Ring Fusion Elevates the Electronic Mobility of Azabenzannulated Perylene Diimide

The backwardness of n‐type organic semiconductors still exists compared with the p‐type counterparts. Thus, the development of high‐performance n‐type organic semiconductors is of great importance for organic electronic devices and their integrated circuits. In recent years, azabenzannulated perylene diimide (PDI), as one of immense bay‐region‐annulated PDI derivatives, has drawn considerable attentions. However, the electronic mobilities of azabenzannulated PDI derivatives are barely satisfactory. In this contribution, the peripheral benzene ring in azabenzannulated PDI 2 was fused to the ortho position by intramolecular C−H arylation cyclization. This endows the resultant azabenzannulated PDI 4 a planar configuration as well as electron deficient pentagonal ring. As a result, the electronic mobility of 4 is almost two orders of magnitude higher than that of the nonfused azabenzannulated PDI 2. This work shall pave a new avenue in elevating the performance of azabenzannulated PDI in organic electronics. An ortho five‐membered ring‐fused azabenzannulated perylene diimide (AzaBPDI) is synthesized by intramolecular C−H arylation cyclization. The ring‐fused AzaBPDI derivative exhibits planar configuration and superior electronic mobility in organic field‐effect transistor (OFET) devices in comparison to the parent non‐fused one. This result provides a robust design strategy for achieving high‐performance AzaBPDI derivatives.