Influence of Backbone Chlorination on the Electronic Properties of Diketopyrrolopyrrole (DPP)-Based Dimers

Chlorination of π-conjugated backbones is garnering great interest because of fine-tuning electronic properties of conjugated materials for organic devices. Herein we report a synthesis of thiophene-based diketopyrrolopyrrole (DPP) dimers and their chlorinated counterparts by introducing a chlorine atom in the outer thiophene ring to investigate the influence of the chlorination on charge transport. The backbone chlorination lowers both the HOMO and the LUMO of the dimers and leads to a blue-shift of maximum absorption in compared to unsubstituted counterparts. X-ray analysis reveals that the chlorine atom prompts the outer thiophene ring out of the planarity of the backbone with a relatively large torsional angle. The chlorinated dimers exhibit slipped one-dimensional packing decorated with multiple intermolecular interactions, because of a combination of a negative inductive effect and a positive mesomeric effect of the halogen atom, which might facilitate charge transport within the oligomeric backbones. The mobility in the single-crystal OFET devices of the chlorinated dimers is up to 1.5 cm²  V^-1  s^-1 , which is two times higher than that of the non-chlorinated DPP dimers. Our results indicate that the chlorine atom plays a key role in directing non-covalent interactions to lock the slipped stacks, enabling electronic coupling between adjacent molecules for efficient charge transport. In addition, our results also demonstrate that these DPP dimers with straight n-octyl chains exhibit higher mobilities than the dimers with branched 2-ethylhexyl chains.