Supercrystal Engineering of Nanoarrows Enabled by Tailored Concavity

Abstract Self‐assembly of nanoparticles into supercrystals represents a powerful approach to create unique and complex superstructures with fascinating properties and novel functions, but the complexity in spatial configuration, and the tunability in lattice structure are still quite limited compared to the crystals formed by atoms and molecules. Herein, shallowly concave gold nanoarrows with a unique concave‐convex geometry are synthesized and employed as novel building blocks for shape‐directed self‐assembly of a wealth of complex 3D supercrystals with unprecedented configurations. The obtained diverse superstructures including six Interlocking‐type supercrystals and three Packing‐type supercrystals exhibit four types of Bravais lattices (i.e., tP, oI, tI, and oF) and six types of crystallographic space groups (i.e., Pmmm, I222, Pnnm, Ibam, I4/mmm, and Fmmm), which have not been documented in the mesoscale self‐assembled systems. It has been revealed that the relative yield of different supercrystal structures is mainly determined by the packing density and deformability of the supercrystals, which are closely related to the tailored concavity of the nanoparticles and is affected by the particle concentration, thus allowing for programmable self‐assembly into specific supercrystals through particle shape modulation. The concavity‐enabled supercrystal engineering may open a new avenue toward unconventional nanoparticle superstructures with expanded complexity, tunability, and functionality.