Solution Assembly and Behavior of Modular RAFT Block Polyelectrolytes*

The advancement of ion-containing synthetic polymers towards functional applications relies on elucidating structure-property relationships that often involve interplay between chemically–driven and electrostatic interactions. To this end, the materials dynamics and temporal evolution of polyelectrolyte complex (PEC) assemblies are not well understood, especially non-canonical compared to non-charged counterparts. Herein, we systematically explored PECs by utilizing a RAFT block polymer platform. This approach allowed us to tune polymer microstructure and functionalize labile chain ends, enabling control of assembly size and the ability to monitor in situ diffusivity. Complementary scattering and spectroscopy provided structural information on micellar PEC formation as a function of polymer combination, concentration, and salt. These findings highlight how the rational pairing of well-defined, evolving PECs can reveal path-dependent processing pathways over relevant length- and time-scales, thereby guiding future prediction capabilities and accelerating complex materials development for end-use technologies.