Chiral and Catalytic Effects of Site-Specific Molecular Adsorption

Abstract

The changes of properties and preferential interactions based on subtle energetic differences are important characteristics of organic molecules, particularly for their functionalities in biological systems. Only slightly energetically favored interactions are important for the molecular adsorption and bonding to surfaces, which define their properties for further technological applications. Here, prochiral tetracenothiophene molecules are adsorbed on the Cu(111) surface. The chiral adsorption configurations are determined by Scanning Tunneling Microscopy studies and confirmed by first-principles calculations. Remarkably, the selection of the adsorption sites by chemically different moieties of the molecules is dictated by the arrangement of the atoms in the first and second surface layers. Furthermore, we have investigated the thermal effects on the direct desulfurization reaction that occurs under the catalytic activity of the Cu substrate. This reaction leads to a product that is covalently bound to the surface in chiral configurations.

Realization of either physisorption or chemisorption of 2H-tetraphenylporphyrin on the Cu(111) from density functional theory

“…To be able to achieve either physisorption or chemisorption selectively can be important to accomplish certain desired interface properties for molecules on surfaces [66,67]. For example, chemical bonds provide electrical wiring that could result in Ohmic contact between the molecule and substrate, while physical binding usually results in a Schottky barrier through tunneling of electrons.…”

Caught in the Act of Substitution: Interadsorbate Effects on an Atomically Precise Fe/Co/Se Nanocluster

“…Atomistic insights into how interadsorbate effects manifest to facilitate active site speciation and guide surface reactivity are fundamental to the design and implementation of new catalysts . However, these multi-active site dynamics are difficult to resolve experimentally in heterogeneous systems, requiring advanced surface analysis techniques, ,,− and relying primarily on computational modeling …”

Advances in Organic Multiferroic Junctions

“…These layers are used to optimize and tune the spin injection through processes such as solving the energy level mismatch at interfaces or tailoring the bend bending. Moreover, the inserted interfacial layer can improve the interface qualities, like, for example, in vertical junctions, it can reduce the penetration of the top ferromagnetic metallic electrode, or an organic spinterface [90][91][92][93] can ensure a less rough interface or better anchoring and tune the interface resistance [94][95][96][97].…”