A novel semiconductor based on annelated β-trithiophenes is presented, possessing an extraordinary compressed packing mode combining edge-to-face π–π interactions and S…S interactions in single crystals, which is favorable for more effective charge transporting. Accordingly, the device incorporating this semiconductor shows remarkably high charge carrier mobility, as high as 0.89 cm2 V−1 s−1, and an on/off ratio of 4.6 × 107 for vacuum-deposited thin films.
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