Engineering Anisotropy into Organized Nanoscale Matter

Programming the organization of discrete building blocks into periodic and quasi-periodic arrays is challenging. Methods for organizing materials are particularly important at the nanoscale, where the time required for organization processes is practically manageable in experiments, and the resulting structures are of interest for applications spanning catalysis, optics, and plasmonics. While the assembly of isotropic nanoscale objects has been extensively studied and described by empirical design rules, recent synthetic advances have allowed anisotropy to be programmed into macroscopic assemblies made from nanoscale building blocks, opening new opportunities to engineer periodic materials and even quasicrystals with unnatural properties. In this review, we define guidelines for leveraging anisotropy of individual building blocks to direct the organization of nanoscale matter. First, the nature and spatial distribution of local interactions are considered and three design rules that guide particle organization are derived. Subsequently, recent examples from the literature are examined in the context of these design rules. Within the discussion of each rule, we delineate the examples according to the dimensionality (0D–3D) of the building blocks. Finally, we use geometric considerations to propose a general inverse design-based construction strategy that will enable the engineering of colloidal crystals with unprecedented structural control.