Modulating Orientational Order to Organize Polyhedral Nanoparticles into Plastic Crystals and Uniform Metacrystals

Abstract

In nanoparticle self‐assembly, the current lack of strategy to modulate orientational order creates challenges in isolating large‐area plastic crystals. Here, we achieve two orientationally distinct supercrystals using one nanoparticle shape, including plastic crystals and uniform metacrystals. Our approach integrates multi‐faceted Archimedean polyhedra with molecular‐level surface polymeric interactions to tune nanoparticle orientational order during self‐assembly. Experiments and simulations show that coiled surface polymer chains limit interparticle interactions, creating various geometrical configurations among Archimedean polyhedra to form plastic crystals. In contrast, brush‐like polymer chains enable molecular interdigitation between neighboring particles, favoring consistent particle configurations and result in uniform metacrystals. Our strategy enhances supercrystal diversity for polyhedra comprising multiple nondegenerate facets.

Controlled Two-Dimensional Alignment of Metal–Organic Frameworks in Polymer Films

“…Novel strategies for controlling the alignment of MOF particles can be derived from the self-assembly of other inorganic polyhedral nanoparticles (NPs) into two-dimensional (2D) arrays. With these NPs, orientational control is often achieved by tailoring surface tension between NPs and liquid phases. − The alignment of polyhedral NPs (including MOFs) has generally required altering the surface tension of the NP interactions using surfactants or other surface modifications. − An alternative, simpler approach is utilizing different casting solvents, which can directly affect the surface tension and hence control the alignment of the NPs. If the alignment of the polyhedral NPs can be controlled by the casting solvent without changing the surface chemistry of the nanoparticles (including surface modification with surfactants), and maintained after evaporation or mixing, this would prove to be an attractive strategy to easily control the alignment of polyhedral particles, including MOFs.…”

Pervasive orientational and directional locking at geometrically heterogeneous sliding interfaces

“…are pushed across arbitrary crystal surfaces or quasicrystal substrates at low temperature. More generally, they should also be relevant to the rheology of metacrystalline systems, where crystalline monolayers with various periodic and quasiperiodic structures are built and investigated [42,43]. sponding coefficients in Eq.…”