Predictive Modeling of Dendrimer Directed Nanoparticle Self-Assembly*

Traditional methods in nanocrystal self-assembly often rely on linear ligands isotropically grafted onto spherical cores. More recently, there has been a shift towards utilizing cores of varying shapes to expand on the current library of accessible morphologies. However, predictive simulations and designed experiments combining both the effect of ligand architecture as well as their anisotropic grafting onto nonspherical cores for self-assembly are still in their infancy. Here, we present a combined experimental and theoretical study in which a series of dendrimer ligands are used to direct the assembly of nanoplates into 2D and 3D geometries. We show that dendrimer ligands can be used to tune the degree of corona anisotropy about the nanoplates that then drives the formation of an off-set, layer-by-layer nanoplate architecture observed experimentally in 3D films. Our findings show that ligand architecture serves as a handle for layer specific, fine-tuning of self-assembly and provide a systematic approach to theoretically predict morphology purely from experimental design parameters.