Inky flower-like supermicelles assembled from π-conjugated block copolymers

Flower-like hierarchical nano-/meso-structures assembled from different kinds of materials have great application potential due to their advantages of high surface-To-volume ratios, high loading and adsorption capacities. These biomorphic superarchitectures are commonly obtained using inorganic, organic-inorganic hybrid and block copolymer (BCP) materials. However, the self-Assembly of functional π-conjugated BCPs with weak intermolecular interactions has rarely been realized through a facile approach; moreover, the corresponding studies on how the polymer properties and assembly conditions influence the ultimate dimensionality and morphology of micelles are also scarce. Herein, we report the realization of inky flower-like hierarchical supermicelles taking advantage of the ultrashort corona block in the system of poly(2,5-di(2′-octyloxy)-1,4-phenylenevinylene)-block-poly(2-vinylpyridine) (PPV-b-P2VP). The dimensionality and morphology are successfully controlled by altering the block ratio of BCPs and the polarity of the selective solvent. Then, the growth process of the flower-like supermicelles is observed from the initial flower heart to the final flower petals. Furthermore, it is demonstrated that the formation of micelles is driven by the π-π interactions between the PPV blocks. Our study on constructing and regulating hierarchical supermicelles in a new functional π-conjugated system would be valuable to other BCPs-based assembly systems.