Samuel Stolz^1,2*, Marco Di Giovannantonio¹, José I. Urgel¹, Qiang Sun¹, Amogh Kinikar¹, Gabriela Borin Barin¹, Max Bommert¹, Roman Fasel^1,3, Roland Widmer^1*

1 Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600 Dübendorf, Switzerland

2 Institute of Physics, École Polytechnique Fédérale de Lausanne, Laboratory of Nanostructures at Surfaces, 1015 Lausanne, Switzerland

3 Department of Chemistry and Biochemistry, University of Bern, 3012 Bern, Switzerland

* Corresponding authors emails: samuel.stolz@empa.ch, roland.widmer@empa.ch

DOI10.24435/materialscloud:71-t1 [version v1]

Publication date: Mar 02, 2021

How to cite this record

Samuel Stolz, Marco Di Giovannantonio, José I. Urgel, Qiang Sun, Amogh Kinikar, Gabriela Borin Barin, Max Bommert, Roman Fasel, Roland Widmer, Reversible dehalogenation in on-surface aryl-aryl coupling, Materials Cloud Archive 2021.37 (2021), doi: 10.24435/materialscloud:71-t1.

Description

The record contains the data to support the findings of our recent work on reversibility of the dehalogenation process in on-surface aryl-aryl coupling. In the emerging field of on‐surface synthesis, dehalogenative aryl–aryl coupling is unarguably the most prominent tool for the fabrication of covalently bonded carbon‐based nanomaterials. Despite its importance, the reaction kinetics are still poorly understood. Here we present a comprehensive temperature‐programmed x‐ray photoelectron spectroscopy investigation of reaction kinetics and energetics in the prototypical on‐surface dehalogenative polymerization of 4,4′′‐dibromo‐p‐terphenyl into poly(para‐phenylene) on two coinage metal surfaces, Cu(111) and Au(111). We find clear evidence for reversible dehalogenation on Au(111), which is inhibited on Cu(111) owing to the formation of organometallic intermediates. The incorporation of reversible dehalogenation in the reaction rate equations leads to excellent agreement with experimental data and allows extracting the relevant energy barriers. Our findings deepen the mechanistic understanding and call for its reassessment for surface‐confined aryl–aryl coupling on the most frequently used metal substrates.

Materials Cloud sections using this data

Files

File name	Size	Description
ReadMe.yaml MD5md5:eb5859f4da12efe10f592b4d5c472576	56.7 KiB	ReadMe File in yaml format listing the files contained in the record
data.tgz MD5md5:38f3a1e2c634fc41d47d4df57ae20004	38.1 MiB	zipped archive file containing all files of the record

License

Files and data are licensed under the terms of the following license: Creative Commons Attribution 4.0 International.
Metadata, except for email addresses, are licensed under the Creative Commons Attribution Share-Alike 4.0 International license.

External references

Keywords

SNSF H2020 ONR aryl-aryl coupling dehalogenation surface chemistry Experimental