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Decoupling chemically active 2D molecular overlayers from the substrate: chlorophenyl porphyrins on graphene/Ir(111)
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SYSNO ASEP 0583161 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Decoupling chemically active 2D molecular overlayers from the substrate: chlorophenyl porphyrins on graphene/Ir(111) Author(s) Mowbray, D.J. (EC)
Pérez Paz, A. (AE)
de Campos Ferreira, Rodrigo Cezar (FZU-D) ORCID
Milotti, V. (AT)
Schio, P. (BR)
Simoes e Silva, W. (BR)
Pichler, T. (AT)
de Siervo, A. (BR)
Moreno-Lopez, J.C. (AT)Number of authors 9 Source Title Journal of Physical Chemistry C. - : American Chemical Society - ISSN 1932-7447
Roč. 127, č. 18 (2023), s. 8751-8758Number of pages 8 s. Language eng - English Country US - United States Keywords 2D self-assembly ; graphene ; chlorophenyl porphyrin ; STM ; XPS ; ARPES Subject RIV BE - Theoretical Physics OECD category Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect) Method of publishing Open access Institutional support FZU-D - RVO:68378271 UT WOS 000984954800001 EID SCOPUS 85156275533 DOI 10.1021/acs.jpcc.3c00235 Annotation The synthesis of atomically precise chemically active 2D molecular overlayers may be hindered by chemical interactions with the underlying substrate, especially when based on chlorophenyl porphyrins. At the same time, the chlorination of graphene, i.e., the covalent bonding of chlorine atoms with sp2 carbon atoms, is known to have a significant influence on the electronic properties of pristine graphene. In this study, we deposit a chlorinated porphyrin molecule, namely 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin (Cl4TPP), on graphene/Ir(111). Employing a combined experimental and theoretical approach, we demonstrate that the porphyrin layer physisorbed on graphene self-assembles into a periodic square-like arrangement. This carpet-like growth is unperturbed by the step edges of the substrate, neither in its periodicity nor in its orientation. In addition, the molecular overlayer is thermally stable and does not alter the electronic properties of graphene. Remarkably, we show that Cl4TPP does not experience a dechlorination reaction with the underlying substrate, even after postdeposition annealing temperatures as high as 550 K. Moreover, postdeposition annealing at 700 K suggests the Cl4TPP molecules desorb intact without affecting graphene’s electronic properties. In so doing, we demonstrate the effectiveness of graphene physisorbed on Ir(111) to both promote the formation and preserve the properties of chemically reactive 2D overlayers based on chlorophenyl porphyrins. These results show physisorbed graphene’s potential as a general templating material for the formation of highly reactive self-assembled 2D overlayers. Workplace Institute of Physics Contact Kristina Potocká, potocka@fzu.cz, Tel.: 220 318 579 Year of Publishing 2024 Electronic address https://hdl.handle.net/11104/0351153
Number of the records: 1