Consequences of a Single Double Bond within a Side-Group on the Ordering of Supra-Molecular Polymers

By combining atomic force microscopy experiments and full-atomistic computer simulations, we compared the twodimensional ordering dynamics of two variants of supramolecular polymers of bis-urea molecules which differed only by a single cisdouble bond in their side groups. At early stages of ordering, the double bonds favored kinks at the level of individual molecules, which induced transient steric constraints hindering the spontaneous formation of long supramolecular polymers. In addition, due to these kinks, molecule−substrate interactions were disturbed. At later stages, however, due to a progressively increasing number of established directional hydrogen bonds between molecules, the self-assembly process improved and thereby increased the length of the supramolecular polymers. Large domains of micrometer-long and aligned supramolecular polymers were formed, epitaxially guided by the graphite substrate and having a constant width consistent with the length of the molecule. Thus, introducing flexible (kinked) side chains can reduce the nucleation probability and slow the growth of supramolecular polymers due to incommensurablility with the crystalline substrate. Such an elementary control of nucleation and growth via the introduction of a single double bond represents a powerful pathway for the formation of large ordered domains of aligned one-dimensional supramolecular polymers.