1. Strong Metal–Adsorbate Interactions Increase the Reactivity and Decrease the Orientational Order of OH-Functionalized N-Heterocyclic Carbene Monolayers
- Author
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Dery, Shahar, Berg, Iris, Kim, Suhong, Cossaro, Albano, Verdini, Alberto, Floreano, Luca, Toste, F. Dean, Gross, Elad, Dery, S., Berg, I., Kim, S., Cossaro, A., Verdini, A., Floreano, L., Toste, F. D., and Gross, E.
- Subjects
02 engineering and technology ,010402 general chemistry ,Photochemistry ,01 natural sciences ,Metal ,chemistry.chemical_compound ,SELF-ASSEMBLED MONOLAYERS ,Monolayer ,Electrochemistry ,Molecule ,General Materials Science ,Reactivity (chemistry) ,GOLD ,ADSORPTION ,BENZENE ,PT(111) ,CHEMISORPTION ,NANOPARTICLES ,SPECTROSCOPY ,POTASSIUM ,PLATINUM ,Spectroscopy ,Chemistry ,Surfaces and Interfaces ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,0104 chemical sciences ,heterocyclic carbene ,self-assembled monolayer ,visual_art ,visual_art.visual_art_medium ,0210 nano-technology ,N-heterocyclic carbene ,Carbene - Abstract
Fundamental understanding of the correlation between the structure and reactivity of chemically addressable N-heterocyclic carbene (NHC) molecules on various surfacesis essential for the design of functional NHC-based self-assembled monolayers. In this work, we identified the ways by which the deposition of chemically addressable OH–NHCs on Au(111) or Pt(111) surfaces modified the anchoring geometry and chemical reactivity of surface-anchored NHCs. The properties of surface-anchored NHCs were probed by conducting X-ray photoelectron spectroscopy and polarized near-edge X-ray absorption fine structure measurements. While no preferred orientation was identified for OH–NHCs on Pt(111), the anchored molecules adopted a preferred flat-lying position on Au(111). Dehydrogenation and aromatization of the imidazoline ring along with partial hydroxyl oxidation were detected in OH–NHCs that were anchored on Au(111). The dehydrogenation and aromatization reactions were facilitated, along with partial decomposition, for OH–NHCs that were anchored on Pt(111). The spectroscopic results reveal that stronger metal–adsorbate interactions increase the reactivity of surface-anchored OH–NHCs while decreasing their molecular orientational order.
- Published
- 2019
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