Mesoscale Polarization by Geometric Frustration in Columnar Supramolecular Crystals

Columnar supramolecular phases with polarization along the columnar axis have potential for the development of ultrahigh‐density memories as every single column might function as a memory element. By investigating structure and disorder for four columnar benzene‐1,3,5‐trisamides by total X‐ray scattering and DFT calculations, we demonstrate that the column orientation, and thus the columnar dipole moment, is receptive to geometric frustration if the columns aggregate in a hexagonal rod packing. The frustration suppresses conventional antiferroelectric order and heightens the sensitivity towards collective intercolumnar packing effects. The latter finding allows for the building up of mesoscale domains with spontaneous polarization. Our results suggest how the complex interplay between steric and electrostatic interactions is influenced by a straightforward chemical design of the molecular synthons to create spontaneous polarization and to adjust mesoscale domain size. Supramolecular chemistry meets geometric frustration in axially polar bulk phases of benzene‐1,3,5‐trisamides (BTAs). The macrodipole moments generated through the formation of supramolecular stacks frustrate during progressive aggregation into hexagonal rod packings. It is shown by total X‐ray scattering that the frustration can be utilized to induce spontaneous polarization on the mesoscale.