Crystal Engineering in Two Dimensions: An Approach to Molecular Nanopatterning

We describe a surprising cooperative adsorption process observed by scanning tunneling microscopy (STM)
at the liquid−solid interface. The process involves the association of a threefold hydrogen-bonding unit,
trimesic acid (TMA), with straight-chain aliphatic alcohols of varying length (from C7 to C30), which coadsorb
on highly oriented pyrolytic graphite (HOPG) to form linear patterns. In certain cases, the known TMA
“flower pattern” can coexist temporarily with the linear TMA−alcohol patterns, but it eventually disappears.
Time-lapsed STM imaging shows that the evolution of the flower pattern is a classical ripening phenomenon.
The periodicity of the linear TMA−alcohol patterns can be modulated by choosing alcohols with appropriate
chain lengths, and the precise structure of the patterns depends on the parity of the carbon count in the alkyl
chain. Interactions that lead to this odd−even effect are analyzed in detail. The molecular components of the
patterns are achiral, yet their association by hydrogen bonding leads to the formation of enantiomeric domains
on the surface. The interrelation of these domains and the observation of superperiodic structures (moiré
patterns) are rationalized by considering interactions with the underlying graphite surface and within the
two-dimensional crystal of the adsorbed molecules. Comparison of the observed two-dimensional structures
with the three-dimensional crystal structures of TMA−alcohol complexes determined by X-ray crystallography
helps reveal the mechanism of molecular association in these two-component systems.