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An X-ray absorption and photoemission study of the electronic structure of Ni porphyrins and Ni N-confused porphyrin

Författare:
  • S. A. Krasnikov
  • N. N. Sergeeva
  • M. M. Brzhezinskaya
  • Alexei Preobrajenski
  • Y. N. Sergeeva
  • N. A. Vinogradov
  • A. A. Cafolla
  • M. O. Senge
  • A. S. Vinogradov
Publiceringsår: 2008
Språk: Engelska
Sidor: 235207-1-235207-6
Publikation/Tidskrift/Serie: Journal of Physics: Condensed Matter
Volym: 20
Nummer: 23
Dokumenttyp: Artikel
Förlag: IOP publishing

Sammanfattning

Investigations of chemical bonding and electronic structure features for polycrystalline (porphyrinato)nickel (II) (NiP, the simplest Ni porphyrin), (5,10,15,20-tetraphenylporphyrinato)nickel (II) (NiTPP) and
(2-aza-21-carba-5,10,15,20-tetraphenylporphyrinato)nickel (II) (N-confused NiTPP, NiNCTPP) have been performed by means of high-resolution soft x-ray absorption and x-ray
photoemission spectroscopy. The Ni 2p3/2 x-ray absorption spectra show strong pi-back-bonding in these compounds leading to a high-energy shift (1.2 eV for the NiP and
NiTPP) of the entire absorption structure compared to Ni metal. It has been found that the main absorption line of the Ni 2p3/2 spectrum of the NiNCTPP is shifted by an additional 0.5 eV to higher energies in comparison with those for other nickel porphyrins. This shift is evidence of stronger back-donation (metal-to-ligand charge transfer) and a smaller effective number of 3d electrons on the central Ni atom in the NiNCTPP as compared to other Ni porphyrins. The confused N atom in the NiNCTPP is of pyrrolic type (protonated nitrogen), which was confirmed by the N 1s absorption and core-level photoemission spectra.

Disputation

Nyckelord

  • Physics and Astronomy

Övrigt

Published
Yes
  • ISSN: 1361-648X
  • ISSN: 0953-8984

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