Temperature dependent coordinating self-assembly

Self-assemblies dominated by coordination interaction are hardly responsive to thermal stimuli. We show that in case the coordinating mode changes with temperature, the resultant assemblies also exhibit temperature dependence. The self-assemblies are constructed with perylene tetracarboxylate and metal ions. Compounds containing a perylene skeleton often self-assemble into micro-belts, which is also true for the combination of perylene tetracarboxylate and metal ions. However, a unique pinecone structure was observed upon increasing the temperature of the coordinating system. The structural transition is triggered by the change of coordinating mode between the carboxylate group and the metal ion. At low temperature, intermolecular coordination occurs which favours the growth of the coordinating self-assembly along the long axis of the perylene. However, upon the elevation of temperature, the coordination is overwhelmed by intra-molecular mode. This is against the extension of the coordinating assembly due to the loss of connection between neighbouring perylenes. As a result, the pinecone structure is observed. We expect that the cases introduced in this work may inspire the design of structurally controllable temperature-dependent soft materials based on coordinating self-assembly.