Synthesis of a New Ladder-Type Benzodi(cyclopentadithiophene) Arene with Forced Planarization Leading to an Enhanced Efficiency of Organic Photovoltaics

We have developed a new heptacyclic benzodi(cyclopentadithiophene) (BDCPDT) unit, where 3,7-positions of the central benzo[1,2-b:4,5-b']dithiophenes (BDT) subunit are covalently rigidified with 3-positons of the two external thiophenes by two carbon bridges, forming two external CPDT rings that share two thiophene rings with the central BDT core. The distannyl-BDCPDT building block was copolymerized with 1,3-dibromo-thieno[3,4-c]pyrrole-4,6-dione (TPD) by Stille polymerization to afford a new alternating donor-acceptor copolymer PBDCPDT-TPD. The implementation of forced planarization greatly suppresses the interannular twisting to extend the effective conjugated length and preserve the interactions between the donor and acceptor segments. The device using the PBDCPDT-TPD/PC71BM (1:3 in wt%) blend processed with dimethyl sulfoxide as an additive delivered a marked PCE of 6.6% which represents a significant enhancement compared to the device using the corresponding nonfused polymer analogue with a PCE of 0.2%.