Xinmin Gan

SYNTHESIS, STRUCTURE AND SPECTROSCOPIC PROPERTIES OF COMPLEXES OF RARE EARTH DITHIOCARBAMATES WITH 2,2′-BIPYRIDYL OR 1, 10-PHENANTHROLINE

Abstract Two series of rare earth complexes with the general formula [RE(Me2Dtc)3(bipy)](RE = La,Pr,Nd,Sm-Yb,Y;Me2Dtc = N,N-dimethyldithiocarbamate; bipy = 2,2′-bipyridyl) and [RE(Et2-Dtc)3(phen)](RE = La,Pr,Nd,Sm-Lu,Y;Et2Dtc = N,N-diethyldithiocarbamate; phen = 1, 10-phenanthroline) have been prepared and some of their chemical properties, IR spectra, electronic spectra and conductivity properties are reported. The structures of [Eu(Me2Dtc)3(bipy)] and [Eu(Et2Dtc)3(phen)] have been determined by single-crystal X-ray diffraction methods. [Eu(Me2Dtc)3(bipy)] crystallizes in the tetragonal system, space group I41/a with a = 16.753(1), c = 39.523(3) A and Z = 16, while [Eu(Et2Dtc)3(phen)] crystallizes in the monoclinic system, space group P21/c with a = 17.029(3), b = 10.652(3), c = 18.726(3) A, β = 96.41(4)° and Z = 4. The central Eu(III) atoms are both octa-coordinated and in a distorted square antiprismatic geometry, each being coordinated to six sulphur atoms of three bidentate dithiocarbamates and to tw...

Synthesis, crystal structure and fluorescence emission of complexes of lanthanide picrates with 2,2′-[1,2-phenylenebis(oxy)]bis(N,N-diphenylacetamide) (PBD)

Abstract Solid complexes of lanthanide picrates with 2,2′-[1,2-phenylenebis(oxy)]bis(N,N-diphenylacetamide) (PBD) have been prepared in ethanol. These complexes have been characterized by elemental analysis, conductivity measurements, IR, electronic and 1H NMR spectroscopies. The crystal and molecular structures of [Y(pic)3(PBD)]·3.8CH3CN have been determined. The crystal structure shows that the Y(III) ion is coordinated to four oxygen atoms of PBD, four oxygen atoms of one bidentate and two unidentate picrates. The coordination number of yttrium is eight. The structure reveals that PBD acts as a tetradentate ligand, forming a ring-like coordination structure similar to those of crown compounds. The Eu(III) complex shows strong emission when excited with 260 nm radiation in the solid state. The intensity ratio 5D0–7F2/5D0–7F1 is 21.5.

Synthesis and spectroscopic properties of light lanthanide monoalkyldithio carbamate complexes

Abstract The light lanthanide monoalkyldithiocarbamate complexes with the general formula RNH3·[Ln(RHDtc)4] (R = methyl, ethyl; Ln  LaNd, SmGd) have been prepared and characterized by chemical analyses, IR spectra, electronic spectra, conductivity measurements and TG-DTA techniques. The monoalkyldithiocarbamate anions act as bidentate ligands. The electronic spectral bands of [Ln(EtHDtc)4]−, attributed to electronic transitions of intraligand, charge-transfer, f-f and f-d types, have been investigated in ethanol solution in the spectral range 11.1–52.6 kK.

Synthesis and characterization of mixed-ligand 1,3-dithiole-2-thione-4,5-dithiolate and 1,10-phenanthroline complexes of lanthanide chloride and their iodinated materials

Abstract The lanthanide complexes of general formula K 2 [Ln(dmit)( phen ) 2 Cl 3 · 6H 2 O (Ln = La, Nd, Sm, Gd, Er, Y; dmit 2− = 1,3-dithiole-2-thione-4, 5-dithiolate anion; phen = 1,10-phenanthroline) have been prepared and characterized by means of elemental analysis, IR spectra, electronic spectra and conductivity measurements. These complexes behave as insulators at 25°C as compacted pellets. On doping iodine into the complexes, they have been partially oxidized to afford K 2 [Ln(dmit)( phen ) 2 Cl 3 ] · I x (Ln = La, x = 3.5; Ln = Er, x = 3.0), whose electrical conductivities are raised to the range of semi-conductors. The nature of the iodine species in these solids is determined by UV-visible and resonance Raman spectroscopies.

Synthesis and Characterization of Light Lanthanide Complexes with Monosubstituted Dithiocarbamates

Abstract Monosubstituted dithiocarbamate complexes of light lanthanides of the type [(RNHCSS)4Ln]N(Bu-n)4·nH2O (where R [dbnd] Ph, p-MePh; Ln[dbnd]La-Gd, excluding Pm; n = O or 2) have been synthesized and characterized by chemical analysis, IR spectra, UV spectra, conductivity measurements and TG-DTA techniques. Spectral studies show that the dithiocarbamate group behaves as a bidentate ligand. Referee I: K. Kasuga Referee II: S. Yamada

Synthesis, structure and spectroscopic properties of dimethylammonium lanthanide tetrakis(N, N-dimethyldithiocarbamate)

Trivalent lanthanide complexes of the type [Ln(me 2 Dtc) 4 ]H 2 NMe 2 (Ln=La, Pr-Nd, Sm-Ho; Me 2 Dtc= N , N -dimethyldithiocarbamate) have been prepared and characterized by means of elemental analyses, IR spectra, electronic spectra, 1 H NMR spectra and conductivity measurements. The X-ray crystal and molecular structure of the neodymium complex has been determined from diffractometer data. There are two independent [Nd(Me 2 Dtc) 4 ]H 2 NMe 2 monomers in each unit cell; the metal coordination number is 8. Spectroscopic properties of the complexes are discussed.

Studies on crown ether complexes—XXVIII. Synthesis, characterization and structure of the complexes of heavier lanthanide nitrates (Gd-Lu) with dibenzo-24-crown-8

Abstract The heavier lanthanide nitrate complexes with dibenzo-24-crown-8 (DB24C8) have been prepared in acetonitrile. These new complexes with the general formula [Ln(NO3)3(OH2)3]·(DB24C8) (Ln = Gd-Lu) have been characterized by means of elemental analysis, IR spectra, 1H NMR spectra and conductivity measurements. The crystal and molecular structure of [Gd(NO3)3(OH2)3]·(DB24C8) has been determined by single-crystal X-ray diffraction. The gadolinium(III) ion is coordinated to the six oxygen atoms of three bidentate nitrate groups and three water molecules. The crown ether molecule is hydrogen bonded to these three water molecules. The average GdO(nitrate) and GdO(water) distances are 2.464(4) and 2.388(3) A, respectively. The average O(water)⋯O(crown ether) separation is 2.787 A. The coordination polyhedron is a distorted tricapped trigonal prism.

SYNTHESIS, SPECTROSCOPIC PROPERTIES AND STRUCTURE OF BIS(DIMETHYLSULFOXIDE)TRIS(N,N-DIMETHYLDITHIOCARBAMATO)LANTHANIDE(III)

Abstract The title complexes [Ln(Me2Dtc)3(DMSO)2)(Ln = La, Pr-Nd, Sm-Tb; Me2Dtc = N,N-dimethyl-dithiocarbamate; DMSO = dimethylsulfoxide) have been synthesized, and the structure of [La(Me2Dtc)3(DMSO)2] has been determined by the use of single-crystal X-ray methods; the complex crystallizes in the monoclinic system, space group Cc with Z = 4, a = 14.456(2), b = 11.105(2), c = 18.691(2)A, β = 115.33(1)°, V = 2712.1(6)A3. The structure was refined to R = 0.022 for 2493 independent reflections with I ≥ 3σ(I). The central La(III) atom is octacoordinated with dodecahedral geometry to six sulfur atoms of three Me2Dtc ligands and to two oxygen atoms of two DMSO ligands. Spectroscopic properties of the complexes (IR and electronic spectra) are discussed.

Studies on crown ether complexes-XXVII. Synthesis, characterization and crystal structure of [Y(NO3)3(OH2)3]·(dibenzo-24-crown-8)

Abstract The complex [Y(NO3)3(OH2)3]·(dibenzo-24-crown-8) (DB24C8) has been prepared and characterized by elemental analyses, IR spectra and molar conductance. The structure of the complex has been determined by single-crystal X-ray diffraction. The yttrium(III) ion is nine-coordinate, bonded to three bidentate nitrate groups and three water molecules. The crown ether molecule is hydrogen bonded to these three water molecules. The average YO(nitrate) and YO(water) distances are 2.426(4) A and 2.344(4) A, respectively. The average O(water) ⋯ O(crown) hydrogen bonded separation is 2.787 A. The coordination geometry of the yttrium(III) ion is a distorted, tricapped trigonal prism.

Preparation and structure of [bis(8-quinolyloxyethyl) ether · H3+O]3[La(NO3)6]: A hexanitrato lanthanum complex of a hydronium ion podand complex cation

Abstract The complex [bis(8-quinolyloxyethyl)ether-H 3 + O] 3 [La(NO 3 ) 6 ] has been prepared and its structure has been determined by single-crystal X-ray diffraction. This compound represents an example of a hydronium ion complex with an acyclic bis(quinolyl)-terminated oligoether, which forms a counter ion for the complex anion [La(NO 3 ) 6 ] 3- . The cations are stabilized by three hydrogen bonds. Copyright