Neodymium (III) and erbium (III) complexes with new unsaturated β-diketones
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Keywords

complexes, unsaturated β-diketones, synthesis, neodymium, erbium, spectral properties.

How to Cite

Ivakha, N., Rohovtsov, O., Berezhnytska, O., & Trunova, E. (2019). Neodymium (III) and erbium (III) complexes with new unsaturated β-diketones . Ukrainian Chemistry Journal, 85(6), 87-96. https://doi.org/10.33609/0041-6045.85.6.2019.87-96

Abstract

In this work, the new coordination compounds of Nd(III) and Er (III) with b-diketonate ligands containing an unsaturated substituent at the a-position of the chelate ring (dimethylheptendione and dimethyloctendione) were synthesized. The composition and structure of the synthesized compounds were studied using physicochemical methods of analysis such as the elemental, NMR, IR and electron spectroscopy and thermogravimetric analysis. Using IR spectroscopy, it was established that ligands are bidentate-cyclically coordinated to metals. The results of thermogravimetric analysis indicate that the complexes are nonvolatile and decompose to oxides of the corresponding metals, and their coordination sphere is supplemented with water molecules. From the shape and position of the bands in the electronic absorption spectra and diffuse reflection spectra, it was determined that for the complexes Ln (b-dik)3.nH2O (Ln =Nd, Er,  b-dik = dmhpd, dmod, n = 2-3) the tetragonal symmetry of the nearest coordination environment; coordination polyhedron is a square antiprism. When comparing the diffuse reflectance spectra of dimethylheptendionate and dimethyloktendionate complexes among themselves and with the previously studied complexes with methacrylacetophenone, it was noted that the shape of the spectra and the spectral splitting of the bands for the corresponding metals are not significantly different. This allows to conclude, that the coordination environment of the studied b-diketonate compounds is close.Based on the band shifts in the electronic spectra, the covalence parameters of the Ln–O bond and the oscillator strength were calculated, from which it was also shown that the nature of the substituent affects the covalence parameters, but does not affect the symmetry and structure of the coordination polyhedron. Based on the studies conducted, the monomeric structure of the synthesized complexes was definitely confirmed. Accordingly, they can be used in further work as monomers in polymerization reactions and the preparation of precursors of luminescent materials.

https://doi.org/10.33609/0041-6045.85.6.2019.87-96
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References

Synthesis and properties. Russian Journal of Organic Chemistry. 2015. 51. (6): 755.

Binnemans K. Rare-earth beta-diketonates. Handbook on Physics and Chemistry of Rare Earths. 2005. 35: 107.

Vigato P.A., Peruzzo V, Tamburini S. The evolution of -diketone or -diketophenol ligands and related complexes. Coord.Chem.Rev. 2009. 253:1099.

Ivakha N.B., Berezhnytska O.S., Trunova O.K., Savchenko I.O., Smola S.S., Rusakova N.V. Lanthanide

complexes and polymers of Nd(III), Er(III), Yb(III) allyacetoacetates, as precursors of luminescent materials. Ukrainian Chemistry Journal.2018. 84: 3. [in Ukrainian].

Savchenko I.A., Berezhnytska A.S., Ivakha N.B., Trunova E.K. New nanosized systems based lantanide diketonate complexes for OLEDs. In book Springer Proceedings in Physics “Nanocomposites, Nanophotonics, Nanobiotechnology, and Applications”. 2015. 156: 85.

Berezhnytska O., Savchenko I., Ivakha N., Trunova O., Rusakova N., Smola S., Rogovtsov O. Synthesis, characterization and luminescent properties of polymer complexes of Nd(III) with -dicarbonyl ligands. Nanoscale Research Letters. 2017. 12: 338.

Fedorov Ya.V. Ph.D(Chem.) Thesis. (Kyiv, 2016).[in Ukrainian].

Patent of Ukraine on the utility model №100305. Berezhnytska O.S., Trunova O.K., Ivakha N.B., Savchenko I.O., Rogovtsov O.O., Gudyma A.O. A method for obtaining a new nano neodymium metalpolymer. 2015. [in Ukrainian].

Nakamoto K. Infrared Spectroscopy of Inorganic and Coordination Compounds. (Мoscow: Мir,

. [in Russian].

Nehoroshkov V.P., Kamalov G.L., Geltvaiy I.I. About the relationship between IR spectral properties

of -diketonates 3d-transition metals and their structure. Russ. J.Coord.Chem. 1984. 10.(4): 459. [in Russian].

Ivakha N.B., Berezhnytska O.S., Trunova O.K., Savchenko I.O., Smola S.S., Zheleznova L.I. Allylacetoacetate complexes of Nd(III), Er(III), Yb(III) as precursors for luminescent materials. Ukrainian Chemistry Journal. 2015. 81. (12):104. [in Ukrainian].

Pope G.V., Steinbach Y.F., WagnerW.F. Characteristics of the solvates of the rare-earth acetylacetonates..

J. Inorg. Nucl. Chem. 1961. 20 (3–4): 304.

Movchan T.I., Starikov A.G., Ivleva I.N., Voloshanovsky I.S., Pomogailo A.D. Preparation and reactivity of metal-containing monomers. Communication

Complex compounds of transition metals based on methacrylacetone. Bul. Academy of Sciences, ser.chem. 1992. 3: 694. [in Russian].

Sinha S.P. Spectroscopic Investigation of Some Neodymium. Spectrochim. Acta. 1966. 22: 57.

Poluektov N.S. Spectroscopy in coordination and analytical chemistry. (Кyiv: Naukova dumka,

. [in Russian].

Skopenko V.V., Zub V.Ya. Coordination chemistry. (Workshop, 2002). [in Ukrainian].

Choppin G.R., Henrie D.E., Buijus K. Environmental effects of f-f transition Neodimium (III). Inorg. Chem. 1966. 5: 1743.

Ivakha N.B. Іваха Н.Б. Ph.D(Chem.) Thesis.(Kyiv, 2018). [in Ukrainian].

Crosby G.A., Whan R.E., Freeman I.I. Spectroscopic studies of rare earth chelates. J. Chem. Phys. 1962. 66: 2493.

Kostromina N.A. Complexonates of rare-earth elements. (Мoscow: Nauka, 1980). [in Russian].

Davydenko N.K., Yatsymirskiy K.B. The regularities of banding in the spectra of lanthanide ions

at complexing in solutions. TEC. 1970. 6. (5): 620. [in Russian].

Sinha S.P. Spectroscopic Investigation of Some Neodymium. Spectrochim. Acta. 1966. 22: 57.

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