Towards Supramolecular Engineering of Functional Nanomaterials: Pre‐Programming Multi‐Component 2D Self‐Assembly at Solid‐Liquid Interfaces

Abstract

Materials with a pre-programmed order at the supramolecular level can be engineered with a sub-nanometer precision making use of reversible non- covalent interactions. The intrinsic ability of supramolecular materials to recognize and exchange their constituents makes them constitutionally dynamic materials. The tailoring of the materials properties relies on the full control over the self-assembly behavior of molecular modules exposing recognition sites and incorporating functional units. In this review we focus on three classes of weak-interactions to form complex 2D architectures starting from properly designed molecular modules: van der Waals, metallo-ligand and hydrogen bonding. Scanning tunneling microscopy studies will provide evidence with a sub-nanometer resolution, on the formation of responsive multicomponent architectures with controlled geometries and properties. Such endeavor enriches the scientist capability of generating more and more complex smart materials featuring controlled functions and unprecedented properties.

Supramolecular Approaches to Graphene: From Self‐Assembly to Molecule‐Assisted Liquid‐Phase Exfoliation

“…[99,[115][116][117][118] Given that graphite can be seen as a stack of graphene sheets, the Review knowledge gathered on the formation of supramolecular patterns on graphite can be potentially transferred for the non-covalent functionalization of graphene. [119,120] In general, the research on non-covalent functionalization of graphene, i.e., the functionalization of graphene with ordered supramolecular patterns, is targeting two challenges: (i) the understanding and control over the intermolecular and interfacial interactions in order to decorate surfaces with complex multicomponent ordered assemblies, (ii) the modulation of the physico-chemical properties of graphene for technologically relevant purposes such as doping or facilitating atomic layer deposition.…”

Single-molecule studies on individual peptides and peptide assemblies on surfaces

“…Many unique molecular assembly structures, including host-guest complexes, multi-component hydrogen-bonded networks and chiral assemblies, have been fabricated in a controlled way. Readers who are interested in assemblies of organic functional molecules are referred to previous reviews [5][6][7][8][9]. The applications of the STM method in studies of biomolecules also have fascinated many researchers for its high structural resolution without complicated sample preparation, for instance single crystal growth, and for its sensitivity to electronic structure of the molecules.…”

Synthesis of One‐Dimensional Schiff Base Polymers that Contain an Oligothiophene Building Block on the Graphite Surface

“…[5,6] Unfortunately, these supramolecular structures suffer from low thermal and chemical stability, and are very sensitive to changes such as solvent, temperature, and concentration, hence limiting their further applications. [7] Therefore, recently much attention has been focused on designing and synthesizing different dimensional structures by covalent linkages between the molecular building blocks owing to their enhanced thermal and chemical stability.…”