Thermotropic “Plumber’s Nightmare” ‐ A Tight Liquid Organic Double Framework

Abstract Gyroid, double diamond and the body‐centred “Plumber's nightmare” are the three most common bicontinuous cubic phases in lyotropic liquid crystals and block copolymers. While the first two are also present in solvent‐free thermotropics, the latter had never been found. Containing six‐fold junctions, it was unlikely to form in the more common phases with rod‐like cores normal to the network columns, where a maximum of four branches can join at a junction. The solution has therefore been sought in side‐branched mesogens that lie in axial bundles joined at their ends by flexible “hinges”. But for the tightly packed double framework, geometric models predicted that the side‐chains should be very short. The true Plumber's nightmare reported here, using fluorescent dithienofluorenone rod‐like mesogen, has been achieved with, indeed, no side chains at all, but with 6 flexible end‐chains. Such molecules normally form columnar phases, but the key to converting a complex helical column–forming mesogen into a framework‐forming one was the addition of just one methyl group to each pendant chain. A geometry‐based explanation is given.