Vol 50, No 12 (2024)

Aspects of the synthesis and isolation of (Bu₄N)₃[H₃V₁₀O₂₈] (I) and Na₆[V₁₀O28] · 18H₂O (II) from one reaction mixture are considered. The procedure for the synthesis of compound I is optimized. The reaction of compound I and HSO₃CF₃ in dimethyl sulfoxide (DMSO) affords complex [VO₂(DMSO)₄](CF₃SO₃) (III). A possibility of using complex III for the preparation of catalytically active materials based on polyethylene terephthalate (PET) is shown.

A series of mixed-carboxylate EuCd compounds with 1,10-phenanthroline (phen) and anions of benzoic H(Bz), pentabenzoic H(Pfb), 3,5-dinitrobenzoic H(3,5-Nbz), and 3,5-di-tert-butylbenzoic H(Dtbbz) acids is synthesized: [Eu₂Cd₂(Phen)₂(Рfb)_5,4(Bz)_4,6].2MeCN (I), [Eu₂(H₂O)₂Cd₂(Phen)₂(3,5-Nbz)_4,1(Bz)_5,9] (II) and [EuCd₂(EtOH)₄(Dtbbz)₆(Pfb)] (III). The variation of combinations of aromatic anions makes it possible to reveal the influence of diverse factors on the compositions and structures of new compounds. In the case of benzoate‒pentafluorobenzoate compound I and 3,5-dinitrobenzoate‒benzoate compound II, the aromatic substituents of the anions have nonintegral populations and occupy close positions in the structure of the complex. The combination of the more bulky 3,5-di-tert-butylbenzoate and pentafluorobenzoate anions in compound III results in the formation of a compound with integral populations of the positions of the anions. The synthesized compounds are characterized by XRD, IR spectroscopy, and C, H, N elemental analysis.

Lead(II) complexation reactions were studied in the presence of salts of the closo-decaborate anion [B₁₀H₁₀]^2– and azaheterocyclic ligands 2,2΄-bipyridyl (bipy) or 1,10-phenanthroline (phen) in water and organic solvents (acetonitrile, DMF). Binuclear complex Pb(bipy)₂[B₁₀H₁₀] and polymer complex [Pb(phen)[B₁₀H₁₀]] were isolated. The effect of solvents and reagent ratios on the composition and structures of the final complexes was studied. The complex compounds were identified by elemental analysis, IR spectroscopy, and X-ray powder diffraction. The structure of complex [Pb(bipy)₂[B₁₀H₁₀]]₂ ⋅ 2CH₃CN (CCDC no. 2325841) was determined by single-crystal X-ray diffraction.

Heteroleptic copper(I) tetrafluoroborate complexes with pyrazolo[1,5-a][1,10]phenanthrolines (Lⁿ, n = 1–3) and bis[(2-diphenylphosphino)phenyl]ether (POP) were synthesized and structurally characterized. The coordination compounds with the general formula [CuLⁿ(POP)]BF₄ · Solv (n = 1, Solv = 0.5MeCN, complex I; n = 2, Solv = 0.5CH₂Cl₂, complex II; n = 3, Solv = 1.25Et₂O, complex III · Et₂O) were prepared by the reaction of CuBF₄ with Lⁿ and POP in organic solvents (MeCN/CH₂Cl₂/Et₂O) at 1 : 1 : 1 molar ratio. Compound III · Et₂O gradually loses solvate molecules to be converted to the complex [CuL³(POP)]BF₄ (III). According to single-crystal X-ray diffraction data, the complexes (I, II, III · Et₂O) are ionic; in complex cation [CuLⁿ(POP)]⁺ the coordination environment of the copper atom is a distorted tetrahedron with CuN₂P₂ chromophore. The photoluminescence properties of the obtained complexes (I–III) were studied in the solid state and in solution. In the absorption spectra of the complexes, a charge transfer band is observed at 380–385 nm; excitation in this range gives rise to two emission bands at 480 and 650 nm in solution. In the solid state, the complexes show photoluminescence only in the red range (λ_max = 600–610 nm) with microsecond lifetimes. It was found that complexes I and III with a more perfect tetrahedral environment have quantum yields an order of magnitude higher than the quantum yield observed for complex II.