A series of core-perfluoroalkylated perylene bisimides (PBIs) have been efficiently synthesized by copper-mediated perfluoroalkylation of dibrominated PBIs. Their aromatic cores are highly twisted due to the steric encumbrance in the bay regions as revealed by single-crystal X-ray analysis. The organic field-effect transistors (OFETs) incorporating these new n-type semiconductors show remarkable air-stability and good field effect mobility.

Tetraiodinated di(perylene bisimide) has been prepared from tetrabrominated perylene bisimide by the combination of Ullmann-type coupling, C-H transformation, and halogen-exchange. The crystal structure analysis confirmed that the aromatic core is quite distorted because of the electrostatic repulsion and steric encumbrance of iodine substituents in the bay regions.