syn/anti‐Oligothienoacene Diimides with up to 10 Fused Rings

We report a facile and powerful strategy to prepare libraries of oligothienoacene diimides that include anti‐ and syn‐isomers using palladium‐catalyzed C−H activation and an unexpected 1,2‐sulfur migration. Through this strategy, a series of oligothienoacene diimides containing 6, 8, and 10 fused rings were synthesized. The molecular geometry and extent of π‐conjugation have dramatic effects on the electronic properties, degree of crystallinity, and charge‐carrier transport properties. Notably, single‐crystal microfibers of syn‐3 c show electron mobilities up to 4.2 cm2 V−1 s−1, illustrating the significant potential of these materials for organic electronic devices. Our work demonstrates the versatility of this strategy for the development of oligothienoacene diimide libraries, in particular complex and large syn‐oligothienoacene diimides, which are difficult to prepare by present methods. A facile and direct synthetic strategy that features a combination of palladium‐catalyzed C−H activation and unexpected 1,2‐sulfur migration for the synthesis of syn/anti‐oligothienoacene diimides, is present. The resulting oligomers show significant potential for organic electronic devices with the electron mobility up to 4.2 cm2 V−1 s−1.