Direct Arylation Polycondensation of Thiophene‐Based C−H Monomers†

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.