A general strategy for designing complex brush architecture using star‐like polymeric grafts.

Synthetic control over the shape, size, and interactions between nanoscale building blocks remains an open challenge in self‐assembly. Here, we propose to engineer triblock, star‐like polymers to design patterning on nanoparticles. We developed a theory that characterizes the structural organization of grafted polymers as a function of parameters such as grafting density, chain length, block fractions, and core shape/sizes. Stripe‐like patterning and corner/edge patch formation on arbitrarily shaped cores are readily accessible using our framework, all of which can be a priori predicted. Lastly, we employ assembly simulations to show that the resulting particles provide tighter control over structural and orientational orderings during self‐assembly. More importantly, they offer a way to pattern directional interactions that can override face–face alignment tendencies intrinsic to each core geometry. Our theory, therefore, creates a new handle for tuning nanoscale synthesis, enabling designs of complex building blocks that can target novel assemblies for materials fabrication. [ABSTRACT FROM AUTHOR]