This review presents a mechanistic insight into DArP and describes the development of DArP catalytic systems for varied thiophene-based C−H monomers. The control of the primary defects (i.e., branching and homo-coupling) in thiophene-based DArP is also discussed.

Comprehensive Summary

Direct arylation polycondensation (DArP) has emerged as an eco-friendly and atom-efficient methodology for the syntheses of π-conjugated polymers (CPs). This approach features the direct C—H arylation of an aromatic hydrocarbon with an aryl halide. Given the prevalence of thiophene-containing CPs, achieving efficient and defect-free DArP of thiophene-based C−H monomers is of great significance. This review presents a mechanistic insight into DArP and describes the development of DArP catalytic systems for varied thiophene-based C−H monomers. Moreover, the control of the primary defects (i.e., branching and homo-coupling) in thiophene-based DArP is also elaborated. By emphasizing the principles behind monomer selection and catalytic system optimization, this review intends to provide a framework for future advancements in the DArP of thiophene-containing CPs.