Synthesis of conjugated polymers via direct C–H/C–Cl coupling reactions using a Pd/Cu binary catalytic system

Direct arylation polycondensation is regarded as an efficient synthetic method for conjugated polymers. This methodology is difficult to apply to dichloroaryl monomers because of the low reactivity of the C–Cl bonds compared to that of the C–Br bonds in dibromoaryl monomers, which have been widely used in direct arylation polycondensation. In this research, direct arylation polycondensation of dichloroaryl monomers was achieved by the use of a Pd/Cu binary catalytic system. Optimisation of the molar ratio of the Pd and Cu catalyst resulted in the formation of high-molecular-weight polymers in good yields. Structural defects of the polymer at the terminal unit were minimised by logical choice of the monomer ratio on the basis of the reaction mechanism. The obtained polymer with relatively low structural defects showed a higher quantum efficiency of photoluminescence and electroluminescence than that of the polymer with irregular terminal structures.