Structure and Epitaxial Registry on Graphite of a Series of Nanoporous Self-Assembled Molecular Monolayers

Abstract

We have analyzed by STM the detailed structures of a series of nanoporous honeycomb networks stabilized by alkyl chain interdigitation on graphite at the liquid−solid interface, that is, clip-like noncovalent bonding. The variations observed as a function of the length of the peripheral aliphatic chains show that the assembly is directed not only by lateral intermolecular interactions but also by the adsorption site on the substrate. We derive an atomically accurate model for the registry with graphite of our nanoporous model series of systems. In full agreement with the quantitative model, the pore areas vary step-by-step by more than one order of magnitude along the whole series while preserving the detailed features of the graphite-induced alkyl chain interdigitation. The largest pores observed correspond to a ratio of uncovered substrate area as large as 35%.

Hydrogen Bonding Versus van der Waals Interactions: Competitive Influence of Noncovalent Interactions on 2D Self‐Assembly at the Liquid–Solid Interface

“…It has been well documented in the literature that the substrate lattice has a strong bearing on the self-assembly of molecules. [14,[61][62][63] The graphite lattice that is used as a substrate in the present study is built up of layers with a honeycomb arrangement of carbon atoms. The basal (001) plane of graphite has a threefold symmetry and the carbon atoms along the direction of any C 3 axis display the same zigzag extension as the zigzag skeleton of the carbon backbone of an all-trans alkyl chain.…”

“…The lattice match between alkyl chains and the graphite substrate has been confirmed widely. [51,[61][62][63] The lateral arrangement of alkyl chains on the graphite lattice is also governed by the similarity in the lattice parameters. Typically, it has been observed that the distance between unsubstituted alkanes within a lamella (along the lamella axis) is approximately 4.26 , which is in reasonable agreement with the distance between every other carbon row of the graphite lattice (4.24 ).…”

Directed Organization of Platinum Nanocrystals through Organic Supramolecular Nanoporous Templates

“…[21] Regarding the isotropic network, the TSB-3,5-C 12 tecton has been chosen because it can form a honeycomb network the pore diameter of which (1.9 nm) is commensurate with the size of the NCs (2 nm). [19] However, it has been reported that the tecton TSB-3,5-C 12 could self-assemble along various schemes depending on concentration and temperature. [19] At room temperature, below the critical concentration C C =10 -3 mol.L -1 , a honeycomb structure is formed ( Figure 1C 1 and 1C 2 ).…”

Self-assembly: mastering photonic processes at nanoscale

“…A specially flexible example is based on a functional unit comprising interdigitated alkyl chains forming a clip between neighbouring molecules [42]. Mo− lecular building blocks receiving three such "clips" forming 60°angles form a honeycomb structure on a graphite sub− strate with tunable pore size [45]. The molecular structure and the honeycomb network obtained is schematized in Fig.…”