Exploring Solution Behavior of Fully Rigid “Block Copolymers” with Sphere-Rod Molecular Architecture

The rich solution behavior of block copolymers, especially self-assembly of amphiphilic block copolymers in solution, have been extensively explored in past decades. While the traditional block copolymers often involve flexible chains, some novel “copolymers” containing rigid components might also demonstrate interesting self-assembly behavior. Here, we explore solution behavior of fully rigid“block copolymers”hybrid macromolecules based on spherical polyoxometalates and rod-like oligofluorenes. We report here that rigid macromolecules can achieve continuous curvature change and consequently form unexcepted multilayer vesicular structures. The highly uniform, multilayered vesicles have complete onion-like structure from most inner to outer layers with fixed interlayer distance, and the vesicle size/layer number can be accurately controlled by solution conditions including temperature, solvent composition, and salt concentration. Additionally, reversible response of vesicle size/layer number is observed by simplify changing the solution temperature. The effects of rod length and molecular architecture will also be discussed.