Bowl-Shaped Bispyrrole-Fused Perylene-diimide and Its Anions.

Incorporating two pyrrole subunits at the bay positions of perylene-diimide has been a long-pursued goal since 2009, but it has not been achieved due to high strain. Herein, via one step Buchwald-Hartwig reaction, PDI-2N was successfully generated with a bowl depth of 1.52 Å. Though with electron-rich pyrrole embedding, PDI-2N 's radical anion and dianion were facilely prepared and were investigated both experimentally and theoretically. Moreover, PDI-2N crystallized in different manners under distinct conditions, and it formed tubular crystals with infinite two-directional columnar stacking under DMF conditions. This finding develops a dream bowl-shaped PDI derivative that holds great promise in organoelectronics.