Aggregation of Luminophores in Supramolecular Systems-From Mechanisms to Applications

221 Pages·34.644 MB·\221

Aggregation of Luminophores
in Supramolecular Systems

Aggregation of
Luminophores in
Supramolecular Systems
From Mechanisms to Applications
Neetu Tripathi
Manoj Kumar Goshisht
First edition published 2020
by CRC Press
6000 Broken Sound Parkway NW, Suite 300, Boca Raton, FL 33487-2742
and by CRC Press
2 Park Square, Milton Park, Abingdon, Oxon, OX14 4RN
© 2020 Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, LLC
Reasonable efforts have been made to publish reliable data and information, but the author and publisher
cannot assume responsibility for the validity of all materials or the consequences of their use. The authors
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ISBN: 9780367462437 (hbk)
ISBN: 9781003027706 (ebk)
Typeset in Times
by Lumina Datamatics Limited
Dedicated to Almighty God and our loving parents.
First edition published 2020
by CRC Press
6000 Broken Sound Parkway NW, Suite 300, Boca Raton, FL 33487-2742
and by CRC Press
2 Park Square, Milton Park, Abingdon, Oxon, OX14 4RN
© 2020 Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, LLC
Reasonable efforts have been made to publish reliable data and information, but the author and publisher
cannot assume responsibility for the validity of all materials or the consequences of their use. The authors
and publishers have attempted to trace the copyright holders of all material reproduced in this publication
and apologize to copyright holders if permission to publish in this form has not been obtained. If any
copyright material has not been acknowledged please write and let us know so we may rectify in any
future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted,
or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including
photocopying, microfilming, and recording, or in any information storage or retrieval system, without written
permission from the publishers.
For permission to photocopy or use material electronically from this work, access www.copyright.com or
contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400.
For works that are not available on CCC please contact [email protected]
Trademark notice: Product or corporate names may be trademarks or registered trademarks, and are used
only for identification and explanation without intent to infringe.
ISBN: 9780367462437 (hbk)
ISBN: 9781003027706 (ebk)
Typeset in Times
by Lumina Datamatics Limited

Contents
Preface.......................................................................................................................xi
Acknowledgment ...................................................................................................xiii
Authors .....................................................................................................................xv
Chapter 1 Supramolecular Chemistry: Preface ....................................................1
1.1 Introduction ...............................................................................1
1.2 Host-Guest Chemistry ...............................................................1
1.3 Aggregation: Introduction .........................................................2
1.3.1 Aggregation—Thermodynamics Point of View ............4
1.3.2 Aggregation—Kinetics Point of View ...........................5
1.4 Aggregation and Self-Assembly: Discrimination ......................5
References ............................................................................................9
Chapter 2 Intermolecular Interactions: Driving Forces for the Formation
of Supramolecular Structures .............................................................11
2.1 Introduction .............................................................................11
2.2 Ionic and Molecular Recognition ............................................11
2.3 Hydrogen Bonds ......................................................................12
2.4 Halogen Bond ..........................................................................13
2.5 Electrostatic Interactions .........................................................15
2.6 Ionic and Dipolar Interactions .................................................15
2.7 Charge Transfer Interactions ...................................................16
2.8 Coordination Interactions ........................................................18
2.9 Van der Waals Interactions ......................................................19
2.10 π-Interactions ...........................................................................21
2.11 Hydrophobic Effects ................................................................25
References ..........................................................................................26
Chapter 3 Stimuli Inducing Aggregation of Luminophores ...............................29
3.1 Introduction .............................................................................29
3.2 Solvent .....................................................................................29
3.3 Ion ............................................................................................31
3.4 Light.........................................................................................33
3.5 Heat ..........................................................................................37
3.6 Concentration ..........................................................................41
3.7 pH ............................................................................................41
3.8 Miscellaneous ..........................................................................45
References ..........................................................................................52
vii
viii Contents
Chapter 4 Photophysical Phenomenon of Aggregation ......................................55
4.1 Introduction .............................................................................55
4.1.1 Monomer .....................................................................55
4.1.2 H- vs. J-Aggregates .....................................................57
4.2 Aggregation-Induced Quenching ............................................58
4.3 Aggregation-Induced Emission ...............................................60
4.3.1 Aggregation-Induced Quenching and
Aggregation-Induced Emission Comparison ..............61
4.4 Aggregation-Induced Emission Enhancement ........................63
4.5 Aggregation-Induced Phosphorescence ..................................64
4.6 Aggregation-Induced Electrochemiluminescence ..................67
4.7 Aggregation-Induced Delayed Fluorescence ...........................68
4.8 Aggregation-Induced Energy Transfer ....................................71
4.9 Aggregation-Induced Photon Upconversion ............................72
4.10 Aggregation-Induced Resonance Raman Optical Activity .....73
References ..........................................................................................73
Chapter 5 Key Mechanisms That Generate New Spectroscopic
Properties of Aggregates ....................................................................79
5.1 Photo-Induced Electron Transfer (PET) ..................................79
5.2 Resonance Energy Transfer (RET) .........................................82
5.3 Electron Exchange or Dexter Interactions ...............................89
5.4 Intramolecular Charge Transfer ..............................................90
5.5 Excited-State Intramolecular Proton Transfer .........................92
5.6 Restriction of Intramolecular Rotation (RIR) .........................95
5.7 Restriction of Intramolecular Vibrations (RIV) ......................97
5.8 Restriction of Intramolecular Motions (RIM) .......................100
5.9 C=N Isomerization ................................................................101
References ........................................................................................104
Chapter 6 Aggregation of Luminophores: Examples .......................................107
6.1 Supramolecular Systems .......................................................107
6.1.1 Macrocycles ...............................................................107
6.1.1.1 Cyclophanes ................................................107
6.1.1.2 Cyclodextrins ..............................................110
6.1.1.3 Calix[n]arenes .............................................112
6.1.2 Metallocages ..............................................................113
6.1.3 Dendrimers ................................................................116
6.1.4 Supramolecular Polymers ..........................................119
6.1.5 Metal-Organic Frameworks (MOFs) .........................122
6.2 Short Oligomers .....................................................................126
6.3 Conjugated Polymers .............................................................127
6.4 Small Molecule Luminophores .............................................129
Contents ix
6.5 Bio-inspired Luminophores ....................................................131
6.6 Acyclic Structure with Dyes....................................................133
References ........................................................................................135
Chapter 7 Technological Applications ..............................................................139
7.1 Biological Sensing ...................................................................139
7.1.1 Biomolecular Sensing .................................................139
7.1.1.1 Sensing of Biogenic Small Molecules ..........139
7.1.1.2 Natural Macromolecules...............................142
7.1.2 Biological Imaging ......................................................146
7.1.2.1 Organic Nanoparticles (NPs) ........................147
7.1.2.2 Polymeric NPs ..............................................154
7.2 Chemical Sensing ....................................................................157
7.2.1 Ions ..............................................................................157
7.2.2 pH ................................................................................164
7.2.3 Gases ...........................................................................169
7.2.4 Explosives ....................................................................173
7.2.5 Fingerprints .................................................................176
7.3 Optoelectronic Systems ...........................................................179
7.3.1 Organic Light-Emitting Diodes (OLEDs) ...................179
7.3.2 Photovoltaics ...............................................................183
7.3.3 Liquid Crystals (LCs) ..................................................185
7.3.4 Organic Field-Effect Transistors (OFETs) ..................189
7.4 Applications in the Drug Delivery Field .................................191
References ........................................................................................197
Index ......................................................................................................................203