2 research outputs found
Controlling Molecular Self-Assembly on an Insulating Surface by Rationally Designing an Efficient Anchor Functionality That Maintains Structural Flexibility
Molecular self-assembly on surfaces is dictated by the delicate balance between intermolecular and molecule–surface interactions. For many insulating surfaces, however, the molecule–surface interactions are weak and rather unspecific. Enhancing these interactions, on the other hand, often puts a severe limit on the achievable structural variety. To grasp the full potential of molecular self-assembly on these application-relevant substrates, therefore, requires strategies for anchoring the molecular building blocks toward the surface in a way that maintains flexibility in terms of intermolecular interaction and relative molecule orientation. Here, we report the design of a site-specific anchor functionality that provides strong anchoring toward the surface, resulting in a well-defined adsorption position. At the same time, the anchor does not significantly interfere with the intermolecular interaction, ensuring structural flexibility. We demonstrate the success of this approach with three molecules from the class of shape-persistent oligo(<i>p</i>-benzamide)s adsorbed onto the calcite(10.4) surface. These molecules have the same aromatic backbone with iodine substituents, providing the same basic adsorption mechanism to the surface calcium cations. The backbone is equipped with different functional groups. These have a negligible influence on the molecular adsorption on the surface but significantly change the intermolecular interaction. We show that distinctly different molecular structures are obtained that wet the surface due to the strong linker while maintaining variability in the relative molecular orientation. With this study, we thus provide a versatile strategy for increasing the structural richness in molecular self-assembly on insulating substrates
One-Pot Synthesis and AFM Imaging of a Triangular Aramide Macrocycle
Macrocyclizations in exceptionally
good yields were observed during
the self-condensation of <i>N</i>-benzylated phenyl <i>p</i>-aminobenzoates in the presence of LiHMDS to yield three-membered
cyclic aramides that adopt a triangular shape. An <i>ortho</i>-alkyloxy side chain on the <i>N</i>-benzyl protecting
group is necessary for the macrocyclization to occur. Linear polymers
are formed exclusively in the absence of this Li-chelating group.
A model that explains the lack of formation of other cyclic congeners
and the demand for an <i>N-</i>(<i>o</i>-alkoxybenzyl)
protecting group is provided on the basis of DFT calculations. High-resolution
AFM imaging of the prepared molecular triangles on a calcite(10.4)
surface shows individual molecules arranged in groups of four due
to strong surface templating effects and hydrogen bonding between
the molecular triangles