Combining Two Powerful Living Polymerizations Using Rationally Designed Bifunctional Initiators for Versatile Synthesis of Conjugated Rod–Coil Block Copolymers

Living polymerization has played a pivotal role in producing conjugated rod–coil block copolymers, offering a means to harness the functions of two distinct materials within nanoscale regions. Nevertheless, the accessibility of a diverse array of such copolymers has been restricted, primarily due to the lack of an efficient synthetic approach. To address this issue, we developed a bifunctional initiator approach that integrates two versatile living polymerizations: atom transfer radical polymerization (ATRP) and Suzuki–Miyaura catalyst-transfer polymerization (SCTP). This approach produces various conjugated rod–coil block copolymers with high precision, molecular weight control, low dispersity, and architecture control. Moreover, the one-pot synthesis of conjugated block copolymers was successfully demonstrated using consecutive photo-ATRP and SCTP. In addition, we systematically investigated the film morphology of the synthesized conjugated block copolymers by addressing the effects of the molecular weight, architecture, and regioisomeric linker units.