Synthesis and Characterization of Chiral Mercury(II) and Cadmium(II) Complexes with 3,3'-Bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl

Two homochiral mercury （1） and cadmium （2） complexes derived from chiral twisted biphenyl pyridine ligand （3,3＇-bipyridine-5,5＇,6,6＇-tetramethyl-2,2＇-dimethoxy-1,1＇-biphenyl） have been synthesized and characterized by IR, microanalysis, TGA, UV-Vis, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 2. For 1, a = 14.2038（16）, b = 14.3630（17）, c = 7.0257（8）, V = 1433.3（3）3, Mr = 878.91, Dc = 2.037 g/cm3, μ = 7.549 mm-1, F（000） = 824, the final GOF = 1.017, R = 0.0296 and wR = 0.0645 for 2925 observed reflections with I 2σ（I）. For 2, a = 14.212（3）, b = 14.392（3）, c = 7.0498（14）, V = 1442.0（5）3, Mr = 790.72, Dc = 1.821 g/cm3, μ = 2.924 mm–1, F（000） = 760, the final GOF = 1.075, R = 0.0340 and wR = 0.0834 for 3144 observed reflections with I 2σ（I）. The crystal structures of 1 and 2 are isostructural and each adopts a two-dimensional supramolecular network which contains the C–H···π interactions.

Synthesis and Structural Characterization of a New Cadmium(II) Complex with a Double Betaine

A new flexible double betaine L （L = 1,4-bis（pyridinio-4-carboxylato-N-methyl）benzene, C20H16N2O4） and its cadmium（Ⅱ） complex [Cd（H2O）aL（NO3）]NO3.H2O 1 were synthesized. Complex 1 was obtained by self-assembly reaction of [Cd（NO3）2]-4H2O and L in hot water,and its crystal structure was determined by single-crystal X-ray diffraction analysis. Crystallographic data for complex 1： C20H24CdN4O14.H2O, Mr = 674.85, monoclinic, space group P21/c, a =13.7854（3）, b = 14.2820（3）, c = 14.9188（4） ,A°, β = 116.418（1）°, V = 2630.5（1）A°^3, Z = 4, Dc= 1.704g/cm^3,/J（MoKα） = 0.911 mm^-1, F（000） = 1368, the final R = 0.0315 and wR = 0.0768 for 3637 observed reflections with I 〉 2σ（I）. In complex 1, L acts as a monodentate ligand to link a Cd（Ⅱ） ion in a novel coordination mode of double betaines. The mononuclear [Cd（H2O）aL（NO3）] units are connected through intermolecular hydrogen bonds and π-π stacking reactions to generate a 3D network.

Crystal Structure,Electrochemical and Fluorescent Properties of a New Cadmium(II) Complex[Cd(C_(12)H_6O_4N_2)(Phen)_2(H_2O)]·3H_2O

A new Cd（II） complex [Cd（C12H6OaN2）（Phen）ffH2O）]＇3H2O with 2,2＂-bipyridine- 3,3＂-dicarboxylic acid as a ligand has been synthesized. Crystal data for the title complex are as follows： monoclinic, space group P2dn, a = 12.8458（5）, b = 17.9131（7）, c = 15.2960（6） A, β = 111.7430（10）°, V = 3269.3（2） A3, Dc = 1.581 g/cm3, Z = 4,/a（MoKa） = 0.731 mm-1, F（000） = 1580, the R = 0.0244 and wR = 0.0605. In the title complex, the central Cd（ll） ion is located in a distorted octahedral coordination environment. The electrochemical and fluorescent properties of the title complex were studied. The results show that the electron transfer of the title complex is irreversible in the electrode reaction and it has a broad emission peak in the range of 470-508 nm with the excitation wavelength of 488 nm.

Synthesis and Electrochemical, Fluorescent and Magnetic Properties of a New Cadmium(II) Complex with 2-Benzoylbenzoic Acid

A new cadmium(II) complex Cd(OBBA)2(2,2A-bipy)2 with 2-benzoylbenzoic acid(HOBBA) and 2,2-bipyridine(2,2A-bipy) as ligands has been synthesized. Crystal data for the complex are as follows: monoclinic, space group P21/c with a = 16.402(3), b = 10.4191(18), c = 23.395(4) A, β = 91.765(2)o, V = 3996.2(12) A3, Dc = 1.455 gAcm-3, Z = 4, μ(Mo Kα) = 0.603 mm-1, F(000) = 1784, the final R = 0.0218 and w R = 0.0558. In the electrode reaction, its electron transfer is quasi reversible and the electrode reaction corresponds to Cd(II)/Cd(0). Under 618 nm radiation, the title complex shows a strong fluorescent band at around 326 nm. In addition, in the range of 2~300 K, this complex displays diamagnetic property.

Cadmium(II)-1,4-phenylenediacetate Complex with Green Luminescence

The title complex, formulated as {[Cd（pda）（phen）]·3H2O}, 1 （pda = 1,4-phenylenediacetate, phen = 1,10′-phenanthroline）, has been hydrothermally synthesized and determimned by X-ray crystallography. Crystallographic data： triclinic, space group P1^-, a = 10.375 （7）, b = 10.435（1）, c = 12.040（1） A.α = 68.503（1）, ,β= 86.371（1）, γ= 66.231（1）°, Mr = 538.82, V = 1104.5（8） ,A^3, Z = 2, Dc = 1.620 g/cm^3,μ = 1.035 mm^-1, F（000） = 544, the final R = 0.0380 and wR = 0.0985 （w = 1/[σ^2（F0^2） ＋ （0.0559P）^2 ＋ 1.5319P], where P = （F0^2＋ 2Fc^2）/3） based on 3444 observed reflections with I 〉2σ（I）. Complex 1 features a two-dimensional layer. Fluorescent analysis reveals that it exhibits intense green luminescence with the maximum at around 516 nm.

Synthesis, Crystal Structure and Luminescent Property of a Novel 1-D Cadmium(II) Complex: [Cd_2(C_8H_3NO_6)_2(H_2O)_4]_n·2nH_2O

A novel one-dimensional chain-like coordination polymer constructed from 3-nitrobenzene- 1,2-dicarboxylic acid, [Cd2（C8H3NO6）2（H2O）4]n·2nH2O, has been synthesized and its structure was determined by X-ray crystallography method. The crystal belongs to monoclinic, space group P21/c with a = 6.1252（8）, b = 20.706（3）, c = 8.8067（11）A, β = 95.608（2）^o, V = 1111.6（2）A^3, Mr = 751.12, De= 2.244 g/cm^3, F（000） = 736,μ = 2.011 mm^-1, Z= 2, the final R = 0.0262 and wR = 0.0692 for 2338 observed reflections with I 〉 2a（I）. The structure of the title compound presents a 1-D chain-like structure constructed by dimer units, [Cd2（C8H3NO6）2（H2O）4]n, through two carboxylate oxygen atoms. The fluorescence of the title compound has been also discussed in this paper.

Synthesis of Branched Polyethylene via Bulky α-Diimine Nickel(II)-Catalyzed Ethylene Chain-Walking Polymerization

The catalysis of olefin polymerization through the chain-walking process is a subject of great interest. In this contribution, the successful synthesis of a Brookhart-type unsymmetrical α-diimine nickel catalyst Ni, which contains both dibenzhydryl and phenyl groups, was determined by X-ray crystallography. The compound has a pseudo-tetrahedral geometry at the Ni center, showing pseudo-C2-symmetry. Upon activation with modified methylaluminoxane (MMAO), Ni1 exhibits high catalytic activity up to 1.02 × 107 g PE (mol Ni h)−1 toward ethylene polymerization, enabling the synthesis of high molecular weight branched polyethylene. The molecular weights and branching densities could be tuned over a very wide range. The polymerization results indicated the possibility of precise microstructure control, depending on the polymerization temperature. The branching densities were decreased with increasing the polymerization temperature.

Crystal Structure of a Cadmium(Ⅱ) Complex Containing an Amide Type Ligand

The compound [Cd（L）2（NO3）]NO3·0.5H2O （L = N-benzyl-2-（quinolin-8-yloxy）aceta- mide） 1 has been synthesized and structurally determined by single-crystal X-ray diffraction, elemental analysis, IR and UV spectroscopy. The crystal belongs to the triclinic system, space group P1 with a = 11.7175（13）, b = 11.8873（13）, c = 14.0958（16） A, α = 74.889（2）, β= 78.228（2）, γ = 78.831（2）°, V= 1835.0（4） A3, Z= 1, Dc= 1.502 Mg/m3, Mr = 1660.17,μ = 0.662 mm-1, F（000） = 846, 2（MoKa） = 0.71073 A, the final R = 0.0585 and wR = 0.0577 for all observed reflections. The results show that the Cd（II） ion with a square antiprismatic geometry is coordinated by a N206 donor set, two NO2 sets from two ligands and two O atoms from a bidendate nitrate group. In the crystal, the O-H...O and N-H...O hydrogen bonds are helpful to consolidate the three- dimensional network.

Preparation of Platinum(II) Complexes with 1-β-D-Ribofuranosyl-1,2,4-triazole-3-carboxamide and its Deoxy-analogue

The platinum (II) complexes of the [Pt (N4,N7-Ribavirin) (DMSO) Cl], [Pt (N4,N7-De-oxyribavirin) (DMSO) Cl] were obtained by the reactions of cis-[Pt (DMSO)2 Cl2] and K[Pt (DMSO) Cl3] with 1-??-D-ribofuranosyl-1,2,4-triazole-3-carboxamide (Ribavirin) and its deoxy-analogue (deoxyribavirin). The preparation of 1-(2'-deoxy-?-D-ribofuranosyl) -1,2,4-triazole-3-carboxamide was also performed through a four-step procedure, protection of 3', 5'-dihydroxyl group of Ribavirin with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane (TPDS-Cl), phenoxythio-carbonylation of the 2'-hydroxyl group of 3', 5'-O-TPDS-Ribavirin with phenoxythiocarbonyl-chloride (PTC-Cl), reduction of 2′-O-phenoxythiocarbonyl ester of 3', 5'-O-TPDS-Ribavirin with tri-n-butyltin hydride and AIBN, deprotection of 3', 5'-O-TPDS-Ribavirin with tetrabutylammon-ium fluoride in THF.

Synthesis, Structure and Physical Properties of a Barium(II) Complex with 5-Sulfoisophthalic Acid Sodium

An alkaline earth metal-organic framework [Ba（Hsip）（H2O）4]n （1, NaH2sip = 5-sulfoisophthalic acid sodium） has been constructed, and characterized by single-crystal X-ray diffraction. In complex 1, each Ba（II） atom coordinates to one ligand Hsip3- and four water molecules with a distorted nine-coordinated monocapped tetragonal antiprism geometry. Each Hsip2- anion acts as a μ3-bridging ligand, in which two carboxylate groups adopt the same bidentate chelating coordinating model and the sulfonate group takes a monodentate coordinating model, resulting in a wave-like two-dimensional network with a （6, 3） topological structure. The two-dimensional networks are further linked by O–H···O to form a three-dimensional structure. Luminescent property and thermal stability of complex 1 are investigated. 1 belongs to the orthorhombic system, space group Pna21 with a = 7.3333（2）, b = 16.7044（3）, c = 10.4817（2）, Z = 4, V = 1283.99（5）3, Mr = 453.58, Dc = 2.346 g/cm3, F（000） = 880, μ = 3.314 mm–1, the final R = 0.0261 and wR = 0.0592 for 2425 observed reflections with I 2σ（I）.

Dioxygen Affinity and Catalytic Performance of Bis-(furaldehyde) Schiff Bases Co(II) Complexes in Cyclohexene Oxidation

Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of these complexes in pyridine at different temperature. These complexes could activate molecular oxygen and were used as catalysts in cyclohexene oxidation. The influence of ligand structure on the dioxygen affinity and catalytic activity of the complexes were discussed.

Synthesis, Structure and Fluorescence of a Copper(II) Complex [Cu_2(bipy)_2(Hpht)_2Cl](Hpht)(bipy=2,2'-Bipyridine,H_2pht=o-Phthalic Acid)

The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.

Synthesis and Crystal Structure of a Zinc(II) Complex with 2-(4′-Chlorine-benzoyl)-benzoic Acid and 1,10-Phenanthroline

A new metal-organic complex Zn2（cbba）4（phen）2 （Hcbba = 2-（4＇chlorine-ben- zoyl）benzoic acid, phen = 1,10-phenanthroline） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The compound crystallizes in orthorhombic, space group Pbcn with a = 12.0821（II）, b = 18.3140（17）, c = 30.961（3） A, V= 6850.7（11） A^3, C80H48C14N4O12Zn2, Mr= 1529.76, Dc = 1.483 g/cm^3,μ（MoKa） = 0.925 mm^-1, F（000） = 3120, Z = 4, the final R = 0.0559 and wR = 0.1146 for 3963 observed reflections （I〉 2σ（I））. In the crystal structure, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three different cbba ligands and two nitrogen atoms from the phen ligand, showing a distorted square-pyramidal geometry. Furthermore, it exhibits a 3D supramolecular network through π-π interactions and shows yellow photoluminescent property at room temperature.

Synthesis,Crystal Structure and Luminescent Property of Cadmium Complex Based on 2-(2-(1Hbenzo[d]imidazol-2-yl)benzyl)-1H-benzo[d]-imidazole

The complex [Cd（bbb）Cl2]·DMF·H2O, where bbb is 2-（2-（1H-benzo[d]imidazol-2-yl）benzyl）-1H-benzo[d]imidazole, was synthesized and characterized by X-ray single-crystal structure analyses. For the complex： C24H25Cl2CdN5O2, Mr = 598.77, crystal system, triclinic, space group P1, a = 9.9878（12）, b = 10.0008（12）, c = 13.2217（15） , α = 80.674（2）, β = 72.158（2）, γ = 86.776（2）°, V = 1240.5（3） 3, Z = 2, Dc = 1.598 g/cm3, λ = 0.71073, μ（MoKα） = 1.127 mm–1, F（000） = 600, S = 1.04, R = 0.0905 and wR = 0.3088 for 4805 observed reflections with I 〉 2σ（I）. It is a neutral complex. The distorted tetrahedral geometry of cadmium ion is coordinated by two nitrogen atoms of ligand and two chloride ions. The complex emits blue green luminescence with emission peaks at 480 nm in DMF solution.

Synthesis, Crystal Structure and DNA Binding Studies of a Nickel(II) Complex with 2-Aminomethylbenzimidazole and Demethylcantharate

A new mixed-ligand nickel（Ⅱ） complex, [Ni（L）（DCA）（H2O）]·2H2O （L = C8H9N3, 2-aminomethyl-benzimidazole, DCA2- = 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylate, demethylcantharate, C8H8O5）, has been synthesized and characterized. The structure of the complex was determined by single-crystal X-ray diffraction. It is of monoclinic system, space group P21/c with a = 7.7211（7）, b = 12.0799（12）, c = 19.7867（19）, β = 100.390（6）°, V = 1815.2（3） nm3, Dc = 1.625 g·cm-3, Ζ = 4, F（000） = 928, R = 0.0314 and wR = 0.0822. In addition, the interaction between the complex and DNA was studied by means of fluorescence spectra and viscosity. The results indicate that the complex binds to DNA by the mode of partial intercalation with the Stern-Volmer constants Ksv of 3.81 × 104 mol·L-1.

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.

Synthesis, Crystal Structure and Calculated β Value of a Tetrahedral Zinc (II) Complex——Zn(2-NH_2py)_2Br_2

A new zinc(II) complex, Zn(2-NH2py)2Br2 (py=pyridine), has been synthesized, and its molecular structure has been confirmed by IR, elemental analysis and -ray crystal structure analysis. Its space group is P21/n with Mr=413.43 (C10H12Br2N4Zn), a=7.435(2), b=12.865(3), c=14.186(4)? b=94.08(2)? V=1353.5(5) 3, Z=4, Dc=2.029 g/cm3, F(000)=328, ?2.378mm－1, R=0.0283, wR=0.0501. The total observed reflections with I≥2?I) were 5314, of which the independent reflections were 3106. The complex structure contains a distorted tetrahedron formed by four atoms coordinated to zinc atom, namely two bromide atoms and two nitrogen atoms. The two ZnBr bond lengths within one molecule, 2.3763(6) and 2.4002(5)? respectively, are not equal; and so are the two ZnN bond lengths, which are 2.031(2) and 2.044(2)?respectively. The calculation results using PM3 method through MOPAC software package in Chem 3D show that its first molecular hyperpolarizability b value is 5.210－30esu, which is comparable with that of p-nitroaniline. No bulk SHG effect has been detected due to the centrosymmetric space group.

Synthesis and Crystal Structure of a Seven-coordinate Cadmium(Ⅱ) Complex

The reaction of 4-hydroxybenzoic acid (H2L),4, 4-diaminodiphenylmethane (DADPM) and Cd(NO3)2?H2O in methane/water gave rise to a seven-coordinate Cd(Ⅱ) complex [Cd2(HL)4(H2O)6]?H2O which has been characterized by single-crystal X-ray diffraction. The complex crystallizes in the orthorhombic system, space group Pna21 with unit cell parameters: a = 10.3352(3), b = 12.0481(3), c = 28.2016(1) ? V = 3511.65(13) 3, Z = 4, C28H36Cd2O20, Mr = 917.37, Dc = 1.735 g/cm3, F(000) = 1840, (MoK? = 1.29mm-1. The final R and wR are 0.0536 and 0.1086 for 4898 observed reflections with I ≥ 4(I). The Cd(Ⅱ) is seven-coordinated in a distorted pentagonal bipyramidal geometry. The inter-molecular hydrogen bonds lead to the formation of a two-dimensional layer structure.

Syntheses, Structures and Photoluminescence of the Cadmium(Ⅱ) and Copper(Ⅱ) Complexes Based on 4'-(4''-Pyridyl)-2,2':6',2''-terpyridine and 1,4-Benzenedicarboxylic Acid Ligands

Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid） have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.

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.