T. E. Kokina

Synthesis, structures, and photoluminescence of heteroligand complexes Ln(L)(iso-Bu2PS2)2(NO3) (Ln = Sm, Tb, Dy; L = Phen, 2,2′-Bipy)

Heteroligand complexes Ln(L)(iso-Bu2PS2)2(NO3) (Ln = Sm, Tb, Dy; L = Phen, 2,2′-Bipy) (I–VI) are synthesized. The structure of Dy(Phen)(iso-Bu2PS2)2(NO3) (III) is determined from the data of X-ray structure analysis. The crystal structure of complex III is based on discrete mononuclear molecules in which the Dy atom has distorted dodecahedral coordination (polyhedron N2O2S4). The ligands Phen, iso-Bu2PS2− and NO3− are bidentate-cyclic. According to the X-ray diffraction analysis data, complexes I and II are isostructural to compound III. Complexes I–VI have photoluminescence in the visible spectral range. The photoluminescence spectra of solid samples of compounds I–VI exhibit bands corresponding to the radiative electron transitions of the Sm3+, Tb3+, and Dy3+ ions. Among the studied compounds I–VI, the Tb(III) complexes are characterized by the most intense photoluminescence.

Binuclear Pd(II) complexes with chiral ethylenediaminodioxime (H2L) and bis-α-thiooxime (H2L1), the derivative of monoterpenoid(+)-3-carene. Crystal structures of [Pd2(H2L)Cl4] and [Pd2(H2L1)Cl4] · 3CDCl3

Diamagnetic Pd(II) complexes with the chiral ethylenediaminodioxime (H 2 L) and bis-α-thiooxime (H2L1), the derivatives of monoterpenoid (+)-3-carene, of the composition Pd2(H2L)Cl4(I), Pd2(H2L1)Cl4 (II), and the solvate Pd2(H2L1)Cl4·3DCl3 (III) were synthesized. The crystal structures of complex I and solvate III were determined from X-ray diffraction data. The structures consist of acentric binuclear molecules with the coordination cores PdN2Cl2 (in I) and PdNSCl2 (in III) in the form of the distorted squares. In complex I, each Pd atom coordinates two N atoms of the tetradentate bridge-cyclic ligand H2L and two Cl atoms; in compound III, one N and one S atom of the tetradentate bridge-cyclic ligand H2L1, and 2 Cl atoms. The CDCl3 molecules in compound III lie in the cavities formed by the molecules of complex II. In both structures, the PdCl2 fragments are in the trans-positions. The 1H NMR spectra indicate that the structures of complexes I, II in solutions are similar to the structures of compounds I, III in the solid state.

Structure of [Dy(Phen)(C4H8NCS2)3]·3CH2Cl2 solvate. Magnetic properties and photoluminiscence of [Ln(Phen)(C4H8NCS2)3] (Ln = Sm, Eu, Tb, Dy, Tm) complexes

It is found that diffraction patterns of complexes I–V of the composition [Ln(Phen)(C4H8NCS2)3] (Ln = Sm, Eu, Tb, Dy, and Tm respectively) are similar. Single crystals of [Dy(Phen)(C4H8NCS2)3]·3CH2Cl2 (VI) obtained are. According to the X-ray crystallographic data, in the structure of VI the unit cell contains two crystallographically independent molecules of the [Dy(Phen)(C4H8NCS2)3] complex and six CH2Cl2 molecules. The N2S6 coordination polyhedron of the Dy atom is a distorted square antiprism. In the range of 2–300 K the magnetic properties of complexes I–V are studied. It is found that complex III passes to the magnetically ordered state; the spontaneous magnetization at 2 K is 24 600 G·cm3/mol. At 300 K compounds I–IV exhibit photoluminescence in the visible spectral range. It is found that the photoluminescence intensity of complex I is several times higher than the photoluminescence intensity of complexes II–IV.

Synthesis and photoluminescence of the heteroligand Sm(III) complexes containing nitrogen heterocycles (Phen, 2,2′-Bipy) and anions C4H8NCS2−, iso-Bu2PS2−, (iso-PrO)2PS2−, and NO3−. Crystal structure of Sm(2,2′-Bipy)2(NO3)3

The photoluminescence spectra of the known complexes, Sm(L)2(NO3)3 (I, II), Sm(L)(iso-Bu2PS2)3 (III, IV), Sm(L)(iso-Bu2PS2)2(NO3) (V, VI) (L = Phen, 2,2′-Bipy), and Sm(Phen)(C4H8NCS2)3 (VIII), and new compounds, Sm(Phen)((iso-PrO)2PS2)3 (VII), Sm(2,2′-Bipy)(C4H8NCS2)3 · 0.5CH2Cl2 (IX), are obtained and interpreted. Using the X-ray structure analysis data, the crystal structure of the [Sm(2,2′-Bipy)2(NO3)3] complex (II) is determined. Structure II consists of discrete mononuclear molecules having a ten-vertex coordination polyhedron N4O6. The ligands 2,2′-Bipy and NO3− are bidentate-cyclic. The influence of the composition of the complexes on the photoluminescence (PL) intensity in the series I–VI is considered. The dependence of the intensity of the band with λmax = 647 nm in the PL spectra of complexes III, VII, and VIII on the type of the sulfur-containing ligand in their composition is established. The band intensity changes in the series VIII > III > VII.

Nickel(II) and copper(II) complexes with chiral bis-α-thiooxime, the derivative of natural terpenoid (+)-3-carene: Synthesis and structures

Chiral bis-α-thiooxime (H2L1), the derivative of the natural monoterpenoid (+)-3-carene, was synthesized and used to prepare paramagnetic complexes of the composition M(H2L1)Cl2 (M=Ni, Cu). The crystal structures of [Ni(H2L1)Cl2] (I) and [Cu(H2L1)Cl2] (II) were determined by X-ray diffraction analysis. Crystals I and II consist of mononuclear acentric molecules. The Ni2+ ion in a molecule of complex I coordinates two N atoms and two S atoms of a tetradentate chelating ligand (the H2L1 molecule) and two Cl atoms. The NiCl2N2S2 coordination core forms octahedron compressed along the apical N atoms. In a molecule of complex II, the Cu2+ ion coordinates two S atoms and the N atom of a tridentate chelating H2L1 ligand and two Cl atoms. The CuCl2NS2 coordination core forms a trigonal bipyramid.

Synthesis and structure of Cu(II) and Pd(II) coordination compounds with chiral α-thiooxime, a derivative of natural terpenoid (−)-α-pinene

The paramagnetic complex Cu(HL)Cl2(I) (μeff = 1.88 μB) and the diamagnetic complex Pd(HL)Cl2(II) with chiral α-thiooxime, a derivative of natural terpenoid (−)-α-pinene (HL), were synthesized. The crystal structures of these complexes were determined from single-crystal X-ray diffraction data (X8 APEX diffractometer, MoKα radiation, 2975 Fhkl, R = 0.0258 for I and 3270 Fhkl, R = 0.0222 for II). The crystals of complex I are monoclinic, a = 9.3376(3) Å, b = 6.8619(2) Å, c = 14.6540(5) Å, β = 97.814(1)°, V = 930.22(5) Å3, Z = 2, ρcalc = 1.513 g/cm3, space group P21. The crystals of complex II are orthorhombic, a = 7.0084(6) Å, b = 9.2113(9) Å, c = 29.081(3) Å, V = 1877.4(3) Å3, Z = 4, ρcalc = 1.651 g/cm3, space group P212121. The structures are composed of mononuclear molecules. The coordination cores MNSCl2 (M = Cu, Pd) are tetrahedrally distorted squares. According to NMR data, complex II has a similar structure in a CDCl3 solution. The intermolecular contacts in structure I generate supramolecular polymeric ribbons lying parallel to axis b. No short intermolecular contacts are present in complex II.

Copper(II) and silver(I) complexes with chiral N-substituted aminoacetic acid derivatives containing the natural monoterpenes (+)-3-carene and (–)-α-pinene: Synthesis and structures

The complexes [Cu(HL)Cl] · 0.25H2O (I), [Cu(HL1)Cl] · 0.5H2O (II), [Ag(HL)] · 0.5H2O (III) were obtained; HL– and (HL1)– are the anions of the chiral N-substituted aminoacetic acid derivatives containing the natural monoterpenes (+)-3-carene and (–)-α-pinene, respectively. The µeff values for paramagnetic complexes I and II are 1.92 and 1.81 µB, respectively. Single crystals of the coordination 1D polymer [Cu(HL)Cl · 2H2O]n (IV) were grown. According to the X-ray diffraction data (CIF file CCDC No. 1035219), the crystal structure of complex IV is made up of the zigzag chains [Cu(HL)Cl]n and water molecules. The coordination polyhedron of the Cu atom is a distorted square pyramid (ClN2O2). The anion HL– acts as a chelating and bridging tetradentate ligand coordinated through the N atoms of the NH and NOH groups as well as through the O atoms of the COO–groups linking two adjacent Cu atoms together. The IR spectra of complexes I and II also provide evidence for the coordination of the functional COO–, NOH, and NH groups. In complex III, the coordination sphere of the Ag atom is made up of the O atoms of the COO–group. Complex III shows weak green photoluminescence (λmax = 530 nm).

Ni(II) Complexes with Diisobutyldithiophosphinate Ions and o-Phenanthroline Molecules. Structure of [Ni(Phen)2(i-Bu2PS2)](i-Bu2PS2)

Paramagnetic compounds [Ni(Phen)(i-Bu2PS2)2] (I), [Ni(Phen)2(i-Bu2PS2)](i-Bu2PS2) (II), and [Ni(Phen)3](i-Bu2PS2)2 (III) (μeff = 3.03–3.14 μB) were synthesized by reacting Ni(i-Bu2PS2)2 chelate with Phen. Their single crystals were grown. X-ray diffraction analysis of II was performed (CAD4 diffractometer, МоKα radiation, 1181 Fhkl, R = 0.0378). The crystals are monoclinic: a = 14.039(2) Å, b = 18.030(2) Å, c = 18.118(2) Å β = 105.52(1)°, V = 4418.9(9) Å3, Z = 4, ρ(calcd) = 1.259 g/cm3, space group P21/c. The structure is built of individual [Ni(Phen)2(i-Bu2PS2)]+ cations and i-Bu2PS2- anions. The coordination polyhedron of NiN4S2 is a distorted octahedron with four N atoms of two bidentate chelate ligands (Phen molecules) and with two S atoms of a bidentate cyclic ligand i-Bu2PS2-. The electronic spectroscopy data for molecular complex I and ionic complex III suggest the octahedral structure of the NiN2S4 and NiN6 chromophores, respectively.

Nickel(II) Diisobutyldithiophosphinate Complexes with Hexamethylenetetramine and Triethylenediamine: Synthesis and Properties. Crystal and Molecular Structure of [Ni2(C6H12N4){(i-C4H9)2PS2}4]

The paramagnetic compounds [Ni2(HMTA)(i-Bu2PS2)4] (I) and [Ni2(TEDA)(i-Bu2PS2)4] (II) (μeff = 3.11 and 3.23 μB, respectively) were synthesized by reacting diamagnetic Ni(i-Bu2PS2)2 with hexamethylenetetramine (HMTA) and triethylenediamine (TEDA) in ethanol. The crystal structure of I was established by single-crystal X-ray diffraction analysis (CAD4 diffractometer, MoKα radiation, 1483 Fhkl, R = 0.0648). The crystals are monoclinic: a = 35.212(7) Å, b = 9.313(2) Å, c = 22.622(5) Å; β = 129.97(3)°, V = 5685(2) Å3, Z = 4, ρ(calcd) = 1.281 g/cm3, space group C2/c. The structure is built of discrete binuclear molecules. The coordination polyhedron of the Ni atom is a distorted tetragonal pyramid with four S atoms of two bidentate cyclic ligands i-Bu2PS2– in the base and the N atom of the bidentate bridging ligand HMTA at the axial vertex. Complexes I and II have similar electronic reflection spectra, which agrees with the C4v symmetry of the ligand field.

Syntheses, structures, magnetic properties, and photoluminescence of compounds Ln(2,2′-Bipy)(C4H8NCS2)3 · 0.5CH2Cl2 (Ln = Sm, Eu, Tb, Dy, and Tm)

Five compounds of the composition Ln(2,2′-Bipy)(C4H8NCS2)3 · 0.5CH2Cl2 (Ln = Sm (I), Eu (II), Tb (III), Dy (IV), and Tm (V); 2,2′-Bipy = 2,2′-bipyridine) are synthesized. According to the X-ray diffraction data (CIF file CCDC 986259), the crystal structure of compound I consists of molecules of the mononuclear complex [Sm(2,2′-Bipy)(C4H8NCS2)3] and solvate molecules CH2Cl2 (2 : 1). The coordination polyhedron N2S6 of the Sm atom is a distorted tetragonal antiprism. The X-ray diffraction analysis shows that compounds I–V are isostructural. The magnetic properties of compounds I–V are analyzed in the temperature range from 2 to 300 K. At 300 K compounds I and III are photoluminescent in the visible spectral range. The photoluminescence intensity of compound I considerably exceeds that of complex III.