Self-assembly protocol design for periodic multicomponent structures

Assembling molecular superstructures with many distinct components will allow unprecedented control over morphology at the nanoscale. Recently, this approach has been used to assemble periodic structures with precisely defined features, such as repeating arrays of pores and channels, using a large number of building blocks. Here we propose a predictive tool that allows us to optimize the nucleation and growth of unbounded, ordered structures. In what follows, we call these structures 'crystals', even though they may only be periodic in one or two dimensions. We find that the nucleation barriers and growth pathways for crystals consisting of many components exhibit generic features that are very different from those of simple crystals. To illustrate the very non-classical nature of the nucleation and growth of such structures, we study the formation of one and two-dimensional crystals with multicomponent unit cells. We find that, whilst the boundaries in the non-periodic dimensions significantly affect the stabilities of these crystals, the nucleation barriers are largely determined by the local connectivity of the associated bulk crystal and are independent of the number of distinct components in the unit cell. We predict that the self-assembly of crystals with complex morphologies can be made to follow specific pathways toward the target structure that successively incorporate key features of the three-dimensional target structure. In contrast with simple crystals, it is possible to tune the kinetics of nucleation and growth separately, thus minimizing defect formation. We show how control over self-assembly pathways can be used to optimize the kinetics of formation of extended structures with arbitrary nanoscale patterns.