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Role of Adatoms for the Adsorption of F4TCNQ on Au(111).

ABSTRACT: Organic adlayers on inorganic substrates often contain adatoms, which can be incorporated within the adsorbed molecular species, forming two-dimensional metal-organic frameworks at the substrate surface. The interplay between native adatoms and adsorbed molecules significantly changes various adlayer properties such as the adsorption geometry, the bond strength between the substrate and the adsorbed species, or the work function at the interface. Here, we use dispersion-corrected density functional theory to gain insight into the energetics that drive the incorporation of native adatoms within molecular adlayers based on the prototypical, experimentally well-characterized system of F4TCNQ on Au(111). We explain the adatom-induced modifications in the adsorption geometry and the adsorption energy based on the electronic structure and charge transfer at the interface.

SUBMITTER: Berger RK

PROVIDER: S-EPMC9082607 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature

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Role of Adatoms for the Adsorption of F4TCNQ on Au(111).

Berger Richard K RK Jeindl Andreas A Hörmann Lukas L Hofmann Oliver T OT

The journal of physical chemistry. C, Nanomaterials and interfaces 20220421 17

Organic adlayers on inorganic substrates often contain adatoms, which can be incorporated within the adsorbed molecular species, forming two-dimensional metal-organic frameworks at the substrate surface. The interplay between native adatoms and adsorbed molecules significantly changes various adlayer properties such as the adsorption geometry, the bond strength between the substrate and the adsorbed species, or the work function at the interface. Here, we use dispersion-corrected density functio ...[more]

PMID: 35558824

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Project description:Chemoselective reduction of nitro groups in multifunctional nitroaromatics is a challenging catalytic process with high interest due to the importance of the resulting anilines for the chemical industry. Molecular-level understanding of the ways by which adsorption geometry of nitroaromatics influence their affinity toward nitro reduction will enable the development of highly selective reactions. Herein, taking advantage of the well-ordered self-assembly of para- and ortho-nitrothiophenol (p-NTP and o-NTP, respectively) monolayers on Au(111), we examined the correlation between adsorption geometry and nitro reduction affinity. The anchoring geometry of NTPs and their nitro reduction affinity were determined by conducting polarized X-ray absorption spectroscopy while the influence of NTPs' adsorption geometry on the interaction with the Au surface was analyzed by density functional theory (DFT) calculations. Exposure of surface anchored p-NTPs to reducing conditions led to their reorientation from a tilt angle of 52° to 25°, which enabled strong interactions between the π system of the molecules and the Au surface. Direct correlation was identified between the surface proximity of the nitro group, its parallel position to the surface and the resulting reduction yield. The asymmetric structure of o-NTP led to a tilted adsorption geometry in which the nitro group was rotated away from the plane of the aromatic ring and therefore was positioned parallel and in high proximity to the Au surface. This positioning led to surface-bonding that involved the oxygen atoms of o-NTP. The higher surface proximity and stronger surface interactions of the nitro group in o-NTP enabled nitro reduction already at 180 °C, while in p-NTP nitro reduction was achieved only at 230 °C, due to the longer distance between the NO2 group and the Au surface that led to weaker adsorbate-surface interactions. Thus, parallel positioning of the nitro group and high surface proximity were found as essential descriptors for nitro reduction affinity in both p-NTP and o-NTP on the Au surface. These findings provide explicit guidelines for tuning the reactant and surface properties in order to control the reactant's adsorption geometry for selective nitro reduction in multifunctional nitroaromatics.

Dataset Information

Role of Adatoms for the Adsorption of F4TCNQ on Au(111).

Publications

Role of Adatoms for the Adsorption of F4TCNQ on Au(111).

Similar Datasets

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