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The impact of tetragonal crystal symmetry on the two-dimensional (2D) confined polymer nanostructure is demonstrated. Our research shows that this chain packing defect in the tetragonal cell can be controlled to develop along the rod long axis in 2D confinement., The symmetry of polymer crystals greatly affects the optical, thermal con­ductivity and mechanical properties of the materials. Past studies have shown that the two-dimensional (2D) confined crystallization of polymer nanorods could produce anisotropic structures. However, few researchers have focused on understanding confined nanostructures from the perspective of crystal sym­metry. In this research, we demonstrate the molecular chain self-assembly of tetragonal crystals under cylindrical confinement. We specifically selected poly(4-methyl-1-pentene) (P4MP1) with a 41 or 72 helical conformation (usually crystallizing with a tetragonal lattice) as the model polymer. We found a coherent crystal branching of the tetragonal crystal in the P4MP1 nanorods. The unusual 45°- and 135°-{200} diffractions and the meridional 220 diffraction (from 45°-tilted crystals) have shown a uniform crystal branching between the a 1-axis crystals and the 45°-tilted crystals in the rod long axis, which originates from a structural defect associated with tetragonal symmetry. Surprisingly, this chain packing defect in the tetragonal cell can be controlled to develop along the rod long axis in 2D confinement.

We have successfully synthesized a series of monodispersed chain-like giant molecules with precisely controlled macromolecular composition and sequence based on polyhedral oligomeric silsesquioxane (POSS) nanoparticles using an orthogonal “click” strategy. Their nonspherical supramolecular structures, such as lamellae, double gyroids, and hexagonal packed cylinders, are mainly determined by the composition (namely, the number of incorporated amphiphilic nanoparticles). In addition, by precisely alternating the sequence of arranged nanoparticles in the giant molecules with identical chemical compositions, the domain sizes of their supramolecular structures could be fine-tuned. This is attributed to the macromolecular conformational differences caused by collective hydrogen bonding interactions in each set of sequence isomeric giant molecules. This work has demonstrated multilevel manipulation of supramolecular structures of giant molecules: coarse tuning by composition and fine-tuning by sequence.

Controlled assembly of nanoscale building blocks is a promising approach to obtain functional materials with unique properties. Here, we report a way to manipulate the supramolecular structures of ...

It has been recognized that macromolecular chains can self-assemble into a hierarchical structure from lamellae to spherulites in bulk crystallization. However, little account has been taken of crystal symmetry effects on the hierarchical nanostructure in polymers under cylindrical confinement. In this research, a model polymer, nylon 6,12, most commonly occurring in the triclinic α phase, was chosen in order to demonstrate the effect of triclinic symmetry on the 2D-constrained polymer nanostructure. The self-arranging unit of nylon 6,12 takes various forms, including stems, unit cells, hydrogen-bonded sheets, lamellae and complex spherulites, which is an essential structural feature for investigating hierarchical nanostructure. The rod nanostructure in confinement was examined by cross-checking electron and X-ray diffraction techniques. It is found that the a* axis of the α-phase cell is inclined at about ±6–11° to the rod long axis within the a*b* plane around the c axis (c axis ⊥ rod long axis). The rotation of the a*b* plane most likely results from the impact of the triclinic symmetry on the molecular chain packing under 2D confinement. A mechanism for this a*b* plane tilting is proposed.

In this work, we studied the linker effect on the nanostructures of a serious of specifically designed, functionalized polyhedral oligomeric silsesquioxane (POSS) based Dendron-like macro-isomers. The varying linkers between hydrophilic and hydrophobic POSS cages lead to topological isomers with identical composition but different molecular shapes. Their unique phase behaviors highlight remarkable effects of molecular architectures on the formation of nanostructures. Due to topological constraints, these macro-isomers assume either a fan- or a cone-molecular shape, which assembles into either hexagonally packed cylindrical phase (HEX) or Frank-Kasper A15 phase. This work provides guiding rules on designing precise molecular nanostructures with desired properties via linker engineering.

The bottom-up construction of Frank–Kasper (FK) phases in soft matter requires intricating tuning to balance entropic and enthalpic interactions. In contrast, sophisticated rules have been established in Metallurgy to dictate the packing structures of metal alloys. Inspired by alloy metallurgy, we develop a new self-sorting approach to construct nanostructures in condensed soft matters. This approach utilizes blends of nano-sized giant molecules to construct supramolecular motifs (“mesoatoms”) with controlled size heterogeneity, which is the key in rational design of diverse FK nanostructures. Especially, the scarcely observed thermodynamically stable Laves C14 and C15 phases are widely found. This approach sheds light on next-generation material engineering which allows nanostructure construction in a more predictable and straightforward way

Understanding polymer nanostructures is a prerequisite to manipulate their physical properties. Molecular self-assembly under confinement effectively generates novel polymer nanostructures. However, in one confined system, diffraction signals of different nanostructures are merged in a typical two-dimensional (2D) wide-angle X-ray diffraction (WAXD) measurement. For comparison, selected-area electron diffraction (SAED) of transmission electron microscopy can precisely capture the “local” diffraction signal of an individual nanoscale entity. Here, using isotactic polypropylene (i-PP) as a model polymer, we have demonstrated a cross-analysis of global X-ray and local electron diffraction results to fully reveal the structural details of i-PP nanorods. For the first time, we have decomposed completely the “mixed” 2D WAXD patterns of i-PP nanorods into five types of α-phase nanostructures: (a). Left-tilted daughter crystals; (b) Right-tilted daughter crystals; (c) Double-tilted daughter crystals; (d) a*-axis oriented crystals; (e) b-axis oriented crystals.