Bicomponent Supramolecular Architectures at the Vacuum–Solid Interface

Abstract

This review aims at giving the readers the basic concepts needed to understand two-dimensional bimolecular organizations at the vacuum–solid interface. The first part describes and analyzes molecules–molecules and molecules–substrates interactions. The current limitations and needs in the understanding of these forces are also detailed. Then, a critical analysis of the past and recent advances in the field is presented by discussing most of the key papers describing bicomponents self-assembly on solid surface in an ultrahigh vacuum environment. These sections are organized by considering decreasing molecule–molecule interaction strengths (i.e. starting from strong directional multiple H bonds up to weaker nondirectional bonds taking into account the increasing fundamental role played by the surface). Finally, we conclude with some research directions (predicting self-assembly, multi-components systems, and nonmetallic surfaces) and potential applications (porous networks and organic surfaces).

Nonisotropic Self‐Assembly of Nanoparticles: From Compact Packing to Functional Aggregates

“…Regarding the size of these building blocks, various types of forces are at the origin of the assembled structures. For molecular selfassembly for instance, the relative strength of the interactions generates motifs that can be tuned according to the molecular specificity of the units [25]. At a larger scale, some interactions vanish (hydrogen bonding, covalent interaction, substrate-mediated interaction...) whereas others are averaged (electrostatic and magnetic interactions by example) or get a new form (van der Waals and Casimir forces...) [26][27][28].…”

Triphenylene‐Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge‐Transfer Complexes with Common Unoccupied Molecular States

“…In order to unravel the interplay of intermolecular and molecule–substrate interactions, which play a key role in the device performance, considerable fundamental research on homomolecular layers on different metal substrates has been performed over the last three decades . In contrast, studies on the electronic and structural properties of binary systems have only emerged in the last few years . Special focus has been put on the organic–inorganic and organic–organic interface, which determines key properties like contact resistance, charge injection, and extraction …”

Polycyclic Aromatic Hydrocarbon Molecule-Surface Binding Energies in Site Specific Graphene Bilayer Nanopores: A Puzzle-ene Force Field Calculation

“…There is a recent and excellent review (432 references) on the general topic of supramolecular structures and interactions at the vacuum-solid interface [25]. A summary of the forces and interactions that may be present and how they manifest themselves in self-assembly is given.…”

“…They provide an overview of the strengths of the wide variety of other molecule-surface interactions and molecule-molecule interactions that guide the assembly of two-dimensional molecular structures on surfaces. Many self-assembled structural examples are presented [25]. Self-assembly can create repeated flat pore structures.…”