu South China University of Technology
State Key Laboratory for Supramolecular Guangzhou, China
Structure and Materials
Jilin University, Changchun T. P. Radhakrishnan
Jilin, China School of Chemistry
University of Hyderabad
Yali Liu Hyderabad, India
Materials and Devices Bibhisan Roy
Guangdong Provincial Key Laboratory of Faculty of Chemistry (Organic Chemistry)
Luminescence from Molecular Aggregates University of Duisburg-Essen
Center for Aggregation-Induced Emission Essen, Germany
Xueliang Shi
Guangzhou, China
Shanghai Key Laboratory of Green Chemistry
and Chemical Processes
Elena Lucenti
School of Chemistry and Molecular Engineering
Institute of Sciences and Chemical Technologies
East China Normal University
“Giulio Natta” (SCITEC) of CNR
Shanghai, P. R. China
Milan, Italy
N. Senthilnathan
Xiang Ma School of Chemistry
Key Laboratory for Advanced Materials and University of Hyderabad
Institute of Fine Chemicals Hyderabad, India
xx List of Contributors
Siyu Sun Aijun Tong

Key Laboratory for Advanced Materials and Department of Chemistry
Institute of Fine Chemicals Tsinghua University
East China University of Science & Beijing, China
Technology
Shanghai, China Jens Voskuhl
Faculty of Chemistry (Organic Chemistry)
Kazuo Tanaka University of Duisburg-Essen
Department of Polymer Chemistry Essen, Germany
Graduate School of Engineering
Kyoto University Zhennan Wu
Katsura, Kyoto, Japan Department of Chemical and Biomolecular
Engineering
National University of Singapore
Ben Zhong Tang
Singapore, Singapore
Materials and Devices
Jianping Xie
Guangdong Provincial Key Laboratory of
Department of Chemical and Biomolecular
Luminescence from Molecular Aggregates
Engineering
National University of Singapore
Guangzhou, China
Shenzhen Institute of Aggregate Science and Bin Xu
Technology State Key Laboratory for Supramolecular
School of Science and Engineering Structure and Materials
The Chinese University of Hong Kong Jilin University, Changchun
Shenzhen Jilin, China
Guangdong, China
Department of Chemistry Xuzhou Yan
Hong Kong Branch of Chinese National School of Chemistry and Chemical
Engineering Research Center for Tissue Engineering
Restoration and Reconstruction Frontiers Science Center for Transformative
The Hong Kong University of Science & Molecules
Technology Shanghai Jiao Tong University
Clear Water Bay, Kowloon Shanghai, China
Hong Kong, China
Hai-Bo Yang
Shanghai Key Laboratory of Green
Wenjing Tian
Chemistry and Chemical Processes
State Key Laboratory for Supramolecular
School of Chemistry and Molecular
Structure and Materials
Engineering
Jilin University, Changchun
East China Normal University,
Jilin, China
Shanghai, China
List of Contributors xxi
Qiaofeng Yao Yue Zheng

Department of Chemical and Biomolecular Department of Chemistry
Engineering Tsinghua University
National University of Singapore Beijing, China
Shuang-Quan Zang
Henan Key Laboratory of
Crystalline Molecular Functional Materials
Henan International Joint Laboratory of
Tumor Theranostical Cluster Materials
Green Catalysis Center
College of Chemistry, Zhengzhou University
Zhengzhou, China
xxiii
Preface to Handbook of Aggregation-Induced Emission
Aggregation-induced emission (AIE) describes a photophysical phenomenon in which molecular

aggregate exhibits stronger emission than its single-molecule counterpart. AIE research provides
an excellent platform to explore aggregate behaviours since it emphasizes the new properties
endowed by molecular aggregates beyond the microscopic molecular level. The 21-year develop-
ment of AIE research has witnessed the great achievements in this area, including mechanistic
understanding, structure-property relationship, and high-tech applications. The achievements of
AIE research demonstrate that many behaviours and functions that are absent in molecular spe-
cies can be founded in molecular aggregates. Since the properties of molecular ensembles are
closer to those of macroscopic materials, AIE research is of both scientific value and technological
importance for real applications.
Due to its great value and huge potential, AIE research is attracting more and more attention
from chemistry, physics, materials science, medical and biomedical science and shows promising
applications in these fields. Noteworthy, as a general platform to study aggregate science, AIE
keeps integrating with other research fields involving materials, biology, medicine, energy and
environment, and injects new vitality into these fields. When more researchers are working on
this field, more breakthroughs in both fundamental research and application are envisioned in
the future.
This handbook is an essential reading for scientists and engineers who are designing
optoelectronic materials and chemical/biomedical sensors. It is also a valuable reference book to
academic researchers in materials science, physical and synthetic organic chemistry as well as
physicists and biological chemists.
xxv
Preface to Volume 2: Typical AIEgens Design
This Volume highlighted the recent advances in the development of various aggregation-induced
emission (AIE) systems, including traditional tetraphenylethenes based, 9,10-distyrylanthracene
based, salicylaldehyde Schiff based, and multi-phenyl-substituted pyrrole based AIE systems,
and systems with extended π-conjugations to those even without typical AIE chromophores.
Meanwhile, novel AIE systems in small molecule organogels, polymersomes, metal-organic
coordination complexes, metal nanoclusters and others are demonstrated in this volume. The
fluorescent behaviours of these AIE system toward different application are also explored.
Youhong Tang, Flinders University, Australia

Ben Zhong Tang, The Chinese University of Hong Kong, Shenzhen, China
1
Tetraphenylpyrazine-based AIEgens: Synthesis and Applications

Ming Chen1, Anjun Qin3, and Ben Zhong Tang2,3,4
1
College of Chemistry and Materials Science, Jinan University, Guangzhou, China
2
Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and
Reconstruction, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China
3
State Key Laboratory of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Luminescence from Molecular
Aggregates, Center for Aggregation-Induced Emission, South China University of Technology, Guangzhou, China
4
Shenzhen Institute of Aggregate Science and Technology, School of Science and Engineering, The Chinese University of Hong Kong,
Shenzhen, Guangdong, China
1.1 Introduction
Luminescent materials have been widely applied in display, illumination, and information transfer,
etc [1–3]. However, in real-word applications, they are most employed in the aggregate state (e.g.
solid-state-emissive thin film in organic light-emitting diodes (OLEDs) and nanoimaging materi-
als) [4–8]. The traditional chromophores show extremely strong emissions in the solution but
exhibit almost quenched emission behavior upon aggregation. For such a reason, scientists are in
enthusiastic pursuit of highly efficient luminescent materials in the solid state. One would consider
it to be better if the aggregation could be utilized to play a positive instead of a negative role in
enhancing luminescence. This idea had come true until 2001 when Tang had a beautiful encounter
with aggregation-induced emission (AIE) [9–12]. AIE luminogens (AIEgens) possess the lumines-
cence behavior opposite to the traditional luminogens as their twisted and flexible molecular con-
formation allows them to dissipate the excited-state energy nonradiatively by molecular motion in
the solution, while such motion is suppressed in the aggregate state to open up the radiation chan-
nel [13–16]. Thus, the problem of aggregation-caused quenching (ACQ) effect perplexed in tradi-
tional dyes has been overcome thoroughly by AIE, and more than 10 000 works aiming at mechanism
study, molecular design, and functionality exploitation have been published based on this hot topic.
It is crucial to develop a great variety of AIEgens because molecules with different structures
may cause different properties and functions. By choosing suitable AIE archetypal molecules for
structural decoration, such a target can be achieved readily. Up to date, dozens of archetypal
AIEgens have been developed. Among them, hydrocarbon AIEgens like tetraphenylethene (TPE),
triphenylethene, tetraphenyl-1,4-butadiene (TPBD), and distyrylanthracene (DSA) are very popu-
lar because they are competent in designing materials with high luminescence efficiencies
Chart 1.1 [17–20].So far, TPE is regarded as the most famous AIEgen because it is very easy to syn-
thesize and modify, making that the majority of AIE researches are established based on this sys-
tem. The mechanism for elaborating AIE phenomenon of TPE is still in debate [21]. The early
studies show that the restriction of rotation of peripheral phenyl rings against the central double
Handbook of Aggregation-Induced Emission: Volume 2 Typical AIEgens Design, First Edition.

Edited by Youhong Tang and Ben Zhong Tang.
© 2022 John Wiley & Sons Ltd. Published 2022 by John Wiley & Sons Ltd.
2 1 Tetraphenylpyrazine-based AIEgens: Synthesis and Applications
Hydrocarbon AIEgens
TPE Triphenylethene TPBD DSA
Heterocycle-based AIEgens
Si N
S O
O
HPS PentaPP DP-BTO TPP
Chart 1.1 Molecular structures of AIEgens of tetraphenylethene (TPE), triphenylethene, tetraphenyl-1,4-

butadiene (TPBD), distyrylanthracene (DSA), hexaphenylsilole (HPS), pentaphenylpyrrole (PentaPP),
phenyl-substituted oxidized benzothiophene (DP-BTO), and tetraphenylpyrazine (TPP).
bond is the essential cause. Zheng reveals that photoisomerization of the central double bond in
TPE plays an important role in quenching its emission in the solution based on the studies of pho-
tophysical behaviors of TPEs with its adjacent phenyl rings chemically locked at different sides [22].
In other words, the double bond in TPE is unstable and easy-to-form free radicals under irradiation
and heat. On the other hand, Chi observed a photochromism of Cl-substituted triphenylethene as
a result of the cyclization reaction taking place between the phenyl rings in the molecule under UV
light stimuli [23]. Thus, the stability of AIE materials based on these hydrocarbon AIEgens needs
to be considered and improved.
By contrast, no central double bond exists in the heterocycle-based AIEgens, making them free
of such trouble. The typical heterocycle-based AIEgens are hexaphenylsilole (HPS), pentaphe-
nylpyrrole (PentaPP), phenyl-substituted oxidized benzothiophene (DP-BTO), and so on
Chart 1.1 [24–30]. The introduction of heteroatoms in these AIEgens obviously endows them with
different electronic properties. For example, in HPS, the interaction of σ* orbital of the silicon atom
and π* orbital of the carbon atom enables it to possess low-lying LUMO energy level. It imparts
HPS with high electron affinity, which can act as an electron-accepting unit in molecular design
and increase the electron-transporting property as material [31]. On the other hand, the orbitals of
the nitrogen atom in PentaPP is sp2-hybridized, while the lone pair electrons occupy the p orbital,
which arrays parallelly with the p orbitals from adjacent carbon atoms. It remarkably increases the
p–π interaction and makes the central pyrrole ring electron-rich. Some electron-donating and hole-
transporting properties of PentaPP are thus obtained in molecular and material designs [32].
However, although these heterocycle-based AIEgens show good photo- and thermal stabilities,
their chemical stability should be improved. For example, the silole ring in HPS is easy to decom-
pose under basic atmosphere. Besides, their synthesis is always tedious, the reaction condition is
rigorous, and the purification is difficult. Thus, it is urgent to develop new AIEgens in combination
with the advantages from the above hydrocarbon and heterocycle ones.
1.2 Synthesis of TPP-based AIEgen 3
In 2015, Tang reported a heterocycle-based AIEgen, namely, tetraphenylpyrazine (TPP), with its
structure possessing four phenyl rings attaching to the central pyrazine heterocycle ring
Chart 1.1 [33–37]. The rotation of the peripheral phenyl ring against the pyrazine ring makes the
molecule less emissive in the solution. The twisted conformation of TPP prohibits the formation of
π–π stacking in the aggregate state, while the multiple intermolecular C–H⋯π interactions exist to
lock the molecular motions. These factors collectively contribute to the AIE effect. A more detailed
mechanism is still under investigation because the central pyrazine ring is possible to participate
in the molecular motions in the excited state. The preparation of TPP is very simple even when
compared with that of TPE, and many routes are alternative according to various requirements.
The stability of TPP is pretty good due to the whole aromatic structure of the molecule and the
high bond energy of the C–N bond in the central heterocycle. Different from pyrrole, the nitrogen
atom forms a double bond with one of the neighboring carton atoms in pyrazine. The lone pair
electrons, therefore, occupy one of the sp2 orbitals of the nitrogen atom, which parallels to the
pyrazine plane. The interaction of lone pair electrons and π electrons will never occur, whereas the
strong electronegativity of the nitrogen atom in C–N bonds induces the polarization of an electron
cloud in the ring, which makes the pyrazine ring in TPP electron-deficient [38, 39]. Indeed, by
decorating TPP with phenyl rings or weakly electron-donating methoxyl groups, the resulting
donor–acceptor (D–A) effect can finely tune the emissions of derivatives in the whole blue light
region. These features indicate that the AIE-active TPP is a promising candidate utilized for further
development of high-performance materials.
With the development in the last five years, more and more works with TPP as motif have
emerged. Firstly, besides the conventional methods, the new methodologies in the preparation of
TPP and its derivatives have been established. By using the new catalytic systems, rather high
yields (>98%) are obtained in the preparation. A recent work shows that TPP can even be prepared
efficiently by direct heating of the starting materials in the solid phase. Secondly, many lumines-
cent applications (e.g. highly efficient OLEDs, gas, explosive, and ion sensors, etc.) based on TPP
have been developed. On the other hand, due to the symmetry of TPP, its researches on the reticu-
lar chemistry have sprung up. For example, TPP-based organic cage and metal–organic framework
(MOF) can be designed easily to exhibit self-assembling and sensing properties. Herein, we sum-
marize recent research efforts on the development of this AIE system, including synthesis and
functions, and we hope, with this chapter, new ideas could be stimulated to exploit the advanced
functional materials based on TPP.
1.2 Synthesis of TPP-based AIEgens
1.2.1 Cyclization Reaction

Although TPP was found to be AIE-active by Tang in 2015, its research dates back to the mid-
nineteenth century. The early synthesis of TPP was carried out by Laurent in 1845 and later by
Erdmann in 1865 [40, 41]. The reaction was carried out by heating benzoin with ammonium chlo-
ride at 100 °C for four to six hours. Three main products formed after the reaction named as ben-
zoinam (formula C28H24N2O), benzoinimide (formula C14H11N), and lophine, respectively. In
1886, Japp and Wilson reinvestigated the reaction. They found that a yellow crystalline powder of
benzoinimide formerly obtained was actually impure. After recrystallization with a large amount
of alcohol, colorless, slender, and lustrous crystals were collected. Further elemental analysis study
indicated that the formula of the compound agreed better with C28H20N2 than with C14H11N. That
is, the name of benzoinimide given by Erdmann is misleading. They thus renamed the compound
as ditolane-azotide and also gave the prototype structure of TPP in the text [42]. It is the first
report of TPP.
Since that, the researches on TPP were burgeoning. In 1937, Davidson, Weiss, and Jelling studied
the action of ammonia on benzoin [43]. Besides the generated TPP, an imidazole derivative of
2-methyl-4,5-dipenylglyoxaline and tetraphenyldihydropyrazine was formed. It represented the
most classical rudiment in the later preparation of TPP. The reaction mechanism was given as
below: the carbonyl group of benzoin was possible to convert to imine in the presence of ammonia,
followed by generating carbinamine by structural rearrangement, while the hydroxyl group nearby
was converted to the carbonyl group. Two formed intermediates can undergo cyclization reaction
by condensation and removal of water. After structural tautomerization, a resembling product of
tetraphenyldihydropyrazine was formed to oxidize to TPP. On the other hand, the intermediate
was also easy to react with the solvent of acetic acid by the amino group and then formed
2-methyl-4,5-dipenylglyoxaline by cyclization (Scheme 1.1). The formation of tetraphenyldihydro-
pyrazine was evidenced by the orange color of the reaction mixture soon after refluxing of the
starting materials. Remarkably, oxygen plays a crucial role in the conversion of tetraphenyldihy-
dropyrazine to TPP. It is proved that the yield of reaction solution bubbled with air is higher than
that in the closed environment. Nevertheless, the total yield of TPP is in the range from 53 to 57%,
and the tetraphenyldihydropyrazine cannot convert to TPP completely even in the presence of
enough oxygen. After filtering out the formed crude TPP precipitates, the unreacted tetraphenyl-
dihydropyrazine in the mother liquor can be further oxidized to TPP by adding nitric acid until the
orange color of solution was discharged.
Tang also reported the synthesis of TPP by refluxing benzoin, ammonium acetate, and acetic
anhydride in acetic acid for 3.5 hours, while the acetic anhydride acts as a dehydrating agent to
remove the water after cyclization (Scheme 1.2, Route A, Condition 1) [33]. TPP shows the same
polarity with the byproducts as monitored by the silica gel plate. The blue emission of TPP disap-
peared, while only the orange emission was observed on the plate. It is mainly due to energy trans-
fer taking place from TPP to the byproducts, which dramatically quenches its emission. It implies
that the purity of TPP after purification must be rather high because the trace of impurities in TPP
will obviously affect its photo-physical properties. TPP and its byproducts show different solubility
in acetic acid. TPP is badly dissolved in acetic acid. It precipitates during the reaction, while most
of the byproducts were still left in the solution. The crude TPP powder is collected by filtration and
OH OH NH 2 NHAc
NH 3 AcOH
O NH O O
–H2O –H2O
H N
N –H2 N N
NH
N N N
H
TPP
Scheme 1.1 Reaction mechanism of synthesizing TPP with benzoin and ammonia.
OH
Condition 1: AcONH 4, Ac2O, AcOH, reflux
Route A Condition 2: AcONH 4, SnCl2 2H2O, solvent-free, 80 °C
Condition 3: AcONH 4, catalyst-free, solvent-free, 80 °C
Route C
Route B
N Ru@Xantphos O
EtAlCl2, Mg, Cp2TiCl 2 HCOONH 4
N
o
THF DMF, 85 C, 1 h O
N
TPP
D Ro
te Pd ute
u (O
Ro Ac
)2 ,
E
K P(C
3 PO
y)
OH 4, t
olu
Ac en
3
e
NH2 O OH
Cl N Cl B
+ + OH
NH2 O Cl N Cl
Scheme 1.2 Current synthetic routes to TPP.
shows a yellow appearance due to the presence of trace impurities. However, repeated recrystalli-
zation of crude products in a larger amount of heat acetic acid can afford very pure TPP crystals.
The yield (34%) is lower than the above studies, probably due to the loss of product during the
purification. The convenience in preparation and purification of TPP makes it very promising for
further deep investigations.
This method not only affords TPP readily but is also useful for preparing its derivatives with
diverse structures. For example, by using mono- or disubstituted benzoin, di- or tetrasubstituted
TPP derivatives can be easily obtained. The reaction is less affected by the electronic effect of sub-
stituents. However, if the substituents are bulky, the crude products are difficult to purify by recrys-
tallization. It is worth noting that two isomers are usually formed by using monosubstituted
benzoin in the reaction. Such behavior is similar to that in the preparation of disubstituted TPE
derivatives by the McMurry coupling reaction [44]. The presence of isomerization in TPP deriva-
tives is proved by the fact that four resonance signals exist around 148 ppm in their 13C NMR spec-
tra due to the four different chemical environments of carbon atoms in the pyrazine ring [33].
Tamaddon used SnCl2·2H2O as a catalyst to synthesize α-amino ketones with benzoin and ani-
line as starting materials under solvent-free conditions at either 80 °C or microwave irradia-
tion [45]. Although the yields of reaction are high (up to 83%), the undesired byproduct of 1,4-dib
enzyl-2,3,5,6-tetraphenyl-1,4-dihydropyrazine is formed as examined by the NMR analysis, which
is possibly due to the self-condensation of the in situ formed α-amino ketones. Further investiga-
tion indicated that under the same catalytic condition, a [2 + 1 + 1 + 2] four-component reaction
of benzoin and ammonium acetate can generate TPP in a high yield of 90% (Scheme 1.2, Route A,
Condition 2). It provides a convenient strategy to prepare tetrasubstituted tetraphenylpyrazines in
high yields. The substituents on benzoin are widely alternative. For example, by using methoxyl-,
methyl-, bromine-, chlorine-, and fluorine-substituted benzoins, the reactions can proceed
smoothly. However, as the electron-donating property of substituents increases, the yield of reac-
tions slightly decreases.
Subsequently, Tamaddon found that the multicomponent reaction can be carried out without
SnCl2·2H2O as catalyst (Scheme 1.2, Route A, Condition 3) [46]. That is, SnCl2·2H2O is not neces-
sary in the reactions. By directly heating the solid mixture of benzoin and ammonium acetate at
80 °C, the product can be obtained in a very high yield. Overall, this reaction is very close to the
original one reported by Laurent, Erdmann, Japp, and Wilson, except that the ammonium chloride
has been replaced by ammonium acetate. This optimal reaction condition was confirmed by the
author after evaluation of the influence of ammonium salt, solvent, and reaction temperature on
the reaction efficiency. The yields remain high in the reaction of benzoin derivatives regardless of
the electron effect of the substituents. The reaction mechanism was similar to the previous one.
Ammonium acetate releases the ammonia by heating to react with benzoin to generate an inter-
mediate. Because the ammonium acetate is subtly excess, few acetic acid is formed, which can
hardly react with the intermediate to produce 2-methyl-4,5-dipenylglyoxaline. On the other hand,
the solid-state reaction allows the full contact of reactant with air. Both the factors may decide a
high yield of reaction.
Khafizova reported a new one-pot synthesis of tetrasubstituted TPP derivatives based on the
reaction of nitriles with EtAlCl2 catalyzed by metallic Mg and Cp2TiCl2 (Scheme 1.2, Route B) [47].
The reaction is efficient, and the product can be obtained in good yields of 60–90%. The catalytic
system of Ti and Zr complexes such as Cp2TiCl2, Ti(PriO)4, TiCl4, Cp2Ti(PMe3)2, Ti(acac)2Cl2,
Ti(Net2)4, and Cp2ZrCl2 is investigated to examine the influence on the reaction. Only Cp2TiCl2
and Ti(PriO)4 display superior catalytic activity and selectivity. Besides, the reaction has a wide
universality of nitriles. For example, by using the starting materials of 2-methyl-, 3-methyl-,
4-methyl-, 4-isopropyl-, 3,5-dimethyl-, and 4-methoxy-substituted benzonitriles, different TPP
derivatives with the tetrasubstituents can be obtained efficiently. The probable mechanism of this
reaction was also given. Cp2TiCl2 was first reduced to the coordinatively unsaturated Cp2Ti(II)
complex by activated Mg. Then, two nitriles can coordinate with the Cp2Ti(II) complex to form
titanium-nitrile π-complexes, followed by transforming to diazatitanacyclopentadiene intermedi-
ate A. Subsequently, two additional nitrile molecules are inserted into the active Ti–N bonds of the
intermediate, which gives rise to ring expansion to form the unsaturated tetraaza derivative B. The
excess EtAlCl2 reacts with B to replace the metal center to generate intermediate C, which further
results in TPP by skeletal isomerization after elimination of aluminadiazirine (Scheme 1.3).
Catalytic system based on ruthenium chemistry has been widely investigated because it plays an
important role in arene hydrogenation, hydrogenation of carbonyl compound, click reaction, and
so on. Leeuwen employed ligand-modified ruthenium nanoparticles (RuNPs) to catalyze the trans-
fer hydrogenation of α-diketone. Interestingly, the unexpected product of TPP was produced by
reacting the mixture of benzyl and ammonium formate in dimethyl formamide (DMF) at 85 °C
with dbdocphos-stabilized RuNPs as catalyst (Scheme 1.2, Route 3) [48]. A very high yield (>98%)
of product was monitored by GC analysis, and the byproducts are water, carbon dioxide, and dihy-
drogen. However, the reaction affords another product of triphenyloxazole in a yield of 30% in the
absence of catalyst, proving that the Ru-based catalyst is indispensable in the reaction process.
Besides dbdocphos, other phosphines such as dppp, DPEphos, and Xantphos are also used to pre-
pare RuNPs. Among these, Xantphos-supported RuNPs behave similarly to the dbdocphos-based
catalyst in activity and selectivity. The influence of nitrogen source on the reaction was studied. By
replacing ammonium formate with ammonium acetate, ammonium chloride, and aqueous ammo-
nia solution, no product of TPP can form, whereas, in the first case, only triphenyloxazole in a 30%
conversion is obtained. The efficient catalytic system also has good group tolerance to provide
RC N Ph Ph
Mg 2RCN
Cp2TiCl2 "Cp2Ti" Cp2Ti N N
Ti
Cp Cp
RC N
A
2RCN
Ph Ph Ph Ph
N N N EtAlCl2 N N
Ph N N Ph Ph Ph
N N N
N C
Al Et
Al Ti B
TPP N Et Cp Cp
Scheme 1.3 Proposed mechanism of synthesizing TPP catalyzed by Mg and Cp2TiCl2.
O NH NH2
HCOONH 4 −HCO 2 / H
O
–HCO 2 , H O RuNP O
O O H
–CO2
N N O
RuNP
–H2 N –2H 2O H2N
N
TPP
Scheme 1.4 Proposed mechanism of preparing TPP catalyzed by RuNPs.
tetrasubstituted TPP derivatives with different structures. The proposed mechanism of the reac-
tion assumes that the benzyl first undergoes reductive amination under transfer hydrogenation
conditions to generate α-amino ketone with RuNPs as catalyst. Then, the molecule self-condenses
by removing the water, followed by tautomerization and oxidation to give TPP (Scheme 1.4).
Different from the above reactions, benzil can directly react with dipenylethylenediamine in
acetic acid under reflux for four hours to afford TPP (Scheme 1.2, Route 4) [33]. The product was
obtained in a satisfactory yield of 47% after recrystallization. A large amount of benzil derivatives
with mono-or disubstituents can be prepared readily or purchased at low cost. However, the syn-
thesis and purification of dipenylethylenediamine derivatives are difficult. Thus, this method is
very helpful to prepare mono-or disubstituted tetraphenylpyrazines.
1.2.2 Suzuki–Miyaura Reaction

Normally, tetraphenylpyrazines are prepared by cyclization reaction with benzoin and benzil, etc,
as starting materials, and nearly all the structures can be designed based on the above routes.
However, Langer reported a new route to synthesize tetrasubstituted tetraphenylpyrazines by the

classical Suzuki–Miyaura reaction (Scheme 1.1, Route 5) [49]. In this case, the molecules are pre-
pared by the carbon–carbon coupling of tetrachloropyrazine and arylboronic acid with palladium
complexes, phosphorus compounds, and potassium phosphate as catalyst, ligand, and base,
respectively. It is probably due to the withdrawing property of central pyrazine that increases the
reactivity of peripheral chlorine. Compared with Pd(PPh3)4, Pd(OAc)2 shows a higher catalytic
activity. By applying Pd(OAc)2 as catalyst, choosing different ligands like S-phos, CataCXium, and
tricyclohexylphosphine exhibits similar reaction efficiency. The university of arylboronic acids is
extremely wide, while the electronic effect of substituents and the steric effect exert less influence
on the reaction reactivity.
The tetrachloropyrazine is prepared by heating a mixture of glycine anhydride, PCl5, and POCl3
at 120 °C. Most of the starting materials are toxic, and the purification process after the reaction is
difficult. Although the tetrachloropyrazine is commercially available, the cost is relatively high. It
is thus considerable to choose this method for preparation. However, it possesses some difference
when compared with the above reactions. For example, it is almost impossible to synthesize
tetraldehyde-substituted TPP with the cyclization reaction. By contrast, reacting tetrachloropyra-
zine with 4-formylphenylboronic acid by the Suzuki–Miyaura reaction may afford the product
readily.
1.3 Functionalities of TPP-based AIEgens
TPP is easy to synthesize and modify. In association with its AIE activity, many luminescent func-
tionalities based on tetraphenylpyrazines have been developed. Herein, we will give some exam-
ples of their development in OLEDs, bio- and chemosensors, self-assembled materials, and
MOFs, etc.
1.3.1 Organic Light-emitting Diodes

TPP is electron-deficient and shows emissions around 400 nm, which is helpful for designing blue
emission materials by further structural decoration. When TPP is modified by the strong electron-
donating triphenylamine group, a derivative of TPP–TPA is obtained (Chart 1.2). TPP–TPA shows
a twisted intramolecular charge transfer (TICT) effect in the polar solvents, while the AIE effect
was activated in the aggregate state. The photoluminescence (PL) studies of TPP–TPA indicate that
it emits at 455 nm at powder state with an absolute quantum yield (ΦF) of 35.2% recorded by the
integrating sphere. Since the AIE materials are competent to act as luminescent materials to fabri-
cate highly efficient nondoped OLEDs, it is thus very promising to utilize this material for
blue OLED fabrication. A typical triple-layer device with a configuration of ITO/NPB
N N N
N
N N N
TPP–TPA TPP–PPI
Chart 1.2 Molecular structures of TPP–TPA and TPP–PPI.

1.3 Functionalities of TPP-based AIEgen 9
Table 1.1 EL performance of devices.
λEL (nm) Vona (V) Lmaxb (cd/m2) ηCb (lm/W) ηPb (lm/W) EQEb (%) CIE (x, y)b
TPP–TPA (I) 482 3.7 17 459 5.49 3.18 2.88 —

TPP–TPA (II) 472 2.8 19 170 6.57 6.55 4.08 0.15, 0.21
c
TPP–PPI 474 2.9 16 460 8.34 8.18 4.85 0.16, 0.23c
a
Von = turn-on voltage at 1 cd/m2.
b
The maximum luminescence (Lmax), current efficiency (ηC), power efficiency (ηP), and external quantum
efficiency at the maximum values for the devices.
c
Data recorded at a luminescence of 1000 cd/m2.
(60 nm)/TPP–TPA (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al is designed, while ITO, NPB (N,N′-di(1-
naphthyl)-N,N′-diphenyl-benzidine), TPBI (1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl),
LiF, and Al are used as anode, hole-transporting layer, electron-transporting layer, electron-
injecting layer, and cathode, respectively. The device emits at 482 nm with a turn-on voltage (Von),
a maximum luminescence (Lmax), and an external quantum efficiency (EQE) of 3.7 V, 17 459 cd/
m2 and 2.88%, respectively (Table 1.1, Device I). Although a high-lying highest occupied molecular
orbital energy level (−5.04 eV) of TPP–TPA is evaluated by cyclic voltammetry, a simplified double-
layer device without the hole-transporting layer (TPP–TPA is expected to act as both light-emitting
and hole-transporting layers) does not show an improved device performance [50].
It was later reported that TPP derivatives with a D–A structure possess a planarized intramolecu-
lar charge transfer (PLICT) effect in the excited state in the polar media. For example, the ΦF of
TPP–TPA in toluene, ethyl acetate, dichloromethane, and DMF changes from 22.7, 50.9, 80.7 to
80.9% as the polarity of the solvent increases. It is due to the formation of planarization conforma-
tion or quinone conformation with a good conjugation in the excited state to increase the probabil-
ity of transition. In that work, another TPP–TPA-based blue OLED (configuration: ITO/HATCN
(5 nm)/TAPC (40 nm)/TCTA (5 nm)/TPP–TPA (20 nm)/Bepp2 (45 nm)/Liq (2 nm)/Al) is fabri-
cated with HATCN (2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphe-nylene), TAPC (1,1-bis(4-
di-p-tolylaminophenyl)cyclohexane), TCTA (4,4′,4′′-tri-9-carbazolytriphenylamine), and Bepp2
(bis(2-(2-hydroxyphenyl)-pyridine)beryllium) functioned as hole-injecting layer, hole-transporting
layer, hole-transporting and electron-blocking layer, and electron-transporting and hole-blocking
layer, respectively. However, a very good device performance with Von, Lmax, and EQE of 2.8 V,
19 170 cd/m2, and 4.08%, respectively, is obtained (Table 1.1, Device II) [51].
The PLICT effect also takes places in phenanthroimidazole derivative-modified TPP (TPP–PPI),
though the phenanthroimidazole-based group is not so electron-donating (Chart 1.2). TPP-PPI
shows the AIE effect in THF/water mixtures and emits at 470 nm in the film with ΦF of 28.1%.
While fabricating it into the device with a configuration of ITO/HATCN (5 nm)/NPB (40 nm)/TcTa
(5 nm)/TPP–PPI (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al, an excellent device performance of Von
(2.9 V), Lmax (16 460 cd/m2), and EQE (4.85%) is achieved. It is worth noting that the theoretical
limit of EQE of OLEDs fabricated with typical fluorescent materials is 5%. Thus, it demonstrates
the huge potential of developing OLEDs with TPP-based luminescent materials [52].
1.3.2 Fluorescent Sensors

Hydrogen sulfide (H2S) is a natural gas with a rotten egg smell. It is poisonous, corrosive, and flam-
mable. Exposure of H2S with a small amount can give rise to headache, dizziness, and even death.
On the other hand, H2S is an indispensable endogenous gas in human body by metabolism. It is
related to different physiological processes like cell growth, vasodilation, regulation of inflamma-
tion, and so on. The abnormal level of H2S is associated with symptoms such as Alzheimer’s dis-
eases and diabetes [53].
Tang synthesized an AIEgen of malonitrile-functionalized TPP (TPP-PDCV) to act as a ratiomet-
ric fluorescent probe to detect H2S with high sensitivity and good selectivity [54]. TPP-PDCV shows
an orange emission at 565 nm in the DMSO/PBS buffer mixture (v/v = 9 : 1) due to the TICT from
the TPP part to the strong electron-withdrawing malonitrile group. However, upon addition of
NaHS, the orange emission disappears gradually, whereas a blue emission centered at 429 nm in
the short-wavelength region enhances accordingly. Such a fluorescent response (I429/I565) to H2S
changes less until 10 minutes, indicating that the detection is efficient and can be finished in
10 minutes (Figure 1.1). It is due to the activity of the double bond in the malonitrile group, which
can undergo nucleophilic addition by H2S. Thus, the double bond is easy to break to prohibit the
TICT effect. On the other hand, TPP-PDCV is transformed to a thiol-substituted TPP derivative
(TPP-PSH) after addition and elimination reactions, which continues to oxidize to form the dithio-
containing derivative of TPP-2PS. Because the resulting TPP-2PS shows a lower polarity and lager
Figure 1.1 Fluorescent detection of H2S by TPP-PDCV. (a) Time-dependent PL spectra of TPP-PDCV (25 μM)
in the DMSO/PBS buffer mixture (v/v = 9 : 1) in the presence of NaHS (250 μM). (b) Plot of the relative PL
intensity (I429/I565) versus the number of scan in 25 minutes, where I429 and I565 are the PL intensity at 429
and 565 nm, respectively. Inset: the photographs of the TPP-PDCV solution before and after the addition of
NaHS taken under an irradiation of a 356 nm UV light. (c) PL spectra of TPP-PDCV in the DMSO/PBS buffer
mixture (v/v = 9 : 1) with different NaHS concentrations (0–500 μM). (d) Plot of the relative PL intensity
(I429/I565) versus NaHS concentration. For all the tests, the excitation wavelength is 372 nm.
rigidity, it displays a bad solubility in the DMSO/water mixture. The TPP-2PS is easy to aggregate
to produce a blue light signal contributed by the TPP unit.
The sensor can analyze the H2S quantificationally. For example, the sensor possesses a response
with the NaHS concentration range from 0 to 250 μM. However, in the concentration range of 0–75
and 150–225 μM, the linear responses can be observed, thus providing a platform to detect H2S at
low concentration (Figure 1.1). Besides, the sensor shows a good selectivity against other anions
(e.g. AcO−, F−, ClO−, IO4−, N3−, NO2−, and OH−, etc.), except for CO32−, which exerts subtle effect
on the detection. The biothiols of cysteine, homocysteine, and glutathione also pose some effect
because of the presence of thiol in the structures. However, such an influence can be neglected in
comparison to the strong signal in the presence of H2S.
Study on the influence of molecular structure on the sensing property is particularly valuable to
provide the clues for designing advanced functional materials. With this regard, Tang prepared three
conjugated isomers of TPP-p-TPE, TPP-m-TPE, and TPP-o-TPE by connecting TPP and triphenyle-
thene at the para-, meta-, and ortho-positions, respectively (Figure 1.2a) [55]. The isomers show the
AIE effect due to the melding of the typical AIEgens of TPP and triphenylethene in the structures.
Their conformations evolve from an extended to a folded one due to the different linkages between
two units, which makes the emissions blue-shifted and luminescence efficiency to decrease gradu-
ally. It is reasonable because the molecular conjugation gets worse as the structure changes.
Interestingly, TPP-o-TPE is an easy-to-form organic porous crystal thanks to its fold conforma-
tion locked by the strong intramolecular C–H···N hydrogen bond. It is an easy-to-form DCM-
captured porous crystal (Figure 1.2b). In the crystal, every four molecules coordinately generate a
cylinder-like pore with a volume of around 0.27 nm3, which is enough for accommodating two
DCM molecules. The pores are distributed uniformly in the crystal and connected in a straight line
as long-ranged nanochannels. The porous crystal produces a fixed framework structure regardless
of the guest molecules. For example, each pore can also capture two THF molecules, with the
structure of crystal less changed (Figure 1.2c). However, the size of the pore is tunable to fit differ-
ent volumes of guest molecules.
Considering the difference in the influence of molecular conjugation and porosity caused by the
isomerization effect, it is desirable to investigate their sensing behavior. 2,4,6-Trinitrophenol (pic-
ric acid, PA) is chosen as the first analyte because it is a well-known model explosive and the accu-
rate detection of explosive meets current needs in antiterrorist and protection of country safety.
The detection is basically carried out with the nanoaggregates in solution because of the strong
emissions of AIE isomers in the aggregate state. Upon addition of PA, the isomers show similar
quenching behavior as the concentration of PA increases. The lifetime of the three sensors has a
negligible change before and after analyte addition, demonstrating that a static quenching model
dominates the sensing mechanism. Since the process normally takes place from the ground state
of isomers to the excited state of PA, no excited-state behaviors of sensors such as fluorescence
resonance energy transfer (FRET) and photoinduced electron transfer (PET) will occur, while the
interaction between the sensor and the analyte plays a crucial role. Overall, the quenching effect of
TPP-p-TPE is somewhat higher than those of the others at high PA concentration. It is due to the
stronger Lewis acid–base interactions preferred to take place between PA and AIE isomers with
better conjugation. On the other hand, although TPP-o-TPE possesses the worst molecular conju-
gation, its quenching effect is a bit larger than TPP-m-TPE at a PA concentration of 400–500 μM,
which is because of its best porosity that increases the binding capacity between TPP-o-TPE and
PA. Therefore, both factors collectively determine the detection of PA by nanoprobes (Figure 1.2d).
The study is then focused on the sensing of another analyte of Ru3+ by the nanoaggregates
because it is important in catalysis but harmful to the environment and toxic to the human beings
Figure 1.2 Fluorescent detection of PA and Ru3+ by AIE isomers. (a) Molecular structures of AIE isomers.
(b) DCM-and (c) THF-containing organic porous crystals of TPP-o-TPE. (d) Plots of I0/I-1 versus PA
concentration. Inset: molecular structure of PA. (e) Plots of I0/I-1 versus Ru3+ concentration. Inset: molecular
structure of PA. In (d) and (e), I0 and I are the peak intensity of probes before and after the addition of
analytes, respectively, and the excitation wavelengths of TPP-p-TPE, TPP-m-TPE, and TPP-o-TPE are 350,
336, and 332 nm, respectively.
(Figure 1.2e) [55]. Different from the above research, the isomers show a partial quenching behav-
ior upon addition of Ru3+. The quenching keeps linear at a low-concentration range of Ru3+ and
reaches plateaus at high concentrations. Besides, the quenching constant of TPP-p-TPE, TPP-m-
TPE, and TPP-o-TPE increases accordingly. The lifetime study indicates that an obvious decrease
of lifetime of sensors is observed after addition of Ru3+. Thus, the quenching mechanism is mainly
ascribed to a dynamic (collisional) quenching model, which requires a close contact of the excited
molecules and the analyte. The Dexter energy transfer is dominated because a short distance of the
donor and the acceptor may help the electron exchange between them. On the other hand, the
possible influence of FRET on the sensing is ruled out because all the emissions should be
quenched if it exists. It seems that the change of the quenching constant of the sensors is related
to the variation in the PL quantum efficiency of isomers. It is more likely that the interaction of the
isomers and Ru3+ plays a major role and a much strong interaction will be produced between Ru3+
and isomers with better conjugation.
Although the quenching efficiency of TPP-m-TPE is larger than that of TPP-o-TPE at low con-
centrations, it displays the same quenching extent at high concentrations. As the TPP-o-TPE is an
easy-to-form pore in the aggregates, the sensor will encapsulate more Ru3+ into the nanoaggre-
gates, which will enhance their interactions. On the other hand, the presence of 3D voids in the
probes may help Ru3+ to diffuse and contact more fluorogens to annihilate the emission. Both
factors enable the TPP-o-TPE to possess similar quenching extent with TPP-m-TPE, while the pla-
teaus of the former will be reached at a higher Ru3+ concentration. However, the isomerization
effect has less influence on the selectivity of the sensors.
For examples, by addition of other metal ions like Ag+, Fe3+, and Cu2+, etc., no fluorescent
response can be observed.
1.3.3 Chiral Cage for Self-assembly to Achieve White-light Emission

Organic cage compounds have drawn considerable attention due to their wide functionalities in
self-assembly, gas adsorption, and catalysis, etc [56]. Currently, the organic cages are basically
designed based on the classical organic reactions of specific building units. The conjugated units
are promising in organic cage design, and the study of optical properties of organic cage is attrac-
tive by introduction of these units. However, most of the conjugated units possess ACQ effect.
There are few studies on AIE unit-based organic cages because of lack of AIE prototype structures
with good symmetry for design.
As we know, TPP is an AIEgen with four peripheral phenyl rings symmetrically attached to the
central pyrazine. Thus, utilization of TPP to develop a luminescent cage is very promising. Tang
reported the synthesis of an amphiphilic organic cage with tetrahydroxyl-substituted TPP
(TPP-4OH) and substituted 2,6-dichloro-1,3,5-triazine (Figure 1.3a) [57]. TPP-4OH shows very
weak emission in the solution due to the vigorous molecular motion under excitation. However,
the TPP cage shows a strong emission at 397 nm with a ΦF of 34.3% (Figure 1.3b). Theoretical stud-
ies reveal that the rotational energy barrier for the phenyl rings’ flipping in the TPP cage is much
larger than that in TPP-OH, which is due to the congested array of each unit in the cage. As the
motion of TPP is greatly prohibited in the cage, TPP cage thus exhibits strong emission by sup-
pressing the nonradiative transition. This study also verifies that the restriction of molecular
motion is the cause of the AIE effect.
The studies of chirality are closely related to medicinal chemistry and 3D organic electronics. So
far, the introduction of a chiral carbon atom into the structure can be regarded as the main source
in designing chiral compounds. Interestingly, the TPP cage here also possesses a chirality though
Figure 1.3 TPP-based chiral cage for self-assembly to achieve white-light emission. (a) Synthetic route to
the TPP cage. (b) PL spectra of TPP-4OH and TPP cage in THF; their concentration is 50 μM. Inset: their
photographs taken under a UV light irradiation. CD spectra of the TPP cage in (c) acetonitrile and
(d) acetonitrile/water mixture with a 95% water content; the concentration is 100 μM. (e) Photographs of
the TPP cage, DPP, and complex in THF and THF/water taken under a UV light irradiation. (f) Photographs of
the complex-doped PEG film-casted flashlight during different times and the CIE coordinate of its emission
spectra.
no chiral carbon atom is incorporated. Circular dichroism (CD) spectroscopy indicates that a
Cotton effect occurs in the absorption regions of the phenyl rings and TPP units in both the solu-
tion and aqueous suspensions (Figure 1.3c, d). It is due to the clockwise or anticlockwise rotation
of the phenyl rings of TPP against the pyrazine ring caused by the steric effect. Such a special
molecular conformation enables it to possess mirror asymmetry to show chirality. Theoretically,
the TPP cage with the clockwise or anticlockwise propeller is often obtained in a ratio of 1 : 1 after
synthesis, and the resulting racemic mixture should quench the chirality. The reason for inducing
chirality awaits further investigation. On the other hand, only a stable right-handed crystal can be
obtained in the air, which shows a positive Cotton effect that originates from the crystallization-
induced asymmetric transformation by destroying the mirror symmetry. Moreover, the CD signals
of the TPP cage in the aggregates are much larger than those in the solution, indicative of an
aggregation-induced chirality that has rarely been reported.
Obviously, the TPP cage has a hydrophobic cavity and is potential to capture the guest molecules.
Thus, the investigation of its host–guest chemistry is expected. Diketopyrrolopyrrole (DPP) is an
ACQ chromophore with a yellow emission in the solution. However, the size of DPP can fit the
cavity volume of the TPP cage properly and the supramolecular assembly complex between them
can be obtained readily. The successful formation of the complex is proved by the NMR titration
and analysis, and the UV–vis spectra indicate a complex ratio of 1 : 1. As DPP has an ACQ effect,
its emission is easy to be quenched once aggregated. However, DPP shows a strong yellow emission
in the cage even when the complex is in the aggregate state (Figure 1.3e). It demonstrates that the
DPP molecules have been isolated by the TPP cage while the π–π stacking has been prohibited to
overcome the ACQ effect, therefore providing a flexible strategy to design highly efficient solid-
state luminescent materials with ACQ luminophores. On the other hand, the strong blue emission
of the TPP cage sustains. The combined emissions of blue and yellow lights can be observed in the
assembly. The emissions of the complex change somewhat from the solution state to the aggregate
state. For example, it shows a pink emission in THF. Upon addition of water, the spectrum shifts
to white light, which is probably to the subtle variation in emissions of the TPP unit and DPP by
changing the microenvironment. Finally, Tang also demonstrates its potential application as
white-light emitters. By doping the complex in the PEG with a weight ratio of 1%, a white-light-
emissive PEG film can be formed. Further casting the film onto the UV flashlight gives a stable
white-light source for illumination (Figure 1.3f).
1.3.4 Metal–organic Framework

MOFs are a kind of organic–inorganic crystals that consist of metal ions and organic molecules as
center and ligand, respectively. The two-or three-dimensional rigid framework makes them porous
with a large specific surface area and tunable pore size, thus very promising for utilization as
porous materials [58]. MOFs can also be developed as luminescent materials because of their
potential luminescent properties of metal ions and ligands. Recently, some luminescent MOFs
with TPE-based units as ligand have been designed to exhibit sensing and photocatalytic behav-
iors [59, 60]. As TPP shows the similar structural symmetry to TPE, TPP-based MOFs are thus
desired to be developed.
Yin developed MOFs with Ln3+ ions, including Eu3+, Tb3+, and Gd3+ as centers and tetracarboxyl-
substituted TPP (TPP-4COOH) as ligand [61]. The coordination process can proceed in the mixed
solution and be monitored by turn-on emission, indicative of a coordination-induced emission.
However, different ion centers may cause different optical properties of MOFs (Figure 1.4a). Eu3+-
MOF possesses obvious dual emissions at around 420 and 630 nm, which are originated from the
TPP unit and Eu3+, while only the emission of TPP can be observed in Gd3+-MOF. The emission of
Tb3+ in Tb3+-MOF in the long-wavelength region is weak but still can be discerned. This is due to
the different energy gaps between the singlet state and triplet state of a ligand and the triplet state
of a ligand and the excited state of metal ions, which determines the different intersystem crossing
and sensitization efficiencies (Figure 1.4a). In other words, the emission of metal ions is influ-
enced by the combined consideration of the orbital properties of both metal centers and organic
ligands.
Although the various metal ions have been employed, their MOFs show similar structural mor-
phologies as revealed by PXRD analysis, indicative of the university of choosing TPP to design
MOFs. Moreover, the emission of the TPP unit in MOFs is somewhat blue-shifted than those of
(a) (b)
6P
35 7/2
S1
30 ET
ISC
T1’
25 ΔE1 12.1 Å
E/103 cm–1
ΔE2 sD
sD 4
20 T1 0
A F P L
15
9.3 Å
10
5
S0
0
L1 Eu3+ Tb3+ Gd3+
(c) (d)
0 μM
10 000
10 μM
20 μM
8 000 30 μM
intensity (a.u.)
50 μM
6 000 70 μM
100 μM
4 000 130 μM
160 μM
2 000
300 450 600 750

Wavelength (nm)
Figure 1.4 Functional MOFs with TPP-4COOH as ligand for sensing. (a) Intersystem crossing and
sensitization effect determined by the energy level properties of ligands and metal ions. (b) Crystal
structure of Eu3+-MOF. (c) PL spectra of Eu3+-MOF upon the addition of arginine with different
concentrations. (d) Model of hydrogen formation between MOF and arginine.
TPP-4COOH. As the formation of MOF can be regarded as a crystallization process, TPP must
adjust the conformation to fit the crystal lattice, while a much twisted molecular structure will
shorten the conjugation to blue-shift the emission, which is in accordance with the results obtained
by the single-crystal diffraction analysis (Figure 1.4b). On the other hand, the ΦF of TPP-4COOH
was measured to be 12.9% in the solid state. However, after being introduced into MOF, the Eu3+-
MOF shows dual emissions with a remarkably increased ΦF of 60.8%. It demonstrates a useful
strategy to construct highly efficient luminescent materials by utilizing coordination-induced
emission and antenna effect.
As two fluorescent channels are observed in the Eu3+-MOF, it is potential to develop a ratiomet-
ric fluorescent probe based on it. Interestingly, Eu3+-MOF has a fluorescent response to arginine,
which is an essential amino acid in the body associated with a variety of diseases like cardiovascu-
lar and cerebrovascular diseases and hyperammonemia, etc [61]. Upon the addition of arginine,
the emission of the TPP unit enhances gradually, while those of Eu3+ changes less, thus making
the signals ratiometrically detectable (Figure 1.4c). It is due to the nitrogen atoms in the central
pyrazine ring of the TPP unit, which provides sites for binding. On the other hand, the pores in the
MOFs are competent in accommodating the arginine. The arginine, therefore, can enter into the
MOF and form a hydrogen bond with TPP, thus offering an additional steric hindrance to restrict
molecular motions to enhance emission (Figure 1.4d). The emission behavior of Eu3+ is less
1.4 Conclusio 17
influenced because no interaction is found between Eu3+ and arginine. Besides, by replacing the
TPP-4COOH ligand with tetracarboxyl-substituted tetraphenylbenzene, the resulting MOF does
not possess a response to arginine, further proving the importance of the introduction of an AIE-
active TPP unit. The sensor also shows a good selectivity against other amino acids and high sen-
sitivity with a detection limit as low as 15 nM.
1.4 Conclusion
The study of TPP dated back to the mid-nineteenth century, while its real structure was established
by Japp and Wilson in 1886. Since that, more studies are focused on synthetic methodologies and
medicinal chemistry. It is until 2015 that Tang found TPP to be AIE-active and have merits of easy
synthesis, facile medication, good stability, and tunable electronic property, etc. This, therefore,
evolves from a variety of functionalities based on tetraphenylpyrazines and makes its researches
very attractive.
TPP can be synthesized by cyclization and Suzuki–Miyaura reactions. In the former case, several
routes are provided to prepare TPP and its derivatives with mono-, di-, and tetrasubstitutions. For
disubstituted TPP, the molecules even with substitutions at different sides can be obtained. By
choosing a suitable method, TPP can be synthesized under a very simple and green condition and
the purification of TPP can be carried out by recrystallization instead of chromatographic column.
The Suzuki–Miyaura reaction can also give tetrasubstituted TPP efficiently and replenish the prod-
ucts that cannot be obtained by the former methods. Encouraged by this, a large amount of desired
structures based on TPP can be designed.
TPP-based luminescent materials show different functionalities to indicate their application
potentials. Electron-donating group-modified TPPs often show high luminescent efficiencies in
the aggregate state and can be utilized to fabricate OLEDs, with EQE approaching theoretic limit.
By decorating TPP with an active group, the resulting AIEgen can function as a ratiometric fluores-
cent sensor to detect H2S with good selectivity and high sensitivity. Besides, by constructing TPP
derivatives with different isomerization effects, a model can be established to elaborate the influ-
ence of molecular conjugation and porosity on the sensing properties. TPP can also catch the eyes
of researchers in reticular chemistry. For example, the chiral TPP-based organic cage can be
obtained from the achiral TPP unit, which can form a host–guest complex with ACQ molecules to
construct stable white-light emission materials in the film state. Also, MOFs can be designed based
on the TPP unit as ligand, which shows strong emissions due to coordination-induced emission
and antenna effect and displays a sensitive and selective ratiometric detection of arginine.
Overall, the researches on TPP are still in an embryonic stage. Many applications are worth
being further explored. For example, pyrazines are widely found in natural products and known as
antitumor, antibacterial, diuretic, anti-TB, and antidiabetic drugs. Hydroxyl-substituted TPPs are
regarded as regulators of estrogen receptors. Thus, it is feasible to develop luminescent drugs and
imaging agents to monitor the therapeutic process and life process. On the other hand, functional
materials with diversified architectures are very easy to achieve based on TPP. The investigations
of TPP-based macrocycles, organic–inorganic coordinated cages, conjugated microporous poly-
mers, covalent organic frameworks, and hydrogen-bonded organic frameworks are still blank. We
hope, with this chapter, a picture of the past, now, and future of TPP can be clearly painted and
more sparks and opportunities can be motivated to boost the development of TPP-based lumines-
cent materials.
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seem to involve them in suspicion; but I am certain that there is
some fallacy—that there are some facts which did not transpire at
the inquest but which might be brought to the surface if you took the
case in hand.”
“Why not let the police disinter those facts?”
“Because the police evidently suspect the members of the
household and they will certainly pursue the obvious probabilities.”
“So should I, for that matter,” said he; “and in any case, we can’t
prevent the police from bringing a charge if they are satisfied that
they can support it. And your own experience will tell you that they
will certainly not take a case into the Central Criminal Court unless
they have enough evidence to make a conviction a virtual certainty.
But I remind you, Mayfield, that they have got it all to do. There is
grave suspicion in respect of a number of persons, but there is not,
at present, a particle of positive evidence against any one person. It
looks to me as if it might turn out to be a very elusive case.”
“Precisely,” said I. “That is why I am anxious that the actual
perpetrator should be discovered. Until he is, all these people will be
under suspicion, with the peril of a possible arrest constantly hanging
over them. I might even say, ‘hanging over us’; for you, yourself,
have included me in the group of possible suspects.”
He reflected for a few moments. At length he replied:
“You are quite right, Mayfield. Until the perpetrator of a crime is
discovered and his guilt established, it is always possible for
suspicion to rest upon the innocent and even for a miscarriage of
justice to occur. In all cases it is most desirable that the crime should
be brought home to the actual perpetrator without delay for that
reason, to say nothing of the importance, on grounds of public policy,
of exposing and punishing wrong-doers. You know these people and
I do not. If you are sufficiently confident of their innocence to take the
risk of associating yourself with the agencies of detection, I have no
more to say on that point. I am quite willing to go into the case so far
as I can, though, at present, I see no prospect of success.”
“It seems to you a difficult case, then?”
“Very. It is extraordinarily obscure and confused. Whoever
poisoned that unfortunate man, seems to have managed most
skilfully to confuse all the issues. Whatever may have been the
medium through which the poison was given, that medium is
associated equally with a number of different persons. If the
medicine was the vehicle, then the responsibility is divided between
Dimsdale, who prepared it, and the various persons who
administered it. If the poison was mixed with the food, it may have
been introduced by any of the persons who prepared it or had
access to it on its passage from the kitchen to the patient’s bedroom.
There is no one person of whom we can say that he or she had any
special opportunity that others had not. And it is the same with the
motive. No one had any really, adequate motive for killing
Monkhouse; but all the possible suspects benefited by his death,
though they were apparently not aware of it.”
“They all knew, in general terms, that they had been mentioned in
the will though the actual provisions and amounts were not
disclosed. But I should hardly describe Mrs. Monkhouse as
benefiting by her husband’s death. She will not be as well off now as
she was when he was alive and the whole of his income was
available.”
“No. But we were not including her in the group since she was
not in the house when the poison was being administered. We were
speaking of those who actually had the opportunity to administer the
poison; and we see that the opportunity was approximately equal in
all. And you see, Mayfield, the trouble is that any evidence
incriminating any one person would be in events which are past and
beyond recall. The depositions contain all that we know and all that
we are likely to know, unless the police are able to ascertain that
some one of the parties has purchased arsenic from a chemist;
which is extremely unlikely considering the caution and judgment
that the poisoner has shown. The truth is that, if no new evidence is
forthcoming, the murder of Harold Monkhouse will take its place
among the unsolved and insoluble mysteries.”
“Then, I take it that you will endeavour to find some new
evidence? But I don’t see, at all, how you will go about it.”
“Nor do I,” said he. “There seems to be nothing to investigate.
However, I shall study the depositions and see if a careful
consideration of the evidence offers any suggestion for a new line of
research. And as the whole case now lies in the past, I shall try to
learn as much as possible about everything and everybody
concerned. Perhaps I had better begin with you. I don’t quite
understand what your position is in this household.”
“I will tell you with pleasure all about my relations with the
Monkhouses, but it is a rather long story, and I don’t see that it will
help you in any way.”
“Now, Mayfield,” said Thorndyke, “don’t begin by considering
what knowledge may or may not be helpful. We don’t know. The
most trivial or seemingly irrelevant fact may offer a most illuminating
suggestion. My rule is, when I am gravelled for lack of evidence, to
collect, indiscriminately, all the information that I can obtain that is in
the remotest way connected with the problem that I am dealing with.
Bear that in mind. I want to know all that you can tell me, and don’t
be afraid of irrelevant details. They may not be irrelevant, after all;
and if they are, I can sift them out afterwards. Now, begin at the
beginning and tell me the whole of the long story.”
He provided himself with a note-book, uncapped his fountain pen
and prepared himself to listen to what I felt to be a perfectly useless
recital of facts that could have no possible bearing on the case.
“I will take you at your word,” said I, “and begin at the very
beginning, when I was quite a small boy. At that time, my father, who
was a widower, lived at Highgate and kept the chambers in the
Temple which I now occupy. A few doors away from us lived a
certain Mr. Keene, an old friend of my father’s—his only really
intimate friend, in fact—and, of course, I used to see a good deal of
him. Mr. Keene, who was getting on in years, had married a very
charming woman, considerably younger than himself, and at this
time there was one child, a little girl about two years old.
Unfortunately, Mrs. Keene was very delicate, and soon after the
child’s birth she developed symptoms of consumption. Once started,
the disease progressed rapidly in spite of the most careful treatment,
and in about two years from the outset of the symptoms, she died.
“Her death was a great grief to Mr. Keene, and indeed, to us all,
for she was a most lovable woman; and the poor little motherless
child made the strongest appeal to our sympathies. She was the
loveliest little creature imaginable and as sweet and winning in
nature as she was charming in appearance. On her mother’s death, I
adopted her as my little sister, and devoted myself to her service. In
fact, I became her slave; but a very willing slave; for she was so
quick and intelligent, so affectionate and so amiable that, in spite of
the difference in our ages—some eight or nine years—I found her a
perfectly satisfying companion. She entered quite competently into
all my boyish sports and amusements, so that our companionship
really involved very little sacrifice on my part but rather was a source
of constant pleasure.
“But her motherless condition caused Mr. Keene a good deal of
anxiety. As I have said, he was getting on in life and was by no
means a strong man, and he viewed with some alarm the, not very
remote, possibility of her becoming an orphan with no suitable
guardian, for my father was now an elderly man, and I was, as yet,
too young to undertake the charge. Eventually, he decided, for the
child’s sake, to marry again; and about two years after his first wife’s
death he proposed to and was accepted by a lady named Ainsworth
whom he had known for many years, who had been left a widow with
one child, a girl some two years younger than myself.
“Naturally, I viewed the advent of the new Mrs. Keene with some
jealousy. But there was no occasion. She was a good, kindly woman
who showed from the first that she meant to do her duty by her little
step-daughter. And her own child, Barbara, equally disarmed our
jealousy. A quiet, rather reserved little girl, but very clever and quick-
witted, she not only accepted me at once with the frankest
friendliness but, with a curious tactfulness for such a young girl,
devoted herself to my little friend, Stella Keene, without in the least
attempting to oust me from my position. In effect, we three young
people became a most united and harmonious little coterie in which
our respective positions were duly recognized. I was the head of the
firm, so to speak, Stella was my adopted sister, and Barbara was the
ally of us both.
“So our relations continued as the years passed; but presently
the passing years began to take toll of our seniors. My father was the
first to go. Then followed Mr. Keene, and after a few more years,
Barbara’s mother. By the time my twenty-fifth birthday came round,
we were all orphans.”
“What were your respective ages then?” Thorndyke asked.
Rather surprised at the question, I paused to make a calculation.
“My own age,” I replied, “was, as I have said, twenty-five. Barbara
would then be twenty-two and Stella sixteen.”
Thorndyke made a note of my answer and I proceeded:
“The death of our elders made no appreciable difference in our
way of living. My father had left me a modest competence and the
two girls were fairly provided for. The houses that we occupied were
beyond our needs, reduced as we were in numbers and we
discussed the question of sharing a house. But, of course, the girls
were not really my sisters and the scheme was eventually rejected
as rather too unconventional; so we continued to live in our
respective houses.”
“Was there any trustee for the girls?” Thorndyke asked.
“Yes, Mr. Brodribb. The bulk of the property was, I believe, vested
in Stella, but, for reasons which I shall come to in a moment, there
was a provision that, in the event of her death, it should revert to
Barbara.”
“On account, I presume, of the tendency to consumption?”
“Exactly. For some time before Mr. Keene’s death there had been
signs that Stella inherited her mother’s delicacy of health. Hence the
provisions for Barbara. But no definite manifestations of disease
appeared until Stella was about eighteen. Then she developed a
cough and began to lose weight; but, for a couple of years the
disease made no very marked progress, in fact, there were times
when she seemed to be in a fair way to recovery. Then, rather
suddenly, her health took a turn for the worse. Soon she became
almost completely bed-ridden. She wasted rapidly, and, in fact, was
now the typical consumptive, hectic, emaciated, but always bright,
cheerful and full of plans for the future and enthusiasm for the little
hobbies that I devised to keep her amused.
“But all the time, she was going down the hill steadily, although,
as I have said, there were remissions and fluctuations; and, in short,
after about a year’s definite illness, she went the way of her mother.
Her death was immediately caused, I understand, by an attack of
hemorrhage.”
“You understand?” Thorndyke repeated, interrogatively.
“Yes. To my lasting grief, I was away from home when she died. I
had been recently called to the bar and was offered a brief for the
Chelmsford Assizes, which I felt I ought not to refuse, especially as
Stella seemed, just then, to be better than usual. What made it
worse was that the telegram which was sent to recall me went
astray. I had moved on to Ipswich and had only just written to give
my new address, so that I did not get home until just before the
funeral. It was a fearful shock, for no one had the least suspicion that
the end was so near. If I had supposed that there was the slightest
immediate danger, nothing on earth would have induced me to go
away from home.”
Thorndyke had listened to my story not only with close attention
but with an expression of sympathy which I noted gratefully and
perhaps with a little surprise. But he was a strange man; as
impersonal as Fate when he was occupied in actual research and
yet showing at times unexpected gleams of warm human feeling and
the most sympathetic understanding. He now preserved a thoughtful
silence for some time after I had finished. Presently he said:
“I suppose this poor girl’s death caused a considerable change in
your way of living?”
“Yes, indeed! Its effects were devastating both on Barbara and
me. Neither of us felt that we could go on with the old ways of life.
Barbara let her house and went into rooms in London, where I used
to visit her as often as I could; and I sold my house, furniture and all
and took up residence in the Temple. But even that I could not
endure for long. Stella’s death had broken me up completely. Right
on from my boyhood, she had been the very hub of my life. All my
thoughts and interests had revolved around her. She had been to me
friend and sister in one. Now that she was gone, the world seemed
to be a great, chilly void, haunted everywhere by memories of her.
She had pervaded my whole life, and everything about me was
constantly reminding me of her. At last I found that I could bear it no
longer. The familiar things and places became intolerable to my
eyes. I did not want to forget her; on the contrary, I loved to cherish
her memory. But it was harrowing to have my loss thrust upon me at
every turn. I yearned for new surroundings in which I could begin a
new life; and in the end, I decided to go to Canada and settle down
there to practise at the Bar.
“My decision came as a fearful blow to Barbara, and indeed, I felt
not a little ashamed of my disloyalty to her; for she, too, had been
like a sister to me and, next to Stella, had been my dearest friend.
But it could not be helped. An intolerable unrest had possession of
me. I felt that I must go; and go I did, leaving poor Barbara to
console her loneliness with her political friends.
“I stayed in Canada nearly two years and meant to stay there for
good. Then, one day, I got a letter from Barbara telling me that she
was married. The news rather surprised me, for I had taken Barbara
for an inveterate spinster with a tendency to avoid male friends other
than myself. But the news had another, rather curious effect. It set
my thoughts rambling amidst the old surroundings. And now I found
that they repelled me no longer; that, on the contrary, they aroused a
certain feeling of home-sickness, a yearning for the fuller, richer life
of London and a sight of the English countryside. In not much more
than a month, I had wound up my Canadian affairs and was back in
my old chambers in the Temple, which I had never given up, ready to
start practice afresh.”
“That,” said Thorndyke, “would be a little less than three years
ago. Now we come to your relations with the Monkhouse
establishment.”
“Yes; and I drifted into them almost at once. Barbara received me
with open arms, and of course, Monkhouse knew all about me and
accepted me as an old friend. Very soon I found myself, in a way, a
member of the household. A bedroom was set apart for my use,
whenever I cared to occupy it, and I came and went as if I were one
of the family. I was appointed a trustee, with Brodribb, and dropped
into the position of general family counsellor.”
“And what were your relations with Monkhouse?”
“We were never very intimate. I liked the man and I think he liked
me. But he was not very approachable; a self-contained, aloof,
undemonstrative man, and an inveterate book-worm. But he was a
good man and I respected him profoundly, though I could never
understand why Barbara married him, or why he married Barbara. I
couldn’t imagine him in love. On the other hand I cannot conceive
any motive that any one could have had for doing him any harm. He
seemed to me to be universally liked in a rather lukewarm fashion.”
“It is of no use, I suppose,” said Thorndyke, “to ask you if these
reminiscences have brought anything to your mind that would throw
any light on the means, the motive or the person connected with the
crime?”
“No,” I answered; “nor can I imagine that they will bring anything
to yours. In fact, I am astonished that you have let me go on so long
dribbling out all these trivial and irrelevant details. Your patience is
monumental.”
“Not at all,” he replied. “Your story has interested me deeply. It
enables me to visualize very clearly at least a part of the setting of
this crime, and it has introduced me to the personalities of some of
the principal actors, including yourself. The details are not in the
least trivial; and whether they are or are not irrelevant we cannot
judge. Perhaps, when we have solved the mystery—if ever we do—
we may find connections between events that had seemed to be
totally unrelated.”
“It is, I suppose, conceivable as a mere, speculative possibility.
But what I have been telling you is mainly concerned with my own
rather remote past, which can hardly have any possible bearing on
comparatively recent events.”
“That is perfectly true,” Thorndyke agreed. “Your little
autobiography has made perfectly clear your own relation to these
people, but it has left most of them—and those in whom I am most
interested—outside the picture. I was just wondering whether it
would be possible for you to amplify your sketch of the course of
events after Barbara’s marriage—I am, like you, using the Christian
name, for convenience. What I really want is an account of the
happenings in that household during the last three years, and
especially during the last year. Do you think that, if you were to turn
out the garrets of your memory, you could draw up a history of the
house in Hilborough Square and its inmates from the time when you
first made its acquaintance? Have you any sort of notes that would
help you?”
“By Jove!” I exclaimed. “Of course I have. There is my diary.”
“Oh,” said Thorndyke, with obviously awakened interest. “You
keep a diary. What sort of diary is it? Just brief jottings, or a full
record?”
“It is a pretty full diary. I began it more than twenty years ago as a
sort of schoolboy hobby. But it turned out so useful and entertaining
to refer to that I encouraged myself to persevere. Now, I am a
confirmed diarist; and I write down not only facts and events, but
also comments, which may be quite illuminating to study by the light
of what has happened. I will read over the last three years and make
an abstract of everything that has happened in that household. And I
hope the reading of that abstract will entertain you; for I can’t believe
that it will help you to unravel the mystery of Harold Monkhouse’s
death.”
“Well,” Thorndyke replied, as I rose to take my leave, “don’t let
your scepticism influence you. Keep in your mind the actual position.
In that house a man was poisoned, and almost certainly feloniously
poisoned. He must have been poisoned either by some one who
was an inmate of that house or by some one who had some sort of
access to the dead man from without. It is conceivable that the
entries in your diary may bring one or other such person into view.
Keep that possibility constantly before you; and fill your abstract with
irrelevancies rather than risk omitting anything from which we could
gather even the most shadowy hint.”
Chapter IX.
Superintendent Miller is Puzzled
On arriving at my chambers after my conference with Thorndyke I
found awaiting me a letter from a Maidstone solicitor offering me a
brief for a case of some importance that was to be tried at the
forthcoming assizes. At first, I read it almost impatiently, so
preoccupied was my mind with the tragedy in which I was involved. It
seemed inopportune, almost impertinent. But, in fact it was most
opportune, as I presently realized, in that it recalled me to the
realities of normal life. My duties to my friends I did, indeed, take
very seriously. But I was not an idle man. I had my way to make in
my profession and could not afford to drop out of the race, to
sacrifice my ambitions entirely, even on the altar of friendship.
I sat down and glanced through the instructions. It was a case of
alleged fraud, an intricate case which interested me at once and in
which I thought I could do myself credit; which was also the opinion
of the solicitor, who was evidently anxious for me to undertake it.
Eventually, I decided to accept the brief, and having written a letter to
that effect, I set myself to spend the remainder of the evening in
studying the instructions and mastering the rather involved details.
For time was short, since the case was down for hearing in a couple
of days’ time and the morrow would be taken up by my engagements
at Hilborough Square.
I pass over the incidents of the funeral. It was a dismal and
unpleasant affair, lacking all the dignity and pathos that relieve the
dreariness of an ordinary funeral. None of us could forget, as we sat
back in the mourning coach as far out of sight as possible, that the
corpse in the hearse ahead was the corpse of a murdered man, and
that most of the bystanders knew it. Even in the chapel, the majestic
service was marred and almost vulgarized by the self-consciousness
of the mourners and at the grave-side we found one another peering
furtively around for signs of recognition. To all of us it was a profound
relief, when we were once more gathered together in the drawing
room, to hear the street door close finally and the mourning carriage
rumble away down the square.
I took an early opportunity of mentioning the brief and I could see
that to both the women the prospect of my departure came as a
disagreeable surprise.
“How soon will you have to leave us?” Madeline asked, anxiously.
“I must start for Maidstone to-morrow morning,” I replied.
“Oh, dear!” she exclaimed. “How empty the place will seem and
how lost we shall be without you to advise us.”
“I hope,” said I, “that the occasions for advice are past, and I shall
not be so very far away, if you should want to consult me.”
“No,” said Barbara, “and I suppose you will not be away for very
long. Shall you come back when your case is finished or shall you
stay for the rest of the assizes?”
“I shall probably have some other briefs offered, which will detain
me until the assizes are over. My solicitor hinted at some other
cases, and of course there is the usual casual work that turns up on
circuit.”
“Well,” she rejoined, “we can only wish you good luck and plenty
of work, though we shall be glad when it is time for you to come
back; and we must be thankful that you were here to help us through
the worst of our troubles.”
The general tenor of this conversation, which took place at the
lunch table, was not, apparently, to Wallingford’s taste; for he sat
glumly consuming his food and rather ostentatiously abstaining from
taking any part in the discussion. Nor was I surprised; for the obvious
way in which both women leant on me was a reproach to his
capacity, which ought to have made my advice and guidance
unnecessary. But though I sympathized in a way with his
displeasure, it nevertheless made me a little uneasy. For there was
another matter that I wanted to broach; one in which he might
consider himself concerned; namely, my commission to Thorndyke. I
had, indeed, debated with myself whether I should not be wiser to
keep my own counsel on the subject; but I had decided that they
were all interested parties and that it would seem unfriendly and
uncandid to keep them in the dark. But, for obvious reasons, I did not
propose to acquaint them with Thorndyke’s views on the case.
The announcement, when I made it, was received without
enthusiasm, and Wallingford, as I had feared, was inclined to be
resentful.
“Don’t you think, Mayfield,” said he, “that you ought to have
consulted the rest of us before putting this private inquiry agent, or
whatever he is, on the case?”
“Perhaps I ought,” I admitted. “But it is important to us all that the
mystery should be cleared up.”
“That is quite true,” said Barbara, “and for my part, I shall never
rest until the wretch who made away with poor Harold is dragged out
into the light of day—that is, if there is really such a person; I mean,
if Harold’s death was not, after all, the result of some ghastly
accident. But is it wise for us to meddle? The police have the case in
hand. Surely, with all their experience and their machinery of
detection, they are more likely to be successful than a private
individual, no matter how clever he may be.”
“That,” I replied, “is, in fact, Dr. Thorndyke’s own view. He wished
to leave the inquiry to the police; and I may say that he will not come
into the case unless it should turn out that the police are unable to
solve the mystery.”
“In which case,” said Wallingford, “it is extremely unlikely that an
outsider, without their special opportunities, will be able to solve it.
And if he should happen to find a mare’s nest, we shall share the
glory and the publicity of his discovery.”
“I don’t think,” said I, “that you need have any anxiety on that
score. Dr. Thorndyke is not at all addicted to finding mare’s nests
and still less to publicity. If he makes any discovery he will probably
keep it to himself until he has the whole case cut and dried. Then he
will communicate the facts to the police; and the first news we shall
have on the subject will be the announcement that an arrest has
been made. And when the police make an arrest on Thorndyke’s
information, you can take it that a conviction will follow inevitably.”
“I don’t think I quite understand Dr. Thorndyke’s position,” said
Madeline. “What is he? You seem to refer to him as a sort of superior
private detective.”
“Thorndyke,” I replied, “is a unique figure in the legal world. He is
a barrister and a doctor of medicine. In the one capacity he is
probably the greatest criminal lawyer of our time. In the other he is,
among other things, the leading authority on poisons and on crimes
connected with them; and so far as I know, he has never made a
mistake.”
“He must be a very remarkable man,” Wallingford remarked, drily.
“He is,” I replied; and in justification of my statement, I gave a
sketch of one or two of the cases in which Thorndyke had cleared up
what had seemed to be a completely and helplessly insoluble
mystery. They all listened with keen interest and were evidently so
far impressed that any doubts as to Thorndyke’s capacity were set at
rest. But yet I was conscious, in all three, of a certain distrust and
uneasiness. The truth was, as it seemed to me, that none of them
had yet recovered from the ordeal of the inquest. In their secret
hearts, what they all wanted—even Barbara, as I suspected—was to
bury the whole dreadful episode in oblivion. And seeing this, I had
not the courage to remind them of their—of our position as the actual
suspected parties whose innocence it was Thorndyke’s function to
make clear.
In view of my impending departure from London, I stayed until the
evening was well advanced, though sensible of a certain impatience
to be gone; and when, at length, I took my leave and set forth
homeward, I was conscious of the same sense of relief that I had felt
on the previous day. Now, for a time, I could dismiss this horror from
my mind and let my thoughts occupy themselves with the activities
that awaited me at Maidstone; which they did so effectually that by
the time I reached my chambers, I felt that I had my case at my
fingers’ ends.
I had just set to work making my preparations for the morrow
when my glance happened to light on the glazed bookcase in which
the long series of my diaries was kept; and then I suddenly
bethought me of the abstract which I had promised to make for
Thorndyke. There would be no time for that now; and yet, since he
had seemed to attach some importance to it, I could not leave my
promise unfulfilled. The only thing to be done was to let him have the
diary, itself. I was a little reluctant to do this for I had never yet
allowed any one to read it. But there seemed to be no alternative;
and, after all, Thorndyke was a responsible person; and if the diary
did contain a certain amount of confidential matter, there was nothing
in it that was really secret or that I need object to any one reading.
Accordingly, I took out the current volume, and, dropping it into my
pocket, made my way round to King’s Bench Walk.
My knock at the door was answered by Thorndyke, himself, and
as I entered the room, I was a little disconcerted at finding a large
man seated in an easy chair by the fire with his back to me; and still
more so when, on hearing me enter, he rose and turned to confront
me. For the stranger was none other than Mr. Superintendent Miller.
His gratification at the meeting seemed to be no greater than
mine, though he greeted me quite courteously and even cordially. I
had the uncomfortable feeling that I had broken in on a conference
and began to make polite preparations for a strategic retreat. But
Thorndyke would have none of it.
“Not at all, Mayfield,” said he. “The superintendent is here on the
same business as you are, and when I tell him that you have
commissioned me to investigate this case, he will realize that we are
colleagues.”
I am not sure that the superintendent realized this so very vividly,
but it was evident that Thorndyke’s information interested him.
Nevertheless he waited for me and Thorndyke to make the opening
moves and only relaxed his caution by slow degrees.
“We were remarking when you came in,” he said, at length, “what
a curiously baffling case this is, and how very disappointing. At first it
looked all plain sailing. There was the lady who used to prepare the
special diet for the unfortunate man and actually take it up to him
and watch him eat it. It seemed as if we had her in the hollow of our
hand. And then she slipped out. The arsenic that was found in the
stomach seemed to connect the death with the food; but then there
was that confounded bottle of medicine that seemed to put the food
outside the case. And when we came to reckon up the evidence
furnished by the medicine, it proved nothing. Somebody put the
poison in. All of them had the opportunity, more or less, and all about
equally. Nothing pointed to one more than another. And that is how it
is all through. There is any amount of suspicion; but the suspicion
falls on a group of people, not on any one in particular.”
“Yes,” said Thorndyke, “the issues are most strangely confused.”
“Extraordinarily,” said Miller. “This queer confusion runs all
through the case. You are constantly thinking that you have got the
solution, and just as you are perfectly sure, it slips through your
fingers. There are lots of clues—fine ones; but as soon as you follow
one up it breaks off in the middle and leaves you gaping. You saw
what happened at the search, Mr. Mayfield.”
“I saw the beginning—the actual search; but I don’t know what
came of it.”
“Then I can tell you in one word. Nothing. And yet we seemed to
be right on the track every time. There was that secret drawer of Mr.
Wallingford’s. When I saw that packet of white powder in it, I thought
it was going to be a walk-over. I didn’t believe for a moment that the
stuff was cocaine. But it was. I went straight to our analyst to have it
tested.”
As the superintendent was speaking I caught Thorndyke’s eye,
fixed on me with an expression of reproachful inquiry. But he made
no remark and Miller continued: “Then there were those two empty
bottles. The one that I found in the library yielded definite traces of
arsenic. But then, whose bottle was it? The place was accessible to
the entire household. It was impossible to connect it with any one
person. On the other hand, the bottle that I found in Miss Norris’s
cupboard, and that was presumably hers—though she didn’t admit it
—contained no arsenic; at least the analyst said it didn’t, though as it
smelt of lavender and had a red stain at the bottom, I feel convinced
that it had had Fowler’s Solution in it. What do you think, Doctor?
Don’t you think the analyst may have been mistaken?”
“No,” Thorndyke replied, decidedly. “If the red stain had been due
to Fowler’s Solution there would have been an appreciable quantity
of arsenic present; probably a fiftieth of a grain at least. But Marsh’s
test would detect a much smaller quantity than that. If no arsenic
was found by a competent chemist who was expressly testing for it,
you can take it that no arsenic was there.”
“Well,” Miller rejoined, “you know best. But you must admit that it
is a most remarkable thing that one bottle which smelt of lavender
and had a red stain at the bottom, should contain arsenic, and that
another bottle, exactly similar in appearance and smelling of
lavender and having a red stain at the bottom, should contain no
arsenic.”
“I am entirely with you, Miller,” Thorndyke agreed. “It is a most
remarkable circumstance.”
“And you see my point,” said Miller. “Every discovery turns out a
sell. I find a concealed packet of powder—with the owner lying like
Ananias—but the powder turns out not to be arsenic. I find a bottle
that did contain arsenic, and there is no owner. I find another, similar
bottle, which has an owner, and there is no arsenic in it. Rum, isn’t
it? I feel like the donkey with the bunch of carrots tied to his nose.
The carrots are there all right, but he can never get a bite at ’em.”
Thorndyke had listened with the closest attention to the
superintendent’s observations and he now began a cautious cross-
examination—cautious because Miller was taking it for granted that I
had told him all about the search; and I could not but admire his
discretion in suppressing the fact that I had not. For, while
Thorndyke, himself, would not suspect me of any intentional
concealment, Miller undoubtedly would, and what little confidence he
had in me would have been destroyed. Accordingly, he managed the
superintendent so adroitly that the latter described, piecemeal, all the
incidents of the search.
“Did Wallingford say how he came to be in possession of all this
cocaine and morphine?” he asked.
“No,” replied Miller. “I asked him, but he refused to say where he
had got it.”
“But he could be made to answer,” said Thorndyke. “Both of
these drugs are poisons. He could be made to account for having
them in his possession and could be called upon to show that he
came by them lawfully. They are not ordinarily purchasable by the
public.”
“No, that’s true,” Miller admitted. “But is there any object in going
into the question? You see, the cocaine isn’t really any affair of ours.”
“It doesn’t seem to be,” Thorndyke agreed, “at least, not directly;
but indirectly it may be of considerable importance. I think you ought
to find out where he got that cocaine and morphine, Miller.”
The superintendent reflected with the air of having seen a new
light.
“I see what you mean, Doctor,” said he. “You mean that if he got
the stuff from some Chinaman or common dope merchant, there
wouldn’t be much in it; whereas, if he got it from some one who had
a general stock of drugs, there might be a good deal in it. Is that the
point?”
“Yes. He was able to obtain poisons from somebody, and we
ought to know exactly what facilities he had for obtaining poisons
and what poisons he obtained.”
“Yes, that is so,” said Miller. “Well, I will see about it at once.
Fortunately he is a pretty easy chappie to frighten. I expect, if I give
him a bit of a shake-up, he will give himself away; and if he won’t, we
must try other means. And now, as I think we have said all that we
have to say at present, I will wish you two gentlemen good night.”
He rose and took up his hat, and having shaken our hands, was
duly escorted to the door by Thorndyke; who, when he had seen his
visitor safely on to the stairs, returned and confronted me with a look
of deep significance.
“You never told me about that cocaine,” said he.
“No,” I admitted. “It was stupid of me, but the fact is that I was so
engrossed by your rather startling observations on the case that this
detail slipped my memory.
“And it really had not impressed me as being of any importance. I
accepted Wallingford’s statement that the stuff was cocaine and that,
consequently, it was no concern of ours.”
“I don’t find myself able to agree to that ‘consequently,’ Mayfield.
How did you know that the cocaine was no concern of ours?”
“Well, I didn’t see that it was, and I don’t now. Do you?”
“No; I know very little about the case at present. But it seems to
me that the fact that a person in this house had a considerable
quantity of a highly poisonous substance in his possession is one
that at least requires to be noted. The point is, Mayfield, that until we
know all the facts of this case we cannot tell which of them is or is
not relevant. Try to bear that in mind. Do not select particular facts as
important and worthy of notice. Note everything in any way
connected with our problem that comes under your observation and
pass it on to me without sifting or selection.”
“I ought not to need these exhortations,” said I. “However, I will
bear them in mind should I ever have anything more to
communicate. Probably I never shall. But I will say that I think Miller
is wasting his energies over Wallingford. The man is no favourite of
mine. He is a neurotic ass. But I certainly do not think he has the
makings of a murderer.”
Thorndyke smiled a little drily. “If you are able,” said he, “to
diagnose at sight a potential murderer, your powers are a good deal
beyond mine. I should have said that every man has the makings of
a murderer, given the appropriate conditions.”
“Should you really?” I exclaimed. “Can you, for instance, imagine
either of us committing a murder?”
“I think I can,” he replied. “Of course, the probabilities are very
unequal in different cases. There are some men who may be said to
be prone to murder. A man of low intelligence, of violent temper,
deficient in ordinary self-control, may commit a murder in
circumstances that would leave a man of a superior type unmoved.
But still, the determining factors are motive and opportunity. Given a
sufficient motive and a real opportunity, I can think of no kind of man
who might not commit a homicide which would, in a legal sense, be
murder.”
“But is there such a thing as a sufficient motive for murder?”
“That question can be answered only by the individual affected. If
it seems to him sufficient, it is sufficient in practice.”
“Can you mention a motive that would seem to you sufficient?”
“Yes, I can. Blackmail. Let us take an imaginary case. Suppose a
man to be convicted of a crime of which he is innocent. As he has
been convicted, the evidence, though fallacious, is overwhelming.
He is sentenced to a term of imprisonment—say penal servitude. He
serves his sentence and is in due course discharged. He is now free;
but the conviction stands against him. He is a discharged convict.
His name is in the prison books, his photograph and his finger-prints
are in the Habitual Criminals’ Register. He is a marked man for life.
“Now suppose that he manages to shed his identity and in some
place where he is unknown begins life afresh. He acquires the
excellent character and reputation to which he is, in fact, entitled. He
marries and has a family; and he and his family prosper and enjoy
the advantages that follow deservedly from his industry and excellent
moral qualities.
“And now suppose that at this point his identity is discovered by a
blackmailer who forthwith fastens on him, who determines to live on
him in perpetuity, to devour the products of his industry, to
impoverish his wife and children and to destroy his peace and
security by holding over his head the constant menace of exposure.
What is such a man to do? The law will help him so far as it can; but
it cannot save him from exposure. He can obtain the protection of
the law only on condition that he discloses the facts. But that
disclosure is precisely the evil that he seeks to avoid. He is an
innocent man, but his innocence is known only to himself. The fact,
which must transpire if he prosecutes, is that he is a convicted
criminal.
“I say, Mayfield, what can he do? What is his remedy? He has but
one; and since the law cannot really help him, he is entitled to help
himself. If I were in that man’s position and the opportunity presented
itself, I would put away that blackmailer with no more qualms than I
should have in killing a wasp.”
“Then I am not going to blackmail you, Thorndyke, for I have a
strong conviction that an opportunity would present itself.”
“I think it very probable,” he replied with a smile. “At any rate, I
know a good many methods that I should not adopt, and I think
arsenic poisoning is one of them. But don’t you agree with me?”
“I suppose I do, at least in the very extreme case that you have
put. But it is the only case of justifiable premeditated homicide that I
can imagine; and it obviously doesn’t apply to Wallingford.”
“My dear Mayfield,” he exclaimed. “How do we know what does
or does not apply to Wallingford? How do we know what he would
regard as an adequate motive? We know virtually nothing about him
or his affairs or about the crime itself. What we do know is that a
man has apparently been murdered, and that, of the various persons
who had the opportunity to commit the murder (of whom he is one)
none had any intelligible motive at all. It is futile for us to argue back
and forth on the insufficient knowledge that we possess. We can
only docket and classify all the facts that we have and follow up each
of them impartially with a perfectly open mind. But, above all, we
must try to increase our stock of facts. I suppose you haven’t had
time to consider that abstract of which we spoke?”
“That is really what brought me round here this evening. I haven’t
had time, and I shan’t have just at present as I am starting to-morrow
to take up work on the Southeastern Circuit. But I have brought the
current volume of the diary, itself, if you would care to wade through
it.”
“I should, certainly. The complete document is much preferable to
an abstract which might leave me in the dark as to the context. But
won’t you want to have your diary with you?”
“No, I shall take a short-hand note-book to use while I am away.
That is, in fact, what I usually do.”
“And you don’t mind putting this very confidential document into
the hands of a stranger?”
“You are not a stranger, Thorndyke. I don’t mind you, though I
don’t think I would hand it to anybody else. Not that it contains
anything that the whole world might not see, for I am a fairly discreet
diarist. But there are references to third parties with reflections and
comments that I shouldn’t care to have read by Thomas, Richard
and Henry. My only fear is that you will find it rather garrulous and
diffuse.”
“Better that than overcondensed and sketchy,” said he, as he
took the volume from me. He turned the leaves over, and having
glanced at one or two pages exclaimed: “This is something like a
diary, Mayfield! Quite in the classical manner. The common, daily
jottings such as most of us make, are invaluable if they are kept up
regularly, but this of yours is immeasurably superior. In a hundred
years’ time it will be a priceless historical work. How many volumes
of it have you got?”
“About twenty: and I must say that I find the older ones quite
interesting reading. You may perhaps like to look at one or two of the
more recent volumes.”
“I should like to see those recording the events of the last three
years.”

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Handbook of Aggregation Induced

Emission Volume 2 Typical AIEgens

Handbook of Aggregation Induced Emission Volume 1

Aggregation-Induced Emission (AIE): A Practical Guide

Orthopaedic Trauma Surgery: Volume 2: Lower Extremity

Diagnosis and Management of Primary Bone Tumors-Volume

Petroleum Refining Design and Applications Handbook:

Handbook of Research on Food Processing and

Handbook of Academic Integrity, 2nd Volume 2 2nd

Handbook of Archaeological Sciences 2 Volume Set 2nd

Volume 2 Typical AIEgens Design

Ben Zhong Tang

Limit of Liability/Disclaimer of Warranty

Library of Congress Cataloging-­in-­Publication data applied for

Hardback (Volume 2): 9781119642985

Cover Design: Wiley

Set in 9.5/12.5pt STIXTwoText by Straive, Pondicherry, India

List of Contributors xvii

1 Tetraphenylpyrazine-­based AIEgens: Synthesis and Applications 1

2 AIEgens Based on 9,10-­Distyrylanthracene (DSA): From Small Molecules

2.2.4.1 Fluorescent Probes for Chemical Sensing 41

3 Typical AIEgens Design: Salicylaldehyde Schiff Base 53

4 Diaminodicyanoquinodimethanes: Fluorescence Emission Enhancement

4.6.1 Electroluminescence and Nonlinear Optics 110

5 Aggregation-­induced Emission from the Sixth Main Group 119

6 Fluorescence Detection of Dynamic Aggregation Processes Using AIEgens:

7 Cyclic Triimidazole Derivatives: An Intriguing Family of Multifaceted

7.3 ­ alogenated Derivatives of Cyclic Triimidazole 175

8 Synthesis of Multi-­phenyl-­substituted Pyrrole (MPP)-­based AIE Materials

9 Development of a New Class of AIEgens: Tetraarylpyrrolo [3,2-­b]

10 Small Molecule Organogels from AIE Active α-­Cyanostilbenes 255

10.4 ­ timuli–Responsive Organogels 262

11 Stimuli-­responsive Pure Organic Luminescent Supramolecules 277

12 AIE Fluorescent Polymersomes 311

13 Designs for AIE Molecules and Functional Luminescent Materials Based on

14 Aggregation-­induced Emission (AIE) Active Metal–Organic Coordination

15 AIE-­type Luminescent Metal Nanoclusters 411

16 Aggregation-­induced Emission in Coinage Metal Clusters 443

17 Activated Alkynes in Metal-­free Bioconjugation 471

18 AIE-­active BODIPY Derivatives 493

19 Photochemistry-­regulated AIEgens and Their Applications 537

20 Design and Development of Naphthalimide Luminogens 559

Jan Balszuweit Yoshiki Chujo

Rongrong Hu Lathe A. Jones

Min-­Hui Li East China University of Science &

Siyu Sun Aijun Tong

Qiaofeng Yao Yue Zheng

Preface to Handbook of Aggregation-Induced Emission

Aggregation-­induced emission (AIE) describes a photophysical phenomenon in which molecular

Preface to Volume 2: Typical AIEgens Design

Youhong Tang, Flinders University, Australia

Tetraphenylpyrazine-­based AIEgens: Synthesis and Applications

Handbook of Aggregation-Induced Emission: Volume 2 Typical AIEgens Design, First Edition.

TPE Triphenylethene TPBD DSA

HPS PentaPP DP-BTO TPP

Chart 1.1 Molecular structures of AIEgens of tetraphenylethene (TPE), triphenylethene, tetraphenyl-­1,4-­

1.2 ­Synthesis of TPP-­based AIEgens

1.2.1 Cyclization Reaction

Condition 1: AcONH 4, Ac2O, AcOH, reflux

Route A Condition 2: AcONH 4, SnCl2 2H2O, solvent-free, 80 °C

Condition 3: AcONH 4, catalyst-free, solvent-free, 80 °C

Scheme 1.2 Current synthetic routes to TPP.

Scheme 1.3 Proposed mechanism of synthesizing TPP catalyzed by Mg and Cp2TiCl2.

Library of Congress Cataloging-in-Publication data applied for

1 Tetraphenylpyrazine-based AIEgens: Synthesis and Applications 1

2 AIEgens Based on 9,10-Distyrylanthracene (DSA): From Small Molecules

5 Aggregation-induced Emission from the Sixth Main Group 119

7.3 alogenated Derivatives of Cyclic Triimidazole 175

8 Synthesis of Multi-phenyl-substituted Pyrrole (MPP)-based AIE Materials

9 Development of a New Class of AIEgens: Tetraarylpyrrolo [3,2-b]

10 Small Molecule Organogels from AIE Active α-Cyanostilbenes 255

10.4 timuli–Responsive Organogels 262

11 Stimuli-responsive Pure Organic Luminescent Supramolecules 277

14 Aggregation-induced Emission (AIE) Active Metal–Organic Coordination

15 AIE-type Luminescent Metal Nanoclusters 411

16 Aggregation-induced Emission in Coinage Metal Clusters 443

17 Activated Alkynes in Metal-free Bioconjugation 471

18 AIE-active BODIPY Derivatives 493

19 Photochemistry-regulated AIEgens and Their Applications 537

Min-Hui Li East China University of Science &

Aggregation-induced emission (AIE) describes a photophysical phenomenon in which molecular

Tetraphenylpyrazine-based AIEgens: Synthesis and Applications

Chart 1.1 Molecular structures of AIEgens of tetraphenylethene (TPE), triphenylethene, tetraphenyl-1,4-

1.2 Synthesis of TPP-based AIEgens

1.3 Functionalities of TPP-based AIEgens

1.3.1 Organic Light-emitting Diodes

TPP–TPA (I) 482 3.7 17 459 5.49 3.18 2.88 —

1.3.3 Chiral Cage for Self-assembly to Achieve White-light Emission