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. [ABSTRACT FROM AUTHOR]