Control over nanoparticle shape and size is commonly achieved via a seed-mediated approach, where nanoparticle precursors, or seeds, are hypothesized to act as templates for the heterogeneous nucleation of anisotropic products. Despite the wide variety of shapes that have been produced via this approach, high yield and uniformity have been more difficult to achieve. These shortcomings are attributed to limited structural control and characterization of the initial distribution of seeds. Herein, we report how iterative reductive growth and oxidative dissolution reactions can be used to systematically control seed structural uniformity. Using these reactions, we verify that seed structure dictates anisotropic nanoparticle uniformity and show that iterative seed refinement leads to unprecedented noble metal nanoparticle uniformities and purities for eight different shapes produced from a single seed source. Because of this uniformity, the first nanoparticle optical extinction coefficients for these eight shapes were analytically determined.

DNA programmable assembly has been combined with top-down lithography to construct superlattices of discrete, reconfigurable nanoparticle architectures on a gold surface over large areas. Specifically, the assembly of individual colloidal plasmonic nanoparticles with different shapes and sizes is controlled by oligonucleotides containing "locked" nucleic acids and confined environments provided by polymer pores to yield oriented architectures that feature tunable arrangements and independently controllable distances at both nanometer- and micrometer-length scales. These structures, which would be difficult to construct by other common assembly methods, provide a platform to systematically study and control light-matter interactions in nanoparticle-based optical materials. The generality and potential of this approach are explored by identifying a broadband absorber with a solvent polarity response that allows dynamic tuning of visible light absorption.

Whether two species will co-crystallize depends on the chemical, physical and structural complementarity of the interacting components. Here, by using DNA as a surface ligand, we selectively co-crystallize mixtures of two different anisotropic nanoparticles and systematically investigate the effects of nanoparticle size and shape complementarity on the resultant crystal symmetry, microstrain, and effective 'DNA bond' length and strength. We then use these results to understand a more complicated system where both size and shape complementarity change, and where one nanoparticle can participate in multiple types of directional interactions. Our findings offer improved control of non-spherical nanoparticles as building blocks for the assembly of sophisticated macroscopic materials, and provide a framework to understand complementarity and directional interactions in DNA-mediated nanoparticle crystallization.

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