The self-assembly of arachidic acid (C 19 H 39 COOH) at the liquid-solid interface between 1-phenyloctane (C 6 H 5 (CH 2) 7 CH 3) and highly oriented pyrolytic graphite (HOPG) is studied by scanning tunneling microscopy (STM) to identify the structure of the monomolecular film. We observe the formation of highly ordered domains with molecules oriented in three different orientations compatible with the symmetry of the HOPG substrate, a spontaneous enantiomeric separation of the pro-chiral molecules, and reveal structural details with submolecular resolution. To determine the surface unit cell with an intrinsic calibration to the substrate atomic structure, the intermolecular distance is precisely determined from the analysis of a STM image exhibiting a moiré pattern created by the superposition of current contributions from the molecular structure with contributions from the graphite atomic lattice. The dimensions of the unit cell accommodating two molecules are |a|) 0.94 nm and |b|) 2.83 nm with an angle of 85°between unit cell vectors a and b. The respective molecular arrangement allows hydrogen bonding between carboxylic groups with an unrelaxed O-O bond distance of 0.31 nm.

SummaryFibril structures are produced at a solvent–graphite interface by self-assembly of custom-designed symmetric and asymmetric amphiphilic benzamide derivatives bearing C10 aliphatic chains. Scanning tunnelling microscopy (STM) studies reveal geometry-dependent internal structures for the elementary fibrils of the two molecules that are distinctly different from known mesophase bulk structures. The structures are described by building-block models based on hydrogen-bonded dimer and tetramer precursors of hydrazines. The closure and growth in length of building units into fibrils takes place through van der Waals forces acting between the dangling alkyl chains. The nanoscale morphology is a consequence of the basic molecular geometry, where it follows that a closure to form a fibril is not always likely for the doubly substituted hydrazine. Therefore, we also observe crystallite formation.

We present strong experimental evidence for the moiré origin of superlattices on graphite by imaging a live transition from one superlattice to another with concurrent and direct measurement of the orientation angle before and after rotation using scanning tunneling microscopy (STM). This has been possible due to a fortuitous observation of a superlattice on a nanometer-sized graphene flake wherein we have induced a further rotation of the flake utilizing the capillary forces at play at a solid–liquid interface using STM tip motion. We propose a more “realistic” tip–surface meniscus relevant to STM at solid–liquid interfaces and show that the capillary force is sufficient to account for the total expenditure of energy involved in the process.

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