The Viologens Physicochemical Properties, Synthesis and Applications of the Salts of 4,4'-Bipyridine

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ISBN: 9780471986034 | 0471986038
Cover: Hardcover
Copyright: 1/7/1999

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The Viologens Physicochemical Properties, Synthesis and Applications of the Salts of 4,4'-Bipyridine Paul M. S. Monk Manchester Metropolitan University, UK Viologens are salts of 4,4'-bipyridine and are used in such fields as herbicides, electrochromism, solar energy conversion, molecular electronics and supramolecular chemistry. The Viologens is a comprehensive overview of the nature and physicochemical properties of the viologens and details the science behind the applications. Following a broad, discursive and self contained introduction to viologen chemistry, subsequent chapters develop the theory and present a detailed review of the most important properties and concepts in this field. A chapter on viologen synthesis is also included. This book is aimed at researchers in physical and organic chemistry, physics, materials science, biology and environmental engineering.

Introduction

xiii

(4)

Symbols and Abbreviations used in the Text

xvii

Chapter 1 Introduction and Overview

(31)

1.1 Introduction

(9)

1.1.1 The Three Common Redox Forms

(1)

1.1.1.1 Bipyridilium dications--bipm^(2+)

(1)

1.1.1.2 Bipyridilium radical cations--bipm^(+)

(5)

1.1.1.3 Di-reduced bipyridilium compounds--bipm^0

(1)

1.1.2 Other Bipyridilium Species

(1)

1.1.2.1 Di-hydrogen biypridilium compounds--h(2)bipm^0

(1)

1.1.2.2 Oxo-bipyridilium compounds

(1)

1.1.3 Polymeric Bipridilium Salts

(1)

1.1.4 Nuclear Substitution

(1)

1.2 Physical Properties of Bipyridilium Species

(7)

1.2.1 Radical Solubility

(2)

1.2.2 Dimerization of Bipyridilium Radical Cations

(2)

1.2.3 Adsorption

(1)

1.2.4 Association and Charge Transfer

(1)

1.2.5 Micelle Formation

(1)

1.2.6 Conductivity

(1)

1.3 Electron-transfer Reactions: Electrochemistry

(2)

1.3.1 The Comproportionation Reaction

(1)

1.4 Photochemistry

(1)

1.5 Applications of Bipyridilium Systems

(4)

1.5.1 Catalytic Production of Hydrogen from Water

(1)

1.5.2 Electrochromic Displays (ECDs)

(1)

1.5.3 Electron Mediation

(1)

1.5.4 Thin-film Mediators: Derivatised Electrodes for Preparative Electrochemistry

(1)

1.5.5 Phytotoxicity

(1)

1.5.6 Miscellaneous Uses of Bipyridilium Compounds

(1)

References

(8)

Chapter 2 Synthesis of Viologens

(23)

2.1 Pyridines

(1)

2.2 Bipyridine

(4)

2.2.1 Coupling Reactions with Sodium and its Alloys

(1)

2.2.2 Coupling Reactions with Zinc

(1)

2.2.3 Coupling Reactions with Nickel

(1)

2.2.4 Coupling Reactions with Magnesium

(1)

2.2.5 Coupling Reactions with Copper

(1)

2.2.6 Nuclear-substituted 4.4-Bipyridines

(2)

2.3 Viologen Dications

(5)

2.3.1 Dication from Quaternized 4.4-Bipyridine

(2)

2.3.2 Dication from Coupling of 1-Substituted Pyridinium Cations

(1)

2.3.3 Heteroatom Substitution at Nitrogen

(1)

2.3.3.1 Pyridinium N-Oxides

(1)

2.3.3.2 Pyridinium N-Imines and N-Nitroimine Compounds

(1)

2.4 Viologen Radical Cations

(1)

2.5 Di-reduced Viologen Compounds

(1)

2.6 Preparation of Viologen Polymers

(2)

2.7 Specimen Viologen Preparation Procedures

(6)

2.7.1 A Nuclear-Substituted Bipyridine: 2-Ethyl-4,4-Bipyridine

(1)

2.7.2 A Mono-Quaternized Bipyridine: 1-Benzyl-4-(4-Pyridyl)-Pyridinium Chloride

(1)

2.7.3 Methyl Viologen: 1,1'-Dimethyl-4,4'-Bipyridilium bis(Methosulphate)

(1)

2.7.4 1,1'Diheptyl-4,4'-Bipyridilium Dibromide

(1)

2.7.5 An Aryl-Substituted Viologen: 1,1'-bis (2,4-Dinitrophenyl)-4,4'-Bipyridilium Dichloride

(1)

2.7.6 An Aryl-Substituted Viologen Prepared by the Allen Reaction: 1,1'-bis (p-Cyanophenly) 4,4'-Bipyridilium Dichloride

(1)

2.7.7 A Cyclopyridinophane: Cyclobis (Parapheylene-4,4'-Bipyridilium) tetrakis (Perchlorate)

(1)

2.7.8 A Viologen Radical Cation: 1,1'-bis(p-Cyanophenyl)-4,4'-Bipyridilium Perchlorate Radical Cation

(1)

2.7.9 A Polyviologen: tetrakis(1',2',4',5'-Tetramethyl[1-(Methyl-4,4'-Bipyridilium)]Benzene) Tetrachloride Tetrabromide

(1)

References

(3)

Chapter 3 Spectroscopic Properties of Viologen Species

(10)

3.1 Electron Paramagnetic Resonance Spectroscopy

(2)

3.2 UV-Visible Spectroscopy

(1)

3.3 Vibrational Spectroscopy

(3)

3.4 Nuclear Magnetic Resonance Spectroscopy

(1)

References

(2)

Chapter 4 The Structure of Bipyridilium Species

(14)

4.1 The 1,1'-Dialkyl-4,4'-Bipyridilium Dication

(5)

4.2 Structure of CT adducts with TCNQ

(1)

4.3 The 1,1'-Diaryl-4,4'-Bipyridilium Dication

(1)

4.4 Structures of the Bipyridilium Radical Cation

(1)

4.5 Computed Structures of the Bipyridilium Dication and Radical Cation

(1)

4.6 4,4'-Bipyridine

(1)

4.7 Miscellaneous Structures: Cyclopyridinophanes and Use of 4,4'-Bipyridine as Bridging Ligand

(1)

References

(3)

Chapter 5 The Dication: Charge-transfer Equilibria

(36)

5.1 Introduction

(2)

5.2 Elementary Charge-transfer Theory

(5)

5.2.1 Parameters Obtained from CT Spectra

(3)

5.2.2 Determination of Charge-transfer Parameters

(1)

5.3 The Effects of Electrolyte Medium

(4)

5.3.1 Solvent Effects

(3)

5.3.2 The Effect of Ionic Strength

(1)

5.4 The Kinetics of Charge-transfer Complexation

(2)

5.5 Charge-transfer Complexes of Methyl Viologen

(12)

5.5.1 Solution-phase Complexation

(8)

5.5.2 Solid-state Complexes

101

(4)

5.6 Charge-transfer Complexes of Other Viologens than Methyl Viologen

105

(3)

5.6.1 Solution-phase Complexation

105

(1)

5.6.2 Solid-state Complexes

106

(1)

5.6.3 Intramolecular Charge Transfer

107

(1)

5.7 Intervalence Charge Transfer

108

(1)

5.8 Uses of Bipyridilium CT

109

(2)

5.8.1 Photo-excitation of a CT Band to from Radical Cation

109

(1)

5.8.2 Effect of CT on Biological Systems

110

(1)

5.8.3 Incorporation of Viologens in Zeolites

110

(1)

References

111

(4)

Chapter 6 The Radical Cation: Dimer Formation

115

(17)

6.1 Introduction: The Radical Cation

115

(1)

6.2 Dimerization of the Radical Cation

116

(1)

6.3 Thermodynamics of Dimerization

117

(4)

6.4 Kinetics of Dimerization

121

(3)

6.4.1 Kinetics of Dimer Dissociation

122

(2)

6.5 Dimerization and the Solid State

124

(1)

6.6 Structure of the Dimer

124

(6)

References

130

(2)

Chapter 7 The Di-reduced Bipyridilium Species: The Comproportionation Reaction

132

(16)

7.1 Introduction

132

(1)

7.2 Detection of the Comproportionation Reaction

133

(5)

7.2.1 Comproportionation Reactions: UV-Visible Spectroscopic Monitoring

133

(2)

7.2.2 Comproportionation Reactions: Raman Spectroscopic Monitoring

135

(1)

7.2.3 Comproportionation Reactions: Electrochemical Monitoring

135

(2)

7.2.4 Comproportionation Reactions: EPR Spectroscopic Monitoring

137

(1)

7.3 Thermodynamic Aspects of Comporportionation

138

(1)

7.4 Kinetic Aspects of Comproportionation

139

(1)

7.5 Mechanistic Aspects of Comproportionation

140

(6)

7.5.1 Background: Dimerization of the Radical Cation

140

(3)

7.5.2 Comproportionation with Dimer Formation Studied by RRDE

143

(1)

7.5.3 Comproportionation with Dimer Formation Studied by Spectroelectrochemistry

143

(1)

7.5.4 The Comproportionation Mechanism

144

(2)

References

146

(2)

Chapter 8 Adsorption of the Viologens

148

(13)

8.1 Introduction: Adsorption

148

(4)

8.2 Adsorption of Viologens on Metals

152

(5)

8.2.1 Adsorption on to Mercury

152

(2)

8.2.2 Adsorption of Viologens on Solid Metals

154

(3)

8.3 Role of Adsorption in the Mechanism of Electron Transfer

157

(1)

8.4 Adsorption of Viologens on Non-Metals

158

(1)

8.5 Adsorption of Viologens on Adsorbed Layers: Viologen Thin Films

158

(1)

References

159

(2)

Chapter 9 Electrochemistry and Electron-transfer Reactions

161

(47)

9.1 Introduction: Electrode Potentials

162

(20)

9.1.1 Correlations of E with Substituent Constants Sigma from Physical-Organic Chemistry

176

(6)

9.2 Dynamic Electrochemistry: Mechanism and Electrodeposition of Radical-cation Salts

182

(6)

9.3 Electron-transfer Theory: Electron-transfer to Viologen Redox states

188

(15)

9.3.1 Theory of Electron Transfer: Marcus Theory

188

(4)

9.3.2 Heterogeneous Rates of Electron Transfer,k(et) at an Electroded

192

(2)

9.3.3 Homogeneous Chemical Reduction of Bipm^(2+) Species

194

(2)

9.3.4 Homogeneous Chemical Oxidation of Bipm^(+) Species

196

(1)

9.3.5 Reduction of Bipm(2+) within an Ion Pair or Charge-transfer Complex; Intramolecular Electron Transfer

196

(1)

9.3.5.1 Electron transfer in Ion Pairs and Charge-Transfer Complexes

197

(4)

9.3.5.2 Intramolecular Electron Transfer

201

(5)

References

203

(5)

Chapter 10 Photochemistry of the Viologens and Solar-energy Conversion

208

(12)

10.1 Introduction

208

(1)

10.2 Photochemistry of Methyl Viologen

209

(1)

10.3 Photochemistry of Viologen Charge-transfer Complexes

210

(1)

10.3.1 Viologens in Solution

210

(1)

10.3.2 Viologens in the Solid State

211

(1)

10.4 Fluorescence of Viologen Species

211

(2)

10.5 Viologen-mediated Production of Molecular Hydrogen from Water

213

(4)

10.5.1 Photochemical Hydrogen Production from Di-reduced Methyl Viologen

217

(1)

10.6 Photochemistry at Solid Interfaces

217

(1)

References

217

(3)

Chapter 11 Electron Mediation, Herbicidal Activity and Toxicity

220

(19)

11.1 Introduction to Electron Mediation

220

(3)

11.2 Mediated Bio-electrochemistry

223

(6)

11.2.1 Cytochrome-c

225

(1)

11.2.2 Mediation of Ferredoxins and NAD-NADH

226

(1)

11.2.3 Reductase Enzymes

227

(1)

11.2.4 Immobilized Viologens as Mediators

228

(1)

11.2.5 Sensors Utilizing Electron Mediation

228

(1)

11.3 Viologens in Other Mediated Systems

229

(1)

11.3.1 Oxygen

229

(1)

11.4 Toxicity of Methyl Viologen

229

(4)

11.4.1 Phytotoxicity

229

(2)

11.4.2 Cytotoxicity

231

(2)

11.4.3 Reversal of the Paraquat Poisoning

233

(1)

11.4.4 Fatal Paraquat Poisoning

233

(1)

11.5 Toxicity of Other Viologens

233

(1)

References

234

(5)

Chapter 12 Electrochromism in Viologen-based Systems

239

(20)

12.1 Introduction: Electrochromism

239

(1)

12.2 Uses of Electrochromic Devices

240

(3)

12.3 The Design of Electrochromic Devices

243

(3)

12.4 Parameters Defining ECD Operation

246

(7)

12.4.1 Electrochrome Type

246

(1)

12.4.2 Contrast Ratio

247

(1)

12.4.3 Colouration Efficiency

248

(1)

12.4.4 Electrode Substrate

248

(1)

12.4.5 Response Time

248

(2)

12.4.6 Cycle Life

250

(1)

12.4.7 Write-Efficiency

250

(2)

12.4.8 Power Consumption

252

(1)

12.4.9 Polyelectrochromicity

252

(1)

12.5 Soluble-to-Insoluble Viologens for ECDS: Type-II Electrochromes

253

(3)

12.5.1 Inhibition of Viologen `Recrystallization'

254

(2)

References

256

(3)

Chapter 13 Solid-state Conductivity and use of Viologens in Molecular Electronics

259

(16)

13.1 Introduction: Conductivity

259

(5)

13.2 Conductivity of Viologen Systems

264

(6)

13.2.1 Conductivity of Viologen Redox Mixtures

265

(5)

13.3 Molecular Electronics of the Viologens

270

(3)

13.3.1 Applications Based on Conductivity Change

270

(2)

13.3.2 Molecular Electronics of Viologen-based Thin Films

272

(1)

References

273

(2)

Chapter 14 Supramolecular and Self Assembly Chemistry of the Viologens

275

(22)

14.1 Introduction

275

(2)

14.2 Simple Guest-Host Structures

277

(3)

14.2.1 Viologens as Guests

277

(1)

14.2.2 Viologens as Hosts: Cyclopyridinophanes

278

(2)

14.3 Catenanes

280

(2)

14.4 Rotaxanes

282

(8)

14.3.1 Pseudorotaxanes

288

(2)

14.4.2 Polyrotaxanes

290

(1)

14.5 Miscellaneous Self-assembly Structures

290

(2)

References

292

(5)

Chemical Index

297

(4)

Index

301

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The Viologens Physicochemical Properties, Synthesis and Applications of the Salts of 4,4'-Bipyridine

Summary

Author Biography

Table of Contents

Supplemental Materials

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The Viologens Physicochemical Properties, Synthesis and Applications of the Salts of 4,4'-Bipyridine

Summary

Author Biography

Table of Contents

Supplemental Materials

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