126 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

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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 na- nostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supra- molecular 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.

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Volume Editors Pierangelo Metrangolo Giuseppe Resnati Department of Chemistry, Materials, Department of Chemistry, Materials, Chemical Engineering “Giulio Natta” Chemical Engineering “Giulio Natta” Politecnico di Milano Politecnico di Milano Via Mancinelli 7 Via Mancinelli 7 20131 Milano, Italy 20131 Milano, Italy [email protected] [email protected]

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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 thattheelectrondensitydistributionaroundhalogenatomsformsanellipsoid 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. Exper- imental results confirm this anisotropic distribution and prove the amphoteric character of halogens. This can produce interactions in a direction perpendic- ular 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 elec- trophilic 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 bond- ing (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 en- gineeringisdiscussed(P.Metrangolo,G.Resnatietal.).Achapterexploringthe 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 interac- tion 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 interact- – ing partners (as it is the case of dihalogen/halide anion complexes, e.g.,I3). 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 con- sidered 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 Contents of Structure and Bonding, Volume 108 and 111

Supramolecular Assembly via Hydrogen Bonds I ISBN: 978-3-540-20084-0

Probing Hydrogen Bonding in Solids Using Solid State NMR Spectroscopy A. E. Aliev · K. D. M. Harris

Crystal Engineering Using Multiple Hydrogen Bonds A. D. Burrows

Molecular Containers: Design Approaches and Applications D.R.Turner·A.Pastor·M.Alajarin·J.W.Steed

Supramolecular Assembly via Hydrogen Bonds II ISBN: 978-3-540-20086-4

Hydrogen Bonding Interactions Between Ions: A Powerful Tool in Molecular Crystal Engineering D. Braga · L. Maini · M. Polito· F. Grepioni

Hydrogen-Bonded Supramolecular Chain and Sheet Formation by Coordinated Guanidine Derivatives P. Hubberstey · U. Suksangpanya

Hydrogen-Bonding Templated Assemblies R. Vilar

Hydrogen Bonded Network Structures Constructed from Molecular Hosts M. J. Hardie