Combining Two\nPowerful Living Polymerizations Using\nRationally Designed Bifunctional Initiators for Versatile Synthesis\nof Conjugated Rod–Coil Block Copolymers

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