Interfacial Supramolecular Assemblies

INTERFACIAL SUPRAMOLECULAR ASSEMBLIES......Page 4
Acknowledgments......Page 7
Contents......Page 8
1.1 Introductory Remarks......Page 16
1.2 Interfacial Supramolecular Chemistry......Page 17
1.4 Testing Contemporary Theory Using ISAs......Page 19
1.6 Formation and Characterization of Interfacial Supramolecular Assemblies......Page 20
Further Reading......Page 21
2.2 Electron Transfer......Page 24
2.2.1 Homogenous Electron Transfer......Page 25
2.2.2 Heterogeneous Electron Transfer......Page 36
2.3.1 Photochemistry and Photophysics of Supramolecular Materials......Page 43
2.3.2 Photoinduced Electron Transfer......Page 46
2.3.3 Photoinduced Energy Transfer......Page 48
2.3.4 Photoinduced Molecular Rearrangements......Page 51
2.4 Photoinduced Interfacial Electron Transfer......Page 56
2.4.1 Dye-Sensitized Photoinduced Electron Transfer at Metal Surfaces......Page 58
2.4.2 Dye-Sensitized Photoinduced Electron Transfer at Semiconductor Surfaces......Page 59
2.4.3 Photoinduced Interfacial Energy Transfer......Page 60
2.5 Elucidation of Excited-State Mechanisms......Page 61
References and Notes......Page 63
3.1 Structural Characterization of Interfacial Supramolecular Assemblies......Page 66
3.1.1 Scanning Probe Microscopy......Page 67
3.1.2 Scanning Electrochemical Microscopy......Page 68
3.1.3 Contact Angle Measurements......Page 70
3.1.4 Mass-Sensitive Approaches......Page 71
3.1.5 Ellipsometry......Page 74
3.1.6 Surface Plasmon Resonance......Page 75
3.1.7 Neutron Reflectivity......Page 77
3.2.1 Electrochemical Properties of an Ideal Redox-Active Assembly......Page 78
3.2.3 Effect of Lateral Interactions......Page 81
3.2.4 Diffusional Charge Transport through Thin Films......Page 82
3.2.5 Rotating Disk Voltammetry......Page 83
3.3 Spectroscopic Properties of Interfacial Supramolecular Assemblies......Page 85
3.3.1 Luminescence Spectroscopy......Page 86
3.3.2 Fluorescence Depolarization......Page 87
3.3.3 Epifluorescent and Confocal Microscopy......Page 88
3.3.4 Near-Field Scanning Optical Microscopy......Page 89
3.3.5 Raman Spectroscopy......Page 90
3.3.7 Single-Molecule Spectroscopy......Page 93
3.3.8 Spectroelectrochemistry......Page 94
3.3.9 Intensity-Modulated Photocurrent Spectroscopy......Page 95
3.4.1 Flash Photolysis......Page 96
3.4.2 Time-Resolved Luminescence Techniques......Page 97
3.4.3 Femtochemistry......Page 98
References......Page 100
4.1 Introduction......Page 102
4.2 Substrate Choice and Preparation......Page 104
4.3 Formation of Self-Assembled Monolayers......Page 105
4.3.1 Solution-Phase Deposition......Page 106
4.3.2 Electrochemical Stripping and Deposition......Page 108
4.3.3 Thermodynamics of Adsorption......Page 109
4.3.4 Double-Layer Structure......Page 114
4.3.5 Post-Deposition Modification......Page 119
4.4.1 Packing and Adsorbate Orientation......Page 120
4.4.2 Surface Properties......Page 123
4.5.1 General Voltammetric Properties of Redox-Active Monolayers......Page 124
4.5.2 Measuring the Defect Density......Page 125
4.6.1 Electrostatically Driven Assemblies......Page 127
4.6.3 Surfactant-Based Multilayer Assemblies......Page 130
4.7 Polymer Films......Page 132
4.7.1 Film Deposition Methods......Page 133
4.7.2 Synthetic Procedures for the Preparation of Redox-Active Polymers......Page 136
4.7.3 Synthetic Methods for the Preparation of Conducting Polymers......Page 141
4.8.1 Structural Assessment of Redox Polymers using Neutron Reflectivity......Page 149
4.8.2 Structural Features of Electrostatically Deposited Multilayer Assemblies......Page 153
4.8.3 Self-Assembled Monolayer Films of Thiol-Derivatized Polymers......Page 155
4.8.4 Structural Properties of Block Copolymers......Page 156
4.8.5 Domain Control with Styrene–Methyl Methacrylate Copolymers......Page 158
4.8.6 Structure–Conductivity Relationships for Alkylthiophenes......Page 159
4.9 Biomimetic Assemblies......Page 161
4.9.1 Protein Layers......Page 162
4.9.2 Biomolecule Binding to Self-Assembled Monolayers......Page 163
4.9.3 Redox Properties of Biomonolayers......Page 164
4.10 Conclusions......Page 165
References......Page 166
5.1 Introduction......Page 168
5.2 Electron and Energy Transfer Dynamics of Adsorbed Monolayers......Page 169
5.2.1 Distance Dependence of Electron Transfer......Page 170
5.2.2 Resonance Effects on Electron Transfer......Page 172
5.2.3 Electrode Material Effects on Electron Transfer......Page 177
5.2.4 Effect of Bridge Conjugation on Electron Transfer Dynamics......Page 180
5.2.5 Redox Properties of Dimeric Monolayers......Page 182
5.2.6 Coupled Proton and Electron Transfers in Monolayers......Page 184
5.2.7 Redox-Switchable Lateral Interactions......Page 189
5.2.8 Electron Transfer Dynamics of Electronically Excited States......Page 192
5.2.9 Conformational Gating in Monolayers......Page 195
5.2.11 Protein-Mediated Electron Transfer......Page 198
5.3 Nanoparticles and Self-Assembled Monolayers......Page 200
5.3.1 Conductivities of Single Clusters–Molecular Switching......Page 201
5.4.1 Microarray Electrodes......Page 202
5.4.3 Preconcentration and Selective Binding......Page 203
5.4.4 SAM-Based Biosensors......Page 204
5.4.5 Kinetic Separation of Amperometric Sensor Responses......Page 205
5.5 Light-Addressable Assemblies......Page 207
5.6 Surface–Photoactive Substrate Interactions......Page 208
5.8 Photocurrent Generation at Modified Metal Electrodes......Page 209
5.9 Photoinduced Molecular Switching......Page 214
5.10 Luminescent Films......Page 221
5.11 Photoinduced Processes in Bio-SAMs......Page 226
5.12 Photoinduced Electron and Energy Transfer in SAMs......Page 230
5.12.1 Distance Dependence of Photoinduced Electron and Energy Transfer......Page 231
5.12.2 Photoinduced Energy Transfer......Page 234
5.12.3 Monolayer Mobility and Substrate Roughness......Page 235
5.13 Multilayer Assemblies......Page 238
5.13.1 Photoinduced Charge Separation in Multilayers......Page 244
5.14 Electrochemistry of Thin Redox–Active Polymer films......Page 250
5.14.1 Homogeneous Charge Transport......Page 251
5.14.2 Electrochemical Quartz Crystal Microbalance Studies......Page 254
5.14.3 Interfacial Electrocatalysis......Page 255
5.15 Conclusions and Future Directions......Page 262
5.15.1 Challenges for the Next Decade......Page 263
References......Page 264
6.1 Introduction......Page 268
6.2.1 Electronic Properties of Bulk TiO(2)......Page 269
6.2.2 Electronic Properties of Nanoparticles......Page 271
6.2.3 Preparation and Structural Features of Nanocrystalline TiO(2) Surfaces......Page 274
6.3 Physical and Chemical Properties of Molecular Components......Page 277
6.3.1 Charge Separation at Nanocrystalline TiO(2) Surfaces......Page 282
6.4 Photovoltaic Cells Based on Dye-Sensitized TiO(2)......Page 284
6.5 Photoinduced Charge Injection......Page 288
6.5.2 Composition of Electrolyte......Page 290
6.5.3 The Effect of Redox Potential......Page 294
6.6.1 Ruthenium Phenothiazine Assembly......Page 295
6.6.2 Rhodium–Ruthenium Assembly......Page 297
6.6.3 Ruthenium Osmium Assembly......Page 301
6.7 Electrochemical Behavior of Nanocrystalline TiO(2) Surfaces......Page 306
6.7.1 Electrochromic Devices......Page 309
6.8 Alternative Semiconductor Substrates......Page 312
6.9 Concluding Remarks......Page 314
References......Page 315
7.2 Molecular Self-Assembly......Page 316
7.3 Molecular Components and Nanotechnology......Page 317
7.4 Biosystems......Page 318
7.5 ‘Smart Plastics’......Page 319
7.6 Interfacial Photochemistry at Conducting Surfaces......Page 320
7.8 Concluding Remarks......Page 321
Index......Page 324