TY - JOUR
T1 - Elucidating the influence of anchoring geometry on the reactivity of no2-functionalized n-heterocyclic carbene monolayers
AU - Dery, Shahar
AU - Kim, Suhong
AU - Tomaschun, Gabriele
AU - Berg, Iris
AU - Feferman, Daniel
AU - Cossaro, Albano
AU - Verdini, Alberto
AU - Floreano, Luca
AU - Klüner, Thorsten
AU - Toste, F. Dean
AU - Gross, Elad
N1 - Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2019/9/5
Y1 - 2019/9/5
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85072084148&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.9b01808
DO - 10.1021/acs.jpclett.9b01808
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C2 - 31386382
AN - SCOPUS:85072084148
SN - 1948-7185
VL - 10
SP - 5099
EP - 5104
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 17
ER -