Theoretical study on the CH⋯NC hydrogen bond interaction in thiophene-based molecules

► Ab initio and DFT calculations on the CH⋯NC hydrogen bond in thiophene-based molecules. ► The hydrogen bond interaction is weak but distinguishable from pure van der Waals interactions. ► The influence of substitution is largest in the methoxy-substituted 1-cyano-thiophene dimer. ► The highly local character of the hydrogen bond in DCNDBQT chains is demonstrated. ► The structure and the electronic properties of the monomer and the oligomer are similar.