Abstract
Molecular tessellations are known in solid state systems and their formation is often induced or supported by a periodic surface lattice. Here we discover a complex tessellation on the 10 nm length scale, spontaneously formed in the highly dynamic liquid crystalline state. It is composed of overlapping dodecagonal supertiles combining prismatic cells with triangular and square cross sections. This complex honeycomb occurs between a triangular honeycomb at high and a square at low temperature, being opposite to the sequence expected for a thermal expansion of the side chains in the prismatic cells. Formation of the supertiles is supported by the segregation of alkyl chains with different length. The emergent behaviour of this complex soft matter structure is demonstrated, and intriguing connections between self-assembly on surfaces, in liquid crystals, and in block copolymers are drawn. Moreover, the tessellation represents a close approximant of the elusive columnar liquid quasicrystal with dodecagonal symmetry.