Conjugated Polymer Synthesis: Methods and Reactions

319 Pages·2010·4.313 MB·English

Edited by
Yoshiki Chujo
Conjugated Polymer
Synthesis
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Edited by
Yoshiki Chujo
Conjugated Polymer Synthesis
Methods and Reactions
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V
Contents
Preface XI
List of Contributors XIII
1 OrganometallicPolycondensationforConjugatedPolymers 1
TakakazuYamamoto
1.1 BasicOrganometallicC–CCoupling 1
1.2 Synthesesofp-ConjugatedPolymers 4
1.3 OpticalProperties 12
1.3.1 UV–VisData 12
1.3.2 Photoluminescence 14
1.3.3 OtherOpticalProperties 16
1.4 RedoxBehaviorandElectricalConductivity 16
1.5 LinearStructureandAlignmentontheSurfaceofSubstrates 19
1.6 StackingintheSolidandColloid 21
1.7 ChemicalReactivityandCatalysis 22
1.7.1 MetalComplexesandModificationofNitrogen 22
1.8 ElectronicandOpticalDevices(ECD,Battery,EL,Diode,Transistor,
NonlinearOpticalDevice,etc.) 24
1.8.1 RedoxFunctions 24
1.8.2 ElectronicandOpticalDevices 25
1.9 Conclusions 25
References 26
2 Catalyst-TransferCondensationPolymerizationforPrecision
Synthesisofp-ConjugatedPolymers 35
TsutomuYokozawa
2.1 Introduction 35
2.2 Kumada–TamaoCouplingPolymerizationwith
NiCatalyst 36
ConjugatedPolymerSynthesis.EditedbyYoshikiChujo
Copyright(cid:1)2010WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim
ISBN:978-3-527-32267-1
VI Contents
2.2.1 Polythiophene 36
2.2.1.1 DiscoveryandMechanismofCatalyst-TransferCondensation
Polymerization 36
2.2.1.2 AVarietyofMonomers 39
2.2.1.3 BlockPolythiophenes 40
2.2.1.4 BlockCopolymersofPolythiopheneandOtherPolymers 42
2.2.1.5 GraftCopolymers 45
2.2.2 Polyphenylenes 48
2.2.3 Polypyrroles 50
2.2.4 PolyfluorenesandPolycarbazoles 51
2.3 Suzuki–MiyauraCouplingPolymerizationwithPdCatalyst 53
2.3.1 Polyfluorenes 53
2.3.2 Polyphenylenes 54
2.4 Conclusion 55
References 55
3 RegioregularandRegiosymmetricPolythiophenes 59
ItaruOsakaandRichardD.McCullough
3.1 Introduction 59
3.2 SynthesisofPolythiopheneandRegioirregular
Polythiophenes 59
3.3 Head-to-TailCoupledRegioregularPoly(3-Alkylthiophene)s 61
3.3.1 DesignandSynthesisofrrP3ATs 61
3.3.1.1 McCulloughMethod 62
3.3.1.2 RiekeMethod 64
3.3.1.3 GRIMMethod 64
3.3.1.4 Palladium-CatalyzedPolymerizationMethods 64
3.3.2 MechanismoftheNickel-CatalyzedPolymerization 65
3.4 SideChainFunctionalizedHTRegioregular
Polythiophenes 66
3.4.1 Heteroatom-ContainingGroups 68
3.4.2 Aromatic-ContainingGroup 69
3.4.3 ChiralGroups 69
3.4.4 c-FunctionalizedGroups 70
3.5 EndGroupFunctionalizedHTRegioregularPolythiophenes 70
3.5.1 PostpolymerizationEndGroupFunctionalization 70
3.5.2 InSituEndGroupFunctionalization 71
3.6 BlockCopolymersDerivedfromHTRegioregular
Polythiophenes 72
3.6.1 All-ConjugatedBlockCopolymers 73
3.6.2 Conjugated–Non-ConjugatedBlockCopolymers 76
3.7 UniversalUseoftheGRIMMethod 80
3.8 RegiosymmetricPolythiophenes 85
3.9 Summary 86
References 87
Contents VII
4 FunctionalHyperbranchedPolymersConstructedfromAcetylenic
An-TypeBuildingBlocks 91
JianzhaoLiu,JackyW.Y.Lam,andBenZhongTang
4.1 Introduction 91
4.2 HyperbranchedPolymersConstructedfromAcetylenicA -Type
n
BuildingBlocks 94
4.2.1 HyperbranchedPoly(Alkylenephenylene)s(hb-PAPs) 94
4.2.1.1 Synthesis 94
4.2.1.2 Structures 96
4.2.1.3 Properties 98
4.2.2 HyperbranchedPoly(Arylenephenylene)s(hb-PArPs) 100
4.2.2.1 Synthesis 100
4.2.2.2 Structures 102
4.2.2.3 Properties 103
4.2.3 HyperbranchedPoly(Aroylphenylene)s(hb-PAkPs)
andPoly(Aroxycarbonylphenylene)s(hb-PAePs) 106
4.2.3.1 Synthesis 108
4.2.3.2 Structures 110
4.2.3.3 Properties 112
4.2.4 HyperbranchedPolytriazoles(hb-PTAs) 114
4.2.4.1 Synthesis 114
4.2.4.2 Structures 115
4.2.4.3 Properties 116
4.2.5 HyperbranchedPoly(Aryleneethynylene)s(hb-PAEs) 117
4.2.5.1 Synthesis 117
4.2.5.2 Properties 117
4.2.6 HyperbranchedPolydiynes(hb-PDYs) 119
4.2.6.1 Synthesis 119
4.2.6.2 ThermalCuring 121
4.2.6.3 MicropatternFormation 122
4.2.6.4 MetalComplexation 123
4.2.6.5 MagneticCeramization 125
4.3 Conclusions 127
References 128
5 Through-SpaceConjugatedPolymers 133
YasuhiroMorisakiandYoshikiChujo
5.1 Introduction 133
5.2 Through-SpaceConjugatedPolymerswiththeLayeredp-Electron
SystemsintheSideChain 134
5.2.1 Polyacenaphthylene 134
5.2.2 Polydibenzofulvene 134
5.2.3 Polybenzofulvene 135
5.2.4 Polystyrene-graft-Poly(4-Phenylquinoline) 137
5.2.5 [3.2]Paracyclophane-ContainingPolymer 138
VIII Contents
5.2.6 Polymethylenewith[2.2]Paracyclophane 139
5.3 Through-SpaceConjugatedPolymerswiththeLayeredp-Electron
SystemsintheMainChain 143
5.3.1 Phenylene-LayeredPolymerBasedonaNorbornaneScaffold 143
5.3.2 AromaticRing-LayeredPolymersBasedonaXantheneScaffold 144
5.3.2.1 [2.2]Paracyclophane-LayeredPolymer 144
5.3.2.2 Oligophenylene-LayeredPolymers 148
5.3.2.3 Ferrocene-LayeredPolymersBasedonaNaphthaleneScaffold 148
5.3.3 Cyclophane-ContainingThrough-SpaceConjugatedPolymers 149
5.3.3.1 [2.2]Metacyclophane-ContainingThrough-SpaceConjugated
Polymers 149
5.3.3.2 [2.2]Paracyclophane-ContainingThrough-SpaceConjugated
Polymers 151
5.4 Conclusion 159
References 160
6 FullyConjugatedNano-SizedMacrocycles:SynthesesandVersatile
Properties 165
MasayoshiTakaseandMasahikoIyoda
6.1 Introduction 165
6.2 Synthesisofp-ConjugatedMacrocycles 166
6.2.1 One-PotSynthesisofPhenylacetyleneMacrocycles 166
6.2.2 TemplateSynthesisofMacrocycles 170
6.2.3 SynthesisofConjugatedThiophene,Porphyrin,andHeteroarylene
Macrocycles 170
6.3 IsolationandSelf-AssociationinSolutionandintheSolidState 183
6.4 VersatilePropertiesofGiantp-ConjugatedMacrocycles 185
6.5 Conclusion 188
References 190
7 OrganoboronConjugatedPolymers 195
AtsushiNagaiandYoshikiChujo
7.1 Introduction 195
7.2 TricoordinateBoronp-ConjugatedPolymers 196
7.2.1 HydroborationPolymerizationofDiyneMonomers 196
7.2.2 Tin–BoronExchangePolymerizationofBis(Trimethylsilyl)
Monomer 198
7.2.3 Haloboration–PhenylborationPolymerizationofDiyneMonomers 199
7.2.4 PolycondensationofAryldimethoxyboraneUsingGrignard
andOrganolithiumReagents 199
7.2.5 StepwiseReactionfromBoraanthracene 200
7.3 TetracoordinateBoronp-ConjugatedPolymers 201
7.3.1 p-ConjugatedPoly(Cyclodiborazane)s 201
7.3.2 Poly(Pyrazabole)s 203
7.3.3 p-ConjugatedOrganoboronQuinolatePolymers 204
Contents IX
7.3.4 p-ConjugatedOrganoboronDiketonatePolymer 206
7.3.5 p-ConjugatedBODIPY-BasedPolymers 207
7.4 p-ConjugatedCarborane-BasedPolymers 209
7.5 Conclusions 210
References 211
8 RecentDevelopmentsinp-ConjugatedMacromolecules
withPhosphorusAtomsintheMainChain 215
PaulW.SiuandDerekP.Gates
8.1 Introduction 215
8.2 Poly(Phosphole)andRelatedPolymers 215
8.3 Poly(p-Phenylenephosphine)andRelatedPolymers 221
8.4 Poly(Vinylenephosphine)sandRelatedPolymers 222
8.5 Poly(p-Phenylenephosphaalkene)sandRelatedPolymers 223
8.6 Poly(p-Phenylenediphosphene)sandRelatedPolymers 225
8.7 Summary 226
References 226
9 Organo-Arsenic,Phosphorus,andAntimonyConjugatedPolymers 229
KensukeNakaandYoshikiChujo
9.1 Introduction 229
9.2 SurveyofGroup15Element-ContainingPolymers 230
9.3 Carbon–MainGroupElementBondFormationViaBismetallation 230
9.4 HomocyclicCompoundsofGroup15Elements 231
9.5 Poly(Vinylene-Arsine)s 234
9.6 Poly(Vinylene-Phosphine)s 237
9.7 Poly(Vinylene-Stibine)s 238
9.8 PeriodicTerpolymerizationofCyclooligoarsine,Cyclooligostibine,
andanAcetylenicCompound 239
9.9 Stability 240
9.10 OpticalProperties 241
9.11 CoordinationAbilityofPoly(Vinylene-Arsine)sTowards
TransitionMetalIons 242
9.12 Cross-LinkedPoly(Vinylene-Arsine)s 244
9.13 Conclusion 246
References 247
10 SyntheticStrategiestoConjugatedMain-ChainMetallopolymers 251
AndreasWild,AndreasWinter,MartinD.Hager,andUlrichS.Schubert
10.1 Introduction 251
10.2 p-ConjugatedPolymerswithTerpyridineUnitsandOtherTridentate
LigandsasPartoftheMainChain 254
10.3 p-ConjugatedPolymerswithPorphyrinUnitsasPartoftheMain
Chain 259
10.4 Rigid-RodPolymetallaynes 268
X Contents
10.5 ConclusionandOutlook 273
References 274
11 HelicalPolyacetylenePreparedinaLiquidCrystalField 289
KazuoAkagi
11.1 Introduction 289
11.2 ChiralDopantsandChiralNematicLCs 290
11.3 AcetylenePolymerizationinChiralNematicLC 292
11.4 CharacterizationofHelicalPolyacetyleneFilm 293
11.5 Summary 298
References 299
Index 303