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Reversible dehalogenation in on-surface aryl-aryl coupling

Samuel Stolz1,2*, Marco Di Giovannantonio1, José I. Urgel1, Qiang Sun1, Amogh Kinikar1, Gabriela Borin Barin1, Max Bommert1, Roman Fasel1,3, Roland Widmer1*

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.

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External 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

Keywords

SNSF H2020 ONR aryl-aryl coupling dehalogenation surface chemistry Experimental

Version history:

2021.37 (version v1) [This version] Mar 02, 2021 DOI10.24435/materialscloud:71-t1