This tutorial review charts the history of gel phase crystallization from its origins in Liesegang ring formation to current research in the generation of new pharmaceutical solid forms in low molecular weight organogels. The growth of molecular crystals under a supersaturation gradient within the same space and timescale as the formation of a gel phase material is placed into context as an example of orthogonal self-assembly. Such multi-component, weakly coupled orthogonal self-assembly processes occurring far from equilibrium represent a powerful conceptual paradigm for generating fascinating emergent behaviour in chemical systems.

A supramolecular gel designed to chemically mimic the structure of a pharmaceutical compound controls the polymorphic outcome of the crystallization of the substrate.

A pyridyl urea based low molecular weight supramolecular hydrogelator has been synthesized; crystallized from its gelling solvents, the single crystal structure of the gelator molecule interacting with its gelling solvents reported herein is the first example in the literature.