Advances in Inorganic Chemistry (eBook)

Cover 1
Copyright page 5
Contents 6
Preface 10
Chapter 1. Self-Assembled Metallo-Supramolecular Systems Incorporating ß-Diketone Motifs as Structural Elements 14
I. Introduction 14
II. Simple ß-Diketone Ligands and Their Complexes 15
III. Supramolecular Systems Incorporating ß-Diketone Motifs 19
IV. Concluding Remarks 46
References 46
Chapter 2. Coordination Polymer Open Frameworks Constructed of Macrocyclic Complexes 52
I. Introduction 52
II. Design Strategies for the Construction of Porous Coordination Polymers 56
III. Porosity 72
IV. Guest Binding Properties 76
V. Single-Crystal-to-Single-Crystal Transformations and Sensing Properties 82
VI. Redox Properties 85
VII. Summary 89
Acknowledgments 89
References 90
Chapter 3. Molecular Devices Based on Metallocyclam Subunits 94
I. Some Peculiar Properties of Metal Complexes of Cyclam 94
II. The Template Synthesis of Cyclam and Azacyclams 97
III. Scorpionands and Scorpionate Complexes 100
IV. Sensors and Dosimeters Based on the Cyclam Motif 104
V. An Anion Sensor for Citrate 109
VI. A Molecular Fluorescent Thermometer Operating Through the NiII/NiIII Redox Change 114
VII. Conclusion 118
References 118
Chapter 4. Molecular Recognition of Neutral and Charged Guests using Metallomacrocyclic Hosts 122
I. Introduction 122
II. Mononuclear Clefts for Binding Neutral Molecules 124
III. Metallomacrocyclic Clefts with Two Appended Receptor Sites for Ditopic Recognition 138
IV. Interactions Between Polyoxoanions and Macrocyclic Cations 168
V. Summary 176
Acknowledgments 178
References 178
Chapter 5. Supramolecular Chemistry of Environmentally Relevant Anions 188
I. Introduction 188
II. Structure and Binding 191
III. Extraction Studies 201
IV. Conclusions 212
Acknowledgments 213
References 213
Chapter 6. Role of Cation Complexants in the Synthesis of Alkalides and Electrides 218
I. Introduction 218
II. Thermodynamics 224
III. Complexant Properties 227
IV. Synthesis Methodology 232
V. Structural Features of Alkalides 234
VI. Electrides – Anionic or Electronic? 237
VII. Possible Future Developments 240
References 241
Chapter 7. Structure–Activity studies and the Design of Synthetic Superoxide Dismutase (SOD) Mimetics as Therapeutics 246
I. Introduction 246
II. Background 247
III. Initial Structure Activity Studies – Catalyst/Drug Design 248
IV. Development of Improved SOD Mimetics Derived from [Mn([15]aneN5)Cl2], Ia. 250
V. Mechanistic Studies 256
VI. Computer-Aided Design (CAD) 258
VII. Continuing Developments 266
VIII. Conclusion 272
IX. Experimental 274
References 274
Chapter 8. Electronic Tuning of the Lability of Inert Co(III) and Pt(II) Complexes 278
I. Electronic Tuning 278
II. Inert Co(III) Complexes 280
III. Inert Pt(II) Complexes 297
IV. Conclusions 320
Acknowledgments 320
References 321
Index 324
Contents of Previous Volumes 328