Oriented assembly of anisotropic nanoparticles into frame-like superstructures.

It is fascinating but challenging for nanoscientists to organize nanoparticles (NPs) into ordered architectures just as it is for chemists to manipulate atoms and molecules to form functional molecules and supramolecules. We explore a strategy to assemble anisotropic NPs into open frame-like superstructures via oriented attachment (OA), experimentally realizing a nanoscale analog to the bonding behavior in M8L12-type supramolecular cubes. We highlight the role of NP shape in the OA-involved assembly for constructing predictable superstructures. In addition, the frame-like superstructures can retain their basic structure when undergoing postcrystallization of the building blocks as well as annealing for conversion toward functional electrocatalytic materials. Our work enables fundamental insights into directional "bonding" among NPs and adds to the growing body of knowledge for bottom-up assembly of anisotropic NPs into sophisticated functional materials.