Communication: The synthesis of polar molecular materials with designed pro
perties is a fundamental target of materials research. Here a fully rationa
l synthesis of polar materials from a given set of precursors (perhydrotrip
henylene and three different guests) is presented. A simulation shows that
varying the relative proportions of each guest permits the level of polarit
y to be tuned with a high degree of control. These results are fundamental
to the understanding of how a complex supramolecular system self-assembles
into a material with polar properties.