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Группа авторов. Halogen Bonding in Solution
Table of Contents
List of Tables
List of Illustrations
Guide
Pages
Halogen Bonding in Solution
Preface
1 Halogen Bonding: An Introduction
1.1 Introduction
1.1.1 The Halogen Bond: Definition, Characteristics, Representations, and Parallels to the Hydrogen Bond
1.1.2 Parallels to the Hydrogen Bond
1.1.3 Notation and Terminology
1.1.4 Solid‐state Halogen Bond Contacts
1.1.5 Halogen Bond Features
1.1.6 Additional Nomenclature
1.2 Historical Perspective
1.2.1 Rediscovery
1.3 Crystallographic Studies
1.3.1 CSD Evaluations
1.3.2 Fundamental Studies and Halogen Bond–Hydrogen Bond Interplay
1.3.3 Metal Complexes and Charge‐assisted Halogen Bonding Systems
1.3.4 Alternative Motifs and Solid‐state Reactivity
1.3.5 Crystallographic Studies Conclusion
1.4 Computational Studies. 1.4.1 Introduction
1.4.2 Electrostatics of the Halogen Bond and the σ‐Hole
1.4.3 Limitations on Electrostatic Potential
1.4.4 Atomic Orbital Theory and the σ‐Hole
1.4.5 Charge Transfer
1.4.6 Dispersion and Polarization Component
1.4.7 Decomposition
1.4.8 Biological Computation of Halogen Bonding
1.4.9 Computational Conclusion
1.5 Materials. 1.5.1 Introduction
1.5.2 Liquid Crystals
1.5.3 Supramolecular Polymers. 1.5.3.1 LC Polymers
1.5.3.2 Light‐sensitive Polymers
1.5.3.3 Block Polymers
1.5.3.4 Self‐healing Polymers
1.5.4 Supramolecular Gels
1.5.5 Materials Conclusion
1.6 Conclusion
Acknowledgments
References
Note
2 Thermodynamics of Halogen Bonding in Solution
2.1 Introduction
2.2 Molecular Halogens and Interhalogens. 2.2.1 Uncharged Lewis Bases
2.3 N‐Halo and N‐Halonium Compounds
2.4 Haloalkynes. 2.4.1 Uncharged Lewis Bases
2.5 Haloarenes. 2.5.1 Uncharged Lewis Bases
2.5.2 Anionic Lewis Bases
2.6 Halogenated Heterocycles
2.6.1 Uncharged Lewis Bases
2.6.2 Anionic Lewis Bases
2.7 Haloalkanes and Haloalkenes
2.7.1 Uncharged Lewis Bases
2.7.2 Anionic Lewis Bases
2.8 Summary and Outlook
References
3 Recognition with Macrocycles and Interlocked Systems
3.1 Introduction
3.2 Recognition by XB Macrocyclic Hosts
3.3 XB Interlocked Hosts for Recognition and Sensing
3.3.1 XB‐Anion Templation of Interlocked Molecules
3.3.2 [2]Rotaxane Hosts for Anion Recognition
3.3.3 [2]Catenanes for Anion Recognition
3.3.4 XB Interlocked Hosts Constructed via Active Metal Template Methodology
3.3.5 Interlocked Host Molecules for Sensing Applications
3.4 Foldamer Architectures for Recognition
3.5 Summary and Conclusions
References
4 The Three‐Center Halogen Bond
4.1 Introduction
4.2 Three‐Center Halogen Bond
4.2.1 Features of the Three‐Center Halogen Bond
4.2.1.1 Symmetry and Dynamics of the Three‐Center Halogen Bonds
4.2.1.2 The Influence of the Identity of Halonium Ions
4.2.1.3 The Influence of Lewis Basicity
4.2.1.4 The Influence of Solvent and Counterions
4.2.2 The Three‐Center Halogen Bond of N‐Halosuccinimides and N‐Halosaccharins
4.2.3 Trihalide Ions
4.2.4 Stability of the Three‐Center Halogen Bond
4.3 Synthetic Applications. 4.3.1 Halonium Transfer Reactions
4.3.2 Oxidation Reactions
4.3.3 Enantioselective Halogenations
4.4 Three‐Center Halogen Bonds in Supramolecular Chemistry
4.5 Summary and Conclusions
References
5 Spectroscopy of Halogen Bonding in Solution
5.1 Introduction
5.2 Vibrational Spectroscopy
5.3 UV–vis Spectroscopy
5.4 NMR Spectroscopy
5.4.1 Solvent Effects
5.4.2 Entropic Effects on Halogen Bonding
5.4.3 NMR Titration Studies
5.4.3.1 Direct Detection Techniques
5.4.3.2 Indirect Detection Techniques
5.4.4 Nuclear Overhauser Effect (NOE) NMR Spectroscopy
5.4.4.1 Homonuclear NOE Spectroscopy
5.4.4.2 Heteronuclear NOE Spectroscopy
5.4.5 Diffusion NMR
5.4.6 The Isotopic Perturbation of Equilibrium Method
5.5 ESR Spectroscopy
5.6 Summary and Conclusions
Acknowledgments
References
6 Anion Transport in Lipid Bilayer Membranes Using Halogen Bonds
6.1 Introduction
6.1.1 Halogen Bonding in the Context of Ion Transport
6.1.2 Organization of This Chapter
6.2 Macrocyclic Systems
6.2.1 Calix[4]arenes
6.2.1.1 Synthesis
6.2.1.2 Ion Transport
6.2.2 Oxacalix[2]arene[2]triazine
6.2.2.1 Synthesis
6.2.2.2 Anion Binding Studies
6.2.2.3 Crystallographic Studies
6.2.2.4 Ion Transport
6.2.2.5 Anticancer Activity
Help Box 6.1 Help Box: Ion Transport Experiments in Large Unilamellar Vesicles (LUVs)
6.3 Small Molecules
6.3.1 Iodoperfluoroarenes
6.3.2 Iodoperfluoroalkanes
Help Box 6.2 Help Box: Conductance Experiments in Planar Lipid Bilayer Membranes
6.3.3 Conductance Experiments in Planar Lipid Bilayers with Small Molecules
6.3.4 Elucidating the Mechanism of Transport with Small Molecules
6.3.4.1 Membrane Composition in the HPTS Assay
6.3.4.2 Hill Coefficients
6.3.4.3 Molecular Modeling: DFT Calculations
6.3.4.4 Crystal Structures
6.4 Halogen Bonding Ion Channels
6.4.1 Halogen Bonding Cascades
6.4.1.1 Synthesis
6.4.1.2 Ion Transport
6.4.2 Halogen Bonding Self‐Assembled Pores and Channels
6.4.2.1 Synthesis
6.4.2.2 Ion Transport
6.4.2.3 Conductance Experiments in Planar Lipid Bilayers
6.4.2.4 Molecular Dynamics Simulations
6.4.2.5 Anticancer Activity
6.5 Discussion and Perspectives
6.6 Summary
Acknowledgments
References
7 Catalysis by Molecular Iodine
7.1 Introduction
7.2 Proposed Activation Mechanisms
7.2.1 Halogen‐Bond Catalysis
7.2.2 Iodonium‐Ion Catalysis
7.2.3 Brønsted‐Acid Catalysis
7.3 Applications in Catalysis. 7.3.1 Scope and Aim
7.3.2 Michael Additions
7.3.3 Knoevenagel Condensations
7.3.4 Cycloadditions and Related Reactions
7.3.5 Nazarov‐type Reactions
7.3.6 Esterifications and Transesterifications
7.3.7 Acetalizations and Related Reactions
7.3.8 Etherification
7.3.9 Friedel–Crafts Alkylations and Arylations
7.3.10 Isomerization of Double Bonds
7.3.11 Polymerization
7.3.12 Cascade Reactions
7.4 Summary and Conclusions
References
8 Halogen Bonding in Organocatalysis
8.1 Introduction
8.2 Organic Reactions Involving XB as Primary Interaction
8.2.1 Activation of Halocarbons
8.2.2 Activation of Organic Functional Groups
8.2.3 XB Organocatalysis Through π‐Activation
8.2.4 Asymmetric Catalysis Through Halogen Bonding
8.3 Reactions Involving XB as Secondary Interaction
8.4 Conclusion
References
9 Halogen Bonding in Electrochemistry
9.1 Introduction
9.2 Methods
9.3 Electrochemistry for Crystal Engineering: Mixed Valence Crystal Structures
9.4 Redox Switching in Homogeneous Solution. 9.4.1 Concept
9.4.2 Redox‐Active XB Acceptors. 9.4.2.1 Quinones
9.4.3 Redox‐Active XB Donors
9.4.3.1 Ferrocenes
9.4.3.2 Tetrathiafulvalenes
9.4.3.3 Viologens
9.5 Interfacial Halogen Bonding. 9.5.1 Anion Detection on Self‐Assembled Monolayers
9.5.2 Photovoltaic Systems
9.6 Activation of Covalent Bonds. 9.6.1 XB‐Mediated Redox Reactions: A Perspective
9.7 Conclusions
References
10 Halogen Bonds in Biomolecular Engineering
10.1 Introduction to Biomolecular Engineering and Halogen Bonds
10.2 Halogen Bonds in Nucleic Acids
10.2.1 Controlling DNA Assembly and Structure
10.2.2 Controlling Conformation
10.2.3 Structure–Energy Relationships
10.3 Halogen Bonds in Peptides and Proteins
10.3.1 Halogen Bonds in Amino Acids and Peptides
10.3.2 Halogen Bonds Engineered into Proteins
10.4 Conclusions and Perspectives
10.4.1 Expanding the Genetic Alphabet
10.4.2 Multimeric Assemblies
10.4.3 New Catalysts
10.4.4 Need for Computational Tools
10.4.5 Conclusion
Acknowledgments
References
11 The Chalcogen Bond in Solution: Synthesis, Catalysis and Molecular Recognition
11.1 Introduction
11.2 Chalcogen Bonding in Synthesis
11.3 Chalcogen Bonding in Catalysis
11.4 Chalcogen Bonding in Molecular Recognition
11.5 Conclusions
Acknowledgments
References
Index
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