N-heterocyclic carbene self-assembled monolayers on copper and gold: dramatic effect of wingtip groups on binding, orientation and assembly

Christian Rodriguez Larrea; Christopher John Baddeley; Mina R. Narouz; Nicholas J. Mosey; J. Hugh Horton; Cathleen M. Crudden

doi:10.1002/cphc.201701045

N-heterocyclic carbene self-assembled monolayers on copper and gold: dramatic effect of wingtip groups on binding, orientation and assembly

Christian Rodriguez Larrea, Christopher John Baddeley^*, Mina R. Narouz, Nicholas J. Mosey, J. Hugh Horton, Cathleen M. Crudden

^*Corresponding author for this work

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

Abstract

Self‐assembled monolayers of N‐heterocyclic carbenes (NHCs) on copper are reported. The monolayer structure is highly dependent on the N,N‐substituents on the NHC. On both Cu(111) and Au(111), bulky isopropyl substituents force the NHC to bind perpendicular to the metal surface while methyl‐ or ethyl‐substituted NHCs lie flat. Temperature‐programmed desorption studies show that the NHC binds to Cu(111) with a desorption energy of E_des=152±10 kJ mol⁻¹. NHCs that bind upright desorb cleanly, while flat‐lying NHCs decompose leaving adsorbed organic residues. Scanning tunneling microscopy of methylated NHCs reveals arrays of covalently linked dimers which transform into adsorbed (NHC)₂Cu species by extraction of a copper atom from the surface after annealing.

Original language	English
Pages (from-to)	3536–3539
Journal	ChemPhysChem
Volume	18
Issue number	24
Early online date	2 Nov 2017
DOIs	https://doi.org/10.1002/cphc.201701045
Publication status	Published - 21 Dec 2017

Keywords

N-heterocyclic carbenes
Copper
Self assembled monolayers
Orientation
Wingtip

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10.1002/cphc.201701045Licence: CC BY

Larrea_2017_CPC_N-heterocyclic_CCBY-VoR
© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 1.09 MBLicence: CC BY

Christopher John Baddeley
- cjb14st-andrews.acuk
- School of Chemistry - Head of School, Professor
- EaSTCHEM
Person: Academic

N-heterocyclic carbene self-assembled monolayers on copper and gold: dramatic effect of wingtip groups on binding, orientation and assembly (dataset)
Larrea, C. R. (Creator), Baddeley, C. J. (Creator), Narouz, M. R. (Creator), Mosey, N. J. (Creator), Horton, J. H. (Creator) & Crudden, C. M. (Creator), University of St Andrews, 10 Oct 2017
DOI: 10.17630/2013958a-4c9f-4859-b66d-ee88c39ef794
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title = "N-heterocyclic carbene self-assembled monolayers on copper and gold: dramatic effect of wingtip groups on binding, orientation and assembly",

abstract = "Self‐assembled monolayers of N‐heterocyclic carbenes (NHCs) on copper are reported. The monolayer structure is highly dependent on the N,N‐substituents on the NHC. On both Cu(111) and Au(111), bulky isopropyl substituents force the NHC to bind perpendicular to the metal surface while methyl‐ or ethyl‐substituted NHCs lie flat. Temperature‐programmed desorption studies show that the NHC binds to Cu(111) with a desorption energy of Edes=152±10 kJ mol−1. NHCs that bind upright desorb cleanly, while flat‐lying NHCs decompose leaving adsorbed organic residues. Scanning tunneling microscopy of methylated NHCs reveals arrays of covalently linked dimers which transform into adsorbed (NHC)2Cu species by extraction of a copper atom from the surface after annealing.",

keywords = "N-heterocyclic carbenes , Copper, Self assembled monolayers, Orientation, Wingtip",

author = "Larrea, {Christian Rodriguez} and Baddeley, {Christopher John} and Narouz, {Mina R.} and Mosey, {Nicholas J.} and Horton, {J. Hugh} and Crudden, {Cathleen M.}",

note = "Funding: EPSRC PhD studentship (EP/M506631/1).",

year = "2017",

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doi = "10.1002/cphc.201701045",

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journal = "ChemPhysChem",

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T1 - N-heterocyclic carbene self-assembled monolayers on copper and gold

T2 - dramatic effect of wingtip groups on binding, orientation and assembly

AU - Larrea, Christian Rodriguez

AU - Baddeley, Christopher John

AU - Narouz, Mina R.

AU - Mosey, Nicholas J.

AU - Horton, J. Hugh

AU - Crudden, Cathleen M.

N1 - Funding: EPSRC PhD studentship (EP/M506631/1).

PY - 2017/12/21

Y1 - 2017/12/21

N2 - Self‐assembled monolayers of N‐heterocyclic carbenes (NHCs) on copper are reported. The monolayer structure is highly dependent on the N,N‐substituents on the NHC. On both Cu(111) and Au(111), bulky isopropyl substituents force the NHC to bind perpendicular to the metal surface while methyl‐ or ethyl‐substituted NHCs lie flat. Temperature‐programmed desorption studies show that the NHC binds to Cu(111) with a desorption energy of Edes=152±10 kJ mol−1. NHCs that bind upright desorb cleanly, while flat‐lying NHCs decompose leaving adsorbed organic residues. Scanning tunneling microscopy of methylated NHCs reveals arrays of covalently linked dimers which transform into adsorbed (NHC)2Cu species by extraction of a copper atom from the surface after annealing.

AB - Self‐assembled monolayers of N‐heterocyclic carbenes (NHCs) on copper are reported. The monolayer structure is highly dependent on the N,N‐substituents on the NHC. On both Cu(111) and Au(111), bulky isopropyl substituents force the NHC to bind perpendicular to the metal surface while methyl‐ or ethyl‐substituted NHCs lie flat. Temperature‐programmed desorption studies show that the NHC binds to Cu(111) with a desorption energy of Edes=152±10 kJ mol−1. NHCs that bind upright desorb cleanly, while flat‐lying NHCs decompose leaving adsorbed organic residues. Scanning tunneling microscopy of methylated NHCs reveals arrays of covalently linked dimers which transform into adsorbed (NHC)2Cu species by extraction of a copper atom from the surface after annealing.

KW - N-heterocyclic carbenes

KW - Copper

KW - Self assembled monolayers

KW - Orientation

KW - Wingtip

U2 - 10.1002/cphc.201701045

DO - 10.1002/cphc.201701045

M3 - Article

SN - 1439-4235

VL - 18

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JO - ChemPhysChem

JF - ChemPhysChem

IS - 24

ER -

N-heterocyclic carbene self-assembled monolayers on copper and gold: dramatic effect of wingtip groups on binding, orientation and assembly

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N-heterocyclic carbene self-assembled monolayers on copper and gold: dramatic effect of wingtip groups on binding, orientation and assembly (dataset)

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