Liquid crystalline and antinematic behavior of shape-persistent macrocycles from molecular-dynamics simulations

In this work we present a molecular-dynamics study of a coarse-grained (CG) model for a system of planar shape-persistent macrocycles (SPMs). SPMs are synthetic organic rigid macromolecules typically comprised of meta- and para-aromatics groups connected by acetylene and/or diacetylene units. In the CG model, each SPM is represented as a rigid hexagonal arrangement of 24 soft-repulsive spheres, resembling a large ring or hoop. The supramolecular arrangement of these macrocycles at high pressures is studied using N-P-T molecular-dynamics simulation both by expansion of an initial hexagonal lattice structure and also by compression of an isotropic phase. In both cases, systems under consideration exhibit an isotropic-smectic-A phase transition, which is detected by monitoring relevant order parameters and analyzing snapshots of equilibrium configurations. The smectic-A phase is unique; although the molecules form layers, the system presents antinematic order where the orientation of the molecular axes is perpendicular to the direction of the layers themselves. Due to their planar geometry, the SPM molecules would be expected to form columnar or nematic phases. On the contrary, these phases seem suppressed by a novel smectic-A phase, formed by the mutual interpenetration of the cycles. These results are a unique example of how molecular nonconvexity can, by itself, induce mesomorphism in anisotropic systems.