Junction‐Controlled Topological Polymerization

Abstract Methodology that enables the controlled synthesis of linear and branched polymers from an identical monomer will be a novel pathway for polymer synthesis and processing. Herein we first describe the control of one or both of the C(3)‐C(3′) and C(6)‐C(6′) coupling reactions of carbazolyl. In a second approach, an identical monomer containing two carbazolyls is polymerized using chemical and electrochemical oxidizers, leading to topologically controllable growth of linear polymers in weak oxidizer or of cross‐linked polymer chains in strong oxidizer, with satisfactory long chain propagation of step growth polymerization (Mn=6.0×104 g mol−1, Mw/Mn=2.3). This very simple polymerization with cheap reagents and low levels of waste has provided a flexible pathway for synthesis and processing of polymers.