Enantiopure Supramolecular Motifs of Self-Assembled Diamine-Based Chiral Molecules on Cu(100)

Abstract

The assembly of two Diphenylethylenediamine enantiomers, separately deposited on Cu(100), is investigated from the first stages of two-dimensional crystallization to the nucleation and growth of the second layer. By means of Scanning Tunneling Microscopy, we show that the chirality of the enantiomers is expressed at different levels of molecular organization. Below the monolayer completion, a disordered phase coexists with domains of a square lattice aligned with the principal crystallographic directions of the substrate. The intrinsic chirality of the molecules is only manifested through specific features contained within the corresponding unit cell. For increasing coverage, this arrangement is accompanied by a second square structure, which appears to be clockwise or counterclockwise rotated with respect to the Cu(100) directions depending on the enantiomer. The nucleation of molecular chains on top of the aligned square structure gives rise to a second layer exhibiting a striped-like configuration with remarkable left-or right-handed helicity that mirrors that of the particular enantiomer. The nearly flat configuration of the first layer molecules is confirmed by angular dependent X-ray absorption experiments and supported by molecular dynamics simulations.