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Despite significant advancements in the synthesis of block copolymers featuring conjugated segments for crystallization-driven self-assembly (CDSA), the effective realization of functional systems remains to be limited to a select number of meticulously engineered conjugated polymers. Current methodologies for controlled/living chain-growth polymerization do not extend to a diverse array of conjugated polymer systems, as most are synthesized through step-growth polymerization techniques. To this end, this research introduces a novel approach for the synthesis of conjugated polymers via controlled step-growth polymerization, facilitating their application in synthesizing narrowly distributed triblock copolymers and further investigation in CDSA. The study demonstrates the formation of rod-like micelles when the conjugated segment exhibits crystallinity, and spherical micelles when the conjugated segment is noncrystalline. This method presents several advantages over traditional techniques, including a broader selection of monomers and streamlined post-processing procedures. Consequently, it holds the potential to incorporate a wider variety of conjugated polymer systems into CDSA, thereby broadening the range of possible applications.

Graphical abstract: Synthesis and crystallization-driven self-assembly of triblock copolymers based on narrowly distributed α,ω-bifunctionalized conjugated polymers

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