N-Heterocyclic Carbene Monolayers on Metal-Oxide Films: Correlations Between Adsorption Mode and Surface Functionality

Overview

Journal Langmuir

Publisher American Chemical Society

Specialty Chemistry

Date 2024 May 3

PMID 38701356

Authors

Einav Amit

Rajarshi Mondal

Iris Berg

Zackaria Nairoukh

Elad Gross

Affiliations

Soon will be listed here.

Abstract

N-Heterocyclic carbene (NHC) ligands have been self-assembled on various metal and semimetal surfaces, creating a covalent bond with surface metal atoms that led to high thermal and chemical stability of the self-assembled monolayer. This study explores the self-assembly of NHCs on metal-oxide films (CuO, FeO, and TiO) and reveals that the properties of these metal-oxide substrates play a pivotal role in dictating the adsorption behavior of NHCs, influencing the decomposition route of the monolayer and its impact on work function values. While the attachment of NHCs onto CuO is via coordination with surface oxygen atoms, NHCs interact with TiO through coordination with surface metal atoms and with FeO via coordination with both metal and oxygen surface atoms. These distinct binding modes arise due to variances in the electronic properties of the metal atoms within the investigated metal-oxide films. Contact angle and ultraviolet photoelectron spectroscopy measurements have shown a significantly higher impact of F-NHC adsorption on CuO than on TiO and FeO , correlated to a preferred, averaged upright orientation of F-NHC on CuO.

Citing Articles

Strong Substrate-Adsorbate Interactions Direct the Impact of Fluorinated N-Heterocyclic Carbene Monolayers on Au Surface Properties.

Berg I, Mondal R, Sims J, Ben-Tzvi T, Lahav L, Friedman B ACS Appl Mater Interfaces. 2024; 16(47):65469-65479.

PMID: 39556756 PMC: 11615852. DOI: 10.1021/acsami.4c12514.

References

Schernich S, Laurin M, Lykhach Y, Steinruck H, Tsud N, Skala T . Functionalization of Oxide Surfaces through Reaction with 1,3-Dialkylimidazolium Ionic Liquids. J Phys Chem Lett. 2015; 4(1):30-5. DOI: 10.1021/jz301856a. View

Wu C, Wolf W, Levartovsky Y, Bechtel H, Martin M, Toste F . High-spatial-resolution mapping of catalytic reactions on single particles. Nature. 2017; 541(7638):511-515. DOI: 10.1038/nature20795. View

Amit E, Berg I, Zhang W, Mondal R, Shema H, Gutkin V . Selective Deposition of N-Heterocyclic Carbene Monolayers on Designated Au Microelectrodes within an Electrode Array. Small. 2023; 20(2):e2302317. DOI: 10.1002/smll.202302317. View

Wang L, Schubert U, Hoeppener S . Surface chemical reactions on self-assembled silane based monolayers. Chem Soc Rev. 2021; 50(11):6507-6540. DOI: 10.1039/d0cs01220c. View

Thissen P, Valtiner M, Grundmeier G . Stability of phosphonic acid self-assembled monolayers on amorphous and single-crystalline aluminum oxide surfaces in aqueous solution. Langmuir. 2009; 26(1):156-64. DOI: 10.1021/la900935s. View

Kang S, Park S, Kang H, Cho S, Song H, Yoon H . Tunneling and thermoelectric characteristics of N-heterocyclic carbene-based large-area molecular junctions. Chem Commun (Camb). 2019; 55(60):8780-8783. DOI: 10.1039/c9cc01585j. View

Dery S, Bellotti P, Ben-Tzvi T, Freitag M, Shahar T, Cossaro A . Influence of N-Substituents on the Adsorption Geometry of OH-Functionalized Chiral N-Heterocyclic Carbenes. Langmuir. 2021; 37(33):10029-10035. PMC: 9234974. DOI: 10.1021/acs.langmuir.1c01199. View

Mayall R, Smith C, Hyla A, Lee D, Crudden C, Birss V . Ultrasensitive and Label-Free Detection of the Measles Virus Using an N-Heterocyclic Carbene-Based Electrochemical Biosensor. ACS Sens. 2020; 5(9):2747-2752. DOI: 10.1021/acssensors.0c01250. View

Haensch C, Hoeppener S, Schubert U . Chemical modification of self-assembled silane based monolayers by surface reactions. Chem Soc Rev. 2010; 39(6):2323-34. DOI: 10.1039/b920491a. View

10.

Aswal D, Lenfant S, Guerin D, Yakhmi J, Vuillaume D . Self assembled monolayers on silicon for molecular electronics. Anal Chim Acta. 2007; 568(1-2):84-108. DOI: 10.1016/j.aca.2005.10.027. View

11.

Crudden C, Horton J, Ebralidze I, Zenkina O, McLean A, Drevniok B . Ultra stable self-assembled monolayers of N-heterocyclic carbenes on gold. Nat Chem. 2014; 6(5):409-14. DOI: 10.1038/nchem.1891. View

12.

Jiang L, Zhang B, Medard G, Seitsonen A, Haag F, Allegretti F . -Heterocyclic carbenes on close-packed coinage metal surfaces: bis-carbene metal adatom bonding scheme of monolayer films on Au, Ag and Cu. Chem Sci. 2018; 8(12):8301-8308. PMC: 5858017. DOI: 10.1039/c7sc03777e. View

13.

Amit E, Dery L, Dery S, Kim S, Roy A, Hu Q . Electrochemical deposition of N-heterocyclic carbene monolayers on metal surfaces. Nat Commun. 2020; 11(1):5714. PMC: 7658200. DOI: 10.1038/s41467-020-19500-7. View

14.

Ulman A . Formation and Structure of Self-Assembled Monolayers. Chem Rev. 1996; 96(4):1533-1554. DOI: 10.1021/cr9502357. View

15.

Lewis R, Koy M, Macino M, Das M, Carter J, Morgan D . N-Heterocyclic Carbene Modified Palladium Catalysts for the Direct Synthesis of Hydrogen Peroxide. J Am Chem Soc. 2022; 144(34):15431-15436. PMC: 9449981. DOI: 10.1021/jacs.2c04828. View

16.

Hopkinson M, Richter C, Schedler M, Glorius F . An overview of N-heterocyclic carbenes. Nature. 2014; 510(7506):485-96. DOI: 10.1038/nature13384. View

17.

Zhukhovitskiy A, MacLeod M, Johnson J . Carbene Ligands in Surface Chemistry: From Stabilization of Discrete Elemental Allotropes to Modification of Nanoscale and Bulk Substrates. Chem Rev. 2015; 115(20):11503-32. DOI: 10.1021/acs.chemrev.5b00220. View

18.

Onclin S, Ravoo B, Reinhoudt D . Engineering silicon oxide surfaces using self-assembled monolayers. Angew Chem Int Ed Engl. 2005; 44(39):6282-304. DOI: 10.1002/anie.200500633. View

19.

Guo C, Fleige M, Janssen-Muller D, Daniliuc C, Glorius F . Cooperative N-Heterocyclic Carbene/Palladium-Catalyzed Enantioselective Umpolung Annulations. J Am Chem Soc. 2016; 138(25):7840-3. DOI: 10.1021/jacs.6b04364. View

20.

Lovat G, Doud E, Lu D, Kladnik G, Inkpen M, Steigerwald M . Determination of the structure and geometry of N-heterocyclic carbenes on Au(111) using high-resolution spectroscopy. Chem Sci. 2019; 10(3):930-935. PMC: 6346291. DOI: 10.1039/c8sc03502d. View