Making reversible synthesis stick: competition and cooperation between intermolecular interactions

The ability to predict and control the assembly of molecular and ionic species into ordered networks is becoming an important target area in chemistry, biochemistry and materials science. In this context, the selectivity and directionality of the hydrogen bond have been instrumental in the preparation of distinctive structural aggregates, and the use of hydrogen bonding as a steering force is now emerging as the most important strategy in crystal engineering. A reliable supramolecular synthetic protocol also requires access to a wide range of reactions that are versatile, selective and give rise to high supramolecular yields. Through a systematic structural study we have examined three issues that are relevant to the development of transferable supramolecular synthesis; (a) structural invariance to molecular isomerism; (b) hierarchy of synthons based upon competition between intermolecular forces and (c) changes in supramolecular yield as a function of molecular substitution.