Samuel Stolz^1,2, Martina Danese¹, Marco Di Giovannantonio¹, José I. Urgel¹, Qiang Sun¹, Amogh Kinikar¹, Max Bommert¹, Shantanu Mishra¹, Harald Brune², Oliver Gröning¹, Daniele Passerone¹, Roland Widmer^1*

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

2 Institute of Physics, École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland

* Corresponding authors emails: roland.widmer@empa.ch

DOI10.24435/materialscloud:pm-8p [version v1]

Publication date: Oct 11, 2021

How to cite this record

Samuel Stolz, Martina Danese, Marco Di Giovannantonio, José I. Urgel, Qiang Sun, Amogh Kinikar, Max Bommert, Shantanu Mishra, Harald Brune, Oliver Gröning, Daniele Passerone, Roland Widmer, Asymmetric elimination reaction on chiral metal surfaces, Materials Cloud Archive 2021.162 (2021), https://doi.org/10.24435/materialscloud:pm-8p

Description

The production of enantiopure materials and molecules is of uttermost relevance in research and industry in numerous contexts, ranging from non-linear optics to asymmetric synthesis. In the context of the latter, we have investigated dehalogenation, which is an essential reaction step for a broad class of chemical reactions. Specifically, dehalogenation of prochiral 5-bromo-7-methylbenz(a)anthracene (BMA) on prototypical, chiral, intermetallic PdGa{111} surfaces under ultrahigh vacuum conditions. Enantioselective halogen elimination is demonstrated by combining temperature-programmed x-ray photoelectron spectroscopy, scanning probe microscopy, and density functional theory. On the PdGa{111} surfaces, the difference in debromination temperatures for the two BMA surface enantiomers amounts up to unprecedented 46 K. The significant dependence of the dehalogenation temperature of the BMA surface enantiomers on the atomic termination of the PdGa{111} surfaces, implies that the ensemble effect is pronounced in this reaction step. These findings evidence enantiospecific control and hence promote intrinsically chiral crystals for asymmetric on-surface synthesis. The record contains input files to reproduce the calculations discussed in the manuscript and the raw data of the experimental images discussed.

Materials Cloud sections using this data

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File name	Size	Description
ReadMe.yaml MD5md5:6cd9b757abb091bd98537880750b222a	27.3 KiB	README file in yaml format detailing the content of the record
data.tgz MD5md5:375dae1b977df5f7b3a34ee46015fa1a	256.6 MiB	tar file containing all data
debromination.aiida MD5md5:a6252cd0acc0dad155c6df8face98a82 Open this AiiDA archive on renkulab.io (https://renkulab.io/)	662.6 MiB	Archive of AiiDA nodes for the calculations of geometry optimization (brominated molecules) desribed in the manuscript and SI.

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External references

Keywords

ab initio scanning probe microscopy enantioselectivity MARVEL/DD3 SNSF