Neutral Terbium(III) Tris(complex) with 4,4,5,5,6,6,6-Heptafluoro-1-(1-methyl-1H-pyrazol-4-yl)hexane-1,3-dione: Synthesis, Structure, and Spectral Luminescence Properties

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Abstract

The reaction of 1,3-diketone containing 1-methyl-1H-pyrazol-4-yl and perfluoropropyl fragments with TbCl3·6H2O in the presence of NaOH in ethanol is studied. The molecular and crystal structures of the complex are studied by single-crystal X-ray diffraction (XRD). Compound [Tb(L)3(EtOH)2] crystallizes in the triclinic crystal system with the space group. The geometry of the coordination polyhedron {LnO8} corresponds to a square antiprism. Intermolecular interactions N…H–O, C–H…O, and C–H…F leading to the formation of supramolecular chains are observed in crystals of the complex. The UV-irradiated complex exhibits green luminescence caused by transitions 5D4 → 7Fj (j = 2–6) characteristic of the Tb3+ ion. The main photophysical luminescence parameters are determined, and the scheme of energy transfer in the complex is proposed. The synthesized compound can be of interest as an independent luminophore or as the initial substance for the synthesis of heteroligand complexes by the substitution of ethanol molecules in the internal coordination sphere.

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About the authors

I. V. Taidakov

Lebedev Physical Institute, Russian Academy of Sciences; National Research Institute Higher School of Economics; Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences

Author for correspondence.
Email: taidakov@gmail.com
Russian Federation, Moscow; Moscow; Moscow

M. T. Metlin

Lebedev Physical Institute, Russian Academy of Sciences

Email: taidakov@gmail.com
Russian Federation, Moscow

D. A. Metlina

Lebedev Physical Institute, Russian Academy of Sciences

Email: metlinada@lebedev.ru
Russian Federation, Moscow

V. E. Goncharenko

Lebedev Physical Institute, Russian Academy of Sciences; National Research Institute Higher School of Economics

Email: taidakov@gmail.com
Russian Federation, Moscow; Moscow

T. S. Vlasova

Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences

Email: taidakov@gmail.com
Russian Federation, Moscow

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Supplementary files

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2. Scheme 1: Synthesis of complex I.

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3. Fig. 1. Molecular structure of compound I. The ellipsoids of thermal vibrations of atoms are given with 50% probability, hydrogen atoms are not represented. The perfluorinated substituents of the -diketonate ligand are depicted as translucent. The atoms of terbium and its coordination environment are numbered.

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4. Fig. 2. System of hydrogen and ... interactions stabilizing the crystal packing of compound I. Hydrogen bonds are depicted by dotted lines, the shortest distance between π-systems is depicted by a dashed line. Only hydrogen atoms of hydroxyl groups of ethanol molecules are represented, and perfluorinated substituents of -diketonate ligand are depicted as translucent.

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5. Fig. 3. Absorption spectra of solutions of complex I (black line) and free ligand HL (red line) in acetonitrile recorded at room temperature.

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6. Fig. 4. Excitation spectrum of complex I in the crystalline phase recorded at room temperature. The registration wavelength is 545 nm.

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7. Fig. 5. Luminescence spectra of complex I in the crystalline phase at 77 K (black line) and 300 K (red line). The excitation source wavelength is 355 nm.

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8. Fig. 6. Color diagram (CIE 1931 color space) for complex I emission.

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9. Fig. 7. Fluorescence (red line) at 300K and phosphorescence (black line) spectra at 77K for complex II in the crystalline phase. The excitation wavelength is 355 nm.

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10. Fig. 8. Luminescence kinetics of complex I in the crystalline phase at 77 and 300 K. The excitation wavelength is 355 nm.

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11. Fig. 9. Energy diagram of complex I and possible pathways of excitation energy transfer in this complex.

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