Elucidating the influence of anchoring geometry on the reactivity of no2-functionalized n-heterocyclic carbene monolayers

Shahar Dery, Suhong Kim, Gabriele Tomaschun, Iris Berg, Daniel Feferman, Albano Cossaro, Alberto Verdini, Luca Floreano, Thorsten Klüner, F. Dean Toste*, Elad Gross

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

28 Scopus citations

Abstract

The development of chemically addressable N-heterocyclic carbene (NHC) based self-assembled monolayers (SAMs) requires in-depth understanding of the influence of NHC's anchoring geometry on its chemical functionality. Herein, it is demonstrated that the chemical reactivity of surface-anchored NO2-functionalized NHCs (NO2-NHCs) can be tuned by modifying the distance between the functional group and the reactive surface, which is governed by the deposition technique. Liquid deposition of NO2-NHCs on Pt(111) induced a SAM in which the NO2-aryl groups were flat-lying on the surface. The high proximity between the NO2 groups and the Pt surface led to high reactivity, and 85% of the NO2 groups were reduced at room temperature. Lower reactivity was obtained with vapor-deposited NO2-NHCs that assumed a preferred upright geometry. The separation between the NO2 groups in the vapor-deposited NO2-NHCs and the reactive surface circumvented their surface-induced reduction, which was facilitated only after exposure to harsher reducing conditions.

Original languageAmerican English
Pages (from-to)5099-5104
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume10
Issue number17
DOIs
StatePublished - 5 Sep 2019

Bibliographical note

Publisher Copyright:
Copyright © 2019 American Chemical Society.

Fingerprint

Dive into the research topics of 'Elucidating the influence of anchoring geometry on the reactivity of no2-functionalized n-heterocyclic carbene monolayers'. Together they form a unique fingerprint.

Cite this