Monolayer self-assembly at liquid–solid interfaces: chirality and electronic properties of molecules at surfaces

Abstract

The spontaneous formation of supramolecular assemblies at the boundary between solids and liquids is a process which encompasses a variety of systems with diverse characteristics: chemisorbed systems in which very strong and weakly reversible bonds govern the assembly and physisorbed aggregates which are dynamic thanks to the weaker interactions between adsorbate and surface. Here we review the interest and advances in the study of chiral systems at the liquid-solid interface, and also the application of this configuration for the study of systems of interest in molecular electronics, self-assembled from the bottom up.

Surface aggregate morphology of chiral porphyrins as a function of constitution and amphiphilic nature

“…The compounds can form quite well ordered linear structures on graphite along the symmetry axes of the substrate, indicating that both molecule-molecule and moleculesubstrate interactions are involved. 40 This situation arises only when non-polar solvents are used. The only case where alignment with the surface symmetry directions is not observed is when strong molecule-molecule interactions arise, in the case of 4, where long fibril architectures are observed.…”

Towards Dynamic Control of Wettability by Using Functionalized Altitudinal Molecular Motors on Solid Surfaces

“…Modifications of surfaces with self-assembled monolayers [2] (SAMs) provide opportunities to create interfaces that exhibit various properties including hydrophilicity/hydrophobicity, [3][4][5][6] conductance, [7,8] catalytic activity, [9,10] and chirality. [11][12][13] Amongst SAM-forming molecules, those that can switch reversibly between distinct geometrical forms accompanied with changes in physical properties such as dipole moment or conductance are particularly interesting. [14][15][16] Such reversible changes in chemical and physical properties facilitates the fabrication of multifunctional and dynamic interfaces that allow for responsive behavior by reversible switching from one desired property to another.…”

“…Control of the assembly and arrangement of molecules1 on surfaces allows for interfaces with tailored properties to be created. Modifications of surfaces with self‐assembled monolayers2 (SAMs) provide opportunities to create interfaces that exhibit various properties including hydrophilicity/hydrophobicity,3–6 conductance,7, 8 catalytic activity,9, 10 and chirality 11–13. Amongst SAM‐forming molecules, those that can switch reversibly between distinct geometrical forms accompanied with changes in physical properties such as dipole moment or conductance are particularly interesting 14–16.…”

Organization of the enantiomeric and racemic forms of an amphiphilic resorcinol derivative at the air–water and graphite–1‐phenyloctane interfaces

“…In addition to the reduced symmetry possibilities in the presence of a substrate, the balance between adsorbate-substrate interactions and adsorbate-adsorbate interactions plays a role. 5 Should the adsorbates have any specific interaction with the surface then symmetry of the surface plays a fundamental role in the possible packing modes of a molecule upon it. So the ability to form a racemic conglomerate will depend on the nature of the substrate because of symmetry, molecular orientation, and the strength of the molecule-surface and molecule-molecule interactions.…”