Microwave Assisted Synthesis of a New Triplet Iridium（Ⅲ） Pyrazine Complex

A new cyclometalated iridium（IlI） complex Ir（DPP）3 （DPP=2,3-diphenylpyrazine） was prepared by reaction of DPP with iridium trichloride hydrate under microwave irradiation. The structure of the complex was confirmed by elemental analysis, ^1H NMR, and mass spectroscopy. The UV-Vis absorption and photoluminescent properties of the complex were investigated. The complex shows strong ^1MLCT （singlet metal to ligand charge-transfer） and aMLCT （triplet metal to ligand charge-transfer） absorption at 382 and 504 nm, respectively. The complex also shows strong photoluminescence at 573 nm at room temperature. These results suggest the complex to be a promising phosphorescent material.

Microwave assisted synthesis, spectroscopic, thermal, and antifungal studies of some lanthanide(Ⅲ) complexes with a heterocyclic bishydrazone

A bishydrazone formed by the condensation of isatinmonohydrazone and salicylaldehyde reacted with lanthanide（Ⅲ） chloride to form complexes of the type [Ln（HISA）2Cl3], where, Ln=La（Ⅲ）, Ce（Ⅲ）, Pr（Ⅲ）, Nd（Ⅲ）, Sm（Ⅲ）, Eu（Ⅲ）, or Gd（Ⅲ） and HISA= [（2-hydroxybenzaldehyde）-3-isatin]bishydrazone. Both reactions were carried out under microwave conditions. The ligand and the metal complexes were characterized on the basis of elemental analysis, molar conductance, magnetic susceptibility measurements, UV visible, infrared, far infrared, and proton NMR spectral data. The ligand acted as neutral tridentate, coordinating through the carbonyl oxygen, azomethine nitrogen, and phenolic oxygen without deprotonation. The ligand and lanthanum（Ⅲ） complex were subjected to X-ray diffraction studies. The X-ray diffraction pattern of ligand exhibited its crystalline nature and that of the lanthanum（Ⅲ） complex indicated its amorphous character. The thermal decomposition behaviour of the complex, [La（HISA）2Cl3], was examined in the temperature range of 40-800 ℃ using TG, DTG, and DTA. The ligand and the metal complexes were screened for their antifungal activities.

Microwave assisted synthesis,spectroscopy and biochemical aspects of lanthanum(Ⅲ) and praseodymium(Ⅲ) complexes with oxadiazole functionalised dithiocarbazinates

The new lanthanum (Ⅲ) and praseodymium (Ⅲ) complexes of the general formula [Ln(L)3] (Ln=La(Ⅲ) or Pr(Ⅲ); LK=potassium salt of dithiocarbazinates) were prepared by both, conventional thermal and by the use of microwave technology. Elemental analyses, electrical conductance, magnetic moment and electronic, infrared, far-infrared, 1H and 13C NMR spectral studies were used to characterize the complexes. The molecular weights of few complexes were determined by FAB-mass spectra. Nephelauxetic ratio, covalency parameter and bonding parameter for these complexes were also calculated. The probable structures of the complexes were proposed. The antifungal and antibacterial activities of the complexes were evaluated. The activities were correlated with the structures of the compounds.

Hydrothermal Synthesis and Crystal Structure of a New Dimeric Lanthanum (Ⅲ) Complex

A new dimeric lanthanum (Ⅲ) complex [La_2(phen)_2(C_7H_3N_2O_6)_6] (phen=1, 10-phenanthroline) was synthesized by the hydrothermal method and determined by single crystal X-ray diffraction analysis. The La(Ⅲ) ion is coordinated to seven oxygen atoms from five carboxylate groups and two nitrogen atoms from a phen ligand, forming a monocapped square antiprismatic geometry. Six carboxylate groups coordinate to two La(Ⅲ) ions in three modes which are chelating bidentate, bridging bidentate and bridging tridentate. The crystal is triclinic with space group P-1, a=1.2030(4) nm, b=1.2962(5) nm, c=1.3330(5) nm, α=104.410(5)°, β=114.048(4)°, γ=100.054 (4)°, V=1.7467 (10) nm^3, M_r=952.46, Z=2, D_c=1.811 g·cm^(-3), F(000)=944, S=1.017, μ=1.320 mm^(-1), with R1=0.0298 and wR2=0.0625.

Science Letters; In-situ synthesis and luminescence properties of titanium oxide gels containing 1,10-phenanthroline europium(Ⅲ) complex

It is difficult to directly dope europium complexes in gel because the excessive water or high acidic condition may lead to their decomposition. We prepared a novel homogeneous TiO2 gel containing Eu-phen complexes by using an in-situ synthesis method. The formation of Eu-phen complexes in sol-gel derived TiO2 was confirmed by luminescence excitation spectra. The effects of temperature and aging time on in-situ synthesis are discussed. The luminescence spectra of gel containing europium complexes were also compared with the pure Eu-phen complexes.

Hydrothermal Synthesis and Crystal Structure of a Zinc Complex:[Zn_(2.5)(phen)(BDC)_2(OH)] (phen = 1,10-Phenanthroline, BDC = Benzene-1,4-dicarboxylic Acid)

A metal-organic coordination polymer [ZnE.s（phen）（BDC）2（OH）]2 （phen = 1,10- phenanthroline, BDC = benzene-1,4-dicarboxylic acid） 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The complex crystallizes in the triclinic system, space group PI with a = 11.199（2）, b = 11.593（2）, c = 11.865（3）/A, α= 99.330（1）, β = 111.506（1）, γ = 104.804（1）^o, V= 1328.4（5）A^3, Dc= 1.722 g/cm^3, Z = 1, Mr = 1377.82, F（000） = 692,μ（MoKa） = 2.306 mm^-1, S = 1.093, R= 0.0281 and wR = 0.0756 for 4179 observed reflections （I 〉 2σ（/））. The coordination polyhedron around Zn（II） can be described as a tetrahedron, trigonal bipyramid and octahedron. It is worth noting that the crystal structure of 1 is composed of tetranuclear zinc clusters linked by {ZnO6} units.

Hydrothermal Synthesis,Crystal Structure and Electrochemical Properties of Complex Cu(α-Furacrylic acid)_2(phen)

The title complex （C26H18CuN206, Mr= 517.96） has been synthesized by the reaction of α-furanacrylic acid with 1,10-phenanthroline （phen） in the solvent mixture of water and methanol. Crystal data： monoclinic, space group C2/c with a = 2.2927（4）, b = 1.01248（18）, c = 1.05061（18） nm, β = 111.188（3）°, V= 2.274（7） nm^3, Dc = 1.513 g/cm^3, Z = 4, F（000） = 1060,μ = 1.007mm^-1, R = 0.0320 and ωR = 0.0781. The crystal structural analysis shows that the copper atom is coordinated with four oxygen atoms from two α-furacrylic acids and two nitrogen atoms from 1,10-phenanthroline, giving a distorted octahedral coordination geometry. The result of electrochemical analysis shows that the electron transfer in the electrode reaction is quasi-reversible.

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of the Complex Cu(o-Methylbenzoic acid)_2(2,2′-bipy)·(H_2O)

The title complex （C26H24CuN2O5, Mr = 508.01） has been synthesized by o-methylbenzoic acid, 2,2＇-bipyridine （bipy） and copper perchlorate in the mixed solvent of water and methanol. It crystallizes in orthorhombic, space group P212121 with a = 0.70814（10）, b = 1.6953（3）, c = 1.9539（3） nm, V= 2.3457（6） nm^3, De= 1.439 g/cm^3, Z = 4,μ = 0.971 mm^-1, F（000） = 1052, R = 0.0432 and wR = 0.0860. The structural determination shows that the copper atom is coordinated by three oxygen atoms from two o-methylbenzoic acids and one water molecule together with two nitrogen atoms from 2,2＇-bipyridine, giving a distorted square-pyramidal coordination geometry. The cyclic voltammetric behavior of the complex is also discussed.

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Binuclear Copper(Ⅱ) Complex with 3-(Pyridin-2-yl)-1,2,4-triazole

One novel binuclear copper（Ⅱ） complex [Cu 2 （Hpt） 2 （CO 3） 2 （H 2 O） 2 ]·H 2 O with copper carbonate and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） was hydrothermally synthesized and characterized by IR and X-ray diffraction analysis.The complex crystallizes in triclinic,space group P2 1 /n with a=0.6862（1）,b=0.7805（1）,c=1.1983（2） nm,α=72.03（2）,β=107.72（3）,γ=75.28（2）o,V=0.5884 nm 3,D c=2.105 g/cm 3,Z=1,F（000）=357,GOOF=1.041,the final R=0.01859 and wR=0.04348.The whole molecule is composed of two cooper ions,two Hpt molecules,two carbonate and three water molecules,forming a binuclear structure.The crystal structure shows that the cooper ion is coordinated with three nitrogen atoms from two Hpt molecules,two oxygen atoms from one carbonic acid and one water molecule,forming a distorted square pyramidal geometry.The TG analysis result shows that the title complex is stable under 131.0 ℃.

Hydrothermal Synthesis and Electrochemical Properties of Complex Cu(CH_3C_6H_4COOH)_2(2,2′-bipy)·(H_2O)

The title complex has been synthesized by 4-methylbenzoic acid and 2,2′-bipyridine （bipy） in the mixed solvent of water and methanol. It crystallizes in the triclinic system, space group P1^- with a = 0.7047（3）, b = 1.1217（5）, c = 1.6718（7） nm, α = 103.826（7）, β = 90.772（6）, γ = 104.195（6）°, C26H25CuN2O5.50, Mr = 517.02, V = 1.2404（9） nm^3, Dc = 1.384 g/cm^3, Z = 2, F（000） = 536,μ（MoKα） = 0.921 mm^-1, R = 0.0782 and wR = 0.2172. Structural analysis shows that the copper atom is coordinated with three oxygen atoms from two 4-methylbenzoic acids and one water molecule together with two nitrogen atoms from 2,2＇-bipyridine, giving a distorted square-pyramid coordination geometry. The cyclic voltametric behavior of the complex has also been described.

Heterometallic Trinuclear Ni_2Zn and Ni_2Mn Complexes of Macrocyclic Oxamide: Synthesis and Crystal Structures

Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn（NiL）2（HBTC）H2O] （1） and [Zn（NiL）2（HBTC）H2O] （2） （NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid） have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595（5）, b = 23.1498（11）, c = 17.2558（8） and =101.2530（10）°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214（8）, b = 20.6566（14）, c = 18.4126（13） and = 92.6770（10）°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O–H…O intermolecular hydrogen bonds.

Hydrothermal Synthesis and Structure of a Copper(II) Complex, [Cu(4,4'bpy)(H_2O)_3]SO_42H_2O

The title complex [Cu(4,4?bpy)(H2O)3]SO42H2O (Mr = 405.86) was synthesized under hydrothermal conditions and its crystal structure has been determined by X-ray diffraction. It crystallizes in the hexagonal system, space group P61 with a = 11.1870(4), c = 21.578(1) ? V = 2338.6(2) ?, Dc = 1.729 g/cm3, Z = 6, m(MoKa) = 1.583 mm-1 and F(000) = 1254. The final R and wR are 0.0253 and 0.0416 for 1458 observed reflections with I≥2s(I), respectively. It was revealed that the square pyramidal Cu(II) sites are linked through 4,4?bipyridine groups, forming infinite one-dimensional chains, with the sulfate anions and lattice water molecules occupying the inter-chain positions. During the electrostatic interactions, there exist O…O hydrogen bonds and p-p stacking interactions between the parallel aromatic bipy rings in the structure.

Characterization and performance of Cu/ZnO/Al_2O_3 catalysts prepared via decomposition of M(Cu,Zn)-ammonia complexes under sub-atmospheric pressure for methanol synthesis from H_2 and CO_2

Methanol synthesis from hydrogenation of CO2 is investigated over Cu/ZnO/Al2O3 catalysts prepared by decomposition of M（Cu,Zn）-ammonia complexes （DMAC） at various temperatures.The catalysts were characterized in detail,including X-ray diffraction,N2 adsorption-desorption,N2O chemisorption,temperature-programmed reduction and evolved gas analyses.The influences of DMAC temperature,reaction temperature and specific Cu surface area on catalytic performance are investigated.It is considered that the aurichalcite phase in the precursor plays a key role in improving the physiochemical properties and activities of the final catalysts.The catalyst from rich-aurichalcite precursor exhibits large specific Cu surface area and high space time yield of methanol （212 g/（Lcat·h）;T=513 K,p=3MPa,SV=12000 h-1）.

Hydrothermal Synthesis,Crystal Structure and Electrochemical Properties of the Copper(II) Complex [Cu_4O_4(phen)_4(ClC_6H_4COO)_2(H_2O)_2]·(H_2O)_3

The title complex of copper（Ⅱ） with m-chlorobenzoic acid, 1,10-phenanthroline （phen） and copper perchlorate has been synthesized and characterized in the solvent mixture of water and methanol. Crystal data for this complex： triclinic, space group PI^-, a = 1.06853（12）, b = 1.30740（16）, c = 1.49546（17） nm, α= 101.791（2）,β = 103.413（2）, γ = 105.815（2）°, V= 1.8736（4） nm^3, Mr = 904.67, Dc = 1.604 g/cm^3, Z = 2,/7（000） = 924,μ = 1.34 mm^-1, GOOF = 1.049, the final R = 0.0324 and wR = 0.0797. The structure analysis shows that a chair-like structure [Cu4O4] is defined by three quadrilaterals shaped by four copper and four oxygen atoms, and every copper ion is coordinated by three oxygen atoms from three wate： molecules and two nitrogen atoms from one 1,10-phenanthroline molecule, giving a distorted square-pyramidal coordination geometry. The CV analysis results indicate that the electron transfer in the electrode reaction is quasi-reversible.

Hydrothermal Synthesis, Crystal Structure and Fluorescent Property of a Cd(Ⅱ) Complex Based on Biimidazole and Isonicotinate-N-oxide

A new complex [Cd（H2biim）2（H2O）2]·（ino）2·4H2O （H2biim = 2,2＇-biimidazole, ino = isonicotinate-N-oxide） has been prepared and characterized by single-crystal X-ray diffraction analysis, IR and fluorescence spectra analysis. The crystal is of triclinic system, space group P1 with a = 7.5380（6）, b = 8.0402（7）, c = 13.5094（11） , α = 104.269（1）, β = 93.604（1）, γ = 98.349（1）°, V = 780.93（11） 3, Mr = 765.00, Dc = 1.627 g/cm3, F（000） = 390, μ = 0.776 mm-1 and Z = 1. The final R = 0.0322 and wR = 0.0825 for 7038 observed reflections with I 2σ（I） and R = 0.0341 and wR = 0.0832 for all data. The title complex exhibits an infinite chain-like structure through bridging isonicotinate-N-oxide. Strong interchain hydrogen bonds between isonicotinate-N-oxide and H2biim result in the robust 3-D supramolecular architecture. Moreover, the complex shows strong photoluminescence with emission maximum at λ = 401 nm upon λex = 330 nm.

Hydrothermal Synthesis,Crystal Structure and Thermal Analysis of a Dinuclear Complex Cd_2(3,5-Dinitrobenzoate)_4(pyridine)_4

A dinuclear complex Cd2（dnba）4（pyridine）4 （dnba = 3,5-dinitrobenzoate） has been synthesized by hydrothermal method and characterized by X-ray single-crystal diffraction, elemental analysis, FT-IR spectroscopy, DSC and TG-DTG techniques. The complex with empirical formula C48H32Cd2NI2024 （Mr = 692.83） crystallizes in monoclinic, space group P21/n with a - 12.0344（14）, b = 10.5752（13）, c = 21.578（3） A, β = 104.150（2）°, V = 2662.8（6） A^3, Z = 2, D, = 1.728 g/cm^3,μ（MoKa） = 0.897 mm^-1, F（000） = 1384, S = 1.016 and （△/σ）max = 0.001. R = 0.0638 and wR = 0.0737 for all data; the final R = 0.0337 and wR = 0.0644. In this complex, four carboxylates are bidentate-or chelate-coordinated with the Cd（Ⅱ） centers to give the dinuclear structure. The other coordination positions of Cd（Ⅱ） are occupied by the lone pair electrons from N of four pyridines. Thermal analyses DSC and TG-DTG have been used to determine the thermal decomposition mechanism of the title complex.

A Novel Cadmium(Ⅱ) Complex Based on Asymmetric Dicarboxylate and N-Auxiliary Ligand: Synthesis, Crystal Structure and Properties

One Cd（II） complex based on dicarboxylate and N-auxiliary ligand, namely, [Cd（aip）（m-bix）]n （1, H2aip = 5-aminoisophthalic acid, m-bix = 1,3-bis（imidazol-l-yl-methyl）ben- zene）, was successfully synthesized under hydrothermal conditions. Single-crystal X-ray diffraction analysis reveals that 1 belongs to the orthorhombic system, space group Pbca with a = 14.0790（11）, b = 17.0038（15）, c = 17.3191（16）, V= 4146.1（6） A3, Z = 8, D,. = 1.698 g.cm＂3, p = 1.095 mm-1, F（000） = 2128, the final R = 0.0268 and wR = 0.0623. Complex 1 is a three-dimensional architecture with fsc-3,5-Cmce-1 topology, in which the metal ions act as rare 5-connected nodes. The TGA, XRD and luminescent properties of I were studied.

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a Zinc(II) Complex with 2,2′-Diphenic Acid and 2,2′-Bipyridine Ligands

A new dinuclear complex [Zn（dpa）（bipy）（H2O）]2 （dpa = 2,2＇-diphenic acid, bipy = 2,2＇-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/c with a = 10.960（2）, b = 9.4841（18）, c = 20.599（4）, β = 104.452（3）o, V = 2073.4（7）3, C48H36N4O10Zn2, Mr = 959.55, Dc = 1.537 g/cm3, μ（MoKα） = 1.225 mm-1, F（000） = 984, Z = 2, the final R = 0.0364 and wR = 0.0843 for 2788 observed reflections （I 〉 2σ（I））. In the crystal structure, the zinc atom is five-coordinated with two carboxylate oxygen atoms from different dpas, one coordinated water molecule and two nitrogen atoms from bipy ligands, showing a slightly distorted triangular bipyramidal geometry. Furthermore, it exhibits a zero-dimensional network structure with a sixteen-membered ring and shows yellow photoluminescent property at room temperature.

Hydrothermal Synthesis and Crystal Structure of a New Manganese(II) Complex with 2,4-Pyridine-dicarboxylic Acid and 2,2′-Bipyridine Ligands

A new metal-organic complex [Mn2（PDC）2（bipy）2（H2O）2] （H2PDC = 2,4-pyridine-dicarboxylic acid, bipy = 2,2′-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The compound crystallizes in triclinic, space group P ^-1 with a = 7.376（3）, b = 9.990（4）, c = 11.950（5） A^°, α= 75.217（5）, β = 78.052（5）, γ = 70.655（5）°, V = 796.0（5）A^°3, C34HE6Mn2N6O10, Mr = 788.49, De = 1.645 g/cm^3,μ（MoKa） = 0.866 mm^-1, F（000） = 235, Z = 1, the final R = 0.0425 and wR = 0.0700 for 1971 observed reflections （I 〉 2σ（I））. In the crystal structure, the manganese atom is six-coordinated by two carboxylate oxygen atoms from two different PDC ligands, one aqua ligand, and three nitrogen atoms from 2,2′-bipy and PDC ligands, giving a distorted octahedral geometry. It exhibits a three-dimensional supramolecular network defined by O-H…O hydrogen-bonding interactions.