Intermolecular vs molecule–substrate interactions: A combined STM and theoretical study of supramolecular phases on graphene/Ru(0001)

Abstract

SummaryThe competition between intermolecular interactions and long-range lateral variations in the substrate–adsorbate interaction was studied by scanning tunnelling microscopy (STM) and force field based calculations, by comparing the phase formation of (sub-) monolayers of the organic molecules (i) 2-phenyl-4,6-bis(6-(pyridin-3-yl)-4-(pyridin-3-yl)pyridin-2-yl)pyrimidine (3,3'-BTP) and (ii) 3,4,9,10-perylene tetracarboxylic-dianhydride (PTCDA) on graphene/Ru(0001). For PTCDA adsorption, a 2D adlayer phase was formed, which extended over large areas, while for 3,3'-BTP adsorption linear or ring like structures were formed, which exclusively populated the areas between the maxima of the moiré structure of the buckled graphene layer. The consequences for the competing intermolecular interactions and corrugation in the adsorption potential are discussed and compared with the theoretical results.

Mapping spin distributions in electron acceptor molecules adsorbed on nanostructured graphene by the Kondo effect

“…In both cases, the molecules lie planar and present a spatial selectivity in the adsorption. As it was previously studied for other molecules in the same substrate [22][23][24][25][26], this behavior has its origin in the nanostructured graphene surface which forces the molecules to adsorb in the lower areas of moiré pattern, where the . Three features, two at negative bias voltage (occupied states) and one at positive bias voltages (empty states) marked with black arrows, not present in the curve measured on graphene can be observed.…”

Organic molecules deposited on graphene: A computational investigation of self-assembly and electronic structure

“…9 The self-assembly is mainly due to (i) upon the absence of strong moleculesubstrate interactions. On the other hand, upon the formation of molecule-surface chemical bonds (ii) will also play an important role for the self-assembly process.…”

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

“…Behm and co-workers also explored the influence of graphene superlattice on molecular adsorption, [147] and showed that the influence of moiré corrugation is even more drastic in the case of 2-phenyl-4,6-bis(6-(pyridin-3-yl)-4-(pyridin-3-yl) pyridin-2-yl)-pyrimidine (3,3′-BTP, Figure 2). 3,3′-BTP molecules form supramolecular networks stabilized by weak C-H … N intermolecular hydrogen bonds and π-π molecule/graphene interactions.…”