Table Of ContentFunctional Supramolecular Materials
From Surfaces to MOFs
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Monographs in Supramolecular Chemistry
Series Editors:
Philip Gale, The University of Sydney, Australia
Jonathan Steed, Durham University, UK
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F Titles in this Series:
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7 1: Cyclophanes
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1 2: Calixarenes
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8 3: Crown Ethers and Cryptands
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8 4: Container Molecules and Their Guests
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9/ 5: Membranes and Molecular Assemblies: The Synkinetic Approach
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10 6: Calixarenes Revisited
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1 7: Self-assembly in Supramolecular Systems
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d 8: Anion Receptor Chemistry
org | 9: Boronic Acids in Saccharide Recognition
sc. 10: Calixarenes: An Introduction, 2nd Edition
bs.r 11: Polymeric and Self Assembled Hydrogels: From Fundamental
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htt 12: Molecular Logic-based Computation
on 13: Supramolecular Systems in Biomedical Fields
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1 14: Synthetic Receptors for Biomolecules: Design Principles and
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0 16: Boron: Sensing, Synthesis and Supramolecular Self-Assembly
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sh 18: Pillararenes
ubli 19: Supramolecular Chemistry at Surfaces
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20: Aromatic Interactions: Frontiers in Knowledge and Application
21: Naphthalenediimide and its Congeners: From Molecules to Materials
22: Functional Supramolecular Materials: From Surfaces to MOFs
How to obtain future titles on publication:
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Functional Supramolecular
Materials
From Surfaces to MOFs
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78 Edited by
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doi: EPUBeISBN:978-1-78801-141-9
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F Preface
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0.1 Supramolecular chemistry and crystal engineering are two extremely well
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oi: known,aswellasrelevant,subjectsinmoderndayscience.Supramolecular
g | d materials have great potential in materials science, as the reversibility of
or intermolecularinteractionscancreatenewfunctionsthatareunavailablein
c.
s.rs covalently bonded materials. This book highlights multiple aspects of
ub structure and function in organic as well as metal organic supramolecular
p
p:// materials. It also highlights the chemical functions of supramolecular
htt materials.Thechaptersofthisbookwillprovideanoverviewoforganicand
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o metal organic supramolecular materials (from surfaces to MOFs) and their
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01 assembly at various length scales (including the formation of 2D-polymers
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y and molecular cages) and how this determines their usage for novel appli-
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5 cations in molecular recognition, catalysis, light harvesting and environ-
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n mental remediation. This book will also provide an idea about the role of
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d intermolecular interactions in the solid state and solution state supra-
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s molecular self-assembly. Another highlight of this book will be the role of
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u chemical bonding on the molecular and supramolecular architectures.
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This book consists of 12 chapters that have been contributed by leading
expertsinthefieldofstructuralchemistry,coveringtheareasofsurfaceself-
assembly,softsupramolecularmaterials,supramolecularreceptors,electron
transfer reactions, morphology control and solid-state photo-reactivity,
new devices with tunable electrical and optical properties, bio-materials,
supramolecular polyhedral capsules and cages and metal organic frame-
works. As the development of new materials is key to the continuous
improvement of the performance of organic and metal organic supra-
molecular materials, a significant portion of this book have been dedicated
to discussing the design concept and synthesis of novel organic and metal
organic supramolecular materials for diverse applications.
MonographsinSupramolecularChemistryNo.22
FunctionalSupramolecularMaterials:FromSurfacestoMOFs
EditedbyRahulBanerjee
rTheRoyalSocietyofChemistry2017
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
v
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vi Preface
Champness and Yang describe how intermolecular interactions can be
exploited to control molecular organisation on surfaces, demonstrating
the use of hydrogen bonds, van der Waals interactions, metal–ligand
coordinationandcovalentcouplingtoconstructlow-dimensionalstructures
on surfaces. The idea behind the design of soft supramolecular materials
05 using intermolecular interactions and guest binding within the supra-
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P molecular capsular assemblies are covered in detail by Dastidar and co-
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76- workers and Ghosh et al. in Chapters 2 and 3 respectively. Photochemistry
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10 featuresheavilyinthenexttwochaptersbyMukhopadhyayetal.,andQuah
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88 and Vittal on supramolecular materials for electron transfer reactions and
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81 photo-reactivity in solid-state supramolecular materials. Nidamanuri and
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9/9 Saha in Chapter 6 and D’Alessandro et al. in Chapter 7 describe framework
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0 materialsforelectrical,opticalandphotoconduction.Maetal.inChapter8
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10. describe the structure-based evolution of porous biomaterials. Comparing
oi: andcontrastingthecontrolledreleasefromtheseporousbiomaterialsisan
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g | area of active debate. This aspect of ‘‘Intrinsic vs. Extrinsic Porosity’’ has
or
c. beendiscussedbyGreenandLloydinChapter9.Researchonmetalorganic
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s.r frameworks (MOFs) and covalent organic frameworks (COFs) continues to
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p evolve rapidly and has recently seen new applications in areas such as
http:// storage and separation, conduction and catalysis. In the last three chapters
n of this book, Clegg et al., Arab and El-Kaderi and Maji et al. discuss many
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7 new examples from their own research and the literature.
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2 I would like to thank Professor Jonathan W. Steed and Professor Philip
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Ma Gale for their invitation to contemplate a book project on the topic of
05 ‘‘FunctionalSupramolecularMaterials:FromSurfacetoMOFs’’fortheRoyal
on Society of Chemistry series Monographs in Supramolecular Chemistry, and
d
he RowanFrame,KatieMorrey,RachelWoodandHarrietManningattheRoyal
s
bli Society of Chemistry for their support throughout the production of the
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P book. I sincerely thank all the authors of the chapters for their time and
sincere efforts as well as their commitment to this project. I sincerely
hope that this book will be of interest among undergraduate and graduate
students, research scholars, academicians (including technical service
providers) and industrial chemists interested in supramolecular chemistry
and materials science.
IdedicatethisbooktoProfessorGautamR.Desirajuontheoccasionofhis
65th birthday.
Rahul Banerjee
CSIR-National Chemical Laboratory
India
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05 Symmetry 26
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Chapter 2 Designing Soft Supramolecular Materials Using
Intermolecular Interactions 37
Parthasarathi Dastidar, Rajdip Roy, Rumana Parveen,
Sumi Ganguly, Joydeb Majumder and Mithun Paul
2.1 Introduction 37
2.2 Designing LMWGs 38
2.2.1 Molecular Engineering Approach 39
2.2.2 Crystal Engineering Approach 46
MonographsinSupramolecularChemistryNo.22
FunctionalSupramolecularMaterials:FromSurfacestoMOFs
EditedbyRahulBanerjee
rTheRoyalSocietyofChemistry2017
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
vii
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viii Contents
2.3 Metallogels 63
2.4 Summing Up and Future Direction 65
Acknowledgements 68
References 69
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htt 3.7 Anion Recognition with Tripodal Pyridinium
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Chapter 4 Functional Molecular and Supramolecular Materials for
Electron Transfer Reactions and their Applications 110
Sudhir Kumar Keshri, Srikanta Dana, M. R. Ajayakumar,
Deepak Asthana and Pritam Mukhopadhyay
4.1 Introduction 110
4.2 Tetracyanoquinodimethanes 112
4.2.1 Introduction to Tetracyanoquinodimethanes 112
4.2.2 TCNQ-based Radical Anion and Dianion 113
4.3 Arylenediimides 116
4.3.1 Introduction to NDIs 118
4.3.2 ET Reactions of NDI 119
4.3.3 Electron Delocalization/Stabilization by
Noncovalent Means in NDI Radical Ions 121
4.3.4 PhotochemicalReactionsandPhotoexcitation
of NDIs and NDI Radical Ions 125
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Contents ix
4.4 Perylenediimides 128
4.4.1 Introduction to PDIs 128
4.4.2 Electron Injection and Transport With PDIs 130
4.4.3 ET Reactions of PDIs 135
4.4.4 ET in PDI-based Supramolecular Systems 141
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doi: 4.7 Applications 155
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5.2.1 Role of Argentophilic Interactions
Influencing the Photoreactivity in Ag(I)
Complexes 182
5.2.2 Argentophilic Interactions versus
Donor–Acceptor Interactions 184
5.2.3 Intra versus Intermolecular Photoreaction:
Influence of C–H(cid:2)(cid:2)(cid:2)p Interactions 185
5.3 Ligand Design in Controlling Photoreactivity of
1,2-Bi(4-pyridyl)ethylene (bpe) Pairs 187
5.4 Diphosphine Ligands as Clipping Agents 187
5.4.1 Photoreactive Gold(I) Macrocycles 188
5.5 Photoreactive Organometallic Cages and
Molecular Rectangles 189
5.5.1 Organometallic Rectangles Containing
Bisimidazolate Derivatives 189
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5.5.2 Photoreactive Organometallic Rectangles
Containing Oxalate Ligands 190
5.5.3 Unusual Formation of tpcb Isomer from the
Crisscrossed Alignment of bpe in
Photoreactive Organometallic Cages 191
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org | Anthracene Derivatives 194
sc. 5.7 Unusual Fusion of Interlocked Cages by [2þ2]
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htt Cycloaddition of Metal Complexes 197
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5.9 PhotoreactivePolymorphsofCo-crystalsContaining
aMetalComplexandanOrganicMoleculeYielding
Two Different Cyclobutane Isomers 200
5.9.1 Photoreactivity in Similar Metal Complexes
with Asymmetrical Bipyridyl Spacer Ligand 202
5.10 Photoreactive Zwitter Ionic Metal Complexes
Containing bpe-H1 Cationic Ligand 202
5.11 Making the Terminal Ligands of the Metal
Complexes Photoreactive 204
5.11.1 Photoreactivity of 4-Strylpyridine Ligands
in Metal Complexes 204
5.11.2 Unusual Solid-state Intermolecular
Phenyl–Olefin Dimerization in a Zn(II)
Complex 206
5.12 Photosalient Behaviour of Photoreactive Metal
Complexes 207
