Understanding the Photovoltaic Behavior of A–D–A Molecular Semiconductors through a Permutation of End Groups

-alkylthiazolonethione revealed the strongest electron-withdrawing character, resulting in the lowest band gap, the highest stability, and the best photovoltaic device performance. The crystallographic analysis of two IDT derivatives yielded a highly unusual three-dimensional packing of the conjugated backbone, which is likely responsible for the remarkable photovoltaic performance of such A-D-A semiconductors.