Crystallization-Driven Self-Assembly of Metallo-PolyelectrolyteBlock Copolymers with a Polycaprolactone Core-Forming Segment

We report crystallization-driven self-assembly (CDSA) of metallo-polyelectrolyte block copolymers that contain cationic polycobaltocenium in the corona-forming block and crystallizable polycaprolactone (PCL) as the core-forming block. Dictated by electrostatic interactions originating from the cationic metalloblock and crystallization of the PCL, these amphiphilic block copolymers self-assembled into two-dimensional platelet nanostructures in polar protic solvents. The 2D morphologies can be varied from elongated hexagons to diamonds, and their stability to fragmentation was found to be dependent on the ionic strength of the solution.