Synthesis and Characterization of Bis[1]benzothieno[3,2-b:2′,3′-d]pyrroles: Quantitative Effects of Benzannulation on Dithieno[3,2-b:2′,3′-d]pyrroles

The synthesis of four N-functionalized bis[1]benzothieno[3,2-b:2′,3′-d]pyrroles (BBTPs) is reported in order to provide a more detailed characterization of these fused-ring units, as well as increase the scope of known BBTP units available for application to conjugated materials. The optical, electronic, and structural properties of the resulting BBTP units have been compared to the parent N-alkyl- and N-aryl-dithieno[3,2-b:2′,3′-d]pyrroles (DTPs), as well as their corresponding 2,6-diphenyl derivatives, in order to fully quantify the relative electronic effects resulting from benzannulation of the parent DTP building block. Such comparative analysis reveals that benzannulation results in a red-shifted absorbance, but to a lesser extent than simple phenyl-capping of the DTP. More surprising is that benzannulation results in stabilization of the BBTP HOMO, compared to the destabilization normally observed with extending the conjugation length of the backbone.