Tetraphenylporphyrin picks up zinc atoms from a silver surface

Kretschmann, Andreas; Walz, Marie‐Madeleine; Flechtner, Ken; Steinrück, Hans‐Peter; Gottfried, J. Michael

doi:10.1039/b614427f

Cited by 101 publications

(158 citation statements)

References 6 publications

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“…3,8 . If Ag atoms diffuse (preferably along silver rows) underneath the molecular layer, then one could be trapped under the center of the metalfree phthalocyanine without being lifted up inside the molecule.…”

Section: Stm Results Of the Molecular Adlayermentioning

confidence: 99%

“…During the past decade, the on-surface metalation of ordered molecular layers of prototypical porphyrin [1][2][3][4][5][6][7][8] and phthalocyanine 9,10 molecules was developed and has gained considerable interest. This is achieved by evaporating metal atoms onto the surface after or before the deposition of molecules under ultrahighvacuum (UHV) conditions.…”

Section: Introductionmentioning

confidence: 99%

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Self-Metalation of Phthalocyanine Molecules with Silver Surface Atoms by Adsorption on Ag(110)

et al. 2015

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We report that metal-free phthalocyanine (H 2 Pc) molecules with a central cavity are able to incorporate Ag atoms from an Ag(110) surface thus creating silver-phthalocyanine (AgPc). The reaction was investigated by means of scanning tunneling microscopy (STM) under ultrahigh vacuum, and the metalation of H 2 Pc at the interface was confirmed with X-ray photoelectron spectroscopy. Three different kinds of molecules were found on the surface that are assigned to H 2 Pc, the corresponding dehydrogenated molecules (Pc) and AgPc. The relative amounts of Pc and AgPc increase with increasing annealing temperature. We suggest that the reaction with Ag atoms from the steps of the surface occurs favorably only for already dehydrogenated molecules; thus, the metalation of H 2 Pc is likely limited by the heat-induced dehydrogenation. Density functional theory simulations of the reaction path are presented to corroborate this hypothesis.

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Section: Stm Results Of the Molecular Adlayermentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Self-Metalation of Phthalocyanine Molecules with Silver Surface Atoms by Adsorption on Ag(110)

et al. 2015

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“…4,32,35,36,56,58,[72][73][74][75][76][77][78][79][80][81][82][83][84][85] It is nowadays well established that metalloporphyrins can be synthesised readily on a metal surface by the reaction of a corresponding free base porphyrin with an ''available'' metal atom. The respective metal atom can be provided on the surface by pre-or postdeposition, or originate from the surface itself.…”

Section: Diffusion and Rotation Of 2htppmentioning

confidence: 99%

“…[10][11][12][13][14][15] The enormous potential of porphyrins for the fabrication of tailor-made functional molecular architectures on well-defined substrates has stimulated significant activities in fundamental research. 4,[16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] In this contribution, we review recent advances in the understanding of the dynamic behaviour of porphyrins, as representatives of organic molecules, adsorbed on a Cu(111) single crystal surface in ultra-high vacuum (UHV). Based on temperaturedependent measurements of individual molecules, the kinetics and energetics of diffusion 33,34 and rotation, 34 of the so-called self-metalation reaction 35,36 and finally of conformational switching of particular free base porphyrins 37 can be determined.…”

Section: Introductionmentioning

confidence: 99%

Studying the dynamic behaviour of porphyrins as prototype functional molecules by scanning tunnelling microscopy close to room temperature

Marbach

Steinrück

2014

Chem. Commun.

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Scanning tunnelling microscopy (STM) enables us to directly observe the dynamic behaviour of organic molecules on surfaces. While imaging atoms and molecules using STM is certainly fascinating by itself, corresponding temperature-dependent measurements allow for the quantitative determination of the energetics and kinetics of the underlying molecular surface processes. Herein, we review recent advances in the STM investigation of the dynamic behaviour of adsorbed porphyrins at and close to room temperature.Three different case studies are discussed, providing insight into the dynamics of diffusion, rotation, reaction, and molecular switching at surfaces, based on isothermal STM measurements. The reviewed examples demonstrate that variable temperature STM can be a suitable tool to directly monitor the dynamic behaviour of individual adsorbed molecules, at and close to room temperature. Free base porphyrins on Cu(111) proved to be particularly suitable for these studies due to the strong bonding interaction between the iminic nitrogen atoms in the porphyrin macrocycle and the Cu substrate atoms. As a consequence, the corresponding activation energies for surface diffusion, self-metalation reaction and conformational switching are of a magnitude that allows for monitoring the processes at and around room temperature, in contrast to most previous studies, which were performed at cryogenic temperatures. The kinetic analysis of the surface diffusion and self-metalation was performed using an Arrhenius approach, yielding the corresponding activation energies and preexponential factors. In contrast, the conformational switching process was analysed in the framework of transition state theory, based on the Eyring equation. This approach provides a more detailed insight into interpretable thermodynamic potentials, i.e., the enthalpic and entropic contributions to the activation barrier. The analysis shows that at room temperature the adsorption and switching behaviour of the investigated free base porphyrin on Cu(111) is dominated by entropic effects. Since the entropic energy contribution vanishes at low temperatures, the importance of experiments conducted at temperatures close to room temperature is emphasized.

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“…[9,14] Die Fähigkeit von 2H-Porphyrinen, abgeschiedene Metalle (z. B. Fe, [15] Cu, [9] Zn [16] ) aufzunehmen und mit ihnen zu reagieren, wurde auf Ag(111) und Au(111) nachgewiesen. Abhängig vom Metall erfolgt die Metallierungsreaktion entweder bei RT oder durch Heizen auf Temperaturen bis zu 550 K. Die Reaktion erwies sich immer als selektiv, d. h., es trat keine Metallierung mit den Silber-oder Goldsubstratatomen auf, was vermutlich auf den Edelmetallcharakter der Substrate zurückzuführen ist.…”

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Bestimmung der Aktivierungsenergie für die Selbstmetallierungsreaktion von 2H‐Tetraphenylporphyrin auf Cu(111)

et al. 2012

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Tetraphenylporphyrin picks up zinc atoms from a silver surface

Cited by 101 publications

References 6 publications

Self-Metalation of Phthalocyanine Molecules with Silver Surface Atoms by Adsorption on Ag(110)

Self-Metalation of Phthalocyanine Molecules with Silver Surface Atoms by Adsorption on Ag(110)

Studying the dynamic behaviour of porphyrins as prototype functional molecules by scanning tunnelling microscopy close to room temperature

Bestimmung der Aktivierungsenergie für die Selbstmetallierungsreaktion von 2H‐Tetraphenylporphyrin auf Cu(111)

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