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Defects are symmetry breaking features within a crystal. They can be created during growth as well as by applied mechanical forces. We address point, line and surface defects in block copolymer crystals, concentrating on the structure of defects in the tubular network double gyroid and double diamond phases. Experimental results using 3D slice and view scanning electron microscopic tomographic imaging for many types of defects are presented and the nature of the structural details and symmetries are described. Often defects are considered detrimental to the properties and performance of the material, but if the mesoscale defects in 3D periodic block copolymers can be controlled, they can be utilized to achieve various advantageous such as new optical functionalities. 

We have designed and synthesized a pair of sequence isomeric giant surfactants based on polystyrene (PS) and polyhedral oligomeric silsesquioxane (POSS) nanoparticles. Although these two macromolecules possess identical compositions as “sequence isomers”, the distinctly arranged POSS sequences lead to different molecular packing conformations, and further induce distinguished self-assembly behaviors in DMF/water solutions. 

Abstract 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.