Assembling Ordered Crystals with Disperse Building Blocks

Conventional colloidal crystallization techniques typically require low dispersity building blocks in order to make ordered particle arrays, resulting in a practical challenge for studying or scaling these materials. Nanoparticles covered in a polymer brush therefore may be predicted to be challenging building blocks in the formation of high-quality particle superlattices, as both the nanoparticle core and polymer brush are independent sources of dispersity in the system. However, when supramolecular bonding between complementary functional groups at the ends of the polymer chains are used to drive particle assembly, these "nanocomposite tectons" can make high quality superlattices with polymer dispersities as large as 1.44 and particle diameter relative standard deviations up to 23% without any significant change to superlattice crystallinity. Here we demonstrate and explain how the flexible and dynamic nature of the polymer chains that comprise the particle brush allows them to deform to accommodate the irregularities in building block size and shape that arise from the inherent dispersity of their constituent components. Incorporating "soft" components into nanomaterials design therefore offers a facile and robust method for maintaining good control over organization when the materials themselves are imperfect.