Hydrogen bonding and π-stacking in highly organized arenes-based molecular wire

We have theoretically investigated the stacking of promising arenes-based molecules into a highly organized columnar structure in which hydrogen bonding plays a major role. The nature of the functional groups attached to benzene creates a strong net dipole moment which initiates and favors a symmetric π-stacking of the molecules. The formation of multiple hydrogen bonds between molecular units enforces the stacking of arenes, dramatically improves the overall stability of the assemblies, and leads to relatively large intermolecular distances. In contrast, the variation of electronic properties, such as a decreasing band gap, during the formation of the molecular wire indicates the presence of a significant delocalization of π-electron over the entire assembly. The asymptotic variation of cohesion energy and other calculated properties over a relatively small molecular assembly indicates a rapid convergence of the electronic structure of the system toward its extended 1D limit.