Bolapolyphiles With Bulky Carbosilane-Based Lateral Groups-Reticular Design of Liquid Crystalline Pentagonal Honeycombs.

Periodic pentagon tessellations are rarely observed in self-assembled molecular systems. Here, it is reported that p-terphenyl-based bolapolyphiles with sticky glycerol groups at both ends and highly branched carbosilane-based side-groups self-assemble into liquid crystalline honeycombs composed of type-2 pentagonal prismatic cells and p2gg plane group symmetry over wide temperature and side-group volume ranges. It is shown that bulky side-groups with two cycloalkyl (cyclobutyl, cyclohexyl) or branched alkyl chains (iso-pentyl, iso-hexyl, and tert-hexyl) at the silicon branching point favor the formation of pentagon tilings, while three of them reduce the pentagonal honeycomb range, mainly by favoring crystalline phases.