Supramolecular Interactions in the Solid State

IUCrJ. 2015 Sep 22;2(Pt 6):675-90. doi: 10.1107/S2052252515014608. eCollection 2015 Nov 1.


In the last few decades, supramolecular chemistry has been at the forefront of chemical research, with the aim of understanding chemistry beyond the covalent bond. Since the long-range periodicity in crystals is a product of the directionally specific short-range intermolecular interactions that are responsible for molecular assembly, analysis of crystalline solids provides a primary means to investigate intermolecular interactions and recognition phenomena. This article discusses some areas of contemporary research involving supramolecular interactions in the solid state. The topics covered are: (1) an overview and historical review of halogen bonding; (2) exploring non-ambient conditions to investigate intermolecular interactions in crystals; (3) the role of intermolecular interactions in morphotropy, being the link between isostructurality and polymorphism; (4) strategic realisation of kinetic coordination polymers by exploiting multi-interactive linker molecules. The discussion touches upon many of the prerequisites for controlled preparation and characterization of crystalline materials.

Keywords: coordination polymers; crystal engineering; halogen bonding; intermolecular interactions; kinetic assembly; non-ambient conditions; phase transitions; polymorphism; self-assembly.

Publication types

  • Review