Programmable Atom Equivalents: Atomic Crystallization as a Framework for Synthesizing Nanoparticle Superlattices

Decades of research efforts into atomic crystallization phenomenon have led to a comprehensive understanding of the pathways through which atoms form different crystal structures. With the onset of nanotechnology, methods that use colloidal nanoparticles (NPs) as nanoscale “artificial atoms” to generate hierarchically ordered materials are being developed as an alternative strategy for materials synthesis. However, the assembly mechanisms of NP‐based crystals are not always as well‐understood as their atomic counterparts. The creation of a tunable nanoscale synthon whose assembly can be explained using the context of extensively examined atomic crystallization will therefore provide significant advancement in nanomaterials synthesis. DNA‐grafted NPs have emerged as a strong candidate for such a “programmable atom equivalent” (PAE), because the predictable nature of DNA base‐pairing allows for complex yet easily controlled assembly. This Review highlights the characteristics of these PAEs that enable controlled assembly behaviors analogous to atomic phenomena, which allows for rational material design well beyond what can be achieved with other crystallization techniques. The unique characteristics of DNA‐grafted colloids enable the design and synthesis of nanoparticle‐based crystals by drawing on well‐understood atomic crystallization phenomena to understand and explain particle assembly behavior. This Review explores how these “programmable atom equivalents” are a unique tool to rationally design and synthesize complex nano‐ and microstructured materials.