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STRUCTURE, LUMINESCENCE, AND RAMAN SPECTROSCOPY OF EUROPIUM AND TERBIUM DIPIVALOYLMETHANATES AND OTHER β-DIKETONATES WITH 2,2′-BIPYRIDINE

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Abstract

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.

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Funding

The study was performed in the framework of the State Assignement of the Ministry of Science and Higher Education of the Russian Federation and as a part of the program of the Ministry of Science and Higher Education of Poland.

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Authors and Affiliations

  1. Kotelnikov Institute of Radioengineering and Electronics, Russian Academy of Sciences, Fryazino, Moscow reg., Russia

    V I Tsaryuk & K P Zhuravlev

  2. Faculty of Chemistry, University of Wrocław, Wrocław, Poland

    R Szostak

  3. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia

    A V Vologzhanina

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  1. V I Tsaryuk
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  2. K P Zhuravlev
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  4. A V Vologzhanina
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Correspondence to V I Tsaryuk.

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Tsaryuk, V.I., Zhuravlev, K.P., Szostak, R. et al. STRUCTURE, LUMINESCENCE, AND RAMAN SPECTROSCOPY OF EUROPIUM AND TERBIUM DIPIVALOYLMETHANATES AND OTHER β-DIKETONATES WITH 2,2′-BIPYRIDINE. J Struct Chem 61, 1026–1037 (2020). https://doi.org/10.1134/S0022476620070045

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