Adsorption of cobalt (II) octaethylporphyrin and 2H-octaethylporphyrin on Ag(111): new insight into the surface coordinative bond

Details Adsorption of cobalt (II) octaethylporphyrin and 2H-octaethylporphyrin on Ag(111): new insight into the surface coordinative bond Adsorption of cobalt (II) octaethylporphyrin and 2H-octaethylporphyrin on Ag(111): new insight into the surface coordinative bond

Dec 2009

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2009njph...11l5004b&link_type=abstract

New Journal of Physics, Volume 11, Issue 12, pp. 125004 (2009).

Physics

5

Scientific paper

The adsorption of cobalt (II) octaethylporphyrin (CoOEP) and 2H-octaethylporphyrin (2HOEP) on Ag(111) was investigated with scanning tunneling microscopy (STM) and photoelectron spectroscopy (XPS/UPS), in order to achieve a detailed mechanistic understanding of the surface chemical bond of coordinated metal ions. Previous studies of related systems, especially cobalt (II) tetraphenylporphyrin (CoTPP) on Ag(111), have revealed adsorption-induced changes of the oxidation state of the Co ion and the appearance of a new valence state. These effects were attributed to a covalent interaction of the Co ion with the silver substrate. However, recent studies show that the porphyrin ligand of adsorbed CoTPP undergoes a pronounced saddle-shape distortion, which could alter the electronic structure and thus provide an alternative explanation for the new valence state previously attributed to the formation of a surface coordinative bond. With the octaethylporphyrins investigated here, which were found to adsorb in a flat, undistorted conformation on Ag(111), the effects of geometric distortion can be separated from those of the electronic interaction with the substrate. The CoOEP monolayer gives rise to an adsorption-induced shift of the Co 2p signal (-1.9 eV relative to the multilayer), a new valence state at 0.6 eV below the Fermi energy, and a work-function shift of -0.84 eV (2HOEP: -0.44 eV) relative to the clean surface. Comparison with data for the distorted CoTPP confirms the existence of a covalent ion-surface interaction that is insensitive to the conformation of the ligand.

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