T. G. Leonova

Luminescence properties of complexes Ln(Phen)(C6F5COO)3 (Ln = Tb, Eu) and Ln(C6F5COO)3 · nH2O (Ln = Tb, n = 2; Ln = Eu, n = 1). Structures of the [Tb2(H2O)8(C6F5COO)6] complex and its isomer in the supramolecular compound [Tb2(H2O)8(C6F5COO)6] · 2C6F5COOH

Complexes Ln(Phen)(C6F5COO)3 (Ln = Tb, Eu; Phen = 1,10-phenanthroline) (I, II) are synthesized. At 300 K these complexes and compounds Ln(C6F5COO)3 · nH2O (Ln = Tb, n = 2; Ln = Eu, n = 1) (III, VI) possess photoluminescence (bright in the case of I and II). In the spectrum of compound I the line at 545 nm (transition 5D4 → 7F5) is most intense, whereas in the spectrum of compound II the most intense is the line at 613 nm (transition 5D0 → 7F2). The replacement of Phen by water decreases the luminescence intensity. The compound [Tb2(H2O)8(C6F5COO)6] · 2C6F5COOH (IV) is synthesized. According to the X-ray diffraction data, in structure IV the molecules of the binuclear Tb(III) complex with the C6F5COOH molecules form a supramolecular ensemble due to hydrogen bonding. The C6F5COO− ligands perform the monodentate and bidentate bridging function, resulting in the opening of the eight-membered cycle Tb2C2O4. The TbO8 polyhedron is a distored tetragonal antiprism. The crystals of the binuclear complex [Tb2(H2O)8(C6F5COO)6] (V) are obtained in which the C6F5COO− ligands are monodentate and tridentate bridging cyclic, which results in the closure of two four-membered cycles TbO2C and one four-membered cycle Tb2O2. The TbO9 polyhedron is a distorted monocapped tetragonal antiprism.

Synthesis of heteroligand complex Nd(Phen){(iso-C4H9)2PS2}2(NO3). Crystal structure of [Nd(Phen){(iso-C4H9)2PS2}3] and luminescent properties of these compounds

AbstractThe heteroligand complex Nd(Phen){(iso-C4H9)2PS2}2(NO3) (I) was synthesized and its IR spectrum was analyzed. The anions (iso-C4H9)2PS2/− and N3/− act as bidentate cyclic ligands. The single crystals of [Nd(Phen){iso-C4H9)2PS2}3] (II) were obtained on evaporation of a solution of complex I in a mixture CH2Cl2-hexane and were studied by X-ray diffraction. Crystals II are triclinic: a = 10.5509(5); b = 14.7432(8), c = 16.8503(10) Å; α = 102.882(2)°, β = 97.211(2)°, γ= 108.087(2)°, V = 2374(2) Å3, Z = 2, ρ(calcd.) = 1.332 g/cm3, space group

Two Modifications of the Mixed-Ligand Complex ZnPhen(i-C3H7OCS2)2 with Monodentate and Bidentate Ligands i-C3H7OCS 2 -

P\bar 1

Crystal structure of the complex Zn(2,2′-Bipy)(C2H5OCS2)2 with mono- and bidentate ethylxanthate ligands

. The coordination polyhedron of the Nd atom in a separate mononuclear molecule II is a distorted dodecahedron N2S6. The molecules are bound by weak van der Waals and π-π interactions. The photoluminescence spectra of complexes I, II were measured and interpreted.

Synthesis and crystal and molecular structure of the complex Zn(Phen)(S2COC4H9-i)2

Hydrates of Eu(III) and Tb(III) salts with anions (L) 4-CF3C6F4COO− and 4-(CF3)2CFC6F4COO−, and also mixed-ligand complexes Ln(phen)(L)3 were obtained. The compounds show red and green photoluminescence characteristic of Eu3+ and Tb3+ ions, respectively, in the visible region of spectrum. The intensity of the photoluminescence of the complexes containing 1,10-phenanthroline is much higher than that of compounds containing water. It is connected with sensitizing properties of phen in relation to Eu3+ and Tb3+ ions.

Synthesis and crystal and molecular structure of mixed-ligand complexes Cd(2,2′-Bipy)(i-PrOCS2)2 and (2,2′-Bipy)(i-BuOCS2)2

Two crystal modifications (m-1 and m-2) of the mixed-ligand complex ZnPhen(i-PrOCS2)2 have been isolated. Their crystal structures were solved using X-ray diffraction data (CAD-4 diffractometer, MoKα radiation, 3141 and 3532 Fhkl, R = 0.0363 and 0.0304). For both modifications, the crystals are monoclinic with unit cell parameters a = 10.543(2), b = 13.494(3), c = 16.875(3) Å, β = 102.08(3)°, V = 2347.6(8) Å3, Z = 4, space group P21/n (m-1) and a = 10.931(2), b = 12.996(3), c = 16.288(3) Å, β = 92.69(3)°, V = 2311.3(8) Å3, Z = 4, space group P21/n (m-2). The structures basically consist of discrete monomer molecules in which the Zn atom has a tetragonal pyramidal (m-1: ZnN2S3, c.n. 5, bidentate and monodentate i-PrOCS2- ligands) or distorted octahedral (m-2: ZnN2S4, c.n. 6, bidentate i-PrOCS2- ligands) environment. Molecular packings and their interactions in the structures are discussed.

Crystal and molecular structure of the [Nd2(H2O)8(C6F5COO)6]·2H2O Compound

We have synthesized high-spin mixed-ligand Mn2+ complexes Mn(S2COR)2L where R=i−C3H7, i−C4H9; [L=1,10-phenanthroline (Phen), 2,2′-bipyridyl (2,2′-Bipy), 4,4′-bipyridyl (4,4′-Bipy)]. As solids, the compounds are stable to oxidation by atmospheric oxygen. An X-ray structural study of the [Mn(S2COC3H7−i)2(2,2′-Bipy)] complex was carried out. The structure is composed of discrete monomeric molecules. The corrdination polyhedron of the Mn atom is a distorted [4S+2N] octahedron. The molecules are bonded by van der Waals interactions.

SYNTHESIS AND CRYSTAL AND MOLECULAR STRUCTURE OF THE MIXED-LIGAND COORDINATION COMPOUND ZnPhen(n-C4H9OCS2)2

While seeking molecular precursors for ZnS films obtained by gas phase chemical deposition [1, 2] we synthesized mixed-ligand compounds ZnL(ROCS2)2 [R = i-Pr. /-Bu; L = 2,2′-bipyridyl (2,2′-Bipy), 1,10-phenanthroline (Phen)] [3]. The volatile complex Zn(2,2′-Bipy)(i-PrOCS2)2 was used as a precursor to obtain electroluminescent ZnS:Mn films [4]. According to XRD data, the compound Zn(Phen)(i-BuOCS2)2 is monomeric. The c.n. of zinc is six. The Phen and 1-B11OCS2 ions behave as cyclic bidentate ligands [3, 5]. It was assumed that other mixed-ligand complexes with Phen and 2,2′-Bipy have an analogous structure [3]. Here we report on the structure of the known mixed-ligand complex of zinc(II) ethylxanthate with 2,2′-bipyridyl [6, 7]. It was found that the behavior of alkylxanthate ligands in mixed-ligand complexes of zinc(II) is more complex.