Nickel-Catalyzed Direct Arylation Polymerization for the Synthesis of Thiophene-Based Cross-linked Polymers.

An earth-abundant nickel(II) bipyridine catalyst, combined with lithium hexamethyldisilazide as base, demonstrates its wide applicability in the direct arylation polymerization of di- and tri-thiophene heteroaryls with poly(hetero)aryl halides. With a nickel catalyst loading of 2.5 mol%, a series of twenty highly cross-linked organic polymers is obtained in 34 to 99 % yields. Using mixed polytopic coupling partners allows obtaining alternating and optically active thiophene-based solids with intrinsic porosity.