Effect of Chemical Modification on Molecular Ordering in Polydiketopyrrolopyrrole Copolymers: From Liquid Crystalline to Crystalline.

The chemical architecture of conjugated polymers is often designed by contemplating and understanding the consequences of structural changes on electronic properties at the molecular level. However, even minor changes to the chemical structure of a polymer can significantly influence the packing arrangement, which also influences the electronic properties of the bulk material. Here, we investigate the molecular arrangement in the ordered state at room temperature of a series of three different polydiketopyrrolopyrroles (PDPPs) in bulk and oriented thin films in detail by wide-angle X-ray scattering and by atomic force microscopy. The changes in the chemical structure of the investigated PDPPs, namely, an additional side chain or a different flanking unit, lead to an increase in long-range order and thereby to a change in the phase state from sanidic ordered via sanidic rectangular or oblique to crystalline.