RT Journal Article
T1 Stabilizing Edge Fluorination in Graphene Nanoribbons
A1 Panighel, Mirco
A1 Quiroga Fernández, Sabela
A1 Brandimarte, Pedro
A1 Moreno, Cesar
A1 García Lekue, Aran
A1 Vilas Varela, Manuel
A1 Rey Vieites, Dulce María
A1 Sauthier, Guillaume
A1 Ceballos, Gustavo
A1 Peña Gil, Diego
A1 Mugarza, Aitor
K1 Precursors
K1 Bond cleavage
K1 Energy
K1 X-ray photoelectron spectroscopy
K1 Scanning tunneling microscopy
AB The on-surface synthesis of edge-functionalized graphene nanoribbons (GNRs) is challenged by the stability of the functional groups throughout the thermal reaction steps of the synthetic pathway. Edge fluorination is a particularly critical case in which the interaction with the catalytic substrate and intermediate products can induce the complete cleavage of the otherwise strong C–F bonds before the formation of the GNR. Here, we demonstrate how a rational design of the precursor can stabilize the functional group, enabling the synthesis of edge-fluorinated GNRs. The survival of the functionalization is demonstrated by tracking the structural and chemical transformations occurring at each reaction step with complementary X-ray photoelectron spectroscopy and scanning tunneling microscopy measurements. In contrast to previous attempts, we find that the C–F bond survives the cyclodehydrogenation of the intermediate polymers, leaving a thermal window where GNRs withhold more than 80% of the fluorine atoms. We attribute this enhanced stability of the C–F bond to the particular structure of our precursor, which prevents the cleavage of the C–F bond by avoiding interaction with the residual hydrogen originated in the cyclodehydrogenation. This structural protection of the linking bond could be implemented in the synthesis of other sp2-functionalized GNRs
PB American Chemical Society
SN 1936-0851
YR 2020
FD 2020
LK http://hdl.handle.net/10347/23318
UL http://hdl.handle.net/10347/23318
LA eng
NO ACS Nano 2020, 14, 9, 11120–11129
NO This document is the unedited Author’s version of a Submitted Work that was subsequently accepted forpublication in ACS Nano, copyright © American Chemical Society after peer review. To access the final editedand published work see https://doi.org/10.1021/acsnano.0c01837
NO C.M. was supported by the Agency for Management of University and Research grants (AGAUR) of the Catalan government through the FP7 framework program of the European Commission under Marie Curie COFUND action 600385 funded by the CERCA Program/Generalitat de Catalunya. We acknowledge support from the Spanish Ministry of Economy and Competitiveness, MINECO (under Contracts Nos. MAT2016-78293-C6 and FIS2017-83780-P and SEV-2017-0706), the Spanish Research Agency (AEI /10.13039/501100011033, under Contracts Nos. PID2019-107338RB, PCI2019-111890-2), the European Regional Development Fund (ERDF), the Interreg V-A España-Francia-Andorra program (Contract No. EFA 194/16 TNSI), the EU project SPRING (863098), the Xunta de Galicia (Centro singular de investigación de Galicia accreditation 2019-2022, ED431G 2019/03)
DS Minerva
RD 4 may 2026