Temperature-Dependent Chemical and Structural Transformations from 2H-tetraphenylporphyrin to Copper(II)-Tetraphenylporphyrin on Cu(111)

Temperature-dependent chemical and structural changes of a submonolayer of 2H-tetraphenylporphyrin (2HTPP) on Cu(111) were studied with photoelectron spectroscopy (XPS/UPS) and scanning tunneling microscopy (STM). 2HTPP reacts with Cu atoms from the substrate to form copper(II)-tetraphenylporphyrin...

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Bibliographic Details
Published in:Journal of physical chemistry. C 2012-06, Vol.116 (22), p.12275-12282
Main Authors: Xiao, Jie, Ditze, Stefanie, Chen, Min, Buchner, Florian, Stark, Michael, Drost, Martin, Steinrück, Hans-Peter, Gottfried, J. Michael, Marbach, Hubertus
Format: Article
Language:English
Subjects:
Condensed matter: electronic structure, electrical, magnetic, and optical properties
Condensed matter: structure, mechanical and thermal properties
Electron and ion emission by liquids and solids
impact phenomena
Equations of state, phase equilibria, and phase transitions
Exact sciences and technology
Interfaces, heterostructures, nanostructures
Photoemission and photoelectron spectra
Physics
Specific phase transitions
Structural transitions in nanoscale materials
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Summary:Temperature-dependent chemical and structural changes of a submonolayer of 2H-tetraphenylporphyrin (2HTPP) on Cu(111) were studied with photoelectron spectroscopy (XPS/UPS) and scanning tunneling microscopy (STM). 2HTPP reacts with Cu atoms from the substrate to form copper(II)-tetraphenylporphyrin (CuTPP). This metalation reaction starts at about 400 K and was investigated at various temperatures up to 500 K. At room temperature, adsorbed 2HTPP adopts an orientation with the molecular plane parallel to the substrate; the same holds for its reaction product CuTPP after annealing to 400 K. In contrast, annealing at 450 K yields a tilted orientation of CuTPP, as indicated by STM and supported by C 1s XPS shifts and changes in the Cu(111) surface state. Subsequent annealing at 500 K restores a flat-lying orientation; however, the appearance of the complex in STM images differs from the original appearance of CuTPP. In summary, 2HTPP undergoes three irreversible transformations upon annealing on Cu(111), a metalation reaction to CuTPP followed by two intramolecular structural changes.
ISSN:1932-7447
1932-7455
DOI:10.1021/jp301757h