Solvent‐Driven Supramolecular Wrapping of Self‐Assembled Structures

Self-assembly relies on the ability of smaller and discrete entities to spontaneously arrange into more organized systems by means of the structure-encoded information. Here we show that the design of the media can play a role even more important than the chemical design. It not only determines the self-assembly pathway, at a single-component level, but in a very narrow solvent composition, a supramolecular homo-aggregate can be non-covalently wrapped by a second component that possess different crystal lattice. Such process has been followed in real time by confocal microscopy thanks to the different emission colours of the aggregates formed by the two isolated Pt(II) complexes. This coating is reversible and controlled by the media composition. Single crystal X-ray diffraction and molecular simulations based on coarse-grained (CG) models allowed the understanding of the properties displayed by the different aggregates. Such findings can open a new way to construct hierarchical supramolecular structures.