Effect of Block Sequence in All-Conjugated Triblock Copoly(3-alkylthiophene)s on Control of the Crystallization and Field-Effect Mobility

Despite recent impressive advances in synthesis of all-conjugated diblock copolymers via facile quasi-living Grignard metathesis (GRIM) polymerization, it remains challenging to achieve well-defined all-conjugated triblock copolymers of interest. Herein, we report the judicious design and synthesis of a series of all-conjugated triblock copoly­(3-alkylthiophene)­s consisting of poly­(3-butylthiophene) (P3BT), poly­(3-hexylthiophene) (P3HT), poly­(3-octylthiophene) (P3OT), or poly­(3-dodecylthiophene) (P3DDT) in all 12 possible combinations. The effects of block sequences and the length of alkyl side chains on their cocrystallization and microphase-separated structures are investigated. Moreover, the correlation between different crystalline structures and charge mobilities in organic field-effect transistors (OFETs) is scrutinized. These rationally synthesized triblock copoly­(3-alkylthiophene)­s self-assemble into cocrystals with an edge-on orientation in as-cast and 150 °C-annealed samples. Remarkably, the combinations with the shortest alkyl side chains placed as the central block (i.e., P3HT-b-P3BT-b-P3OT, P3HT-b-P3BT-b-P3DDT, P3OT-b-P3BT-b-P3DDT, and P3OT-b-P3HT-b-P3DDT) exhibit higher film crystallinity and charge mobilities than the other two combinations where the blocks with shortest alkyl side chains are located at two terminals. Intriguingly, upon thermal annealing near the melting temperature of these combinations, P3BT-b-P3OT-b-P3HT, P3BT-b-P3DDT-b-P3OT, and P3HT-b-P3DDT-b-P3OT can retain their cocrystalline structure while the other combinations are found to microphase separate. Finally, the all-conjugated triblock copoly­(3-alkylthiophene)­s with proper block sequence demonstrate stable charge mobilities at high temperatures and good flexibility in OFET devices. Taken together, this study elucidates that the block sequence is of key importance on control of the crystallization and charge transport behavior of poly­(3-alkylthiophene)-based triblock copolymers.