Synthesis, Molecular and Photovoltaic Properties of Donor–Acceptor Conjugated Polymers Incorporating a New Heptacylic Indacenodithieno[3,2-b]thiophene Arene

We have developed a new multifused indacenodithieno[3,2-b]thiophene arene (IDTT) unit where the central phenylene is covalently fastened with the two outer thieno[3,2-b]thiophene (TT) rings, forming two cyclopentadiene rings embedded in a heptacyclic structure. This rigid and coplanar IDTT building block was copolymerized with electron-deficient acceptors, 4,7-dibromo-2,1,3-benzothiadiazole (BT), 4,7-dibromo-5,6-difluoro-2,1,3-benzothiadiazole (FBT) and 1,3-dibromo-thieno[3,4-c]pyrrole-4,6-dione (TPD) via Stille polymerization, respectively. Because the higher content of the thienothiophene moieties in the fully coplanar IDTT structure facilitates π-electron delocalization, these new polymers show much improved light-harvesting abilities and enhanced charge mobilities compared to PDITTBT copolymer using hexacyclic diindenothieno[3,2-b]thiophene (DITT) as the donor moieties. The device using PIDTTBT:PC71BM (1:4, w/w) exhibited a decent power conversion efficiency (PCE) of 3.8%. Meanwhile, the solar cell us...