Published March 2, 2021 | Version v1
Dataset Open

Reversible dehalogenation in on-surface aryl-aryl coupling

  • 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

* Contact person

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.

Files

File preview

files_description.md

All files

Files (38.1 MiB)

Name Size
md5:9fd98e436dcb5ca9be9c32ca51ba4b60
277 Bytes Preview Download
md5:38f3a1e2c634fc41d47d4df57ae20004
38.1 MiB Download
md5:eb5859f4da12efe10f592b4d5c472576
56.7 KiB Download

References

Journal reference
S. Stolz, M. Di Giovannantonio, J.I. Urgel, Q. Sun, A. Kinikar, G. Borin Barin, M. Bommert, R. Fasel, R. Widmer, Angew. Chem. Int. Ed. 59, 14106 - 14110 (2020)., doi: 10.1002/anie.202005443