Sticking with the Pointy End? Molecular Configuration of Chloro Boron-Subphthalocyanine on Cu(111)

Nahid Ilyas, Shashank S Harivyasi, Percy Zahl, Rocio Cortes, Oliver T Hofmann, Peter Sutter, Egbert Zojer, Oliver L A Monti

Research output: Contribution to journalArticleResearchpeer-review

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).

Original languageEnglish
Pages (from-to)7113-7121
Number of pages9
JournalJournal of Physical Chemistry C
Volume120
Issue number13
Early online date10 Mar 2016
DOIs
Publication statusPublished - 7 Apr 2016

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Boron
boron
Scanning tunneling microscopy
Molecules
Adsorption
scanning tunneling microscopy
configurations
adsorption
molecules
Self assembly
Density functional theory
self assembly
density functional theory
Dechlorination
Semiconducting organic compounds
Surface reactions
organic semiconductors
surface reactions
Vacuum
vacuum

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Sticking with the Pointy End? Molecular Configuration of Chloro Boron-Subphthalocyanine on Cu(111). / Ilyas, Nahid; Harivyasi, Shashank S; Zahl, Percy; Cortes, Rocio; Hofmann, Oliver T; Sutter, Peter; Zojer, Egbert; Monti, Oliver L A.

In: Journal of Physical Chemistry C, Vol. 120, No. 13, 07.04.2016, p. 7113-7121.

Research output: Contribution to journalArticleResearchpeer-review

Ilyas, Nahid ; Harivyasi, Shashank S ; Zahl, Percy ; Cortes, Rocio ; Hofmann, Oliver T ; Sutter, Peter ; Zojer, Egbert ; Monti, Oliver L A. / Sticking with the Pointy End? Molecular Configuration of Chloro Boron-Subphthalocyanine on Cu(111). In: Journal of Physical Chemistry C. 2016 ; Vol. 120, No. 13. pp. 7113-7121.
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AU - Zahl, Percy

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N2 - 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).

AB - 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).

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