Hierarchical, Highly Open Microtubes and Columnar Liquid Crystals Self‐Assembled from Symmetrical and Asymmetrical Colloidal Rings

The use of simple building blocks to produce hierarchical and porous structured materials is highly desired. Rings are simple colloidal particles but unique for their internal cavities. Here we report the self-assembly (SA) of colloidal rings with tunable asymmetry mediated by a depletion force and demonstrate that a variety of porous colloidal superstructures from microtubes, flexible chains, (plastic) crystals to highly open liquid crystals (LCs) can be formed along the predesigned SA paths. In particular, the SA is staged in binary or ternary systems. Large rings first form complex ring-in-ring and ring-in-ring-in-ring assemblies by capturing smaller rings, which, as new building blocks, can further form multi-walled microtubes and open columnar LCs. Moreover, a plastic columnar LC with alternating intracolumnar stacking is found from asymmetrical rings. The SA with colloidal rings opens a new avenue to construct hierarchical and porous ordered metamaterials.