Self-Assembled Monolayers of N-Heterocyclic Olefins on Au(111)

Iris Berg; Luca Schio; Justus Reitz; Elena Molteni; Linoy Lahav; Carolina Gutiérrez Bolaños; Andrea Goldoni; Cesare Grazioli; Guido Fratesi; Max M. Hansmann; Luca Floreano; Elad Gross

doi:10.1002/anie.202311832

Self-Assembled Monolayers of N-Heterocyclic Olefins on Au(111)

Iris Berg, Luca Schio, Justus Reitz, Elena Molteni, Linoy Lahav, Carolina Gutiérrez Bolaños, Andrea Goldoni, Cesare Grazioli, Guido Fratesi, Max M. Hansmann, Luca Floreano, Elad Gross^*

^*Corresponding author for this work

Institute of Chemistry

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

Abstract

Self-assembled monolayers (SAMs) of N-heterocyclic olefins (NHOs) have been prepared on Au(111) and their thermal stability, adsorption geometry, and molecular order were characterized by X-ray photoelectron spectroscopy, polarized X-ray absorption spectroscopy, scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. The strong σ-bond character of NHO anchoring to Au induced high geometrical flexibility that enabled a flat-lying adsorption geometry via coordination to a gold adatom. The flat-lying adsorption geometry was utilized to further increase the surface interaction of the NHO monolayer by backbone functionalization with methyl groups that induced high thermal stability and a large impact on work-function values, which outperformed that of N-heterocyclic carbenes. STM measurements, supported by DFT modeling, identified that the NHOs were self-assembled in dimers, trimers, and tetramers constructed of two, three, and four complexes of NHO−Au-adatom. This self-assembly pattern was correlated to strong NHO−Au interactions and steric hindrance between adsorbates, demonstrating the crucial influence of the carbon-metal σ-bond on monolayer properties.

Original language	American English
Journal	Angewandte Chemie - International Edition
DOIs	https://doi.org/10.1002/anie.202311832
State	Accepted/In press - 2023

Bibliographical note

Funding Information:
This research was supported by the European Research Council (ERC) under the European Union's Horizon 2020 and Horizon Europe research and innovation program (Grant Agreement No. 802769, ERC Starting Grant “MapCat” and Grant Agreement No. 101077332, ERC Starting Grant “CC‐CHARGED”). I. B. acknowledges the Clore Israel Foundation, and the Harvey M. Krueger Family Center for Nanoscience and Nanotechnology for their financial support. L.L acknowledges Harvey M. Krueger Family Center for Nanoscience and Nanotechnology for their financial support. This project has received funding from the European Union's Horizon 2020 and Horizon Europe research and innovation program under grant agreement No. 101007417 and 101077332 having benefited from the access to OSMOS STM lab provided by CNR‐IOM in Trieste and by the Physics Department of the University of Milan for theoretical support, within the framework of the NFFA‐Europe Pilot Transnational Access Activity, proposal ID443. We acknowledge the CINECA award under the ISCRA initiative, for the availability of high performance computing resources and support.

Publisher Copyright:
© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Keywords

N-Heterocyclic Olefins
Scanning Tunneling Microscopy
Self-Assembled Monolayers
Surface Chemistry
X-Ray Absorption Spectroscopy

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10.1002/anie.202311832

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@article{673938c6c54d4213bdbd60974f6d0d32,

title = "Self-Assembled Monolayers of N-Heterocyclic Olefins on Au(111)",

abstract = "Self-assembled monolayers (SAMs) of N-heterocyclic olefins (NHOs) have been prepared on Au(111) and their thermal stability, adsorption geometry, and molecular order were characterized by X-ray photoelectron spectroscopy, polarized X-ray absorption spectroscopy, scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. The strong σ-bond character of NHO anchoring to Au induced high geometrical flexibility that enabled a flat-lying adsorption geometry via coordination to a gold adatom. The flat-lying adsorption geometry was utilized to further increase the surface interaction of the NHO monolayer by backbone functionalization with methyl groups that induced high thermal stability and a large impact on work-function values, which outperformed that of N-heterocyclic carbenes. STM measurements, supported by DFT modeling, identified that the NHOs were self-assembled in dimers, trimers, and tetramers constructed of two, three, and four complexes of NHO−Au-adatom. This self-assembly pattern was correlated to strong NHO−Au interactions and steric hindrance between adsorbates, demonstrating the crucial influence of the carbon-metal σ-bond on monolayer properties.",

keywords = "N-Heterocyclic Olefins, Scanning Tunneling Microscopy, Self-Assembled Monolayers, Surface Chemistry, X-Ray Absorption Spectroscopy",

author = "Iris Berg and Luca Schio and Justus Reitz and Elena Molteni and Linoy Lahav and Bola{\~n}os, {Carolina Guti{\'e}rrez} and Andrea Goldoni and Cesare Grazioli and Guido Fratesi and Hansmann, {Max M.} and Luca Floreano and Elad Gross",

note = "Funding Information: This research was supported by the European Research Council (ERC) under the European Union's Horizon 2020 and Horizon Europe research and innovation program (Grant Agreement No. 802769, ERC Starting Grant “MapCat” and Grant Agreement No. 101077332, ERC Starting Grant “CC‐CHARGED”). I. B. acknowledges the Clore Israel Foundation, and the Harvey M. Krueger Family Center for Nanoscience and Nanotechnology for their financial support. L.L acknowledges Harvey M. Krueger Family Center for Nanoscience and Nanotechnology for their financial support. This project has received funding from the European Union's Horizon 2020 and Horizon Europe research and innovation program under grant agreement No. 101007417 and 101077332 having benefited from the access to OSMOS STM lab provided by CNR‐IOM in Trieste and by the Physics Department of the University of Milan for theoretical support, within the framework of the NFFA‐Europe Pilot Transnational Access Activity, proposal ID443. We acknowledge the CINECA award under the ISCRA initiative, for the availability of high performance computing resources and support. Publisher Copyright: {\textcopyright} 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

year = "2023",

doi = "10.1002/anie.202311832",

language = "American English",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

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T1 - Self-Assembled Monolayers of N-Heterocyclic Olefins on Au(111)

AU - Berg, Iris

AU - Schio, Luca

AU - Reitz, Justus

AU - Molteni, Elena

AU - Lahav, Linoy

AU - Bolaños, Carolina Gutiérrez

AU - Goldoni, Andrea

AU - Grazioli, Cesare

AU - Fratesi, Guido

AU - Hansmann, Max M.

AU - Floreano, Luca

AU - Gross, Elad

N1 - Funding Information: This research was supported by the European Research Council (ERC) under the European Union's Horizon 2020 and Horizon Europe research and innovation program (Grant Agreement No. 802769, ERC Starting Grant “MapCat” and Grant Agreement No. 101077332, ERC Starting Grant “CC‐CHARGED”). I. B. acknowledges the Clore Israel Foundation, and the Harvey M. Krueger Family Center for Nanoscience and Nanotechnology for their financial support. L.L acknowledges Harvey M. Krueger Family Center for Nanoscience and Nanotechnology for their financial support. This project has received funding from the European Union's Horizon 2020 and Horizon Europe research and innovation program under grant agreement No. 101007417 and 101077332 having benefited from the access to OSMOS STM lab provided by CNR‐IOM in Trieste and by the Physics Department of the University of Milan for theoretical support, within the framework of the NFFA‐Europe Pilot Transnational Access Activity, proposal ID443. We acknowledge the CINECA award under the ISCRA initiative, for the availability of high performance computing resources and support. Publisher Copyright: © 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

PY - 2023

Y1 - 2023

N2 - Self-assembled monolayers (SAMs) of N-heterocyclic olefins (NHOs) have been prepared on Au(111) and their thermal stability, adsorption geometry, and molecular order were characterized by X-ray photoelectron spectroscopy, polarized X-ray absorption spectroscopy, scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. The strong σ-bond character of NHO anchoring to Au induced high geometrical flexibility that enabled a flat-lying adsorption geometry via coordination to a gold adatom. The flat-lying adsorption geometry was utilized to further increase the surface interaction of the NHO monolayer by backbone functionalization with methyl groups that induced high thermal stability and a large impact on work-function values, which outperformed that of N-heterocyclic carbenes. STM measurements, supported by DFT modeling, identified that the NHOs were self-assembled in dimers, trimers, and tetramers constructed of two, three, and four complexes of NHO−Au-adatom. This self-assembly pattern was correlated to strong NHO−Au interactions and steric hindrance between adsorbates, demonstrating the crucial influence of the carbon-metal σ-bond on monolayer properties.

AB - Self-assembled monolayers (SAMs) of N-heterocyclic olefins (NHOs) have been prepared on Au(111) and their thermal stability, adsorption geometry, and molecular order were characterized by X-ray photoelectron spectroscopy, polarized X-ray absorption spectroscopy, scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. The strong σ-bond character of NHO anchoring to Au induced high geometrical flexibility that enabled a flat-lying adsorption geometry via coordination to a gold adatom. The flat-lying adsorption geometry was utilized to further increase the surface interaction of the NHO monolayer by backbone functionalization with methyl groups that induced high thermal stability and a large impact on work-function values, which outperformed that of N-heterocyclic carbenes. STM measurements, supported by DFT modeling, identified that the NHOs were self-assembled in dimers, trimers, and tetramers constructed of two, three, and four complexes of NHO−Au-adatom. This self-assembly pattern was correlated to strong NHO−Au interactions and steric hindrance between adsorbates, demonstrating the crucial influence of the carbon-metal σ-bond on monolayer properties.

KW - N-Heterocyclic Olefins

KW - Scanning Tunneling Microscopy

KW - Self-Assembled Monolayers

KW - Surface Chemistry

KW - X-Ray Absorption Spectroscopy

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U2 - 10.1002/anie.202311832

DO - 10.1002/anie.202311832

M3 - Article

C2 - 37743324

AN - SCOPUS:85173653420

SN - 1433-7851

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

ER -

Self-Assembled Monolayers of N-Heterocyclic Olefins on Au(111)

Abstract

Bibliographical note

Keywords

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