Reticular liquid crystal design: Controlling complex self-assembly of p-terphenyl rods by side-chain engineering and chirality

A series of K-shaped bolapolyphiles, consisting of a p-terphenyl core, two polar glycerol end-groups and a swallow-tailed alkyl side-chain were synthesized and investigated. By increasing the side-chain volume an astonishing variety of very different liquid crystalline (LC) phases was observed, ranging from a rectangular (Col_rec/c2mm) and a square honeycomb (Col_squ/p4mm) via a highly complex zeolite-like octagon/pentagon honeycomb filled with additional strings of rod-bundles (Col_rec^Z/c2mm), a new 3D-hexagonal (R$\bar{3}$c) double network phase, a double and even a single network cubic phase (double gyroid Cub/Ia$\bar{3}$d and single diamond Cub/Fd$\bar{3}$m, respectively) to a correlated lamellar phase (Lam_Sm/c2mm). Though these LC structures are highly complex and there is a delicate balance of steric and geometric frustration determining the phase formation, there is only a small effect of permanent molecular chirality in the glycerol groups ((R,R)-configuration) on them, which is attributed to a slightly different packing density of uniformly chiral and racemic glycerols, but not to an effect of induced helicity. Compared to related T-shaped bolapolyphiles with a single linear n-alkyl side-chain, which form exclusively honeycomb phases, the complexity of self-assembly is enhanced for the K-shaped compounds due to a competition between the requirements of space filling, chain stretching and geometric frustration, and affected by the shape of the polar glycerol domains at the junctions.