Theoretical exploration of seleno and tellurophenols as promising alternatives to sulfur ligands for anchoring to gold (111) materials

Abstract

Artículo de publicación ISISin acceso a texto completoIt is widely known that sulfur ligands, such as alkanethiols or phenothiols and their derivatives, are useful anchor systems for gold materials due to the high affinity of sulfur to gold surfaces. In this study we use DFT calculations and a 42-atom gold cluster model to study the interaction between selenophenol and tellurophenol-derivatives with the Au(111) surface to gain information towards potential new gold-based materials. We modulated the interaction strength by controlling the charge transfer process of a particular interaction by chemically modifying the ligands. To obtain a complete analysis, we studied the ligands in their protonated, anionic and radical states aiming to cover the three possibilities in which these may interact with the gold cluster. In order to get a deeper insight into the nature of the interaction we used several analysis techniques such as energy decomposition analysis (EDA), non-covalent interactions (NCI) and natural population analysis (NPA). Our results reveal that tellurium in the anionic state provides complexes of better thermodynamic stability by similar to 12.0 kcal mol, when compared with the strongest sulfur-gold complex, also in the anionic state. Furthermore, this indicates that the anionic ligand is probably the dominant state for both selenium and tellurium as observed previously for sulfur. The extent to which the interaction strength could be controlled directly depends on the state of the anchor atom. In our case the anionic state is the most suitable for tuning the interaction. Finally, our main findings suggest that exchanging sulfur with selenium or tellurium involves an important increase of the interaction strength, thus, making these selenophenol and tellurophenol derivatives attractive for the development of new functional materials.FONDECYT 3130383 1140503 1150629 Grant ICM 120082 CONICYT 21130874 German Research Foundation (DFG) EXC 310/

Noncovalent interactions in inorganic supramolecular chemistry based in heavy metals. Quantum chemistry point of view

“…The results presented above set the grounds to study the analogous compounds of selenophenol and tellurophenol‐derivatives with the Au(111) surface to gain information toward potential new gold‐based materials . The results are shown in Table .…”

“…Furthermore, this indicates that the anionic ligand is probably the dominant state for both selenium and tellurium as observed previously for sulfur. [139] This is a very good example of the importance of the dispersion term in the control of the weak interactions. Finally, our main findings suggest that exchanging sulfur with selenium or tellurium involves an important increase of the interaction strength, thus, making these selenophenol and tellurophenol derivatives attractive for the development of new functional materials.…”

“…The result revealed that tellurium in the anionic state provides complexes of better thermodynamic stability by 50 kJ/mol, when compared with the strongest sulfur–gold complex, also in the anionic state. Furthermore, this indicates that the anionic ligand is probably the dominant state for both selenium and tellurium as observed previously for sulfur . This is a very good example of the importance of the dispersion term in the control of the weak interactions.…”

“…[132] In 7 Interaction energies between Au 42 and para substituted thio-, seleno-and tellurophenols. [138,139] The energies listed correspond to the total interaction energies (ΔE int (TPSS-D3) and without the dispersion contribution (ΔE int (TPSS…”

“…The results presented above set the grounds to study the analogous compounds of selenophenol and tellurophenol-derivatives with the Au(111) surface to gain information toward potential new gold-based materials. [139] The results are shown in Table 7. The result revealed that tellurium in the anionic state provides complexes of better thermodynamic stability by 50 kJ/mol, when compared with the strongest sulfur-gold complex, also in the anionic state.…”