Metallofoldamers

List of Contributors xi

Foreword xiii

Preface xv

1 Metalloproteins and Metallopeptides - Natural Metallofoldamers 1
Vasiliki Lykourinou and Li-June Ming

1.1 Introduction 1

1.2 Metalloproteins 2

1.3 Metallopeptides 12

1.4 Conclusion and Perspectives 28

Acknowledgements 30

References 30

2 Introduction to Unnatural Foldamers 51
Claudia Tomasini and Nicola Castellucci

2.1 General Definition of Foldamers 51

2.2 Biotic Foldamers 53

2.3 Abiotic Foldamers 70

2.4 Organization Induced by External Agents 72

2.5 Applications 78

2.6 Conclusions and Outlook 81

References 81

3 Self-Assembly Principles of Helicates 91
Josef Hamacek

3.1 Introduction 91

3.2 Thermodynamic Considerations in Self-Assembly 93

3.3 Cooperativity in Self-Assembly 100

3.4 Kinetic Aspects of Multicomponent Organization 104

3.5 Understanding Self-Assembly Processes 108

3.6 Secondary Structure and Stabilizing Interactions 118

3.7 Conclusions 118

References 120

4 Structural Aspects of Helicates 125
Martin Berg and Arne Lützen

4.1 Introduction 125

4.2 Structural Dynamics 127

4.3 Template Effects 129

4.4 Sequence Selectivity 130

4.5 Self-Sorting Effects in Helicate Formation 135

4.6 Diastereoselectivity I - "Meso"-Helicate versus Helicate Formation 138

4.7 Diastereoselectivity II - Enantiomerically Pure Helicates from Chiral Ligands 139

4.8 Summary and Outlook 150

References 151

5 Helical Structures Featuring Thiolato Donors 159
F. Ekkehardt Hahn and Dennis Lewing

5.1 Introduction 159

5.2 Coordination Chemistry of Bis- and Tris(Benzene-o-Dithiolato) Ligands 162

5.3 Coordination Chemistry of Mixed Bis(Benzene-o-Dithiol)/Catechol Ligands 176

5.4 Subcomponent Self-Assembly Reactions 181

5.5 Summary and Outlook 186

References 186

6 Photophysical Properties and Applications of Lanthanoid Helicates 193
Jean-Claude G. Bünzli

List of Acronyms and Abbreviations 193

6.1 Introduction 194

6.2 Homometallic Lanthanoid Helicates 197

6.3 Heterometallic d-f Helicates 223

6.4 Chiral Helicates 236

6.5 Extended Helical Structures 239

6.6 Perspectives 240

Acknowledgements 241

References 241

7 Design of Supramolecular Materials: Liquid-Crystalline Helicates 249
Raymond Ziessel

7.1 Introduction 249

7.2 Imino-Bipyridine and Imino-Phenanthroline Helicates 252

7.2.1 Liquid Crystals from Imino-Polypyridine Based Helicates 257

7.3 Conclusions 266

7.4 Outlook and Perspectives 267

Acknowledgements 268

References 268

8 Helicates, Peptide-Helicates and Metal-Assisted Stabilization of Peptide Microstructures 275
Markus Albrecht

8.1 Introduction 275

8.2 Selected Examples of Metal Peptide Conjugates 276

8.3 Helicates and Peptide-Helicates 279

8.4 Metal-Assisted Stabilization of Peptide Microstructures 288

8.5 Conclusion 298

References 300

9 Artificial DNA Directed toward Synthetic Metallofoldamers 303
Guido H. Clever and Mitsuhiko Shionoya

9.1 Introduction 303

9.2 The Quest for Alternative Base Pairing Systems 309

9.3 Design and Synthesis of Metal Base Pairs 311

9.4 Assembly and Analysis of Metal Base Pairs Inside the DNA Double Helix 315

9.5 Artificial DNA for Synthetic Metallofoldamers 318

9.6 Functions, Applications and Future Directions 324

References 327

10 Metal Complexes as Alternative Base Pairs or Triplets in Natural and Synthetic Nucleic Acid Structures 333
Arnie De Leon, Jing Kong, and Catalina Achim

10.1 Introduction 333

10.2 Brief Overview of Synthetic Analogues of DNA: PNA, LNA, UNA, and GNA 338

10.3 Metal-Containing, Ligand-Modified Nucleic Acid Duplexes 340

10.4 Duplexes Containing Multiple Metal Complexes 361

10.5 Metal-Containing, Ligand-Modified Nucleic Acid Triplexes 367

10.6 Summary and Outlook 367

Acknowledgement 369

Abbreviations 369

References 370

11 Interaction of Biomimetic Oligomers with Metal Ions 379
Galia Maayan

11.1 Introduction 380

11.2 Single-Stranded Oligomers in Which Metal Coordination Templates, or Templates and Nucleates the Formation of an Abiotic Helix 381

11.3 Folded Oligomers in Which Metal Coordination Nucleates the Formation of an Abiotic Single-Stranded Helix 384

11.4 Folded Oligomers in Which Metal Coordination Enhances Secondary Structure and Leads to Higher-Order Architectures 393

11.5 Concluding Remarks 402

References 402

12 Applications of Metallofoldamers 407
Yan Zhao

12.1 Introduction 407

12.2 Metallofoldamers in Molecular Recognition 409

12.3 Metallofoldamers as Sensors for Metal Ions 414

12.4 Metallofoldamers as Dynamic Materials 419

12.5 Conclusions and Outlook 429

References 430

Index 433