Exceptional Coupling of Tetrachloroperylene Bisimide:  Combination of Ullmann Reaction and C−H Transformation

We present the facile one-pot synthesis of novel triply linked diperylene bisimide (diPBI) and tetrachlorinated diperylene bisimide (4CldiPBI) by l-proline promoted CuI-involved coupling of tetrachloro-PBI, which represents the first step toward the completely bay-region fused oligo-PBIs. The triply linked fused diPBIs display the broad absorption with high extinction coefficients in the region of visible light and the extremely strong electron-accepting ability, which is very promising for use as functional components of photovoltaic devices.