Formation of a hydrogen-bond network via an amide group is a key driving force for the nucleation-elongation-type self-assembly that is often seen in biomolecules and artificial supramolecular assemblies. In this work, rod-coil-like aromatic compounds bearing an amide (1 a-3 a) or urea group (1 u-3 u) were synthesized, and their self-assemblies on a 2-D surface were investigated by scanning tunneling microscopy (STM). According to the quantitative analysis of the concentration dependence of the surface coverage, it was revealed that the strength of the hydrogen bond (i.e., amide or urea) and the number of non-hydrogen atoms in a molecular component (i.e., size of core and length of alkyl side chain) play a primary role in determining the stabilization energy during nucleation and elongation processes of molecular ordering on the HOPG surface.

The effect of molecule-molecule interactions on the size and shape of two-dimensional (2-D) ordering domains was investigated using scanning tunneling microscopy (STM) at the liquid/solid interface. Synthesized alkoxybenzene derivatives bearing amide group tend to form very large domains of 2-D orderings (>0.25 μm), whereas the domain size of corresponding urea derivatives was significantly small in the same condition. The quantitative analysis of the concentration dependence of surface coverage using a nucleation-elongation model suggests that the replacement of amide functionality by urea increased the equilibrium constant of the nucleation process of 2-D self-assembly, which is a key factor for the domain size at the liquid/solid interface. Interestingly, the STM observation revealed that a slight difference of molecular structure influences the shape of 2-D ordering domains, and needle-shaped domains with large aspect ratio around 10 were observed by tuning molecule-molecule intramolecular interactions in 2-D self-assembly formed at a liquid/graphite interface.

Two-dimensional (2-D) self-assembly of diarylethene (DAE)–peptide conjugates at the octanoic acid/graphite interface was investigated by scanning tunnelling microscopy (STM) and strong stabilization effect of β-sheet formation was revealed.

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