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RAS Chemistry & Material ScienceЖурнал общей химии Russian Journal of General Chemistry

  • ISSN (Print) 0044-460X
  • ISSN (Online) 3034-5596

Effect of Coordination Environment on Luminescence of Crystalline Cerium Halides

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PII
S3034559625090127-1
DOI
10.7868/S3034559625090127
Publication type
Article
Status
Published
Authors
D. I. Galimov
  • Affiliation: Institute of Petrochemistry and Catalysis Ufa Federal Research Center of the Russian Academy of Sciences
D. R. Gazeeva
  • Affiliation: Institute of Petrochemistry and Catalysis Ufa Federal Research Center of the Russian Academy of Sciences
S. M. Yakupova
  • Affiliation: Institute of Petrochemistry and Catalysis Ufa Federal Research Center of the Russian Academy of Sciences
K. S. Vasilyuk
  • Affiliation: Institute of Petrochemistry and Catalysis Ufa Federal Research Center of the Russian Academy of Sciences
D. Sh. Sabirov
  • Affiliation: Institute of Petrochemistry and Catalysis Ufa Federal Research Center of the Russian Academy of Sciences
Volume/ Edition
Volume 95 / Issue number 9-10
Pages
465-471
Abstract
The effect of the coordination environment on the photoluminescence of crystalline cerium trihalides CeL (L = F, Cl, Br, I) was investigated. It was found that in the series of anions F > Cl > Br > I a bathochromic shift of luminescence maxima is observed, which is correlated with an increase in the degree of Ce-L bond covalency and anion polarisability. Using PBE/3ζ density functional theory and classical Pauling’s approach, calculations of anion polarisability and Ce-L bonding parameters were carried out, revealing a direct correlation between these values and the long-wavelength shift of maxima. This fact allows us to postulate that the bathochromic shift of maxima in the photoluminescence and photoluminescence excitation spectra of solid CeL is due to the nepheloxetic effect, namely, an increase in the degree of covalency of the Ce-L bond, leading to a decrease in the energy gap between the valence zone (np-levels of L) and the conduction zone (5d-levels of Ce). The results demonstrate the possibility of controlling the spectral characteristics of the luminescence of Ce compounds by changing the coordination environment, which is important for the development of new cerium-containing luminophores.
Keywords
трехвалентный ион церия координационное окружение фотолюминесценция нефелоксетический эффект
Date of publication
21.12.2025
Year of publication
2025
Number of purchasers
0
Views
43

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