The Effect of Alkyl Chain Length on Well-Defined Fluoro-Arylated Polythiophenes for Temperature-Dependent Morphological Transitions

[Image: see text] Understanding the relationship between the molecular structure and morphological behaviors of well-defined semiconducting polymers is essential for developing novel conjugated building blocks and determining the origin of the functional characteristics of semiconducting polymers. Here, we provide insights into the significant temperature-dependent morphological transitions of novel well-defined polythiophene derivatives with m-alkoxy-substituted fluoro-aryl side units: poly(3-(4-fluoro-3-(hexyloxy)phenyl)thiophene) (PHFPT) and poly(3-(4-fluoro-3-(dodecyloxy)phenyl)thiophene) (PDFPT). We found that these unique morphological transitions depend on the alkyl chain length of the substituted fluoro-aryl side units. In PHFPT with short alkyl chains, the thermal treatment promotes a crowded interdigitated packing structure, resulting in narrow lamellar spacings in its crystalline structure. In contrast, the long alkyl chain of PDFPT acts as a physical spacer and disturbs the crowded interdigitation. In addition, the thermal treatment induces the backbone planarization and an ordered packing morphology in PDFPT. These demonstrations provide a critical milestone for the phase transitions of semiconducting polymers with conjugated side units.