Connecting Molecular and Supramolecular Shapeshifting by the Ostwald's Nucleation Stages of a Star Giant Molecule.

The shapeshifting behavior for synthetic matters was found at either the molecular or supramolecular level, but the connection between shapeshifting at the two hierarchical levels remains missing. In this study, an 8-arm star giant molecule, , was synthesized to connect the molecular and supramolecular shapeshifting. Controlling the conditions of bulk self-assembly allowed us to bring into three different Ostwald's stages of nucleation. The high conformational flexibility of facilitates molecular shapeshifting and allows to take the discotic, rod-like and star-like geometries in different Ostwald's stages. Simultaneous changes in the supramolecular scaffolds were observed as the discotic, rod-like and star-like molecules self-assembled into the supramolecular scaffolds of 1D columns, 2D lamellae, and 3D networks, respectively. These changes in the hierarchical structures also affect the CO affinity of . Therefore, the connection between the molecular/supramolecular shapeshifting and the structure-driven property changes of were established by taking advantage of the high conformational freedom of the 8-arm star giant molecule and its diverse self-assembly pathways leading to the different Ostwald's stages.