Unusual packing of soft-shelled nanocubes.

Space-filling generally governs hard particle packing and the resulting phases and interparticle orientations. Contrastingly, hard-shaped nanoparticles with grafted soft-ligands pack differently since the energetically interacting soft-shell is amenable to nanoscale sculpturing. While the interplay between the shape and soft-shell can lead to unforeseen packing effects, little is known about the underlying physics. Here, using electron microscopy and small-angle x-ray scattering, we demonstrate that nanoscale cubes with soft, grafted DNA shells exhibit remarkable packing, distinguished by orientational symmetry breaking of cubes relative to the unit cell vectors. This zigzag arrangement occurs in flat body-centered tetragonal and body-centered cubic phases. We ascribe this unique arrangement to the interplay between shape and a spatially anisotropic shell resulting from preferential grafting of ligands to regions of high curvature. These observations reveal the decisive role played by shell-modulated anisotropy in nanoscale packing and suggest a plethora of new spatial organizations for molecularly decorated shaped nanoparticles.