Lanthanide(III) Complexes Based on Tris(2-pyridyl)phosphine Oxide: First Examples

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Abstract

A series of mononuclear complexes [Ln(Py3PO)2(NO3)3] · 1.5Me2CO (Ln = Sm, Eu, Gd, Tb, Dy) and [Ln(Py3PO)(TTA)3] (Ln = Eu, Tb; TTA‒ is thenoyltrifluoroacetonate ion) based on tris(2-pyridyl) phosphine oxide (Py3PO) is synthesized and studied. In the synthesized compounds, Py3PO acts as the N,O-chelate ligand resulting in the formation of coordination polyhedra N2O8 and NO7 of the Ln atom in complexes [Ln(Py3PO)2(NO3)3] · 1.5Me2CO and [Ln(Py3PO)(TTA)3], respectively. The complexes of Sm3+, Eu3+, Tb3+ and Dy3+ ions exhibit lanthanide-centered photoluminescence in the solid phase at 300 K. The energy of the T1 triplet level of Py3PO is determined to be 21 900 cm‒1 from the ligand-centered phosphorescence spectrum of the Gd(III) complex at 77 K. Among the complexes with the NO3‒ ions, Py3PO exhibits the highest sensibilizing ability toward Tb3+, whereas the ligand environment in the complexes with the TTA‒ ions most efficiently sensibilizes the Eu3+ ion luminescence.

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About the authors

Yu. A. Bryleva

Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the Russian Academy of Sciences

Author for correspondence.
Email: bryleva@niic.nsc.ru
Russian Federation, Novosibirsk

L. A. Glinskaya

Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the Russian Academy of Sciences

Email: bryleva@niic.nsc.ru
Russian Federation, Novosibirsk

K. M. Yzhikova

Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the Russian Academy of Sciences

Email: bryleva@niic.nsc.ru
Russian Federation, Novosibirsk

A. V. Artemyev

Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the Russian Academy of Sciences

Email: bryleva@niic.nsc.ru
Russian Federation, Novosibirsk

M. I. Rakhmanova

Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the Russian Academy of Sciences

Email: bryleva@niic.nsc.ru
Russian Federation, Novosibirsk

A. Yu. Baranov

Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the Russian Academy of Sciences

Email: bryleva@niic.nsc.ru
Russian Federation, Novosibirsk

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Supplementary files

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2. Fig. 1. TG, DTA and DTG curves for complex I

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3. Fig. 2. Molecular structures of complexes II (a) and VI (b). H atoms are not given. Thermal ellipsoids are shown at the level of 40% probability

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4. Fig. 3. Projection of crystal structure II onto the (010) plane illustrating short contacts (shown as dashed lines). H atoms are not shown

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5. Fig. 4. Projection of the crystal structure of VI on the plane (100) illustrating the short contacts between the molecules of the complex (shown in dashed lines)

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6. Fig. 5. Normalised FL excitation (dashed line) and emission (continuous line) spectra of complexes I, II, IV, V (a) and VI, VII (b) in the solid phase at 300 K with the designation of f-f transitions in Ln3+ ions

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7. Fig. 6. Phosphorescence spectrum of complex III in the solid phase at 77 K

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