Crystallization‐Driven Self‐Assembly‐ <i>Substrated</i> ‐Polymerization‐Induced Self‐Assembly (CDSA‐ <i>s</i> ‐PISA). Toward the Next Generation of Supercarriers.

All the objects that surround us can be seen as combinations of elementary shapes like spheres, rods, and squares that perform complex tasks when connected in a well-defined manner. While making a device by assembling those shapes remains relatively easy at the human scale, it is extremely challenging to do so at the nanoscale, due to the difficulty to covalently attach at a defined position a nano-object with a given shape to another one of different geometry. To circumvent this hurdle, here, we introduce an innovative approach that consists in performing polymerization-induced self-assembly (PISA) onto core-crystalline micelles prepared by crystallization-driven self-assembly (CDSA). Because of the intrinsic properties of CDSA, one can construct one- or two-dimensional substrates to initiate PISA at very specific locations. Performing CDSA-substrated-PISA (CDSA-s-PISA) onto triblock co-micelles where only the central block was PISA active, led to the formation of elongated structures bearing one or two beads on their central parts, while CDSA-s-PISA on entirely PISA active micelles and in presence of free macro-CTA, allowed the preparation of uniform elongated micelles fully decorated with beads. These results offer a sneak peek of what the next generation of multitasks polymeric assemblies will be.