A General Room Temperature Suzuki−Miyaura Polymerization Process for Organic Electronics

Abstract

Abstract π-conjugated polymers (CPs) have broad applications in high-performance optoelectronics, energy storage, sensors, and biomedicine. However, developing green and efficient methods to precisely synthesize well-defined CP structures on a large scale remains challenging and critical for their industrialization. Here, a room-temperature, scalable, homogeneous Suzuki − Miyaura-type polymerization methodology is reported with broad generality validated for 24 CPs including donor − donor, donor − acceptor, and acceptor − acceptor connectivity classes, and consistently yielding device-quality polymers with molecular masses greater than 100.0 kDa. Furthermore, the present polymerization protocol significantly reduces homocoupling structural defects, yielding more structurally regular and higher performance electronic materials and opto-electronic devices than in conventional thermally-activated polymerizations. Experimental and theoretical studies reveal that a borate-transmetalation process plays a key role in suppressing protodeboronation, which is critical for large scale structural regularity. Thus, these results provide a general polymerization tool for mass producing device-quality CPs with well-defined structural regularity.