Nestor Merino-Diez¹, Raymond Amador^1*, Samuel T. Stolz¹, Daniele Passerone^1*, Roland Widmer¹, Oliver Gröning^1*

1 Empa, Swiss Federal Laboratories for Materials Science and Technology, CH-8600 Dübendorf, Switzerland

* Corresponding authors emails: raymond.amador@empa.ch, daniele.passerone@empa.ch, oliver.groening@empa.ch

DOI10.24435/materialscloud:fv-ce [version v1]

Publication date: Jan 09, 2025

How to cite this record

Nestor Merino-Diez, Raymond Amador, Samuel T. Stolz, Daniele Passerone, Roland Widmer, Oliver Gröning, Asymmetric molecular adsorption and regioselective bond cleavage on chiral PdGa crystals, Materials Cloud Archive 2025.5 (2025), https://doi.org/10.24435/materialscloud:fv-ce

Description

Homogenous enantioselective catalysis is nowadays the cornerstone in the manufacturing of enantiopure substances, but its technological implementation suffers from well-known impediments like the lack of endurable catalysts exhibiting long-term stability. The catalytically active intermetallic compound Palladium-Gallium (PdGa), conserving innate bulk chirality on its surfaces, represent a promising system to study asymmetric chemical reactions by heterogeneous catalysis, with prospective relevance for industrial processes. In a recent publication we investigate the adsorption of 10,10′-dibromo-9,9′-bianthracene (DBBA) on the PdGa:A(-1-1-1) Pd3-terminated surface by means of scanning tunneling microscopy (STM) and spectroscopy (STS). A highly enantioselective adsorption of the molecule evolving into a near 100% enantiomeric excess below room temperature is observed. This exceptionally high enantiomeric excess is attributed to temperature activated conversion of the S to the R chiral conformer. Tip-induced bond cleavage of the R conformer shows a very high regioselectivity of the DBBA debromination. The experimental results are interpreted by density functional theory atomistic simulations. This work extends the knowledge of chirality transfer onto the enantioselective adsorption of non-planar molecules and manifests the ensemble effect of PdGa surfaces resulting in robust regioselective debromination. This record contains data that support the results discussed in the manuscript.

Materials Cloud sections using this data

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File name	Size	Description
calculations.aiida MD5md5:c1383d47ad52ab309b422edfd913d6da Open this AiiDA archive on renkulab.io (https://renkulab.io/)	298.2 MiB	Archive file containing AiiDA nodes of all the calculations
enantioselective_dbba_calculations.tgz MD5md5:ad5cad0d3b00ebcd641f8914c9f6485d	23.4 MiB	Tar file containing all the non-aiida calculations.

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Keywords

Enantioselectivity density-functional theory Surface chemistry MARVEL/ASM CSCS