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Title: Determination of the structure and geometry of N-heterocyclic carbenes on Au(111) using high-resolution spectroscopy

Abstract

N-heterocyclic carbenes (NHCs) bind very strongly to transition metals due to their unique electronic structure featuring a divalent carbon atom with a lone pair in a highly directional sp2-hybridized orbital. As such, they can be assembled into monolayers on metal surfaces that have enhanced stability compared to their thiol-based counterparts. The utility of NHCs to form such robust self-assembled monolayers (SAMs) was only recently recognized and many fundamental questions remain. Here we investigate the structure and geometry of a series of NHCs on Au(111) using high-resolution X-ray photoelectron spectroscopy and density functional theory calculations. We find that the N-substituents on the NHC ring strongly affect the molecule–metal interaction and steer the orientation of molecules in the surface layer. In contrast to previous reports, our experimental and theoretical results provide unequivocal evidence that NHCs with N-methyl substituents bind to under coordinated adatoms to form flat-lying complexes. In these SAMs, the donor–acceptor interaction between the NHC lone pair and the under coordinated Au adatom is primarily responsible for the strong bonding of the molecules to the surface. NHCs with bulkier N-substituents prevent the formation of such complexes by forcing the molecules into an upright orientation. Finally, our work provides unique insights intomore » the bonding and geometry of NHC monolayers; more generally, it charts a clear path to manipulating the interaction between NHCs and metal surfaces using traditional coordination chemistry synthetic strategies.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1];  [2];  [4]; ORCiD logo [3];  [5]; ORCiD logo [2]; ORCiD logo [6]
  1. Department of Applied Physics and Applied Mathematics, Columbia University, New York, USA
  2. Department of Chemistry, Columbia University, New York, USA
  3. Center for Functional Nanomaterials, Brookhaven National Laboratory, New York, USA
  4. CNR-IOM Laboratorio Nazionale TASC, 34012 Trieste, Italy, Faculty of Mathematics and Physics, University of Ljubljana
  5. CNR-IOM Laboratorio Nazionale TASC, 34012 Trieste, Italy, Department of Physics, University of Trieste
  6. Department of Applied Physics and Applied Mathematics, Columbia University, New York, USA, Department of Chemistry
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1481821
Alternate Identifier(s):
OSTI ID: 1496570
Report Number(s):
BNL-211297-2019-JAAM
Journal ID: ISSN 2041-6520; CSHCBM
Grant/Contract Number:  
SC0012704
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 10 Journal Issue: 3; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Lovat, Giacomo, Doud, Evan A., Lu, Deyu, Kladnik, Gregor, Inkpen, Michael S., Steigerwald, Michael L., Cvetko, Dean, Hybertsen, Mark S., Morgante, Alberto, Roy, Xavier, and Venkataraman, Latha. Determination of the structure and geometry of N-heterocyclic carbenes on Au(111) using high-resolution spectroscopy. United Kingdom: N. p., 2019. Web. doi:10.1039/C8SC03502D.
Lovat, Giacomo, Doud, Evan A., Lu, Deyu, Kladnik, Gregor, Inkpen, Michael S., Steigerwald, Michael L., Cvetko, Dean, Hybertsen, Mark S., Morgante, Alberto, Roy, Xavier, & Venkataraman, Latha. Determination of the structure and geometry of N-heterocyclic carbenes on Au(111) using high-resolution spectroscopy. United Kingdom. doi:10.1039/C8SC03502D.
Lovat, Giacomo, Doud, Evan A., Lu, Deyu, Kladnik, Gregor, Inkpen, Michael S., Steigerwald, Michael L., Cvetko, Dean, Hybertsen, Mark S., Morgante, Alberto, Roy, Xavier, and Venkataraman, Latha. Wed . "Determination of the structure and geometry of N-heterocyclic carbenes on Au(111) using high-resolution spectroscopy". United Kingdom. doi:10.1039/C8SC03502D.
@article{osti_1481821,
title = {Determination of the structure and geometry of N-heterocyclic carbenes on Au(111) using high-resolution spectroscopy},
author = {Lovat, Giacomo and Doud, Evan A. and Lu, Deyu and Kladnik, Gregor and Inkpen, Michael S. and Steigerwald, Michael L. and Cvetko, Dean and Hybertsen, Mark S. and Morgante, Alberto and Roy, Xavier and Venkataraman, Latha},
abstractNote = {N-heterocyclic carbenes (NHCs) bind very strongly to transition metals due to their unique electronic structure featuring a divalent carbon atom with a lone pair in a highly directional sp2-hybridized orbital. As such, they can be assembled into monolayers on metal surfaces that have enhanced stability compared to their thiol-based counterparts. The utility of NHCs to form such robust self-assembled monolayers (SAMs) was only recently recognized and many fundamental questions remain. Here we investigate the structure and geometry of a series of NHCs on Au(111) using high-resolution X-ray photoelectron spectroscopy and density functional theory calculations. We find that the N-substituents on the NHC ring strongly affect the molecule–metal interaction and steer the orientation of molecules in the surface layer. In contrast to previous reports, our experimental and theoretical results provide unequivocal evidence that NHCs with N-methyl substituents bind to under coordinated adatoms to form flat-lying complexes. In these SAMs, the donor–acceptor interaction between the NHC lone pair and the under coordinated Au adatom is primarily responsible for the strong bonding of the molecules to the surface. NHCs with bulkier N-substituents prevent the formation of such complexes by forcing the molecules into an upright orientation. Finally, our work provides unique insights into the bonding and geometry of NHC monolayers; more generally, it charts a clear path to manipulating the interaction between NHCs and metal surfaces using traditional coordination chemistry synthetic strategies.},
doi = {10.1039/C8SC03502D},
journal = {Chemical Science},
number = 3,
volume = 10,
place = {United Kingdom},
year = {2019},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1039/C8SC03502D

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Cited by: 7 works
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