N-Heterocyclic carbenes on copper: a dynamic and sensitive interplay between surface functionalization and etching
5 affiliations
- 1Institute of Organic Chemistry, University of Münster Corrensstraße 36 Münster Germany
- 2Institute for Solid State Theory and Center for Multiscale Theory and Computation, University of Münster Germany
- 3Institute of Physics, University of Münster Germany
- 4Institute of Inorganic and Analytical Chemistry, University of Münster Germany
- 5Institute of Physical Chemistry, University of Münster Germany
Abstract
Within the expanding field of N-heterocyclic carbenes (NHCs) as surface ligands, this work investigates the etching of copper by (benz-)imidazol-2-ylidenes during surface functionalization. In order to control and distinguish between self-assembled monolayer (SAM) formation and NHC-mediated oxidative copper etching, experimental parameters were optimized. NHC design, concentration, solvent choice, temperature, visible light exposure, oxygen level, and deposition time dependencies were investigated, providing insight into the dynamic and sensitive interplay between functionalization and etching. Consistent with all experimental results, we present an etching mechanism driven by the formation of bis(NHC) CuI complexes. A previously unidentified, albeit frequently reported N 1s X-ray photoelectron spectroscopy (XPS) peak with a binding energy (BE) of 398.8(2) eV is cautiously interpreted as two NHCs bound to the same Cu0 adatom – the transient intermediate for metal etching. Its structure, its N 1s BE, and its high reduction potential (ECu0/CuI) are supported by DFT. As this work sheds new light on N 1s XPS spectra interpretation and on NHC-mediated phase transition of copper, it helps to unify seemingly conflicting literature reports.
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BibTeX
@article{nalop2026nheterocyclic,
title = {{N-Heterocyclic carbenes on copper: a dynamic and sensitive interplay between surface functionalization and etching}},
author = {Arne Nalop and Himadri Sekhar Sasmal and Leon Schlosser and Jens Paweletz and Alex-Cristian Tomut and Constantin G. Daniliuc and Ayan Jati and Jakob Henz and Steffen M. Lohrmann and Michael Holtkamp and Alexander Köhrer and Florian Schreiner and Uwe Karst and Bart Jan Ravoo and Nikos Doltsinis and Frank Glorius},
journal = {Chemical Science},
year = {2026},
month = aug,
doi = {10.1039/d6sc04254f},
url = {https://doi.org/10.1039/d6sc04254f},
note = {CC BY 3.0},
}
RIS
TY - JOUR
TI - N-Heterocyclic carbenes on copper: a dynamic and sensitive interplay between surface functionalization and etching
AU - Arne Nalop
AU - Himadri Sekhar Sasmal
AU - Leon Schlosser
AU - Jens Paweletz
AU - Alex-Cristian Tomut
AU - Constantin G. Daniliuc
AU - Ayan Jati
AU - Jakob Henz
AU - Steffen M. Lohrmann
AU - Michael Holtkamp
AU - Alexander Köhrer
AU - Florian Schreiner
AU - Uwe Karst
AU - Bart Jan Ravoo
AU - Nikos Doltsinis
AU - Frank Glorius
PY - 2026
DA - 2026/08/26
JO - Chemical Science
DO - 10.1039/d6sc04254f
UR - https://doi.org/10.1039/d6sc04254f
AB - Within the expanding field of N-heterocyclic carbenes (NHCs) as surface ligands, this work investigates the etching of copper by (benz-)imidazol-2-ylidenes during surface functionalization. In order to control and distinguish between self-assembled monolayer (SAM) formation and NHC-mediated oxidative copper etching, experimental parameters were optimized. NHC design, concentration, solvent choice, temperature, visible light exposure, oxygen level, and deposition time dependencies were investigated, providing insight into the dynamic and sensitive interplay between functionalization and etching. Consistent with all experimental results, we present an etching mechanism driven by the formation of bis(NHC) CuI complexes. A previously unidentified, albeit frequently reported N 1s X-ray photoelectron spectroscopy (XPS) peak with a binding energy (BE) of 398.8(2) eV is cautiously interpreted as two NHCs bound to the same Cu0 adatom – the transient intermediate for metal etching. Its structure, its N 1s BE, and its high reduction potential (ECu0/CuI) are supported by DFT. As this work sheds new light on N 1s XPS spectra interpretation and on NHC-mediated phase transition of copper, it helps to unify seemingly conflicting literature reports.
SN - 2041-6520
SN - 2041-6539
ER -