Supramolecular main-chain liquid crystalline polymers and networks with competitive hydrogen bonding: networks and linear polymers created from tris- and bis-functionalised pyridyl networking agents

A series of supramolecular polymers and networks with variable liquid crystalline characteristics have been created. These species are formed through the benzoic acid/pyridine hydrogen bonding of a flexible bis-acid and a mixture of a rigid bis-pyridyl and non-mesogenic tris- and bis-pyridyl molecules. The tris networked systems displayed liquid crystalline characteristics up to and including 31.0% netpoint inclusion. Above this concentration, only crystalline and melting behaviours were observed. The bis-containing polymer system displayed liquid crystalline characteristics up to and including 22.5% inclusion. The phenomenon observed in the tris system would seem to be linked to a statistical correlation of hydrogen bond acceptors and donors. The elimination of liquid crystallinity at lower concentrations of the bis-pyridyl dopant could be attributed to the lower melting nature of that species. Smectic phases were found in both series of complexes in loadings up to 10% of the non-liquid crystalline component. There was also no observed phase segregation of the species after multiple heat/cool cycles and extended periods of time in the isotropic state. This would indicate that the thermodynamically more stable mesogenic phase cannot out-compete the non-liquid crystalline network.