Direct Heteroarylation Guidelines for Well-Defined Thiophene-Based Conjugated Molecules.

Direct (hetero)arylation polymerization (DHAP) shows great promise for simple, low cost, and benign preparation of conjugated polymers. However, coupling selectivity has always posed a problem. Herein, direct (hetero)arylation was studied on small molecule models to develop suitable conditions for C-C couplings between 2-methylthiophene acting as an electron-donating moiety and 2-thiophenecarbonitrile acting as an electron-withdrawing moiety, when one of the partners is brominated. We observed that the best conditions are obtained when the electron-withdrawing moiety is halogenated.