Photoluminescent Lanthanide(III) Complexes Based on 2-[((4-Chlorophenyl)amino)methylene]-5,5-dimethylcyclohexane-1,3-dione

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Abstract

Five coordination compounds of the general formula [LnL2(NO3)3]n (Ln3+ = Eu (I), Sm (II), Tb(III), Dy (IV), and Gd (V)) are synthesized from 2-[((4-chlorophenyl)amino)methylene]-5,5-dimethylcyclohexane-1,3-dione (L). The crystal structures of the ligand and complex III are determined by X-ray diffraction (XRD) of single crystals (CIF files CCDC nos. 2298715 (L) and 2298716 (III)). Complex III is polymeric due to the bidentate-bridging coordination of the ligand by the oxygen atoms of the cyclohexanedione fragment, and the coordination number of the central atom is ten. According to the phase XRD data, all synthesized polycrystalline compounds are isostructural to the single crystals of complex III. The photoluminescence properties of the ligand and coordination compounds in the polycrystalline state are studied. The energy transfer from the ligand to lanthanide(III) ion is shown to proceed via the “antenna” mechanism in the case of the europium(III), samarium(III), and terbium(III) compounds. Among the series of the complexes, the highest quantum yield is observed for compound I (21.9%), and the sensibilization efficiency of the europium(III) complex is 43.5%.

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About the authors

K. S. Smirnova

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

Email: lisalider@gmail.com
Russian Federation, Novosibirsk

E. A. Sanzhenakova

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

Email: lisalider@gmail.com
Russian Federation, Novosibirsk

I. V. Eltsov

Novosibirsk National Research State University

Email: lisalider@gmail.com
Russian Federation, Novosibirsk

I. P. Pozdnyakov

Voevodsky Institute of Chemical Kinetics and Consumption, Siberian Branch, Russian Academy of Sciences

Email: lisalider@gmail.com
Russian Federation, Novosibirsk

A. A. Russkikh

Kuban State University

Email: lisalider@gmail.com
Russian Federation, Krasnodar

V. V. Dotsenko

Kuban State University

Email: lisalider@gmail.com
Russian Federation, Krasnodar

E. V. Lider

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

Author for correspondence.
Email: lisalider@gmail.com
Russian Federation, Novosibirsk

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Supplementary files

Supplementary Files
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2. Scheme 1. Possible routes for the synthesis of 2-[((4-chlorophenyl)amino)methylene]-5,5-dimethyl-cyclohexane-1,3-dione

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3. Scheme 2. Structural formula of 2-[((4-chlorophenyl)amino)methylene]-5,5-dimethyl-cyclohexane-1,3-dione (L) and correlation of the ligand bands from NMR spectroscopy data

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4. Scheme 3. Scheme of synthesis of complexes I-V

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5. Fig. 1. Calculated from single crystal structure (orange line) and experimental powder diffractograms of the complexes [LnL2(NO3)3]n

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6. Fig. 2. Ligand structure and C(H)-C-N-C(H) torsion angle (φt) in L

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7. Fig. 3. Coordination unit of the [TbL2(NO3)3]n (III) complex (a) and the polymer layered structure (b). Hydrogen atoms are not shown

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8. Fig. 4. Overlay of crystal structures of the complexes [TbL2(NO3)3]n (III, purple colour) and [Tb(Lʹ)2(NO3)3]n (KBSD, turquoise colour)

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9. Fig. 5. Diffuse reflectance (dashed lines), luminescence excitation and emission spectra for ligand and complexes I-II. Emission spectra were recorded at λvozb = 370 nm and luminescence excitation spectra at λisl = 460 nm for L, λisl = 613 nm for the europium(III) complex, λisl = 594 nm for the samarium(III) complex and λisl = 545 nm for the terbium(III) complex

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10. Fig. 6. Kinetic luminescence curves of the ligand and complexes: the kinetic curve of L is indicated in red at λvozb = 375 nm and λisl = 470 nm, the biexponential approximation in blue with lifetimes of 0.6 ns (52%) and 1. 7 ns (48%), instrument response function in black (a); the kinetic curve of the europium(III) complex is in blue at λvozb = 370 nm and λisl = 615 nm, the approximation is in red with characteristic times of 1. 17 ms (b); the kinetic curve of the samarium(III) complex is in blue at λvozb = 370 nm and λisl = 595 nm, the approximation is in red with a characteristic time of 0.034 ms (c)

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11. Fig. 7. Phosphorescence spectrum of complex V at 77 K and decomposition of the spectrum into Gaussian components

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12. Fig. 8. CIE1931 colour space reflecting the emission colour of the ligand and complexes I and II

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