LAUSR

Abstract Since dibromo perylene diimides (DBPDIs) contain two isomers that are difficult to separate, isomeric effect on properties and applications of PDI polymers has been rarely studied. Few ladder-type polymers have been used in organic solar cells. Herein, single-strand polymers (PrPDIT) were synthesized by the polymerization of regioisomerically-pure 1,7-dibromo-PDIs (1,7-DBPDIs) and 2,5-bis(trimethylstannyl)thiophene. Furthermore, ladder-type polymers (FPrPDIT) were obtained by the highly efficient photo-induced cyclization of polymers PrPDIT. The effects of isomers and molecular weight on the absorption, electrochemistry, thermal stability, and photovoltaic application of polymers were studied. Pure 1,7-DBPDIs lead to polymers with molecular weight distribution as low as 1.08. These polymers with strong absorption in 300–700 nm, low-lying lowest unoccupied molecular orbital (LUMO) energy levels around −4.0 eV and high thermal stability could be excellent electron acceptors. Regioisomerically-pure polymers demonstrate better photovoltaic performance than that of mixed ones. The highest power conversion efficiency (PCE) of all-polymer solar cells based on PrPDIT and FPrPDIT is up to 5.95% and 4.52% respectively.