Hydrogen bonding vs. molecule–surface interactions in 2D self-assembly of [C60]fullerenecarboxylic acids

Abstract

The adsorption of C-malonic derivatives C(COH) and C(COH) on Au(111) and a pentafluorobenzenethiol-modified Au substrate (PFBT@Au) has been investigated using scanning tunneling microscopy (STM) at a liquid-solid interface. Monofunctionalized C(COH) forms a hexagonal close-packed overlayer on Au(111) and individual aligned dimers on PFBT@Au(111). The difference is attributed to the nature of the substrateC(COH) interaction (isotropic π-Au bonding vs. anisotropic PFBTCOOH interactions). Surprisingly, in both cases, the directionality of the COOHCOOH motif is compromised in favor of synergistic van der Waals/H bonding interactions. Such van der Waals contacts are geometrically unfeasible in hexafunctionalized C(COH) and its assembly on Au(111) leads to a 2D molecular network controlled exclusively by H bonding. For both molecules, the "free" COH groups on the monolayer surface can engage in out-of-plane H bonding interaction resulting in the epitaxial growth of subsequent molecular layers.

Optimizing the self‐assembly of conjugated polymers and small molecules through structurally programmed non‐covalent control

“…49 Hydrogen bonding can be responsible for the supramolecular assembly of popular electronic building blocks, such as diketopyrrolopyrrole, perylene diimide, and napthylene diimide. [50][51][52][53] However, the group of Dmitrii Perepichka has demonstrated across multiple publications that hydrogen bonding can also promote energy transfer between complimentary pairs of electron donor and acceptor small molecules. In an initial 2014 communication, they described the three unique assemblies of diphenyldipyrollopyridine and naphthalenetetracarbox ydiimides.…”

“…For example, the donor‐acceptor design paradigm has become commonplace in organic semiconductors with specialized building blocks, joined together through covalent bonding, serving as electron rich donors and electron poor acceptors 49 . Hydrogen bonding can be responsible for the supramolecular assembly of popular electronic building blocks, such as diketopyrrolopyrrole, perylene diimide, and napthylene diimide 50–53 . However, the group of Dmitrii Perepichka has demonstrated across multiple publications that hydrogen bonding can also promote energy transfer between complimentary pairs of electron donor and acceptor small molecules.…”

Polymorphic Self-Assemblies of 2,7-Bis(decyloxy)-9-fluorenone at the Solid/Gas Interface: Role of C–H···O═C Hydrogen Bond

“…Geometry optimization was performed using the M06-2X and the B3LYP functional with the polarized 6-31G (d) basis set. It is well acknowledged that the M06-2X functional could provide more accurate calculation result for systems involving noncovalent interactions, which was chosen for the description of intermolecular hydrogen bonding in our work . The topological properties of electron densities in all complexes were carried out using the Multiwfn program and visualized with the VMD program …”

“…Structural polymorphism of 2D self-assemblies at the solid/liquid or solid/gas interface has attracted increasing attention in recent years, owing to their potential applications in new material fields, such as OLEDs, , organic photovoltaic cells (OPVs), , and organic field effect transistors (OFETs). , Thus it requires us to gain deep insight into the underlying mechanism behind the formation of specific monolayer morphology to guide the design of optical devices with desirable performance. In general, the outcome of a self-assembled monolayer is determined by a delicate balance of noncovalent intermolecular interactions, including hydrogen bonding, , van der Waals force, , dipole–dipole interaction, , electrostatic force, − and so on. Great efforts have been made by researchers to understand the influence of chemical design of molecular building blocks on the self-assembled structures. − In addition, other factors, such as solute concentration, , nature of solvent, , and temperature, , are also manifested to have great impact on the outcome of the self-assemblies.…”

Enhancing intramolecular features and identifying defects in organic and hybrid nanoarchitectures on a metal surface at room temperature using a NaCl-functionalized scanning tunneling microscopy tip

“…Characterizing two-dimensional nanostructures and nanoarchitectures [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] at the atomic scale is a challenge of nanosciences for the development of new functionalized nanomaterials for nanotechnology. 20,21 Scanning probe microscopy (SPM) is a powerful technique to assess locally the topographic and electronic properties of nanostructured surfaces.…”