Supramolecular Polymers and Assemblies
From Synthesis to Properties and Applications

Explore modern characterization methods and new applications in this modern overview of supramolecular polymer chemistry

Supramolecular Polymers and Assemblies: From Synthesis to Properties and Applications delivers a superlative summary and description of general concepts and definitions in the field. The book offers informative and accessible treatments of crucial concepts like metal-containing compounds, hydrogen bonding, ionic interactions, pi-pi stacking, and more.

Characterization remains a primary focus of the book throughout, making it extremely useful for practitioners in the field. Emphasis is also placed on metallo-supramolecular polymers and materials which have found applications in areas like smart or intelligent materials and systems with special photochemical and photophysical properties, like LEDs and solar cells. Applications, including self-healing materials, opto-electronics, sensing, and catalysis are all discussed as well.

The book details many of the exciting developments in the field of supramolecular chemistry that have occurred since the 1987 Nobel Prize was awarded to pioneers in this rapidly developing field. Readers will also benefit from the inclusion of:

• A thorough introduction to supramolecular assemblies based on ionic interactions
• Explorations of supramolecular polymers based on hydrogen-bonding interactions, metal-to-ligand interactions, p-Electronic interactions, crown-ether recognition, cucurbiturils, and host-guest chemistry of calixarenes
• A discussion of cyclodextrins in the field of supramolecular polymers
• Examinations of supramolecular polymers based on the host-guest chemistry of pillarenes, and those formed by orthogonal non-covalent interactions
• A treatment of the characterization of supramolecular polymers

Supramolecular Polymers and Assemblies: From Synthesis to Properties and Applications will earn a place in the libraries of researchers and practitioners of the material science, as well as polymer chemists seeding a one-stop reference for supramolecular polymers.

Preface xi

Abbreviations xiii

About the Authors xix

1 Supramolecular Polymers: General Considerations 1

1.1 Introduction 1

1.2 Classification Schemes 2

1.3 Supramolecular Polymerization Mechanisms 4

1.4 Beyond Classical Supramolecular Polymerization 20

1.5 Concluding Remarks 22

2 Supramolecular Assemblies Based on Ionic Interactions 29

2.1 General Aspects 29

2.2 Basic Binding Modes and Discrete Model Assemblies 30

2.3 Supramolecular Polymers, Based on Ionic Interactions 35

2.4 Concluding Remarks 52

3 Supramolecular Polymers, Based on Hydrogen-Bonding Interactions 57

3.1 General Aspects 57

3.2 From H-Bonding Interactions to Supramolecular Polymers 63

3.3 Conclusion Remarks 107

4 Supramolecular Polymers, Based on Metal-to-Ligand Interactions 117

4.1 General Aspects 117

4.2 Synthesis and Design Principles 119

4.3 Linear Metallo-supramolecular Polymers 121

4.4 Concluding Remarks 176

5 Supramolecular Polymers, Based on Π—Electronic Interactions 195

5.1 General Aspects 195

5.2 Columnar Supramolecular Polymers, Based on Π—Π Stacking Interactions 197

5.3 From Π—Π Stacking to Advanced Donor--Acceptor-Type Charge--Transfer Interactions 209

5.4 From Charge--Transfer to Π-Electronic Ion-Pairing Interactions 213

5.5 Linear Supramolecular Polymers, Based on Π-Electronic Interactions 218

5.6 Conclusion and Outlook 232

6 Supramolecular Polymers, Based on Crown Ether Recognition 239

6.1 General Aspects 239

6.2 From Crown Ether Molecular Recognition Toward Supramolecular Polymers 240

6.3 Mechanical Interlocking: From Pseudorotaxanes to Rotaxanes 258

6.4 Poly(pseudo)rotaxanes, Derived from Preformed Polymers 263

6.5 Supramolecular Amphiphiles 266

6.6 Concluding Remarks 269

7 Supramolecular Polymers, Based on Cucurbiturils 275

7.1 General Aspects 275

7.2 Interactions of CB[n]s with Small Organic Guest Molecules 276

7.3 Supramolecular Polymers Incorporating CB[n] Units 278

7.4 Concluding Remarks 295

8 Supramolecular Polymers, Based on the Host--Guest Chemistry of Calixarenes 301

8.1 General Aspects 301

8.2 Calixarene-Based Supramolecular Polycaps 302

8.3 Supramolecular Polymers Featuring Vacant Calixarene Scaffolds 309

8.4 Supramolecular Polymers, Formed by Host--Guest Interactions 311

8.5 Beyond Classical Calix[n]arenes: Calix[4]pyrroles 322

8.6 Miscellaneous Supramacromolecular Assemblies, Based on Calixarenes 327

8.7 Concluding Remarks 337

9 Cyclodextrins in the Field of Supramolecular Polymers 343

9.1 General Aspects 343

9.2 Cyclodextrins and Supramolecular Polymers 344

9.3 End-Capping: From Polypseudorotaxanes to Polyrotaxanes 362

9.4 Polymerization of Pre-assembled Pseudorotaxanes 364

9.5 Supramolecular Polymerization, Based on CD Recognition 368

9.6 Amphiphilic Supramolecular Diblock Copolymers 375

9.7 Concluding Remarks 379

10 Supramolecular Polymers, Based on the Host--Guest Chemistry of Pillarenes 387

10.1 General Aspects 387

10.2 Host--Guest Complexation Between Pillarenes and Linear Polymers 389

10.3 Supramolecular Polymers, Derived from Pillarene-based Host--Guest Interactions 391

10.4 Hyperbranched and Cross-linked Assemblies 401

10.5 Supramolecular Assemblies, Based on Amphiphilic Pillar[5]arenes 405

10.6 Concluding Remarks 410

11 Supramolecular Polymers, Formed by Orthogonal Non-covalent Interactions 415

11.1 Introduction 415

11.2 Orthogonal Combinations of Supramolecular Interactions Involving Metal-to-Ligand Coordination 417

11.3 Orthogonal Combinations of Supramolecular Interactions Involving H-Bonding 428

11.4 Miscellaneous Orthogonal Combinations of Supramolecular Interactions 438

11.5 Biomimetic Orthogonal Self-Assembly: Protein Recognition 443

11.6 Concluding Remarks 447

12 Characterization of Supramolecular Polymers 453

12.1 Introduction 453

12.2 Estimation of the Molar Mass from the Theories of Supramolecular Polymer Science 454

12.3 Size-Exclusion Chromatography 460

12.4 Viscometry 463

12.5 Light Scattering 465

12.6 Vapor Pressure Osmometry 467

12.7 Analytical Ultracentrifugation 468

12.8 NMR Spectroscopy 470

12.9 Mass Spectrometry 475

12.10 Microscopy Imaging 476

12.11 Small/Wide-Angle X-Ray Scattering 484

12.12 X-Ray Crystallography 486

12.13 Small-Angle Neutron Scattering 487

12.14 Asymmetric Flow Field-Flow Fractionation 490

12.15 Taylor Dispersion Analysis 492

12.16 They Are Very Complex Structures but Totally Timely… 494

References 495

Index 503

Ulrich S. Schubert, PhD,is Full-Professor at the Friedrich-Schiller-University Jena (Chair of Organic and Macromolecular Chemistry) in Germany. He has published over 530 scholarly papers, 20 patents, and edited or written 5 scientific books.

George R. Newkome, PhD,is Affiliate Research Professor at the Center for Molecular Biology and Biotechnology in Jupiter, Florida, USA.

Andreas Winter, PhD,joined the group of Professor U. S. Schubert at the Eindhoven University of Technology in The Netherlands and the Friedrich-Schiller University Jena, Germany. His research is focused on the synthesis of emissive and luminescent metallo-supramolecular assemblies.