Halogen_Bonding
.pdf126
Structure and Bonding
Series Editor: D. M. P. Mingos
Editorial Board:
P. Day · X. Duan · T. J. Meyer
G. Parkin · H. W. Roesky · J.-P. Sauvage
Structure and Bonding
Series Editor: D. M. P. Mingos
Recently Published and Forthcoming Volumes
Halogen Bonding |
Magnetic Functions Beyond |
Fundamentals and Applications |
the Spin-Hamiltonian |
Volume Editors: Metrangolo, P., Resnati, G. |
Volume Editor: Mingos, D. M. P. |
Vol. 126, 2008 |
Vol. 117, 2005 |
High Energy Density Materials |
Intermolecular Forces and Clusters II |
Volume Editor: Klapötke, T. H. |
Volume Editor: Wales, D. J. |
Vol. 125, 2007 |
Vol. 116, 2005 |
Ferroand Antiferroelectricity |
Intermolecular Forces and Clusters I |
Volume Editors: Dalal, N. S., |
Volume Editor: Wales, D. J. |
Bussmann-Holder, A. |
Vol. 115, 2005 |
Vol. 124, 2007 |
|
|
Superconductivity in Complex Systems |
Photofunctional Transition Metal Complexes |
Volume Editors: Müller, K. A., |
Volume Editor: V. W. W. Yam |
Bussmann-Holder, A. |
Vol. 123, 2007 |
Vol. 114, 2005 |
Single-Molecule Magnets |
Principles and Applications |
and Related Phenomena |
of Density Functional Theory |
Volume Editor: Winpenny, R. |
in Inorganic Chemistry II |
Vol. 122, 2006 |
Volume Editors: |
|
Kaltsoyannis, N., McGrady, J. E. |
Non-Covalent Multi-Porphyrin Assemblies |
Vol. 113, 2004 |
Synthesis and Properties |
|
Volume Editor: Alessio, E. |
Principles and Applications |
Vol. 121, 2006 |
of Density Functional Theory |
|
in Inorganic Chemistry I |
Recent Developments in Mercury Sience |
Volume Editors: |
Volume Editor: Atwood, David A. |
Kaltsoyannis, N., McGrady, J. E. |
Vol. 120, 2006 |
Vol. 112, 2004 |
Layered Double Hydroxides |
Supramolecular Assembly |
Volume Editors: Duan, X., Evans, D. G. |
via Hydrogen Bonds II |
Vol. 119, 2005 |
Volume Editor: Mingos, D. M. P. |
|
Vol. 111, 2004 |
Semiconductor Nanocrystals |
|
and Silicate Nanoparticles |
Applications of Evolutionary Computation |
Volume Editors: Peng, X., Mingos, D. M. P. |
in Chemistry |
Vol. 118, 2005 |
Volume Editors: Johnston, R. L. |
|
Vol. 110, 2004 |
Halogen Bonding
Fundamentals and Applications
Volume Editors: P. Metrangolo · G. Resnati
With contributions by
H. D. Arman · S. Biella · D. W. Bruce · M. Fourmigué · T. W. Hanks A. Karpfen · J. K. Kochi · A. C. Legon · P. Metrangolo
W. T. Pennington · T. Pilati · G. Resnati · S. V. Rosokha
123
The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entire Periodic Table. It focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant.
As a rule, contributions are specially commissioned. The editors and publishers will, however, always be pleased to receive suggestions and supplementary information. Papers are accepted for Structure and Bonding in English.
In references Structure and Bonding is abbeviated Struct Bond and is cited as a journal.
Springer WWW home page: springer.com
Visit the Struct Bond content at springerlink.com
Library of Congress Control Number: 2007936637
ISSN 0081-5993
ISBN 978-3-540-74329-3 Springer Berlin Heidelberg New York
DOI 10.1007/978-3-540-74330-9
This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer. Violations are liable for prosecution under the German Copyright Law.
Springer is a part of Springer Science+Business Media
springer.com
c Springer-Verlag Berlin Heidelberg 2008
The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use.
Cover design: WMXDesign GmbH, Heidelberg
Typesetting and Production: LE-TEX Jelonek, Schmidt & Vöckler GbR, Leipzig
Printed on acid-free paper 02/3180 YL – 5 4 3 2 1 0
Series Editor
Prof. D. Michael P. Mingos
Principal
St. Edmund Hall Oxford OX1 4AR, UK
michael.mingos@st-edmund-hall.oxford.ac.uk
Volume Editors
Pierangelo Metrangolo
Department of Chemistry, Materials, Chemical Engineering “Giulio Natta” Politecnico di Milano
Via Mancinelli 7 20131 Milano, Italy
pierangelo.metrangolo@polimi.it
Giuseppe Resnati
Department of Chemistry, Materials, Chemical Engineering “Giulio Natta” Politecnico di Milano
Via Mancinelli 7 20131 Milano, Italy
giuseppe.resnati@polimi.it
Editorial Board
Prof. Peter Day
Director and Fullerian Professor of Chemistry
The Royal Institution of Great Britain 21 Albermarle Street
London W1X 4BS, UK pday@ri.ac.uk
Prof. Xue Duan
Director
State Key Laboratory
of Chemical Resource Engineering
Beijing University of Chemical Technology 15 Bei San Huan Dong Lu
Beijing 100029, P.R. China duanx@mail.buct.edu.cn
Prof. Thomas J. Meyer
Department of Chemistry Campus Box 3290
Venable and Kenan Laboratories The University of North Carolina and Chapel Hill
Chapel Hill, NC 27599-3290, USA tjmeyer@unc.edu
Prof. Gerard Parkin
Department of Chemistry (Box 3115) Columbia University
3000 Broadway
New York, New York 10027, USA parkin@columbia.edu
Prof. Herbert W. Roesky
Institut for Anorganic Chemistry University of Göttingen Tammannstr. 4
37077 Göttingen, Germany hroesky@gwdg.de
Prof. Jean-Pierre Sauvage
Faculté de Chimie Laboratoires de Chimie Organo-Minérale Université Louis Pasteur 4, rue Blaise Pascal
67070 Strasbourg Cedex, France sauvage@chimie.u-strasbg.fr
Structure and Bonding
Also Available Electronically
For all customers who have a standing order to Structure and Bonding, we offer the electronic version via SpringerLink free of charge. Please contact your librarian who can receive a password or free access to the full articles by registering at:
springerlink.com
If you do not have a subscription, you can still view the tables of contents of the volumes and the abstract of each article by going to the SpringerLink Homepage, clicking on “Browse by Online Libraries”, then “Chemical Sciences”, and finally choose Structure and Bonding.
You will find information about the
–Editorial Board
–Aims and Scope
–Instructions for Authors
–Sample Contribution
at springer.com using the search function.
Preface
Halogen atoms in organic compounds can typically be found at the periphery of molecules. For this reason, they are ideally positioned to be involved in intermolecular interactions. Indeed, halogen atoms are frequently involved in a wide variety of non-covalent interactions which can be remarkably different regarding their energetic and geometric features. Theoretical studies predict that the electron density distribution around halogen atoms forms an ellipsoid elongated in the direction perpendicular to the covalent bond axis. A clear trend of increasing electropositive potential develops along the covalent bond axis upon increasing the polarizability and atomic mass of the halogen. Experimental results confirm this anisotropic distribution and prove the amphoteric character of halogens. This can produce interactions in a direction perpendicular to the covalent bond axis when the halogen is the electron donor (Lewis base), and along the axis when the halogen is the electron acceptor (Lewis acid).
This book focuses on the interactions wherein halogens work as electrophilic species and interact with electron rich sites (namely, electronegative partners). Of the numerous non-covalent interactions involving halogens, this particular subset is typically referred to as halogen bonding. The book begins by introducing theoretical calculations on the characteristics of halogen bonding (A. Karpfen), then focuses on the adducts wherein the electron donor is a lone pair possessing species (n donor). The complexes formed by halogens and interhalogens in the gas (A. Legon) and solid phase (W. T. Pennington et al.) are presented and the role of halocarbons in halogen bonding-based crystal engineering is discussed (P. Metrangolo, G. Resnati et al.). A chapter exploring the complexes in which halogen atoms interact with π electron donors (J. K. Kochi et al.) concludes the part of the book that deals with the generalities of halogen bonding. In contrast, the last two chapters of this book discuss halogen bonded adducts endowed with useful applicative properties. Among the many novel applications of halogen bonding, liquid crystals (D. Bruce) and conducting or magnetic materials (M. Fourmigue) are discussed as prototypical examples.
The findings presented throughout this book consistently converge towards the use of the term halogen bonding, independent of the energy of the interaction or its prevailing character, whether electrostatic or charge-transfer. The effectiveness of a scientific concept and the associated terminology often rest
X |
Preface |
on an optimized balance between generality, resulting in a wide applicability, and specificity, enabling it to predict specific phenomena. In this respect, it is our opinion that the concept of halogen bonding is beneficial if it is defined as comprehensively as possible, while assigning the specific role of the positive site in the interaction to the halogen. At one extreme, the term can be used for interactions in which a very strong polarity difference exists between interacting partners (as it is the case of dihalogen/halide anion complexes, e.g., I–3 ). At the other extreme, the term halogen bonding can be used for interactions wherein the polarity difference between the interacting partners is very small (e.g., in the triangular bromocarbon trimer synthon).
This book is a first in the field of halogen bonding. Focussing on interactions in which halogens work as the electrophilic sites, this book identifies the boundaries of the concept of halogen bonding. In addition, it organizes the diversified profile of intermolecular interactions involving halogens.
In order to reflect the differences in geometric and electronic parameters, a term different from halogen bonding might be used to address interactions wherein halogens work as electron donor sites. Halide bonding could be considered for this purpose, however, the best terminology to be used will emerge from the increasing interest in interactions involving halogens and will be spontaneously identified by the consensus of the scientific community.
The field of halogen bonding is still in its infancy. Nevertheless, this book proves its potential in the numerous and diverse fields in which recognition and self-assembly processes are crucial. Hopefully, this book will prompt new studies in the field that deepen the basic understanding of halogen interactions and implement its potential in the design of useful materials.
Milan, |
Pierangelo Metrangolo |
September 2007 |
Giuseppe Resnati |
Contents
Theoretical Characterization of the Trends in Halogen Bonding |
|
A. Karpfen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . |
1 |
The Interaction of Dihalogens and Hydrogen Halides |
|
with Lewis Bases in the Gas Phase: An Experimental Comparison |
|
of the Halogen Bond and the Hydrogen Bond |
|
A. C. Legon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . |
17 |
Halogen Bonding with Dihalogens and Interhalogens |
|
W. T. Pennington · T. W. Hanks · H. D. Arman . . . . . . . . . . . . . . . |
65 |
Halogen Bonding in Crystal Engineering |
|
P. Metrangolo · G. Resnati · T. Pilati · S. Biella . . . . . . . . . . . . . . . |
105 |
X-ray Structures and Electronic Spectra of the π-Halogen Complexes |
|
between Halogen Donors and Acceptors with π-Receptors |
|
S. V. Rosokha · J. K. Kochi . . . . . . . . . . . . . . . . . . . . . . . . . |
137 |
Halogen-bonded Liquid Crystals |
|
D. W. Bruce . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . |
161 |
Halogen Bonding in Conducting or Magnetic Molecular Materials |
|
M. Fourmigué . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . |
181 |
Author Index Volumes 101–126 . . . . . . . . . . . . . . . . . . . . . . |
209 |
Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . |
219 |