Conjugated Objects: Developments, Synthesis, and Applications

555 Pages·2017·16.059 MB·English

by  Atsushi Nagai, Koji Takagi

Conjugated Objects

Pan Stanford Series on Renewable Energy — Volume 2
Conjugated Objects
Developments, Synthesis, and Applications
edited by
editors
Atsushi Nagai
Preben Maegaard
Anna Krenz
Koji Takagi
Wolfgang Palz
The Rise of Modern Wind Energy
Wind Power
for the World
Published by
Pan Stanford Publishing Pte. Ltd.
Penthouse Level, Suntec Tower 3
8 Temasek Boulevard
Singapore 038988
Email: [email protected]
Web: www.panstanford.com
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library.
Conjugated Objects: Developments, Synthesis, and Applications
All rights reserved. This book, or parts thereof, may not be reproduced in any form
Copyright © 2017 by Pan Stanford Publishing Pte. Ltd.
or by any means, electronic or mechanical, including photocopying, recording
or any information storage and retrieval system now known or to be invented,
without written permission from the publisher.
For photocopying of material in this volume, please pay a copying fee through
the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923,
USA. In this case permission to photocopy is not required from the publisher.
ISBN 978-981-4774-03-1 (Hardcover)
ISBN 978-1-315-22962-1 (eBook)
Printed in the USA
Contents
Preface
1. Un ique Electronic and Stereochemical Properties xv
of Salen Complexes 1
Takuya Kurahashi
1.1 Introduction 1
1.1.1 Syntheses of Salen Complexes 1
1.1.2 Salen Complex as an Asymmetric Catalyst 3
1.1.3 Role of a Redox-Active Salen Ligand in
Catalysis 4
1.1.4 Building Block for Multimetallic Systems 5
1.2 Electronic and Stereochemical Properties
Revealed by Experimental Studies 6
1.2.1 Role of Axial Ligands in Stereochemical
Properties 6
1.2.2 Characterization of Salen Ligand Radicals 11
1.2.3 Localized versus Delocalized Salen
Ligand Radicals 17
1.2.4 Stable Salen Ligand Radical with Cobalt 20
2. 1Fu.3s ed PoCloyncyclculisci oAnrosm atic Compounds: [n]Acenes, 21
[n]Helicenes, and Their Heterocyclic Analogues 25
Koji Nakano
n
2.1 Introduction 26
2.2 [ ]Acenes n 28
2.2.1 Introduction 28
2.2.2 Hydrocarbon [ ]Acenes 29
2.2.3 Hneteroacenes 32
2n.2.4 Semiconducting Properties of
[ ]Acenes and Heteroacenes 40
2.3 [ ]Helicenes n 42
2.3.1 Introduction 42
2.3.2 Hydrocarbon [ ]Helicenes 43
vi Contents
2.3.3 Heterohelicenes 48
2.4 Synthesis of Heteroacenes and Heterohelicenes
via Ring Construction by Carbon−Heteroatom
Bond Formation 51
2.4.1 Introduction 51
2.4.2 Heteroacene Synthesis via Ring
Construction Including Carbon−
Heteroatom Bond Formation 52
2.4.3 Heterohelicene Synthesis via Ring
Construction Including Carbon–
Heteroatom Bond Formation 56
3. 2Po.5ly (ortChoon-Pchluesniyolnesn e)s and Their Derivatives: 58
Synthesis, Conformation, and Physical Properties 67
Koichiro Mikami
ortho
3.1 Introduction 68
3.2 Synthesis of Oligo-/Poly( -Phenylene)s 69
3.2.1 Stepwise Synthesis through Transition
Metal–Mediated Reactions 69
3.2.2 Polymerization by Homocoupling
Reactions 70
3.2.3 Polymer Reactions 71
3.2.4 Direct Polymeroirztahtoion of Aromatic
Components 72
3.3 Conformationo orft hPooly( -Phenylene)s 74
3.3.1 Open and Closed Helix Models 74
3.3.2 Oligo( -Phenylene)s with
Disubsotritthuoted Side Chains on
Monomer Units 75
3.3.3 Oligo( -Phenylene)s with and
without Monosubstituted Side Chains
ortohno Monomer Units 77
3.4 Physical Properties and Applications of
Poly( -Phenylene)s 80
3.4.1 As a Surface Modifier for π-Conjugated
ortDhiosks 80
3.5 Poly(Quinoxaline-2,3-Diyl)s: “Cousin” of
Poly( -Phenylene)s 81
3.5.1 Synthesis of Poly(Quinoxaline-2,3-Diyl)s 81
Contents vii
3.5.2 Conformation of
Poly(Quinoxaline-2,3-Diyl)s 82
3.5.3 Circular Polarized Luminescence and
Reflection 83
3.5.4 Chiral Catalysts for Asymmetric
Reactions 84
4. 3El.e6c trocChoenmcilsutsryio onfs C aonndju Oguattleodo Pko lymers: Synthesis, 85
Properties, and Reactions 91
Shinsuke Inagi
4.1 Introd uction 91
4.2 Electrochemical Polymerization 93
4.2.1 Electro-Oxidative Polymerization of
Aromatic Monomers 93
4.2.2 Method of Electrochemical
Polymerization 94
4.2.3 Conditions for Electrochemical
Polymerization 96
4.2.4 Electrochemical Doping 96
4.2.5 Electroreductive Polymerization of
Aromatic Monomers 97
4.2.6 Copolymer Synthesis by
Electrochemical Methods 98
4.2.7 Application of Conducting Polymers 98
p
4.3 El.ectrochemical Postfunctionalization of
-Conjugated Polymers 99
43.1 Anodic Substitution Reaction of
Conducting Polymers 99
4.3.2 Cathodic Reaction and Paired Reactions 104
4.3.3 The CRS Method 106
5. 4Ch.4a in-GCroowncthlu Psoiolynms erization for the Synthesis of 107
π-Conjugated Polymers 113
Yoshihiro Ohta and Tsutomu Yokozawa
5.1 Introduction 113
5.2 Kumada–Tamao Coupling Polymerization 115
5.2.1 Mechanism 115
5.2.2 Initiators 117
viii Contents
5.2.3 Ligands of Catalysts 119
5.2.4 Monomers 120
5.3 Suzuki–Miyaura Coupling Polymerization 127
5.4 Other Methods 130
6. 5Sy.5n thesCiso onfc Pluoslyiothniso phene-Based Architectural 133
Macromolecules: Recent Progress in Controlled
Polymerization 139
Tomoya Higashihara
6.1 Introduction 140
6.2 Polythiophene 141
6.3 Regioregularity 142
6.4 Controlled Synthesis of Polythiophene 144
6.5 Chain-End-Functional Polythiophene 146
6.6 All-Conjugated Block Copolymers 150
6.7 Semiconjugated Block Copolymers 154
6.8 Conjugated Branched Polymers 157
7. 6Th.9r oughC-oSpnacclues-Cioonnsj ugated Compounds 116711
Yasuhiro Morisaki
7.1 Introduction 172
7.2 Synthesis of [2.2]Metacyclophane-Based
Through-Space-Conjugated Compounds 173
7.3 Synthesis of [2.2]Paracyclophane-Based
Through-Space-Conjugated Polymers 174
7.4 [2.2]Paracyclophane-Based Conjugated
Oligomers for Understanding Through-Space
Conjugation 176
7.5 [2.2]Paracyclophane-Based Through-Space-
Conjugated Polymers for Energy Transfer 179
7.6 [2.2]Paracyclophane-Based Through-Space-
Conjugated Oligomers for Unidpiraercational
Energy Torratnhosfer 182
7.7 Conjugation Length of Pseudo- - and
Pseudo- -Disubstituted
[2.2]Paracyclophanes 185
7.8 Conclusions 187
Contents ix
8. Synthesis, Structures, and Functions of Helical
π-Conjugated Polymers 193
Hiromitsu Sogawa, Kazuko Nakazono, and
Toshikazu Takata
8.1 Introduction 193
8.2 Polymerization Catalysts and Configurations
of Substituted Acetylenes 194
p
8.3 Dynamic Secondary Structures of
p
-Conjugated Polyacetylenes 197
p
8.4 Foldamer-Type -Conjugated Helical Polymers 203
8.5 Application of -Conjugated Helical Polymers 209
9. 8Co.6n trol Coof nSeclluf-sAisosnesm bling Behavior of Organic 213
Polymers via Charge Transfer (CT) Interaction of
π-Conjugated Planes 223
Kenta Kokado
9.1 Introd uction 224
9.2 Linea r Polymers Linked by CT Interaction 225
9.2.1 Porphyrin-Based Linear Polymers 226
9.2.2 TTF-Based Linear Polymers 228
9.2.3 Host-Stabilized CT-Based Linear
Polymers 231
9.3 Contr ol of Secondary Structure of Polymeric
Chains via CT Interaction 234
9.3.1 Folding Copolymer System with
Alternating Donor and Acceptor Units 235
9.3.2 Folding Homopolymer System
Affected by External Molecules 239
10. 9Li.q4u id CCryosntacllulinsieo Mnsa terials in Mesoscopic Scale 224563
Tomomichi Itoh
10.1 Introdu ction 253
10.2 What Is a Liquid Crystal? 254
10.2.1 Director Vector and Orientational
Order of LC Molecules 254
10.3 LC Molecules 256
10.3.1 Molecular Structure of a Liquid Crystal 256