Halogen Bonding in Solution

1 Cover

2 Title Page Halogen Bonding in Solution Edited by Stefan Huber

3 Copyright Editor Stefan Huber Ruhr‐Universität Bochum Organische Chemie I Universitätsstr. 150 NC 4/171 44801 Bochum Germany Cover Images © Olga Moonlight/Shutterstock © andrew hall/Alamy Stock Photo All books published by Wiley‐VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No.: applied for British Library Cataloguing‐in‐Publication Data A catalogue record for this book is available from the British Library. Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at < http://dnb.d-nb.de >. © 2021 WILEY‐VCH GmbH, Boschstr. 12, 69469 Weinheim, Germany All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Print ISBN: 978‐3‐527‐34731‐5 ePDF ISBN: 978‐3‐527‐82572‐1 ePub ISBN: 978‐3‐527‐82574‐5 oBook ISBN: 978‐3‐527‐82573‐8

4 Preface

5 1 Halogen Bonding: An Introduction 1.1 Introduction 1.2 Historical Perspective 1.3 Crystallographic Studies 1.4 Computational Studies 1.5 Materials 1.6 Conclusion Acknowledgments References Note

6 2 Thermodynamics of Halogen Bonding in Solution 2.1 Introduction 2.2 Molecular Halogens and Interhalogens 2.3 N‐Halo and N‐Halonium Compounds 2.4 Haloalkynes 2.5 Haloarenes 2.6 Halogenated Heterocycles 2.7 Haloalkanes and Haloalkenes 2.8 Summary and Outlook References

7 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 3.4 Foldamer Architectures for Recognition 3.5 Summary and Conclusions References

8 4 The Three‐Center Halogen Bond 4.1 Introduction 4.2 Three‐Center Halogen Bond 4.3 Synthetic Applications 4.4 Three‐Center Halogen Bonds in Supramolecular Chemistry 4.5 Summary and Conclusions References

9 5 Spectroscopy of Halogen Bonding in Solution 5.1 Introduction 5.2 Vibrational Spectroscopy 5.3 UV–vis Spectroscopy 5.4 NMR Spectroscopy 5.5 ESR Spectroscopy 5.6 Summary and Conclusions Acknowledgments References

10 6 Anion Transport in Lipid Bilayer Membranes Using Halogen Bonds 6.1 Introduction 6.2 Macrocyclic Systems 6.3 Small Molecules 6.4 Halogen Bonding Ion Channels 6.5 Discussion and Perspectives 6.6 Summary Acknowledgments References

11 7 Catalysis by Molecular Iodine 7.1 Introduction 7.2 Proposed Activation Mechanisms 7.3 Applications in Catalysis 7.4 Summary and Conclusions References

12 8 Halogen Bonding in Organocatalysis 8.1 Introduction 8.2 Organic Reactions Involving XB as Primary Interaction 8.3 Reactions Involving XB as Secondary Interaction 8.4 Conclusion References

13 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 9.5 Interfacial Halogen Bonding 9.6 Activation of Covalent Bonds 9.7 Conclusions References

14 10 Halogen Bonds in Biomolecular Engineering 10.1 Introduction to Biomolecular Engineering and Halogen Bonds 10.2 Halogen Bonds in Nucleic Acids 10.3 Halogen Bonds in Peptides and Proteins 10.4 Conclusions and Perspectives Acknowledgments References

15 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

16 Index

17 End User License Agreement

1 Chapter 1 Table 1.1 Common halogen bond donors and acceptors. Table 1.2 Table of iodine V S,maxvalues and interaction energies (Δ E ) of iodob...

2 Chapter 2 Table 2.1 Association constants ( K a) for halogen bonding interactions of Lewi... Table 2.2 Association constants ( K a) for halogen bonding interactions of Lewi... Table 2.3 Formation constants K ffor trihalide anions in acetonitrile and wate... Table 2.4 Association constants ( K a) for interactions of triphenylarsine oxid... Table 2.5 Association constants ( K a) for interactions of Lewis bases with 4‐N... Table 2.6 Enthalpy changes Δ H ° for 1 : 1 halogen bonding of metal fluorides 3... Table 2.7 Apparent association constants K a,appfor interactions of complement...Table 2.8 Association constants for halogen bonding interactions of Lewis bas...Table 2.9 Enthalpies of halogen bonding in liquefied noble gases.Table 2.10 Association constants of representative haloalkanes and haloalkene...

3 Chapter 3Table 3.1 Anion association constants ( K a[M −1]) with axle 10·PF 6and ro...Table 3.2 Association constants, K a(M −1), for 1 : 1 complexes of recept...Table 3.3 Association constants, K a(M −1), for 1 : 1 complexes of recept...Table 3.4 Association constants, K a(M −1), for 1 : 1 complexes of recept...Table 3.5 Pseudorotaxane stability constants, K a(M −1), between macrocyc...Table 3.6 Association constants, K a(M −1), for 1 : 1 complexes of 48–50...Table 3.7 Association constants, K a(M −1), for 1 : 1 complexes of 51and...Table 3.8 Association constants, K a(M −1), for 1 : 1 complexes of 52, 53

4 Chapter 4Table 4.1 Computationally predicted (B3LYP) NX and NN bond lengths for [bis...Table 4.2 Computationally predicted (DFT) substituent effect on the NI and N...

5 Chapter 5Table 5.1 Effect of solvents upon halogen bonding in Taylor's iodoperfluorooc...

6 Chapter 6Table 6.1 Summary of transport and binding data for macrocyclic systems a).Table 6.2 Summary of transport activity for small moleculesa).Table 6.3 Summary of transport activity for halogen bonding ion channelsa).

7 Chapter 7Table 7.1 Selective deactivation of iodine and HI in the Michael addition bet...Table 7.2 Iodine‐catalyzed iso‐Nazarov cyclization [51].

8 Chapter 9Table 9.1 Cathodic shifts of the Fc/Fc +couple (Δ E 1/2in mV) upon addition...

1 Chapter 1 Figure 1.1 Schematic of interactions between a halogen atom and a Lewis base... Figure 1.2 Molecular electrostatic potential maps drawn at the isodensity su... Figure 1.3 Early halogen bonding cocrystals from Hassel. Bromine/benzene add... Figure 1.4 Table from the 1968 solid‐state review by Bent. Figure 1.5 ChemDraw figure highlighting the use of alkyl‐ and aryl‐dihaloper... Figure 1.6 ChemDraw figure depicting the structural scheme for both type I (... Figure 1.7 Halogen bond contacts between DMAP halogen bond acceptor nitrogen... Figure 1.8 Six halogen bond donors were systematically evaluated computation... Figure 1.9 Examples of simultaneous halogen and hydrogen bonding in the cons... Figure 1.10 Methods to enhance the potency of a halogen bond donor. The Chem... Figure 1.11 Representative examples of N ‐iodoimide halogen bond donors (a). ... Figure 1.12 Examples of halogen bond mediated [2 + 2] photodimerization of o... Figure 1.13 Cocrystallization components and pre‐polymerization structures o... Figure 1.14 Computed ESP maps on 0.001 au molecular surfaces of (a) iodobenz... Figure 1.15 Simplified orbital‐interaction diagrams for (a) hydrogen‐bonded ... Figure 1.16 DFT–SAPT decomposition analysis of H 3CBr⋯NH 3(solid lines) and F Figure 1.17 The first example of a halogen bonding LC developed by Bruce. Al... Figure 1.18 The first example of a photoactive halogen bonding LC developed ... Figure 1.19 The first example of a polymeric halogen bonding LC developed by... Figure 1.20 (a) Chemical structure of the halogen bond and hydrogen bond don... Figure 1.21 Monomers M1and M2were subjected to RAFT polymerization with bu...