We report a new class of liquid crystalline system exhibiting columnar mesophases, which are constructed by the hierarchical supramolecular self-organization of a rod-like diacetylene derivative as the primary building block. A series of 1, 3-alkadiynyl-4-benzoic acids (mmDA) with different alkyl chain lengths (m= 8–16) were synthesized and their mesophase properties were investigated by differential scanning calorimetry, polarized ...