Supramolecular Polymers and Assemblies

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.

• Preface xiAbbreviations xiiiAbout the Authors xix1 Supramolecular Polymers: General Considerations 11.1 Introduction 11.2 Classification Schemes 21.3 Supramolecular Polymerization Mechanisms 41.4 Beyond Classical Supramolecular Polymerization 201.5 Concluding Remarks 222 Supramolecular Assemblies Based on Ionic Interactions 292.1 General Aspects 292.2 Basic Binding Modes and Discrete Model Assemblies 302.3 Supramolecular Polymers, Based on Ionic Interactions 352.4 Concluding Remarks 523 Supramolecular Polymers, Based on Hydrogen-Bonding Interactions 573.1 General Aspects 573.2 From H-Bonding Interactions to Supramolecular Polymers 633.3 Conclusion Remarks 1074 Supramolecular Polymers, Based on Metal-to-Ligand Interactions 1174.1 General Aspects 1174.2 Synthesis and Design Principles 1194.3 Linear Metallo-supramolecular Polymers 1214.4 Concluding Remarks 1765 Supramolecular Polymers, Based on Π—Electronic Interactions 1955.1 General Aspects 1955.2 Columnar Supramolecular Polymers, Based on Π—Π Stacking Interactions 1975.3 From Π—Π Stacking to Advanced Donor--Acceptor-Type Charge--Transfer Interactions 2095.4 From Charge--Transfer to Π-Electronic Ion-Pairing Interactions 2135.5 Linear Supramolecular Polymers, Based on Π-Electronic Interactions 2185.6 Conclusion and Outlook 2326 Supramolecular Polymers, Based on Crown Ether Recognition 2396.1 General Aspects 2396.2 From Crown Ether Molecular Recognition Toward Supramolecular Polymers 2406.3 Mechanical Interlocking: From Pseudorotaxanes to Rotaxanes 2586.4 Poly(pseudo)rotaxanes, Derived from Preformed Polymers 2636.5 Supramolecular Amphiphiles 2666.6 Concluding Remarks 2697 Supramolecular Polymers, Based on Cucurbiturils 2757.1 General Aspects 2757.2 Interactions of CB[n]s with Small Organic Guest Molecules 2767.3 Supramolecular Polymers Incorporating CB[n] Units 2787.4 Concluding Remarks 2958 Supramolecular Polymers, Based on the Host--Guest Chemistry of Calixarenes 3018.1 General Aspects 3018.2 Calixarene-Based Supramolecular Polycaps 3028.3 Supramolecular Polymers Featuring Vacant Calixarene Scaffolds 3098.4 Supramolecular Polymers, Formed by Host--Guest Interactions 3118.5 Beyond Classical Calix[n]arenes: Calix[4]pyrroles 3228.6 Miscellaneous Supramacromolecular Assemblies, Based on Calixarenes 3278.7 Concluding Remarks 3379 Cyclodextrins in the Field of Supramolecular Polymers 3439.1 General Aspects 3439.2 Cyclodextrins and Supramolecular Polymers 3449.3 End-Capping: From Polypseudorotaxanes to Polyrotaxanes 3629.4 Polymerization of Pre-assembled Pseudorotaxanes 3649.5 Supramolecular Polymerization, Based on CD Recognition 3689.6 Amphiphilic Supramolecular Diblock Copolymers 3759.7 Concluding Remarks 37910 Supramolecular Polymers, Based on the Host--Guest Chemistry of Pillarenes 38710.1 General Aspects 38710.2 Host--Guest Complexation Between Pillarenes and Linear Polymers 38910.3 Supramolecular Polymers, Derived from Pillarene-based Host--Guest Interactions 39110.4 Hyperbranched and Cross-linked Assemblies 40110.5 Supramolecular Assemblies, Based on Amphiphilic Pillar[5]arenes 40510.6 Concluding Remarks 41011 Supramolecular Polymers, Formed by Orthogonal Non-covalent Interactions 41511.1 Introduction 41511.2 Orthogonal Combinations of Supramolecular Interactions Involving Metal-to-Ligand Coordination 41711.3 Orthogonal Combinations of Supramolecular Interactions Involving H-Bonding 42811.4 Miscellaneous Orthogonal Combinations of Supramolecular Interactions 43811.5 Biomimetic Orthogonal Self-Assembly: Protein Recognition 44311.6 Concluding Remarks 44712 Characterization of Supramolecular Polymers 45312.1 Introduction 45312.2 Estimation of the Molar Mass from the Theories of Supramolecular Polymer Science 45412.3 Size-Exclusion Chromatography 46012.4 Viscometry 46312.5 Light Scattering 46512.6 Vapor Pressure Osmometry 46712.7 Analytical Ultracentrifugation 46812.8 NMR Spectroscopy 47012.9 Mass Spectrometry 47512.10 Microscopy Imaging 47612.11 Small/Wide-Angle X-Ray Scattering 48412.12 X-Ray Crystallography 48612.13 Small-Angle Neutron Scattering 48712.14 Asymmetric Flow Field-Flow Fractionation 49012.15 Taylor Dispersion Analysis 49212.16 They Are Very Complex Structures but Totally Timely… 494References 495Index 503

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