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NOVEL ISOSTRUCTURAL HETEROPOLY SALTS WITH PEACOCK-WEAKLEY TYPE ANION Na9[Ln(W5O18)2]·35H2O AND THULIUM OR YTTERBIUM HETEROATOMS

Mariichak Oleksandra Yu.1, Kaabel Sandra2, Karpichev Yevgen A.2, 3, Kapitanov Illia V.2, 3, Rozantsev Georgiy M.1, Radio Serhii V.1

1 Vasyl' Stus Donetsk National University, Ukraine

2 Tallinn University of Technology, Estonia

3 L.M. Litvinenko Institute of Physical Organic Chemistry & Coal Chemistry NAS of Ukraine

[email protected]

Isostructural neutral sodium heteropoly decatungstolanthanidates(III) Na9[Ln(W5O18)2]·35H2O (Ln = Tm (SI), Yb (SII)) with Peacock-Weakley type anion and Tm, and Yb as heteroatoms were synthesized using procedure, described in [1]. The compounds were obtained as colorless crystals from the aqueous solutions acidified up to Z=0.8 (Z=v(H+)/v(WO42-)) from Ln(NO3)3 – Na2WO4 – HNO3 – H2O systems. The formation of the salts is going according to the reaction:

$$Ln^{3+} + 10 WO_4^{2-} + 8 H^+ = [Ln(W_5O_{18})_2]^{9-} + 4H_2O.$$

The salts were characterized by elemental analysis, FT-IR spectroscopy, and single crystal X-ray diffraction analysis. The latter confirmed that the compounds have Peacock-Weakley type anion, and they are isostructural. There is one case of isostructurality of acidic double salts K3Na4H2[Ln(W5O18)2]·(21-22)H2O (Ln = Pr, Nd, Sm, Gd, Tb, Dy), which crystallize in a monoclinic crystal system, in space group P21/n [2]. Isolated salts with Tm and Yb heteroatoms belong to the second group represented by neutral salts Na9[Ln(W5O18)2]·35H2O (Ln = Y, Nd, Eu [3], Tb, Dy, Ho, Er [4]), which crystallize in a triclinic space group P-1.

Na9[Ln(W5O18)2]·35H2O (Ln= Tm, Yb) consists of decatungstolanthanidate(III) anion, eight octahedrally coordinated Na+ cations, one tetragonal-pyramidal Na+ cation, and 35 H2O molecules. The decatungstolanthanidate(III) anion is comprised of two [W5O18]6- lacunary units, which coordinate to a central Tm3+ or Yb3+ cation in the form of square antiprism.

Figure 1
Fig. 1. Crystal structure of Na9[Tm(W5O18)2]·35H2O (SI) (in (SII) position of Tm is occupied by an Yb atom)

Acknowledgments: The study was carried out within the Fundamental Research Programme funded by the Ministry of Education and Science of Ukraine (Project No. 0119U100025).

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[2] T. Ozeki, T. Yamase, Effect of Lanthanide Contraction on the Structures of the Decatungstolanthanoate Anions in K3Na4H2[LnW10O36]·nH2O (Ln=Pr, Nd, Sm, Gd, Tb, Dy), Crystals Acta Cryst., B50, 128 (1994).

[3] Y. Yan, B. Li, W. Li et al., Controllable vesicular structure and reversal of a surfactant-encapsulated polyoxometalate complex, Soft Matter 5(20): 4047 (2009).

[4] M. Vonci, M.J. Giansiracusa, W. Van den Heuvel et al., Magnetic excitations in polyoxotungstate-supported lanthanoid single-molecule magnets: An inelastic neutron scattering and ab initio study, Inorg. Chem., 56, 378 (2017).