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Structure, luminescence, and Raman spectroscopy of europium and terbium dipivaloylmethanates and other β-diketonates with 2,2'-bipyridine.
Autorzy
Rok wydania
2020
Czasopismo
Journal of Structural Chemistry
Numer woluminu
61
Strony
1026-1037
DOI
10.1134/s0022476620070045
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
The study reveals the relationship between structural and spectroscopic characteristics of lanthanide dipivaloylmethanates with 2,2′-bipyridine derivatives [Ln(DPM)3L] (Ln = Eu, Tb; L = 2,2′-bipyridine, 4,4′-dimethyl-2,2′-bipyridine, 4,4′-diphenyl-2,2′-bipyridine) and fluorinated β-diketonates [Ln(β)3Bpy] (β = TTFA, TFAA, BTFA) with the CN (Ln3+) = 8 and the LnN2O6 coordination polyhedron in the form of a square antiprism. We discuss structural regularities resulting from the difference between Eu–O and Eu–N bond lengths in β-diketonates due to the changes in donor-acceptor properties of substituents and the steric factor. The effect of the main distortion Δ = r(Eu–N) – r(Eu–O) of the Eu coordination polyhedron on the luminescence spectra and vibrational Raman spectra is considered. A qualitative correlation is demonstrated between the relative intensity of the 5D0–7F2 (Eu3+) electric dipole transition, which characterizes the degree of distortion of the nearest environment of the Eu3+ ion, and the lifetimes of excited electronic states 5D0 (Eu3+) and 5D4 (Tb3+). The contribution of nonradiative processes caused by high-frequency vibrations of ligands to the decay rate of 5D0 (Eu3+) and 5D4 (Tb3+) levels is discussed. The Raman spectra are analyzed in terms of studying the changes in vibrational frequencies of the Bpy molecule depending on the distortion Δ of the Eu coordination polyhedron.
Słowa kluczowe
Eu3+, Tb3+, dipivaloylmethanate, fluroinated, ß-diketonates, molecule, 2'-bipyridine, crystal structure, luminescence, Raman spectra
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