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RESEARCH FRONT
Contents Vol 65(10)

Design of Clathrate Compounds that Use Only Weak Intermolecular Attractions

Roger Bishop
+ Author Affiliations
- Author Affiliations

School of Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia. Email: r.bishop@unsw.edu.au




Roger Bishop was educated at George Heriot’s School in Edinburgh, the University of St. Andrews (B.Sc.), and the University of Cambridge where he carried out his Ph.D. work on the photochemistry of alpha-diketones. In 1974, he took up a Lectureship in the School of Chemistry, University of New South Wales, Sydney, where he is now an Emeritus Professor. His principal research interests lie in the areas of alicyclic chemistry, organic inclusion compounds, and crystal engineering.

Australian Journal of Chemistry 65(10) 1361-1370 https://doi.org/10.1071/CH12038
Submitted: 24 January 2012  Accepted: 1 March 2012   Published: 27 April 2012

Abstract

Intermolecular attractive forces that are considerably weaker than hydrogen bonding and coordination complexation may be used in the design of new molecules that function as host molecules in the solid-state. Known literature examples of accidentally discovered hosts (clathrands), which do not involve strong interactions in their crystals, are identified and discussed. Their molecular symmetry and supramolecular interactions are analysed in order to identify structural features that facilitate and promote molecular inclusion. The solid-state properties of a family of designed compounds that embody these principles are then described. Prediction of their inclusion behaviour was 95 % successful and a wide variety of crystal packing arrangements were encountered. This is an inevitable consequence of competition between many different molecular interactions of comparable energy during the crystallisation process. The lowest energy combination of these host–host and host–guest associations generates the observed outcome. One consequence of this behaviour is that detailed prediction of a new clathrate crystal packing arrangement is extremely difficult. However, a second consequence is that crystal structure analysis provides a rich source of information about weak intermolecular forces and new supramolecular synthons that previously had remained hidden.


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