Ilyas, N, Harivyasi, SS orcid.org/0000-0002-2174-5226, Zahl, P et al. (5 more authors) (2016) Sticking with the Pointy End? Molecular Configuration of Chloro Boron-Subphthalocyanine on Cu(111). Journal of Physical Chemistry C, 120 (13). pp. 7113-7121. ISSN 1932-7447
Abstract
In this combined low-temperature scanning tunneling microscopy (STM) and density functional theory (DFT) study, we investigate self-assembly of the dipolar nonplanar organic semiconductor chloro boron-subphthalocyanine (ClB-SubPc) on Cu(111). We observe multiple distinct adsorption configurations and demonstrate that these can only be understood by taking surface-catalyzed dechlorination into account. A detailed investigation of possible adsorption configurations and the comparison of experimental and computational STM images demonstrates that the configurations correspond to “Cl-up” molecules with the B–Cl moiety pointing toward the vacuum side of the interface, and dechlorinated molecules. In contrast to the standard interpretation of adsorption of nonplanar molecules in the phthalocyanine family, we find no evidence for “Cl-down” molecules where the B–Cl moiety would be pointing toward the Cu surface. We show computationally that such a configuration is unstable and thus is highly unlikely to occur for ClB-SubPc on Cu(111). Using these assignments, we discuss the different self-assembly motifs in the submonolayer coverage regime. The combination of DFT and STM is essential to gain a full atomistic understanding of the surface–molecule interactions, and our findings imply that phthalocyanines may undergo surface-catalyzed reactions hitherto not considered. Our results also indicate that care has to be taken when analyzing possible adsorption configurations of polar members of the phthalocyanine family, especially when they are adsorbed on comparably reactive surfaces like Cu(111).
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2016 American Chemical Society. This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Physics and Astronomy (Leeds) > Molecular & Nanoscale Physics |
Depositing User: | Symplectic Publications |
Date Deposited: | 27 Nov 2018 16:42 |
Last Modified: | 27 Nov 2018 16:42 |
Status: | Published |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/acs.jpcc.5b11799 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:137627 |