Front Cover

Supramolecular Chemistry

Copyright

Contents

Contributors

Preface

Feature Article

Chapter One: From Coordination Chemistry to Adaptive Chemistry

1. From Discrete Molecules to Self-Organized Molecular Assemblies

2. From Self-Organization to Constitutional Dynamics and Adaptation

2.1. Self-Organization and Self-Organization by Design

2.2. Supramolecular Architectures Built Around a Single Type of Metal Ion and Relying on a Single Steric Program

2.2.1. Supramolecular Square Grid-Like Complexes

2.2.2. Supramolecular Linear and Circular Helical Complexes

2.3. Supramolecular Architectures Resulting From Two or More Informational Programs

2.3.1. Crossover Between Two Steric Programs

2.3.1.1. Metallosupramolecular Cage-Like and Ladder-Like Coordination Architectures

2.3.1.2. Metallosupramolecular Rack-Like and Rectangular Grid-Like Coordination Architectures

2.3.1.3. Supramolecular Heteroduplex Helical Complexes

2.3.2. From Robustness to Homo-S and Hetero-Self-Sorting Processes

2.3.3. Dominant/Recessive Behaviors Between Two Steric Programs

2.4. Supramolecular Architectures Built Around Multiple Steric Subprograms

3. Constitutional Dynamics and Adaptation

3.1. Supramolecular Constitutional Dynamics

3.2. Motional Dynamic Chemistry

3.2.1. Structural Features of Polyheterocyclic Strands and Related Metal Complexes

3.2.2. Extension/Contraction Motions of Helical Ligands

3.2.3. Extension/Contraction Motions of Linear Ligands

3.2.4. Extension/Contraction Motions in Mixed Linear/Helical Ligands

3.2.5. Shape Changes Induced by the Interconversion of Different Metallosupramolecular Architectures

3.2.6. Dynamic Switching Devices

4. CDC and Constitutional Dynamic Networks

4.1. Combining Constitutional Dynamics at the Supramolecular and Molecular Level

4.1.1. Implementation of CDC in Coordination Chemistry

4.1.2. Applications of CDC: The Example of Metallodynamers

4.2. Constitutional Dynamic Networks

4.2.1. Implementation of Constitutional Dynamic Networks in Coordination Chemistry

4.2.2. Coevolution in Constitutional Dynamic Networks

4.2.3. Constitutional Dynamic Networks as Information Devices

4.2.4. Toward More Complex Constitutional Dynamic Networks

5. Toward Systems Chemistry

Acknowledgement

References

Chapter Two: A Journey From Solution Self-Assembly to Designed Interfacial Assembly

1. Introduction

2. From Coordination Chemistry to Metallosupramolecular Chemistry

2.1. Coordination Chemistry as Molecular Recognition

2.2. Metal-Binding Domains

2.3. Metallosupramolecular Chemistry

2.3.1. Partitioning Metal-Binding Domains in Polydentate Ligands

2.3.2. Symmetrical Partitioning of Metal-Binding Domains in Helical Metallosupramolecules

2.3.3. Asymmetrical Partitioning of Metal-Binding Domains in Helical Metallosupramolecules

2.4. From Pure Compounds to Libraries

3. Supramolecular Chemistry at Surfaces

3.1. Overview of Supramolecular Interactions

3.2. Self-Assembly at Surfaces

3.3. Combining Self-Assembly and Metallosupramolecular Chemistry at Surfaces

3.4. From Self-Assembly to Covalent Attachment

3.4.1. Surface and Anchoring Algorithms: The New Tool Kit

3.5. Taking Metallosupramolecular Chemistry to Surfaces

3.5.1. The Dye-Sensitized Solar Cell

3.5.2. Copper DSCs

3.6. From “Complexes as Metals/Complexes as Ligands” to “Surfaces as Ligands, Surfaces as Complexes”

3.6.1. Sequential Assembly of Copper DSCs: The Library of Anchors

3.6.2. Sequential Assembly of Copper DSCs: The Library of Ancillary Ligands

3.6.3. Atom Economy and Regeneration

3.6.4. The Future

Acknowledgments

References

Chapter Three: From Self-Sorting of Dynamic Metal–Ligand Motifs to (Supra) Molecular Machinery in Action

1. Introduction

2. Self-Sorting of Dynamic Metal–Ligand Libraries

3. Self-Sorting of Multicomponent Metallosupramolecular Assemblies

3.1. Four-Component Self-Sorted Self-Assemblies

3.1.1. Three-Component Structures Containing Guest(s)

3.1.2. Four-Component Structures

3.2. Five-Component to Seven-Component Self-Sorted Aggregates

4. Integrative Self-Sorting of Supramolecular Devices

4.1. Three-Component Devices

4.2. Four-Component Devices

4.3. Five-Component Devices

5. Future Developments—Toward Supramolecular Machinery

6. Conclusion

Acknowledgments

References

Chapter Four: Metallacrowns: Supramolecular Constructs With Potential in Extended Solids, Solution-State Dynamics, Molecu ...

1. Introduction to Metallacrowns

2. Extended Structures of Metallacrowns

2.1. Metallacrowns in Dimensional Coordination Polymers

2.2. One-Dimensional Chains of Metallacrowns

2.3. Two-Dimensional Sheets of Cu2+ 12-MC-4 Complexes With Permanent Porosity

2.4. A Three-Dimensional MOF of 24-MC-6 Metallacrowns

2.5. Metallacrowns as Metal Oxide Precursors

3. Solution-State Examination of Metallacrown Complexes

3.1. Insight Into Solution-State Speciation of MC Complexes and Mechanism for Ln Encapsulation

3.2. Structural Analysis of LnNa(OAc)4[12 - MCMnIIIN(shi) − 4] Complexes Using 1H-NMR

3.3. The Selective Binding of Guest Anions in Dimeric Gd[15-MCCuII(N)pheHA - 5] Capsules

3.4. Investigation of MC Binding to DNA

3.5. Metallacrowns as Scaffolds for Helical Peptide Bundles

4. Magnetic Applications of Metallacrowns: Single-Molecule Magnets and Magnetorefrigerants

4.1. LnIII [12 – MCMnIII(N)shi – 4] SMMs and the Importance of Bridging Carboxylates and Counter Ions

4.2. YbIII-ZnII 12-MC-4 SMMs

4.3. Nontraditional 3d-4f Metallacrown SMMs

4.4. Transition Metal-Only Metallacrown SMMs

4.5. Azametallacrown SMMs

4.6. Perspective on the Superparamagnetic Behavior of Metallacrowns

4.7. Metallacrown Magnetorefrigerants

5. Metallacrowns and Applications in Imaging

5.1. Lanthanide-Based Luminescence and Optical Imaging

5.1.1. The Ln[12–MCZnIIN(pyzHA)–4]2[24–MCZnIIN(pyzHA)–8] as a Stain and Cell Fixation Agent

5.1.2. The Ln[12–MCZnIIN(pyzHA)–4]2[24–MCZnIIN(pyzHA)–8] and Imaging of Necrotic Cells

5.1.3. Yb3+ Luminescence of a Yb[12–MCZnIIN(quinHA)–4(DMF)4(OTf)3

5.1.4. Lanthanide Complexes of Tetrakis-Benzoate and [12–MCGaIIIN(shi)–4]

5.2. MCs as Magnetic Resonance Imaging-Contrast Agents

6. Summary

References

Chapter Five: Metallosupramolecular Complexes Based on Pyrogallol[4]arenes

1. Introduction

2. Hydrogen-Bonded Pyrogallol[4]arene/Resorcin[4]arene Nanocapsules

3. Metal-Seamed Pyrogallol[4]arene Nanocapsules

3.1. M24L6 Metal-Organic Nanocapsules

3.2. M8L2 Metal-Organic Nanocapsules

3.3. Ga12L6 and Mixed Metal-Organic Nanocapsules

3.4. M7L2 Metal-Organic Nanocapsules Using Mixed Macrocycles

4. Hierarchical Assembly Using Metal-Seamed Pyrogallol[4]arene Nanocapsules as Building Blocks

4.1. Direct Linking

4.2. Linking Through Addition of a Bridging Ligand

4.3. Dual Function of C-Propan-3-ol-pyrogallol[4]arene

5. Solution Study of Pyrogallol[4]arene-Based Metallosupramolecular Complexes

5.1. Dimeric and Hexameric Nanocapsules

5.2. Toroidal Structures

5.3. Tubular Assemblies

6. Conclusion

Acknowledgment

References

Chapter Six: Merging Metal–Nucleobase Chemistry With Supramolecular Chemistry

1. Introduction

2. Supramolecular Chemistry: Nucleic Acids and Metal Ions

3. Metal Coordination and Base Pairing

3.1. M-[G-N7]+C

3.2. M-[G-N7]+G

3.3. M-[A-N7]+G

3.4. M-[G-H-N7]+G

3.5. Self-Pairs Between M-[pu-N7]

3.6. Self-Pairs Involving M-[G-H-N7]/M-[G-N7]

3.7. Quartet Structures With Peripheral Metal Entities

4. Cross-Linking of Nucleobases

4.1. Metal-Modified Base Pairs

4.2. Dimerization of Metal-Modified Base Pairs

4.3. Extending Metal Modification to Base Triples

4.4. Three Metals and Four Nucleobases

4.5. Closed Metal-Nucleobase Quartets

4.6. Planar Nucleobase Aggregates With Central Metal Ions

4.7. Inverting the Metal in Metalated Watson-Crick Pairs

4.8. Heteronuclear Adducts of Nucleobases

4.8.1. Tetrakis(Nucleobase) Complexes of PtII

4.8.2. Multinuclear Cytosine Complexes Involving PtII, PdII, and Ag+

5. Cyclic Complexes and Metallacalix[n]arenes

5.1. Triangular Vases as Anion Hosts

5.2. Unsubstituted Pyrimidine Nucleobases

5.3. Hybrids

5.4. Combining cis- and trans-(a)2MII (M=Pt or Pd) and the Effect of pH

6. Stacking Interactions Involving Metalated Nucleobases

7. Conclusions

Acknowledgments

References

Chapter Seven: Anion and Cation Complexes of Expanded Porphyrins

1. Introduction

2. Metal Complexes of Expanded Porphyrins

2.1. Pentaphyrins: Sapphyrin, Smaragdyrin, and Pentaphyrin Metal Complexes

2.1.1. Sapphyrin Metal Complexes

2.1.2. Smaragdyrin Metal Complexes

2.1.3. Pentaphyrin Metal Complexes

2.2. Hexaphyrins: Hexaphyrin, Rubyrin, Amethyrin, and Isoamethyrin Metal Complexes

2.2.1. Hexaphyrin Metal Complexes

2.2.2. Rubyrin Metal Complexes

2.2.3. Amethyrin and Isoamethyrin Metal Complexes

2.3. Heptaphyrin and Octaphyrin Metal Complexes

2.3.1. Heptaphyrin Metal Complexes

2.3.2. Octaphyrin Metal Complexes

3. Anion Binding Properties of Expanded Porphyrins

4. Concluding Remarks

Acknowledgments

References

Chapter Eight: Arene Ruthenium Complexes in Supramolecular Chemistry

1. Introduction

2. Catalysis

3. Crystalline Networks

4. Assemblies in Solution

5. Interactions with DNA and Proteins

6. Liquid Crystals

7. Conclusion

References

Chapter Nine: Mechanochemical Reactions of Metal-Organic Frameworks

1. Introduction

2. Chemical Reactions During Elastic Deformation of MOFs

2.1. Elastic Deformations of MOFs

2.2. Pressure-Induced Reversible Chemical Reactions: Ligation and Deligation

3. Mechanochemistry During Plastic Deformation in MOFs

3.1. Amorphization and Densification of MOFs

3.1.1. Ex Situ Characterization

3.1.2. In Situ Characterization

3.1.3. Effect of Densification on Sorption Properties

3.1.4. Amorphous MOFs for Controlled Release and Sequestration

3.2. Plastic Deformation and Mechanical Energy Absorption

3.2.1. Nanocompression

3.2.2. Mechanochemical Reactions During Nanocompression

3.2.3. Shock Wave Energy Dissipation

4. Conclusions

Acknowledgments

References

Index

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