Dendrimers are branched or hyperbranched synthetic oligomers or macromolecules with their size, molar masses, number of end groups and delicate compositions being precisely controlled. These characteristics have made dendrimers very good candidates as scaffolds of spherical molecules whose size ranges from several to tens of nanometres. When the dendritic segments are densely grafted along a linear polymer, so-called dendronized polymers or denpols are obtained. Owing to the steric hindrance between neighboring dendrons, especially in high generation, the dendronized polymers show a wormlike morphology whose flexibility and diameter are mainly dependent upon the generation of grafted dendrons. Therefore, denpols may be regarded as one-dimensional molecular nanoobjects. In this article, the recent development of a remarkable synthesis, control of composition and morphologies are featured.

Herein we report the fabrication and study of hierarchically structured fibers of a dendronized polymer that were simply prepared by drawing out from their columnar phase in melt. At first, the combined SEM and SAXS results indicate that the fibers contain fibrils that align along the axial direction and have a diameter of ∼200 nm. Further SAXS characterizations confirm an oriented hexagonally packed cylindrical (HPC) structure assembling in the fibrils. At the molecular level, a wormlike single molecular conformation was visualized by AFM, indicating its relatively stiffer structure compared with conventional polymers. Because of this feature, the dendronized polymer can be fabricated into fibers with a highly ordered structure. Therefore, the hierarchical structure that is found in the fibers sheds light on the possible mechanism of the self-organization of the dendronized polymer on different scales.