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 angstrom. 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.

Automated summary

Incorporating two pyrrole subunits at the bay positions of perylene-diimide, PDI-2N, with a bowl depth of 1.52 angstrom, was successfully synthesized via one step Buchwald-Hartwig reaction. Despite the electron-rich pyrrole embedding, the radical anion and dianion of PDI-2N were easily prepared and investigated experimentally and theoretically. Furthermore, PDI-2N crystallized in different manners under distinct conditions, forming tubular crystals with infinite two-directional columnar stacking under DMF conditions. This discovery presents a promising bowl-shaped PDI derivative for organoelectronics.