2D analogues of the inverted hexagonal phase self-assembled from 4,6-dialkoxylated isophthalic acids at solid–liquid interfaces

Abstract

Self-assembly of organic molecules at solid–liquid interfaces is a route for developing novel functional materials on surfaces and modeling assembly phenomena in 3D. 5-Alkoxylated isophthalic acids (ISA) are known to self-assemble into two-dimensional (2D) lamellae at the interface between a surface of Au(111) or HOPG (highly oriented pyrolytic graphite) and a solvent. Presently, the self-assembly of 4,6-dialkoxylated isophthalic acid derivatives with variable alkyl chain length is investigated at Au(111)–water, Au(111)–tetradecane and HOPG–tetradecane interfaces with a particular focus on the first one. The main aspect of this study is to evaluate the role of the molecular geometry and different interactions in the 2D assembly of amphiphilic molecules. In contrast to 5-alkoxylated ISA, 4,6-dialkoxylated ISA derivatives self-assemble preferentially into arrays of cyclic pentameric/hexameric structures, which appear as 2D analogues of the inverted hexagonal phase of lipids. As a general trend, the derivatives bearing shorter alkyl chains show a higher level of ordering at Au(111)–liquid interfaces. In particular, at the Au(111)–water interface, the 4,6-diheptyloxy ISA derivative forms exclusively pentamers, which are arranged in a quasi-hexagonal lattice. Moreover, the cyclic pentameric features are not empty but host a single isophthalic acid residue which is found to be dynamic. Finally, the packing of the diheptyloxy derivative shows a distinct potential dependence: while at more negative potentials the pentameric arrangement is converted into lamellae, at more positive potentials a loosely packed zig-zag pattern is formed. The present results show that at different solid–liquid interfaces 4,6-dialkoxylated ISA derivatives tend to form cyclic structures that are 2D analogues of an inverted hexagonal phase, akin to lipids having two hydrophobic alkyl chains and a small polar head group. Moreover, the substrate potential at the Au(111)–water interface can tune the 2D molecular arrangement.