Adjusting the Local Arrangement of pi-Stacked Oligothiophenes through Hydrogen Bonds: A Viable Route to Promote Charge Transfer

作者：Liu Hongguang^*; Bremond Eric; Prlj Antonio; Gonthier Jerome F; Corminboeuf Clemence

来源：Journal of Physical Chemistry Letters, 2014, 5(13): 2320-2324.

DOI：10.1021/jz501078s

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 angstrom longitudinal and transversal displacements between the pi-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.

• 出版日期2014-7-3