Tuning Packing and Solubility of Donor (D)–Acceptor (A) Polymers by cis–trans Isomerization within Alkenyl Side Chains

Abstract

The impact of alkenyl substituents on the behavior of cyclopentadithiophene–benzothiadiazole (CDT–BTZ) donor (D)–acceptor (A) polymers in organic field-effect transistors (OFETs) and on the supramolecular organization was investigated. Linear cis- and trans-alkenes were attached to the donor unit of CDT–BTZ polymers to demonstrate the dependence of supramolecular ordering and solubility in organic solvents on chemical conformation. The layer interdigitation of the substituents differed due to shape disparities between cis- and trans-alkenes. While trans-alkenes exhibit zigzag structures that are beneficial for close packing, cis-alkenes are curved and thus possess a less regular shape that is disadvantageous to thin film ordering. This was proven by grazing incidence wide-angle X-ray scattering (GIWAXS) studies, which revealed shorter intermolecular distances for the polymer with trans-alkene substituents even in comparison to analogous polymers with saturated alkyl substituents. Furthermore, the isomeriz...