“Inverted” porphyrins: a distorted adsorption geometry of free-base porphyrins on Cu(111)

Lepper, Michael; Köbl, Julia; Schmitt, Thorsten; Gurrath, Martin; Siervo, Abner de; Schneider, M. Alexander; Steinrück, Hans‐Peter; Meyer, Bernd; Marbach, Hubertus; Hieringer, Wolfgang

doi:10.1039/c7cc04182a

Cited by 40 publications

(76 citation statements)

References 31 publications

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“…In contrast 2H-TPP/Cu(111) has significant charge transfer, resulting in repulsive forces between the molecules that prevent molecular adlayer network formation. A similar result was observed by Lepper et al [78] who reported an inverted TPP on Cu(111) surface due to coordination of the two iminic nitrogen atoms to the Cu(111) surface via their lone pairs and thus significant charge transfer.…”

Section: Conformational Studies Of Meso-substituted Porphyrins On Subsupporting

confidence: 86%

Structure, Properties, and Reactivity of Porphyrins on Surfaces and Nanostructures with Periodic DFT Calculations

2020

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Porphyrins are fascinating molecules with applications spanning various scientific fields. In this review we present the use of periodic density functional theory (PDFT) calculations to study the structure, electronic properties, and reactivity of porphyrins on ordered two dimensional surfaces and in the formation of nanostructures. The focus of the review is to describe the application of PDFT calculations for bridging the gaps in experimental studies on porphyrin nanostructures and self-assembly on 2D surfaces. A survey of different DFT functionals used to study the porphyrin-based system as well as their advantages and disadvantages in studying these systems is presented.

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Section: Conformational Studies Of Meso-substituted Porphyrins On Subsupporting

confidence: 86%

Structure, Properties, and Reactivity of Porphyrins on Surfaces and Nanostructures with Periodic DFT Calculations

2020

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“…Zweitens kann die intramolekulare Konformation aller hier untersuchten Freie‐Base‐Cyanporphyrine als “invertierte” Struktur identifiziert werden . Diese enthält zwei vertikal angeordnete Pyrrolringe und ist in Einklang mit der Beobachtung der hellen, zentralen Erhebungen in den submolekular aufgelösten Bildern in Abbildung b (vgl.…”

Section: Figureunclassified

“…] ist unabhängig von der Anzahl n der Cyangruppen (siehe SI, Tabelle S2). Dies ändert sich jedoch, wenn wir berücksichtigen, dass die Freie‐Base‐Porphyrine auf der Cu(111)‐Oberfläche nicht die Sattelkonformation der Gasphase, sondern die invertierte Struktur aufweisen . Die Cyangruppen reduzieren die Energie, die bei der Umwandlung der Sattelkonformation in die invertierte Geometrie aufgewendet werden muss (siehe SI, Tabelle S3).…”

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Kontrolle der Selbstmetallierungsrate von Tetraphenylporphyrinen auf Cu(111) durch Funktionalisierung mit Cyangruppen

et al. 2018

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Die Reaktionsgeschwindigkeit der Selbstmetallierung von Freie‐Base‐Tetraphenylporphyrinen (TPPs) auf Cu(111) nimmt mit zunehmender Zahl der Cyangruppen in para‐Position der Phenylringe (n=0, 1, 2, 4) systematisch ab. Die Ergebnisse basieren auf Messungen mit isothermer Rastertunnelmikroskopie. Bei Raumtemperatur adsorbieren alle untersuchten Freie‐Base‐TPP‐Derivate als individuelle Moleküle mit klar definierter Orientierung entlang den dichtest gepackten Cu‐Substratreihen. Durch Heizen auf 400 K bilden sich durch intermolekulare CN‐Cu‐CN‐Bindungen lineare Dimere und/oder Multimere. Parallel dazu kann die Selbstmetallierung der Freie‐Base‐Porphyrine nach einer Reaktion 1. Ordnung stattfinden. Für Tetracyan‐funktionalisierte Moleküle nimmt die Reaktionsgeschwindigkeit um einen Faktor von >20 gegenüber der von nicht‐funktionalisierten Molekülen ab. Dies entspricht einer Zunahme der Aktivierungsenergie von 1.48 auf 1.59 eV. DFT‐Rechnungen geben einen tieferen Einblick in die Rolle der elektronenziehenden Cyangruppen.

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“…This structure is referred to as "inverted" and exhibits two protrusions, which are aligned along one of the three main crystallographic directions of Cu(111) (Figure 1c). [28] The strong similarity of the adsorption behavior and appearance of 2HTNP on Cu(111) to that of 2HTPP gives sufficient evidence to safely conclude that 2HTNP also adsorbs in the "inverted" structure. The four dimmer protrusions per molecule in Figure 1a resemble the flat lying naphthyl groups.…”

Section: Resultsmentioning

confidence: 92%

“…[23][24][25][26][27] On Cu(111), the strong chemical interaction between the iminic nitrogen atoms and the Cu substrate atoms leads to a peculiar intramolecular conformation, the so called "inverted" structure. [28,29] Based on the detailed knowledge of this structure, we herein now tackle the changes that occur when replacing the phenyl group by a naphthyl group to introduce a rotation axis in the molecular plane. For 2HTNP on Cu(111), assuming flat adsorption of the naphthyl groups, 16 different surface conformations are expected, including chiral and non-chiral species.…”

Section: Introductionmentioning

confidence: 99%

Conformation Controls Mobility: 2H‐Tetranaphthylporphyrins on Cu(111)

et al. 2020

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The adsorption behavior and the mobility of 2H‐Tetranaphthylporphyrin (2HTNP) on Cu(111) was investigated by scanning tunneling microscopy (STM) at room temperature (RT). The molecules adsorb, like the structurally related 2HTPP, in the “inverted” structure with the naphthyl plane restricted to an orientation parallel to the Cu surface. The orientation of the four naphthyl groups yields altogether 16 possible conformations. Due to the existence of rotamer pairs, 10 different appearances are expected on the surface, and all of them are identified by STM at RT. Most interestingly, the orientation of the naphthyl groups significantly influences the diffusion behavior of the molecules on Cu(111). We identify three different groups of conformers, which are either immobile, medium or fast diffusing at RT. The mobility seems to decrease with increasing size of the footprint of the conformers on the surface.

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“Inverted” porphyrins: a distorted adsorption geometry of free-base porphyrins on Cu(111)

Cited by 40 publications

References 31 publications

Structure, Properties, and Reactivity of Porphyrins on Surfaces and Nanostructures with Periodic DFT Calculations

Structure, Properties, and Reactivity of Porphyrins on Surfaces and Nanostructures with Periodic DFT Calculations

Kontrolle der Selbstmetallierungsrate von Tetraphenylporphyrinen auf Cu(111) durch Funktionalisierung mit Cyangruppen

Conformation Controls Mobility: 2H‐Tetranaphthylporphyrins on Cu(111)

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