Hirao Redox Systems Under Nano-Space Control

1. Auflage 2006
ISBN: 978-3-540-29580-8
Verlag: Springer-Verlag
Format: PDF
Kopierschutz: Adobe DRM (»Systemvoraussetzungen)

E-Book, Englisch, 292 Seiten

This is the first book to examine redox systems using the novel principle of nano-space control, one of the most exciting fields in contemporary inorganic and supramolecular chemistry. The authors review the newest research on novel redox systems, showing how they can produce hybrid conjugated systems composed of transition and synthetic metals, metallohosts, redox-active self-assembled monolayers of helical peptides, metal-assisted DNA based pairs, photoactive antibody systems, chiral rotaxanes, and redox-active imprinted polymers. In the future, these systems will be the basis for novel selective electron-transfer reactions as well as new functional materials and catalysts.

Autoren/Hrsg.

Hirao, Toshikazu

Inhaltsverzeichnis

1;Contents;6
2;List of Contributors;13
3;Part I Redox Systems via d,p-Conjugation;17
3.1;Conjugated Complexes with Quinonediimine Derivatives;18
3.1.1;1.1;19
3.1.2;Introduction;19
3.1.3;1.2;20
3.1.4;Architecturally Controlled Formation of Conjugated Complexes;20
3.1.5;with 1,4-Benzoquinonediimines;20
3.1.6;1.3;32
3.1.7;Redox-Switching Properties of Conjugated Complexes;32
3.1.8;with 1,4-Benzoquinonediimines;32
3.1.9;1.4;39
3.1.10;Conclusion;39
3.1.11;1.5;40
3.1.12;References;40
3.2;Realizing the Ultimate Amplification in Conducting Polymer Sensors: Isolated Nanoscopic Pathways;43
3.2.1;Abbrevations;43
3.2.2;2.1;43
3.2.3;Dimensionality in Molecular-Wire Sensors;43
3.2.4;2.2;46
3.2.5;Analyte-Triggered Barrier Creation in Conducting Polymers;46
3.2.6;2.3;48
3.2.7;Isolated Nanoscopic Pathways;48
3.2.8;2.4;48
3.2.9;Langmuir–Blodgett Approaches to Nanofibrils;48
3.2.10;2.5;51
3.2.11;Molecular Scaffolds for the Isolation of MolecularWires;51
3.2.12;2.6;57
3.2.13;Summary and Future Prospects;57
3.2.14;2.7;57
3.2.15;References;57
3.3;Metal-Containing;59
3.4;ConjugatedMaterials;59
3.4.1;Abbreviations;59
3.4.2;3.1;60
3.4.3;Introduction;60
3.4.4;3.2;61
3.4.5;Metal-Complex-Containing Conjugated Materials;61
3.4.6;3.3;65
3.4.7;Metal-Nanoparticle-Containing Conjugated Materials;65
3.4.8;3.4;66
3.4.9;Applications;66
3.4.10;3.5;67
3.4.11;Conclusions;67
3.4.12;3.6;67
3.4.13;References;67
3.5;Redox Active Architectures and Carbon- Rich Ruthenium Complexes asModels forMolecularWires;69
3.5.1;Abbreviations;69
3.5.2;4.1;70
3.5.3;Introduction;70
3.5.4;4.2;71
3.5.5;Ruthenium Allenylidene and Acetylide Building Blocks: Basic Properties;71
3.5.6;4.3;77
3.5.7;Bimetallic Complexes fromthe Ru(dppe);77
3.5.8;System;77
3.5.9;4.4;85
3.5.10;Connection of Two Carbon-Rich Chains with the Ruthenium System;85
3.5.11;4.5;88
3.5.12;Trimetallic and Oligomeric Metal Complexes with Carbon-Rich Bridges;88
3.5.13;4.6;91
3.5.14;Star Organometallic-Containing Multiple Identical Metal Sites;91
3.5.15;4.7;93
3.5.16;Conclusion;93
3.5.17;4.8;93
3.5.18;References;93
3.6;Molecular MetalWires Built from a Linear Metal Atom Chain Supported by Oligopyridylamido Ligands;99
3.6.1;Abbreviations;99
3.6.2;5.1;100
3.6.3;Introduction;100
3.6.4;5.2;101
3.6.5;Synthesis of Oligopyridylamine Ligands;101
3.6.6;5.3;104
3.6.7;Dimerization by Self-Complementary Hydrogen Bonding;104
3.6.8;5.4;105
3.6.9;Complexation of Oligopyridylamine Ligands;105
3.6.10;5.5;105
3.6.11;Mono- and Dinuculear Complexes;105
3.6.12;5.6;106
3.6.13;Structures of Linear Multinuclear Nickel Complexes;106
3.6.14;5.7;112
3.6.15;Structures of Linear Multinuclear Cobalt Complexes;112
3.6.16;5.8;114
3.6.17;Structures of Linear Multinuclear Chromium Complexes;114
3.6.18;5.9;117
3.6.19;Structures of Triruthenium and Trirhodium Complexes;117
3.6.20;5.10;118
3.6.21;Complexes ofModified Ligands;118
3.6.22;5.11;119
3.6.23;Electrochemical Properties of the Complexes;119
3.6.24;5.12;126
3.6.25;Scanning Tunneling Microscopy Studies;126
3.6.26;5.13;128
3.6.27;Summary;128
3.6.28;5.14;129
3.6.29;References;129
3.7;Multielectron Redox Catalysts in Metal- Assembled Macromolecular Systems;132
3.7.1;Abbreviations;132
3.7.2;6.1;132
3.7.3;Introduction;132
3.7.4;6.2;133
3.7.5;Multielectron Redox Systems;133
3.7.6;6.3;135
3.7.7;Multinuclear Complexes as Redox Catalysts;135
3.7.8;6.4;136
3.7.9;Macromolecule-Metal Complexes;136
3.7.10;6.5;137
3.7.11;Metal Ion Assembly on Dendritic Macromolecules;137
3.7.12;6.6;142
3.7.13;Conclusion;142
3.7.14;6.7;142
3.7.15;References;142
4;Part II Redox Systems via Coordination Control;144
4.1;Triruthenium Cluster Oligomers that ShowMultistep/ Multielectron Redox Behavior;145
4.1.1;7.1;145
4.1.2;Introduction;145
4.1.3;7.2;147
4.1.4;Syntheses of Oligomers 1 and 2;147
4.1.5;7.3;148
4.1.6;Redox Behavior of 1 and 2;148
4.1.7;7.4;151
4.1.8;Conclusion;151
4.1.9;7.5;151
4.1.10;References;151
4.2;Molecular Architecture of Redox- Active Multilayered Metal Complexes Based on Surface Coordination Chemistry;153
4.2.1;Abbreviations;153
4.2.2;8.1;153
4.2.3;Introduction;153
4.2.4;8.2;154
4.2.5;Fabrication of Multilayer Nanoarchitectures;154
4.2.6;by Surface Coordination Chemistry;154
4.2.7;8.3;160
4.2.8;Chemical Functions of Redox-ActiveMultilayered Complexes on Surface;160
4.2.9;8.4;165
4.2.10;Conclusion;165
4.2.11;8.5;165
4.2.12;References;165
4.3;Programmed Metal Arrays by Means of Designable Biological Macromolecules;167
4.3.1;Abbreviations;167
4.3.2;9.1;167
4.3.3;Introduction;167
4.3.4;9.2;168
4.3.5;DNA-Directed Metal Arrays;168
4.3.6;9.3;173
4.3.7;Peptide-Directed Metal Arrays;173
4.3.8;9.4;176
4.3.9;Conclusion;176
4.3.10;9.5;176
4.3.11;References;176
4.4;Metal-Incorporated Hosts for Cooperative and Responsive Recognition to External Stimulus;178
4.4.1;Abbreviations;178
4.4.2;10.1;178
4.4.3;Introduction;178
4.4.4;10.2;179
4.4.5;Pseudomacrocycles for Cooperative Molecular Functional Systems;179
4.4.6;10.3;183
4.4.7;Oligo( N2O2- Chelate) Macrocycles;183
4.4.8;10.4;185
4.4.9;Acyclic Oligo( N2O2- Chelate) Ligands;185
4.4.10;10.5;188
4.4.11;Conclusion;188
4.4.12;10.6;188
4.4.13;References;188
4.5;Synthesis of Poly(binaphthol) via Controlled Oxidative Coupling;190
4.5.1;Abbreviations;190
4.5.2;11.1;190
4.5.3;Introduction;190
4.5.4;11.2;192
4.5.5;Asymmetric Oxidative Coupling with Dinuclear Metal Complexes;192
4.5.6;11.3;194
4.5.7;Oxidative Coupling Polymerization of Phenols;194
4.5.8;11.4;195
4.5.9;Oxidative Coupling Polymerization of 2,3-Dihydroxynaphthalene;195
4.5.10;11.5;199
4.5.11;Conclusion;199
4.5.12;11.6;199
4.5.13;References;199
5;Part II Redox Systems via Molecular Chain Control;201
5.1;Nano Meccano;202
5.1.1;Abbreviations and Symbols;202
5.1.2;12.1;203
5.1.3;Introduction;203
5.1.4;12.2;205
5.1.5;Redox-Controllable Molecular Switches in Solution;205
5.1.6;12.3;210
5.1.7;Application of Redox-Controllable Molecular Machines in Electronic Devices;210
5.1.8;12.4;213
5.1.9;Application of Redox-Controllable Molecular Machines in Mechanical Devices;213
5.1.10;12.5;220
5.1.11;Conclusions;220
5.1.12;12.6;221
5.1.13;References;221
5.2;Through-Space Control of Redox Reactions Using Interlocked Structure of Rotaxanes;224
5.2.1;Abbreviations;224
5.2.2;13.1;224
5.2.3;Introduction;224
5.2.4;13.2;226
5.2.5;Redox Behavior and Conformation of Ferrocene-End-Capped Rotaxane;226
5.2.6;13.3;234
5.2.7;Reduction of Ketone by Rotaxane Bearing a Dihydronicotinamide Group;234
5.2.8;13.4;239
5.2.9;Conclusion;239
5.2.10;13.5;240
5.2.11;References;240
5.3;Metal-Containing Star and Hyperbranched Polymers;242
5.3.1;Abbreviations;242
5.3.2;14.1;242
5.3.3;Introduction;242
5.3.4;14.2;244
5.3.5;Metal-Containing Star Polymers;244
5.3.6;14.3;252
5.3.7;Metal-Containing Hyperbranched Polymers;252
5.3.8;14.4;254
5.3.9;Concluding Remarks;254
5.3.10;14.5;255
5.3.11;References;255
5.4;Electronic Properties of Helical Peptide Derivatives at a Single Molecular Level;257
5.4.1;15.1;257
5.4.2;Molecular Electronics;257
5.4.3;15.2;258
5.4.4;Electron Transfer Through Molecules;258
5.4.5;15.3;259
5.4.6;Electronic Properties of Helical Peptides;259
5.4.7;15.4;262
5.4.8;Electron Transfer Mechanism over a Long Distance;262
5.4.9;15.5;262
5.4.10;Effect of Linkers on Electron Transfer;262
5.4.11;15.6;264
5.4.12;Helical-Peptide Scaffold for Electron Hopping;264
5.4.13;15.7;267
5.4.14;Photocurrent Generation with Helical Peptides Carrying Naphthyl Groups;267
5.4.15;15.8;269
5.4.16;Conclusion;269
5.4.17;15.9;269
5.4.18;References;269
5.5;Construction of Redox-Induced Systems Using Antigen- Combining Sites of Antibodies and Functionalization of Antibody Supramolecules;271
5.5.1;Abbreviations;271
5.5.2;16.1;272
5.5.3;Introduction;272
5.5.4;16.2;274
5.5.5;Photoinduced Electron Transfer from Porphyrins;274
5.5.6;to Electron Acceptor Molecules;274
5.5.7;16.3;283
5.5.8;Peroxidase Activity of Fe-Porphyrin-Antibody Complexes;283
5.5.9;16.4;290
5.5.10;Dendritic Antibody Supramolecules;290
5.5.11;16.5;293
5.5.12;Linear Antibody Supramolecules: Application for Novel Biosensing Method;293
5.5.13;16.6;297
5.5.14;Conclusions;297
5.5.15;16.7;298
5.5.16;References;298
6;Subject Index;300