Interfacial Supramolecular Assemblies

, by Vos, Johannes G.; Forster, Robert J.; Keyes, Tia E.

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ISBN: 9780471490715 | 0471490717
Cover: Hardcover
Copyright: 3/14/2003

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Describes the supramolecular properties of molecular assemblies that contain a solid phase, offering an integrated approach to measurement and addressibility. * Offers an integrated approach to measurement and addressibility. * Features case studies describing the major devices developed using this technology. * The prospects for the future of interfacial supramolecular assemblies are considered.

Introduction

(8)

Introductory Remarks

(1)

Interfacial Supramolecular Chemistry

(2)

Objectives of this Book

(1)

Testing Contemporary Theory Using ISAs

(1)

Analysis of Structure and Properties

(1)

Formation and Characterization of Interfacial Supramolecular Assemblies

(1)

Electron and Energy Transfer Properties

(1)

Interfacial Electron Transfer Processes at Modified Semiconductor Surfaces

(3)

Further Reading

(3)

Theoretical Framework for Electrochemical and Optical Processes

(42)

Introduction

(1)

Electron Transfer

(19)

Homogenous Electron Transfer

(11)

Heterogeneous Electron Transfer

(7)

Photoinduced Processes

(13)

Photochemistry and Photophysics of Supramolecular Materials

(3)

Photoinduced Electron Transfer

(2)

Photoinduced Energy Transfer

(3)

Photoinduced Molecular Rearrangements

(5)

Photoinduced Interfacial Electron Transfer

(5)

Dye-Sensitized Photoinduced Electron Transfer at Metal Surfaces

(1)

Dye-Sensitized Photoinduced Electron Transfer at Semiconductor Surfaces

(1)

Photoinduced Interfacial Energy Transfer

(1)

Elucidation of Excited-State Mechanisms

(2)

Conclusions

(3)

References and Notes

(3)

Methods of Analysis

(36)

Structural Characterization of Interfacial Supramolecular Assemblies

(12)

Scanning Probe Microscopy

(1)

Scanning Electrochemical Microscopy

(2)

Contact Angle Measurements

(1)

Mass-Sensitive Approaches

(3)

Ellipsometry

(1)

Surface Plasmon Resonance

(2)

Neutron Reflectivity

(1)

Voltammetric Properties of Interfacial Supramolecular Assemblies

(7)

Electrochemical Properties of an Ideal Redox-Active Assembly

(3)

The Formal Potential

(1)

Effect of Lateral Interactions

(1)

Diffusional Charge Transport through Thin Films

(1)

Rotating Disk Voltammetry

(2)

Interfacial Capacitance and Resistance

(1)

Spectroscopic Properties of Interfacial Supramolecular Assemblies

(11)

Luminescence Spectroscopy

(1)

Fluorescence Depolarization

(1)

Epifluorescent and Confocal Microscopy

(1)

Near-Field Scanning Optical Microscopy

(1)

Raman Spectroscopy

(3)

Second Harmonic Generation

(1)

Single-Molecule Spectroscopy

(1)

Spectroelectrochemistry

(1)

Intensity-Modulated Photocurrent Spectroscopy

(1)

Time-Resolved Spectroscopy of Interfacial Supramolecular Assemblies

(4)

Flash Photolysis

(1)

Time-Resolved Luminescence Techniques

(1)

Femtochemistry

(2)

Conclusions

(2)

References

(2)

Formation and Characterization of Modified Surfaces

(66)

Introduction

(2)

Substrate Choice and Preparation

(1)

Formation of Self-Assembled Monolayers

(15)

Solution-Phase Deposition

(2)

Electrochemical Stripping and Deposition

(1)

Thermodynamics of Adsorption

(5)

Double-Layer Structure

(5)

Post-Deposition Modification

104

(1)

Structural Characterization of Monolayers

105

(4)

Packing and Adsorbate Orientation

105

(3)

Surface Properties

108

(1)

Electrochemical Characterization

109

(3)

General Voltammetric Properties of Redox-Active Monolayers

109

(1)

Measuring the Defect Density

110

(2)

Multilayer Formation

112

(5)

Electrostatically Driven Assemblies

112

(3)

Ordered Protein Layers

115

(1)

Surfactant-Based Multilayer Assemblies

115

(2)

Polymer Films

117

(17)

Film Deposition Methods

118

(3)

Synthetic Procedures for the Preparation of Redox-Active Polymers

121

(5)

Synthetic Methods for the Preparation of Conducting Polymers

126

(8)

Structural Features and Structure--Property Relationships of Thin Polymer Films

134

(12)

Structural Assessment of Redox Polymers using Neutron Reflectivity

134

(4)

Structural Features of Electrostatically Deposited Multilayer Assemblies

138

(2)

Self-Assembled Monolayer Films of Thiol-Derivatized Polymers

140

(1)

Structural Properties of Block Copolymers

141

(2)

Domain Control with Styrene--Methyl Methacrylate Copolymers

143

(1)

Structure--Conductivity Relationships for Alkylthiophenes

144

(2)

Biomimetic Assemblies

146

(4)

Protein Layers

147

(1)

Biomolecule Binding to Self-Assembled Monolayers

148

(1)

Redox Properties of Biomonolayers

149

(1)

Conclusions

150

(3)

References

151

(2)

Electron and Energy Transfer Dynamics

153

(100)

Introduction

153

(1)

Electron and Energy Transfer Dynamics of Adsorbed Monolayers

154

(31)

Distance Dependence of Electron Transfer

155

(2)

Resonance Effects on Electron Transfer

157

(5)

Electrode Material Effects on Electron Transfer

162

(3)

Effect of Bridge Conjugation on Electron Transfer Dynamics

165

(2)

Redox Properties of Dimeric Monolayers

167

(2)

Coupled Proton and Electron Transfers in Monolayers

169

(5)

Redox-Switchable Lateral Interactions

174

(3)

Electron Transfer Dynamics of Electronically Excited States

177

(3)

Conformational Gating in Monolayers

180

(3)

Electron Transfer within Biosystems

183

(1)

Protein-Mediated Electron Transfer

183

(2)

Nanoparticles and Self-Assembled Monolayers

185

(2)

Conductivities of Single Clusters -- Molecular Switching

186

(1)

Electroanalytical Applications

187

(5)

Microarray Electrodes

187

(1)

Selective Permeation

188

(1)

Preconcentration and Selective Binding

188

(1)

SAM-Based Biosensors

189

(1)

Kinetic Separation of Amperometric Sensor Responses

190

(2)

Light-Addressable Assemblies

192

(1)

Surface--Photoactive Substrate Interactions

193

(1)

Photoactive Self-Assembled Monolayers

194

(1)

Photocurrent Generation at Modified Metal Electrodes

194

(5)

Photoinduced Molecular Switching

199

(7)

Luminescent Films

206

(5)

Photoinduced Processes in Bio-SAMs

211

(4)

Photoinduced Electron and Energy Transfer in SAMs

215

(8)

Distance Dependence of Photoinduced Electron and Energy Transfer

216

(3)

Photoinduced Energy Transfer

219

(1)

Monolayer Mobility and Substrate Roughness

220

(3)

Multilayer Assemblies

223

(12)

Photoinduced Charge Separation in Multilayers

229

(6)

Electrochemistry of Thin Redox--Active Polymer films

235

(12)

Homogeneous Charge Transport

236

(3)

Electrochemical Quartz Crystal Microbalance Studies

239

(1)

Interfacial Electrocatalysis

240

(7)

Conclusions and Future Directions

247

(6)

Challenges for the Next Decade

248

(1)

References

249

(4)

Interfacial Electron Transfer Processes at Modified Semiconductor Surfaces

253

(48)

Introduction

253

(1)

Structural and Electronic Features of Nanocrystalline TiO2 Surfaces

254

(8)

Electronic Properties of Bulk TiO2

254

(2)

Electronic Properties of Nanoparticles

256

(3)

Preparation and Structural Features of Nanocrystalline TiO2 Surfaces

259

(3)

Physical and Chemical Properties of Molecular Components

262

(7)

Charge Separation at Nanocrystalline TiO2 Surfaces

267

(2)

Photovoltaic Cells Based on Dye-Sensitized TiO2

269

(4)

Photoinduced Charge Injection

273

(7)

External Factors which Affect Photoinduced Charge Injection

275

(1)

Composition of Electrolyte

275

(4)

The Effect of Redox Potential

279

(1)

Interfacial Supramolecular Assemblies

280

(11)

Ruthenium Phenothiazine Assembly

280

(2)

Rhodium--Ruthenium Assembly

282

(4)

Ruthenium Osmium Assembly

286

(5)

Electrochemical Behavior of Nanocrystalline TiO2 Surfaces

291

(6)

Electrochromic Devices

294

(3)

Alternative Semiconductor Substrates

297

(2)

Concluding Remarks

299

(2)

References

300

(1)

Conclusions and Future Directions

301

(8)

Conclusions -- Where to from Here. . . . . .?

301

(1)

Molecular Self-Assembly

301

(1)

Molecular Components and Nanotechnology

302

(1)

Biosystems

303

(1)

`Smart Plastics'

304

(1)

Interfacial Photochemistry at Conducting Surfaces

305

(1)

Modified Semiconductor Surfaces

306

(1)

Concluding Remarks

306

(3)

Index

309

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Interfacial Supramolecular Assemblies

Summary

Author Biography

Table of Contents

Supplemental Materials