Abstract
We show that substituting quaterthiophene cores with strong H-bond aggregators, such as urea groups, provides an efficient way to adjust the mutual in-plane displacements of the semiconducting units and promote charge transfer. Our 2-D structure-property mapping reveals that the insertion of substituents induces up to 2.0 Å longitudinal and transversal displacements between the π-conjugated moieties. Some of these relative displacements lead to improved cofacial orbital overlaps that are otherwise inaccessible due to Pauli repulsion. Our results also emphasize that the fine-tuning of in-plane displacements is more effective than achieving "tighter" packing to promote charge-transfer properties.