Random Poly(3-hexylthiophene-co-3-cyanothiophene) Copolymers via Direct Arylation Polymerization (DArP) for Organic Solar Cells with High Open-Circuit Voltage

A family of four poly(3-hexylthiophene) (P3HT) based copolymers containing 5, 10, 15, and 20% of 3-cyanothiophene (CNT) incorporated in a random fashion with a regioregular linkage pattern (P3HT-CNT) were successfully synthesized via direct arylation polymerization (DArP). Unique reaction conditions, previously reported for P3HT, were used, which employ very low loadings of Pd(OAc)(2) as a catalyst and an inexpensive bulky carboxylic acid (neodecanoic acid) as an essential part of the palladium catalytic center. The chemical structures and optoelectronic properties of DArP P3HT-CNT polymers were found to be similar to those of previously investigated P3HT-CNT polymers synthesized via Stille polycondensation. All polymers are semicrystalline with high hole mobilities and UV-vis absorption profiles that resemble P3HT, while the polymer highest occupied molecular orbital (HOMO) level decreases with increasing content of cyanothiophene in both DArP and Stifle P3HT-CNT polymers. In photovoltaic devices with a PC61BM acceptor, DArP P3HT-CNT copolymers showed slightly lower open-circuit voltages (V-oc) than their Stile P3HT-CNT analogues but similar fill factors (FF) and significantly enhanced short-circuit current densities (J(sc)), leading to overall power conversion efficiencies for the DArP polymers that rivaled or exceeded those of the Stille polymers. This work further emphasizes the generality and relevance of DArP for the synthesis of conjugated polymers for use in organic solar cells and the attractive simplicity and ease of synthesis of random conjugated polymers.