Synthesis of Conjugated Polymers via Transition Metal Catalysed C-H Bond Activation

Transition metal catalysed C-H bond activation chemistry has emerged as an exciting and promising approach in organic synthesis. This allows us to synthesize a wider range of functional molecules and conjugated polymers in a more convenient and more atom economical way. The formation of C-C bonds in the construction of pi-conjugated systems, particularly for conjugated polymers, has benefited much from the advances in C-H bond activation chemistry. Compared to conventional transition-metal catalysed cross-coupling polymerization such as Suzuki and Stille cross-coupling, pre-functionalization of aromatic monomers, such as halogenation, borylation and stannylation, is no longer required for direct arylation polymerization (DArP), which involve C-H/C-X cross-coupling, and oxidative direct arylation polymerization (Ox-DArP), which involves C-H/C-H cross-coupling protocols driven by the activation of monomers' C(sp² )-H bonds. Furthermore, poly(annulation) via C-H bond activation chemistry leads to the formation of unique pi-conjugated moieties as part of the polymeric backbone. This review thus summarises advances to date in the synthesis of conjugated polymers utilizing transition metal catalysed C-H bond activation chemistry. A variety of conjugated polymers via DArP including poly(thiophene), thieno[3,4-c]pyrrole-4,6-dione)-containing, fluorenyl-containing, benzothiadiazole-containing and diketopyrrolopyrrole-containing copolymers, were summarized. Conjugated polymers obtained through Ox-DArP were outlined and compared. Furthermore, poly(annulation) using transition metal catalysed C-H bond activation chemistry was also reviewed. In the last part of this review, difficulties and perspective to make use of transition metal catalysed C-H activation polymerization to prepare conjugated polymers were discussed and commented.