Halogen-bonded mesogens direct polymer self-assemblies up to millimetre length scale

Aligning polymeric nanostructures up to macroscale in facile ways remains a challenge in materials science and technology. Here we show polymeric self-assemblies where nanoscale organization guides the macroscopic alignment up to millimetre scale. The concept is shown by halogen bonding mesogenic 1-iodoperfluoroalkanes to a star-shaped ethyleneglycol-based polymer, having chloride end-groups. The mesogens segregate and stack parallel into aligned domains. This leads to layers at ~10 nm periodicity. Combination of directionality of halogen bonding, mesogen parallel stacking and minimization of interfacial curvature translates into an overall alignment in bulk and films up to millimetre scale. Upon heating, novel supramolecular halogen-bonded polymeric liquid crystallinity is also shown. As many polymers present sites capable of receiving halogen bonding, we suggest generic potential of this strategy for aligning polymer self-assemblies. Achieving polymeric self-assemblies that are macroscopically aligned up to millimetre length scale remains challenging. Here, Houbenov et al. tackle this problem in a model polymer system, which exhibits an efficient spontaneous organization guided by halogen bonding without external stimuli.