Programming hierarchical supramolecular nanostructures by molecular design

Supramolecular nanostructures with tunable dimensionalities are fabricated by deposition of benzene–carboxylic acids on the Cu(110) surface. By tailoring the number and position of the functional moieties, the structure of the final molecular assemblies can be rationally modified ranging from isolated one-dimensional chains to compact two-dimensional islands. Molecular units are chosen that can assemble through metal–organic and electrostatic interactions. The hierarchy between these intermolecular forces guarantees that a primary organization level, constituted by metal–organic polymeric chains, is developed by all molecular units while the secondary interchain interactions can be arbitrarily adjusted. Scanning tunneling microscopy, density functional theory calculations, and kinetic Monte Carlo simulations are used to characterize and rationalize the experimental findings.