Angular-Shaped 4,9-Dialkylnaphthodithiophene-Based Donor–Acceptor Copolymers for Efficient Polymer Solar Cells and High-Mobility Field-Effect Transistors

Although the tetracyclic angular-shaped naphthodithiophenes (aNDTs) derivatives are an emergent building block for constructing promising semiconductor conjugated polymers, the absence of aliphatic side chains as solubilizing groups on the aNDTs greatly restricted their further application toward polymer synthesis. To create a new class of aNDT-based polymers for widespread applications in solution-processable OFETs and PSCs, side-chain engineering of the aNDT-based structures plays a pivotal role in improving solubility and optimizing electronic/steric properties associated with the resultant solar cell characteristics. In this research, we developed an efficient and straightforward methodology to construct the angular naphthodithophene core with regiospecific introduction of two aliphatic chains at its 4,9-positions via a base-induced double 6π-cyclization. For the first time, the corresponding 2,7-distannylated-4,9-dialkylated aNDT monomers were polymerized with FBT and DPP acceptors to make two new PaNDTDTFBT and PaNDTDPP donor–acceptor copolymers. The photovoltaic devices based on the PaNDTDTFBT:PC71BM blend not only showed a promising PCE of 6.52% with conventional configuration but also achieved a higher PCE of 6.86% with inverted configuration. Moreover, PaNDTDPP with strong intermolecular interaction achieved a high FET hole mobility of 0.202 cm2 V–1 s–1.