Metallofoldamers: Supramolecular Architectures from Helicates to Biomimetics

Metallofoldamers are oligomers that fold into three–dimensionalstructures upon coordination with metal ions, and show an abilityto form helical structures and other three–dimensionalarchitectures. Several metallofoldamers have been applied assensors due to their selective folding when binding to a specificmetal ion, while others show promise for applications as responsivematerials on the basis of their ability to fold and unfold uponchanges in the oxidation state of the coordinated metal ion.

Metallofoldamers: Supramolecular Architectures from Helicatesto Biomimetics describes thevariety of interactions betweenoligomers and metal species, with a focus on non–natural syntheticmolecules. Topics coveredinclude:                   

Extract from Foreword by Nobel Prize Laureate Jean–MarieLehn

The editors have to be congratulated for assembling aremarkable roster of active players in the field, who deserve ourwarmest thanks for their expert contributions.

metalloproteins and metallopeptides introduction to un–natural foldamers helicates: self–assembly, structure and applications metallo–PNA and DNA interactions of biomimetic oligomers with metal ions applications of metallofoldamers

List of Contributors xi

Foreword xiii

Preface xv

1 Metalloproteins and Metallopeptides NaturalMetallofoldamers 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 –Helicateversus Helicate Formation 138

4.7 Diastereoselectivity II Enantiomerically PureHelicates 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– andTris(Benzene–o–Dithiolato) Ligands 162

5.3 Coordination Chemistry of MixedBis(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 LanthanoidHelicates 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–CrystallineHelicates 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 Helicates257

7.3 Conclusions 266

7.4 Outlook and Perspectives 267

Acknowledgements 268

References 268

8 Helicates, Peptide–Helicates and Metal–AssistedStabilization 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 Microstructures288

8.5 Conclusion 298

References 300

9 Artificial DNA Directed toward Synthetic Metallofoldamers303
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 DNADouble 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 inNatural 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 Duplexes340

10.4 Duplexes Containing Multiple Metal Complexes 361

10.5 Metal–Containing, Ligand–Modified Nucleic Acid Triplexes367

10.6 Summary and Outlook 367

Acknowledgement 369

Abbreviations 369

References 370

11 Interaction of Biomimetic Oligomers with Metal Ions379
Galia Maayan

11.1 Introduction 380

11.2 Single–Stranded Oligomers in Which Metal CoordinationTemplates, or Templates and Nucleates the Formation of an AbioticHelix 381

11.3 Folded Oligomers in Which Metal Coordination Nucleates theFormation of an Abiotic Single–Stranded Helix 384

11.4 Folded Oligomers in Which Metal Coordination EnhancesSecondary 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

Overall, the book is an interesting read and a useful reference for the chemistry of helicates and for those interested in metallosupramolecular chemistry more generally.   (Applied Organometallic Chemistry, 31 October 2014)