Programmable coassembly of multicomponent nanoparticles (NPs) into heterostructures has the capability to build upon nanostructured metamaterials with enhanced complexity and diversity. However, a general understanding of how to manipulate the sequence-defined heterostructures using straightforward concepts and quantitatively predict the coassembly process remains unreached. Drawing inspiration from the synthetic concepts of molecular block copolymers is extremely beneficial to achieve controllable coassembly of NPs and access mesoscale structuring mechanisms. We herein report a general paradigm of kinetic pathway guidance for the controllable coassembly of bivalent DNA-functionalized NPs into regular block-copolymer-like heterostructures the stepwise polymerization strategy. By quantifying the coassembly kinetics and structural statistics, it is demonstrated that the coassembly of multicomponent NPs, through directing the specific pathways of prepolymer intermediates, follows the step-growth copolymerization mechanism. Meanwhile, a quantitative model is developed to predict the growth kinetics and outcomes of heterostructures, all controlled by the designed elements of the coassembly system. Furthermore, the stepwise polymerization strategy can be generalized to build upon a great variety of regular nanopolymers with complex architectures, such as multiblock terpolymers and ladder copolymers. Our theoretical and simulation results provide fundamental insights on quantitative predictions of the coassembly kinetics and coassembled outcomes, which can aid in realizing a diverse set of supramolecular DNA materials by the rational design of kinetic pathways.
