Breaking Parallel Orientation of Rods via Dendritic Architecture toward Diverse Supramolecular Structures

: Self-assembled nanostructures of rod-like molecules are commonly limited to nematic or layered smectic structures dominated by the parallel arrangement of the rod-like components. Distinct self-assembly behavior of four categories of dendritic rods constructed by placing a tri(hydroxy) group at the apex of dendritic oligo-fluorenes is observed. Designed hydrogen bonding and dendritic architecture break the parallel arrangement of the rods, resulting in molecules with specific (fan-like or cone-like) shapes. While the fan-shaped molecules tend to form hexagonal packing cylindrical phases, the cone-shaped molecules could form spherical motifs to pack into various ordered structures, including the Frank-Kasper A15 phase and dodecagonal quasicrystal. This study provides a model system to engineer diverse supramolecular structures by rod-like molecules and sheds new light into the mechanisms of the formation of unconventional spherical packing structures in soft matter.