Highly ordered N-heterocyclic carbene monolayers on Cu(111)

Eloise Angove; Federico Grillo; Herbert A. Fruchtl; Alex, J Veinot; Ishwar Singh; J Hugh Horton; Cathleen M Crudden; Christopher J. Baddeley

doi:10.1021/acs.jpclett.1c04073

Highly ordered N-heterocyclic carbene monolayers on Cu(111)

Eloise Angove, Federico Grillo, Herbert A. Fruchtl, Alex, J Veinot, Ishwar Singh, J Hugh Horton, Cathleen M Crudden, Christopher J. Baddeley^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

15 Citations (Scopus)

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Abstract

The benzannulated N-heterocyclic carbene, 1,3-dibenzylbenzimidazolylidene (NHCDBZ) forms large, highly ordered domains when adsorbed on Cu(111) under ultrahigh vacuum conditions. A combination of scanning tunnelling microscopy (STM), high resolution electron energy loss spectroscopy (HREELS) and density functional theory (DFT) calculations reveals that the overlayer consists of vertical benzannulated NHC moieties coordinating to Cu adatoms. Long range order results from the placement of the two benzyl substituents on opposite sides of the benzimidazole moiety, with their aromatic rings approximately parallel to the surface. The organization of three surface-bound benzyl substituents from three different NHCs into a triangular array controls the formation of a highly ordered Kagome-like surface lattice. By comparison with earlier studies of NHCs on Cu(111), we show that the binding geometry and self-assembly of NHCDBZ are influenced by intermolecular and adsorbate-substrate interactions and facilitated by the flexibility of the methylene linkage between the N-heterocycle and the aromatic wingtip substituents.

Original language	English
Pages (from-to)	2051-2056
Journal	The Journal of Physical Chemistry Letters
Volume	13
Issue number	8
Early online date	24 Feb 2022
DOIs	https://doi.org/10.1021/acs.jpclett.1c04073
Publication status	E-pub ahead of print - 24 Feb 2022

Keywords

N-heterocyclic carbene
Scanning tunneling microscopy
High resolution electron energy loss spectroscopy
Cu

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10.1021/acs.jpclett.1c04073Licence: CC BY

Angove_2022_JPCL_Highly_CC
Copyright © 2022 The Authors. Open Access article licensed under Creative Commons Attribution CC-BY 4.0.
Final published version, 5.41 MBLicence: CC BY

N-heterocyclic Carbenes: N-heterocyclic Carbenes on Metal Surfaces - towards applications in corrosion inhibition and catalysis
Baddeley, C. J. (PI)
EPSRC
1/07/19 → 31/12/22
Project: Standard

Highly Ordered N-Heterocyclic Carbene Monolayers on Cu(111) (dataset)
Angove, E. (Creator), Grillo, F. (Creator), Fruchtl, H. A. (Creator), Veinot, A. J. (Creator), Singh, I. (Creator), Horton, J. H. (Creator), Crudden, C. M. (Creator) & Baddeley, C. J. (Creator), University of St Andrews, 2 Mar 2022
DOI: 10.17630/3ceb4033-456e-49bf-b29c-c99314a1fa07
Dataset

File
Investigation of copper and silver surfaces functionalised by N-heterocyclic molecules (thesis data)
Angove, E. (Creator) & Baddeley, C. J. (Supervisor), University of St Andrews, 24 May 2025
DOI: 10.17630/e5bca4e0-b38e-42b5-8c99-9c3d108cb394
Dataset: Thesis dataset

Cite this

@article{3b553f0ddaee44158ed3dc1874a65158,

title = "Highly ordered N-heterocyclic carbene monolayers on Cu(111)",

abstract = "The benzannulated N-heterocyclic carbene, 1,3-dibenzylbenzimidazolylidene (NHCDBZ) forms large, highly ordered domains when adsorbed on Cu(111) under ultrahigh vacuum conditions. A combination of scanning tunnelling microscopy (STM), high resolution electron energy loss spectroscopy (HREELS) and density functional theory (DFT) calculations reveals that the overlayer consists of vertical benzannulated NHC moieties coordinating to Cu adatoms. Long range order results from the placement of the two benzyl substituents on opposite sides of the benzimidazole moiety, with their aromatic rings approximately parallel to the surface. The organization of three surface-bound benzyl substituents from three different NHCs into a triangular array controls the formation of a highly ordered Kagome-like surface lattice. By comparison with earlier studies of NHCs on Cu(111), we show that the binding geometry and self-assembly of NHCDBZ are influenced by intermolecular and adsorbate-substrate interactions and facilitated by the flexibility of the methylene linkage between the N-heterocycle and the aromatic wingtip substituents.",

keywords = "N-heterocyclic carbene, Scanning tunneling microscopy, High resolution electron energy loss spectroscopy, Cu",

author = "Eloise Angove and Federico Grillo and Fruchtl, {Herbert A.} and Veinot, {Alex, J} and Ishwar Singh and Horton, {J Hugh} and Crudden, {Cathleen M} and Baddeley, {Christopher J.}",

note = "EA and FG acknowledge funding from EPSRC grants (EA: EP/R512199/1; FG: EP/S027270/1). We thank the EaStCHEM for computational support via the EaStCHEM Research Computing facility. CMC thanks the Natural Sciences and Engineering Research Council of Canada (NSERC) and the Canada Foundation for Innovation (CFI) for funding of the work from her lab described in this article. AJV acknowledges NSERC for a Vanier scholarship and the Walter C. Sumner foundation for additional financial support. IS acknowledges Queen{\textquoteright}s University for the RT Mohan Scholarship and the Ontario government for an Ontario Graduate Scholarship. ",

year = "2022",

month = feb,

day = "24",

doi = "10.1021/acs.jpclett.1c04073",

language = "English",

volume = "13",

pages = "2051--2056",

journal = "The Journal of Physical Chemistry Letters",

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T1 - Highly ordered N-heterocyclic carbene monolayers on Cu(111)

AU - Angove, Eloise

AU - Grillo, Federico

AU - Fruchtl, Herbert A.

AU - Veinot, Alex, J

AU - Singh, Ishwar

AU - Horton, J Hugh

AU - Crudden, Cathleen M

AU - Baddeley, Christopher J.

N1 - EA and FG acknowledge funding from EPSRC grants (EA: EP/R512199/1; FG: EP/S027270/1). We thank the EaStCHEM for computational support via the EaStCHEM Research Computing facility. CMC thanks the Natural Sciences and Engineering Research Council of Canada (NSERC) and the Canada Foundation for Innovation (CFI) for funding of the work from her lab described in this article. AJV acknowledges NSERC for a Vanier scholarship and the Walter C. Sumner foundation for additional financial support. IS acknowledges Queen’s University for the RT Mohan Scholarship and the Ontario government for an Ontario Graduate Scholarship.

PY - 2022/2/24

Y1 - 2022/2/24

N2 - The benzannulated N-heterocyclic carbene, 1,3-dibenzylbenzimidazolylidene (NHCDBZ) forms large, highly ordered domains when adsorbed on Cu(111) under ultrahigh vacuum conditions. A combination of scanning tunnelling microscopy (STM), high resolution electron energy loss spectroscopy (HREELS) and density functional theory (DFT) calculations reveals that the overlayer consists of vertical benzannulated NHC moieties coordinating to Cu adatoms. Long range order results from the placement of the two benzyl substituents on opposite sides of the benzimidazole moiety, with their aromatic rings approximately parallel to the surface. The organization of three surface-bound benzyl substituents from three different NHCs into a triangular array controls the formation of a highly ordered Kagome-like surface lattice. By comparison with earlier studies of NHCs on Cu(111), we show that the binding geometry and self-assembly of NHCDBZ are influenced by intermolecular and adsorbate-substrate interactions and facilitated by the flexibility of the methylene linkage between the N-heterocycle and the aromatic wingtip substituents.

AB - The benzannulated N-heterocyclic carbene, 1,3-dibenzylbenzimidazolylidene (NHCDBZ) forms large, highly ordered domains when adsorbed on Cu(111) under ultrahigh vacuum conditions. A combination of scanning tunnelling microscopy (STM), high resolution electron energy loss spectroscopy (HREELS) and density functional theory (DFT) calculations reveals that the overlayer consists of vertical benzannulated NHC moieties coordinating to Cu adatoms. Long range order results from the placement of the two benzyl substituents on opposite sides of the benzimidazole moiety, with their aromatic rings approximately parallel to the surface. The organization of three surface-bound benzyl substituents from three different NHCs into a triangular array controls the formation of a highly ordered Kagome-like surface lattice. By comparison with earlier studies of NHCs on Cu(111), we show that the binding geometry and self-assembly of NHCDBZ are influenced by intermolecular and adsorbate-substrate interactions and facilitated by the flexibility of the methylene linkage between the N-heterocycle and the aromatic wingtip substituents.

KW - N-heterocyclic carbene

KW - Scanning tunneling microscopy

KW - High resolution electron energy loss spectroscopy

KW - Cu

U2 - 10.1021/acs.jpclett.1c04073

DO - 10.1021/acs.jpclett.1c04073

M3 - Article

SN - 1948-7185

VL - 13

SP - 2051

EP - 2056

JO - The Journal of Physical Chemistry Letters

JF - The Journal of Physical Chemistry Letters

IS - 8

ER -

Highly ordered N-heterocyclic carbene monolayers on Cu(111)

Abstract

Keywords

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Projects

N-heterocyclic Carbenes: N-heterocyclic Carbenes on Metal Surfaces - towards applications in corrosion inhibition and catalysis

Datasets

Highly Ordered N-Heterocyclic Carbene Monolayers on Cu(111) (dataset)

Investigation of copper and silver surfaces functionalised by N-heterocyclic molecules (thesis data)

Cite this