AbstractLiquid Crystals are thought of as being complex fluids, underpinned by self‐assembly and self‐organisation within partially ordered fluids, and which sit between solid and liquid states of matter. The realm of the field stretches from low molar mass to polymeric materials, from organic to inorganic substances, and from being functional materials to biological organelles. In this article, we explore the cusp of the change over from nano‐ to macro‐sciences through the formation of ‘supermolecular’ systems, and we debate if such materials are in fact oligomers or materials having giant molecules possessing discrete chemical constitutions? We performed this investigation by synthesising mesogenic materials based upon difluoroterphenyls, terminally substituted with a chiral motif based on (S)‐2‐octanol, and which could be appended onto a variety of siloxane scaffolds. We studied the structures and properties of six mesomorphic materials in which we systematically increased the number of mesogenic units attached to the scaffold.