Computationally Guided Assembly of Oriented Nanocubes by Modulating Grafted Polymer−Surface Interactions

The bottom-up fabrication of ordered and oriented colloidal nanoparticle assemblies is critical for engineering functional nanomaterials beyond conventional polymer–particle composites. Here, we probe the influence of polymer surface ligands on the self-orientation of shaped metal nanoparticles for the formation of nanojunctions. We examine how polymer graft–surface interactions dictate Ag nanocube orientation into either edge–edge or face–face nanojunctions. Specifically, we investigate the effect of end-functionalized polymer grafts on nanocube assembly outcomes, such as interparticle angle and interparticle distance. Our assembly results can be directly mapped onto our theoretical phase diagrams for nanocube orientation, enabling correlation of experimental variables (such as graft length and metal binding strength) with computational parameters. These results represent an important step toward unifying modeling and experimental approaches to understanding nanoparticle–polymer self-assembly.