Arrays of giant octagonal and square cylinders by liquid crystalline self-assembly of X-shaped polyphilic molecules.

Nanopatterning by molecular self-assembly has been a topic of intense research in pursuit of 'bottom-up' methods of generating structures for use in nanotechnology. The systems most widely studied have been two- and three-dimensional morphologies of block copolymers. However, T- and X-shaped polyphilic liquid crystals have recently been shown to have great potential for generating soft honeycomb-like structures, surpassing those of polymers in both complexity and degree of order. The cell cross-section of the liquid crystals honeycombs has so far been limited by small molecular size. Here we overcome this limitation by exploiting the inability of the polyphiles to simultaneously achieve optimal packing and complete nanophase separation. This frustration results in a two-dimensional periodic honeycomb consisting of giant octagonal and square cylinders with circumferences of 12 and 8 molecules, respectively. In addition to forming large cells, the two-molecule-long bendy walls give this structure extra versatility and stability.