Defect-Free Alternating Conjugated Polymers Enabled by Room- Temperature Stille Polymerization

Angew Chem Int Ed Engl. 2022 Apr 11;61(16):e202115969. doi: 10.1002/anie.202115969. Epub 2022 Feb 23.

Abstract

The Stille cross-coupling polymerization is one of the most efficient synthetic methods for donor-acceptor (D-A) type π-conjugated polymers (CPs). Nevertheless, thermal-activation Stille polymerization readily produced homocoupling defects, resulting in batch-to-batch variations in copolymers quality and deteriorating the device performance of electronics and optoelectronics. Here, a room-temperature Stille-type polymerization was developed, the utility and generality of which were demonstrated by synthesis of twelve D-A CPs with high molecular weights. Importantly, the resultant copolymers possessed no homocoupling (hc) structural defects, while hc reactions were observed in the thermal-activation Stille reactions. Thus, the organic field-effect transistors (OFETs) based on the former exhibited twofold higher charge transport mobility (2.10 cm2 V-1 s-1 ), since it possessed stronger crystallinity and lower trap density of states (tDOS).

Keywords: Alternating Conjugated Polymers; Buchwald Precatalyst; Homocoupling Defects; Room-Temperature Reactions; Stille Cross-Coupling Polymerization.