Polymerization-Like Co-Assembly of Silver Nanoplates and Patchy Spheres

Highly anisometric nanoparticles have distinctive mechanical, electrical, and thermal properties and are therefore appealing candidates for use as self-assembly building blocks. Here, we demonstrate that ultra-anisometric nanoplates, which have a nanoscale thickness but a micrometer-scale edge length, offer many material design capabilities. In particular, we show that these nanoplates "copolymerize" in a predictable way with patchy spheres (Janus and triblock particles) into one- and two-dimensional structures with tunable architectural properties. We find that, on the pathway to these structures, nanoplates assemble into chains following the kinetics of molecular step-growth polymerization. In the same mechanistic framework, patchy spheres control the size distribution and morphology of assembled structures, by behaving as monofunctional chain stoppers or multifunctional branch points during nanoplate polymerization. In addition, both the lattice constant and the stiffness of the nanoplate assemblies can be manipulated after assembly. We see highly anisometric nanoplates as one representative of a broader class of dual length-scale nanoparticles, with the potential to enrich the library of structures and properties available to the nanoparticle self-assembly toolbox.