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Comparative X-Ray Absorption Analysis of the Spectrum of Vacant Electronic States in Cobalt and Nickel Tetraphenylporphyrin Complexes

Svirskiy, G. I. ; Generalov, A. V. LU ; Klyushin, A. Yu ; Simonov, K. A. LU ; Krasnikov, S. A. ; Vinogradov, N. A. LU orcid ; Trigub, A. L. ; Zubavichus, Ya V. ; Preobrazhenski, A. B. and Vinogradov, A. S. (2018) In Physics of the Solid State 60(3). p.581-591
Abstract

The energy distributions and the properties of the lower vacant electronic states in cobalt and nickel tetraphenylporphyrin complexes CoTPP and NiTPP are studied by X-ray absorption spectroscopy. Quasimolecular analysis of the experimental absorption spectra measured in the region of the 2p and 1s ionization thresholds of complexing metal atoms, as well as the 1s thresholds of ligand atoms (nitrogen and carbon), is based on the comparison of the corresponding spectra with each other and with the spectra of the simplest nickel porphyrin NiP. It has been established that, despite a general similarity of the spectra of nitrogen and carbon in CoTPP and NiTPP, the fine structure of the 2p and 1s absorption spectra of cobalt and nickel atoms... (More)

The energy distributions and the properties of the lower vacant electronic states in cobalt and nickel tetraphenylporphyrin complexes CoTPP and NiTPP are studied by X-ray absorption spectroscopy. Quasimolecular analysis of the experimental absorption spectra measured in the region of the 2p and 1s ionization thresholds of complexing metal atoms, as well as the 1s thresholds of ligand atoms (nitrogen and carbon), is based on the comparison of the corresponding spectra with each other and with the spectra of the simplest nickel porphyrin NiP. It has been established that, despite a general similarity of the spectra of nitrogen and carbon in CoTPP and NiTPP, the fine structure of the 2p and 1s absorption spectra of cobalt and nickel atoms are radically different. The observed differences in the spectra of cobalt and nickel are associated with the features of the energy distribution of vacant 3d electron states. The presence in CoTPP of the partially filled valence 3db2g molecular orbital (MO) results in the appearance in the cobalt spectra of a low-energy band, which is absent in the spectrum of nickel in NiTPP and leads to a doublet structure of transitions to b1g and eg MOs due to the exchange interaction between 3d electrons in partially filled 3db2g and 3db1g or 3deg MOs. The spectrum of vacant states in CoTPP differs from that in NiTPP also due to the smaller energy distance between 3db1g and eg MOs and the different positions of nonbonding MOs with the C2p character of the porphine ligand.

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author
; ; ; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Physics of the Solid State
volume
60
issue
3
pages
11 pages
publisher
MAIK Nauka/Interperiodica
external identifiers
  • scopus:85044192702
ISSN
1063-7834
DOI
10.1134/S1063783418030307
language
English
LU publication?
yes
id
35f3566c-6ba4-41cf-85e8-5a3971eab8f0
date added to LUP
2018-04-05 15:51:13
date last changed
2021-09-22 05:35:12
@article{35f3566c-6ba4-41cf-85e8-5a3971eab8f0,
  abstract     = {<p>The energy distributions and the properties of the lower vacant electronic states in cobalt and nickel tetraphenylporphyrin complexes CoTPP and NiTPP are studied by X-ray absorption spectroscopy. Quasimolecular analysis of the experimental absorption spectra measured in the region of the 2p and 1s ionization thresholds of complexing metal atoms, as well as the 1s thresholds of ligand atoms (nitrogen and carbon), is based on the comparison of the corresponding spectra with each other and with the spectra of the simplest nickel porphyrin NiP. It has been established that, despite a general similarity of the spectra of nitrogen and carbon in CoTPP and NiTPP, the fine structure of the 2p and 1s absorption spectra of cobalt and nickel atoms are radically different. The observed differences in the spectra of cobalt and nickel are associated with the features of the energy distribution of vacant 3d electron states. The presence in CoTPP of the partially filled valence 3db<sub>2g</sub> molecular orbital (MO) results in the appearance in the cobalt spectra of a low-energy band, which is absent in the spectrum of nickel in NiTPP and leads to a doublet structure of transitions to b<sub>1g</sub> and e<sub>g</sub> MOs due to the exchange interaction between 3d electrons in partially filled 3db<sub>2g</sub> and 3db<sub>1g</sub> or 3de<sub>g</sub> MOs. The spectrum of vacant states in CoTPP differs from that in NiTPP also due to the smaller energy distance between 3db<sub>1g</sub> and e<sub>g</sub> MOs and the different positions of nonbonding MOs with the C2p character of the porphine ligand.</p>},
  author       = {Svirskiy, G. I. and Generalov, A. V. and Klyushin, A. Yu and Simonov, K. A. and Krasnikov, S. A. and Vinogradov, N. A. and Trigub, A. L. and Zubavichus, Ya V. and Preobrazhenski, A. B. and Vinogradov, A. S.},
  issn         = {1063-7834},
  language     = {eng},
  month        = {03},
  number       = {3},
  pages        = {581--591},
  publisher    = {MAIK Nauka/Interperiodica},
  series       = {Physics of the Solid State},
  title        = {Comparative X-Ray Absorption Analysis of the Spectrum of Vacant Electronic States in Cobalt and Nickel Tetraphenylporphyrin Complexes},
  url          = {http://dx.doi.org/10.1134/S1063783418030307},
  doi          = {10.1134/S1063783418030307},
  volume       = {60},
  year         = {2018},
}