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(11), b = 18.3140(17), c = 30.961(3), V = 6850.7(11)3, C80H48Cl4N4O12Zn2, Mr = 1529.76, Dc = 1.483 g/cm3, μ(MoKα) = 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 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.

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.

Synthesis, Characterization and DFT Studies of Two Zinc(II) Complexes Based on 2-Isopropylimidazole

Two novel coordination compounds, [Zn(L)2(OOCH)2] (1) and [Zn(L)3(OCHO)](OCHO)]·H2O (2) (where L = 2-isopropylimidazole, C6H10N2) have been prepared by reaction of 2-isopropylimidazole with zinc(II) formate at room temperature using toluene as solvent. These compounds were characterized by elemental and thermal analyses, IR, 1HNMR and 13CNMR spectroscopies, single crystal X-ray diffraction and DFT studies. The Zn centers in 1 and 2 adopt pseudo-tetrahedral coordination geometries. Compound 1 crystallizes in the monoclinic system P2/c space group whereas compound 2 crystallizes in the P-1 space group of the triclinic crystal system. Several types of hydrogen intra-/intermolecular interactions are observed in these materials and extend into a two-dimensional leaf like network in 1 and a two-dimensional lattice of rectilinear pillars in 2. Compounds 1 and 2 were also optimized and their frontier molecular orbitals, global reactivity descriptors, molecular electrostatic potential, natural bond orbitals were investigated using density functional theory (DFT). In fact the induced structural differences from complex 1 to complex 2 led to the reduction of the frontier molecular orbital energy gap by 1.338 eV and a decrease of the chemical hardness by 0.669 eV.

4,5-二氮芴-9-酮Cu(II),Zn(II)配合物的合成、晶体结构、热分析及理论计算

合成了 4,5 二氮芴 9 酮 (dafo)的Cu(II) ,Zn(II)配合物 [Cu(dafo) 2 (H2 O) 2 ] (NO3 ) 2 和 [Zn(dafo) 2 (H2 O) 2 ] (NO3 ) 2 ,通过单晶X射线衍射法确定了它们的结构 .晶体结构分析表明 ,配合物分子中Cu(II) ,Zn(II)分别和来自两配体的四个氮原子及两个水分子中的氧原子配位 ,处于六配位的配位环境中 ,两配体基本处于同一平面 ,两水分子垂直于两配体所在平面 ,Cu(II)处于畸变八面体中心 ,Zn(II)处于正常八面体中心 ,对两种配合物进行了元素分析、红外和热分析表征 ,在实验的基础上 ,采用Gaussian 98w中的DFT

一种锌(II)配合物的合成和晶体结构

合成了目标配合物:碘化双 [3,4 二甲氧基苯甲醛缩氨基硫脲]合锌(II),其结构通过单晶X 射线衍射法确定。晶体属单斜晶系,C2/c空间群。配合物分子中,锌(II)与两个硫原子、两个碘原子配位形成轻微畸变的四面体结构,每一个3,4 二甲氧基苯甲醛缩氨基硫脲配体与锌离子处于同一平面内,在晶体中分子之间以氢键连接形成网状结构。

水杨醛缩-3-羟甲基氨基甲烷锌(II)配合物的合成与荧光性质研究

合成了水杨醛缩-3-羟甲基氨基甲烷锌(II)配合物,通过元素分析、摩尔电导、红外光谱、溶解性对该配合物进行了表征;并对配合物的荧光性质进行了研究。

Zn(II)-NH_4·HCO_3-NH_3-H_2O体系雾化干燥机理研究

以Zn(II)-NH4·HCO3-NH3-H2O溶液为原料,通过雾化干燥、煅烧获得超细氧化锌。试验表明,雾化溶液中游离氨浓度对干燥过程的固体形貌影响较大,随着溶液中游离氨浓度的降低,干燥产物由针状颗粒按照针状颗粒与球形颗粒混合物、球形颗粒顺序演变。对干燥机理进行分析,干燥过程按照氨与水的挥发、前躯体析出、水分蒸发及前躯体分解四个环节依次进行。NH3分子在干燥过程中,先后起Zn2+配体、传递Zn2+及控制Zn的析出方向等作用。液滴与热空气接触后,雾滴与热空气基本保持同步运动,干燥产品基本为碱式碳酸锌。

Bis(L-asparaginato)zinc(Ⅱ)掺Cu^(2+)的能级(英文)

推算出了3d9离子在立方对称下的能级计算公式,并用此公式计算出了Bis(L-asparaginato)zinc(Ⅱ)晶体掺Cu2+从基态2A1(ε)到激发态2A1(θ),2B1(ζ),2B2(η),2B3(ξ)的能级,它们分别为10938cm-1,14288cm-1,19184cm-1,37397cm-1,计算结果跟实验结果吻合的很好.

Biosorption of zinc(Ⅱ) from aqueous solution by dried activated sludge

The biosorption potential of dried activated sludge as a biosorbent for zinc(Ⅱ) removal from aqueous solution was investigated.The effects of initial pH,contact time,initial zinc ion concentration,and adsorbent dosage on the biosorption processes were determined,and the equilibrium data were modeled by the Langmuir and Freundlich isotherms.The Langmuir isotherm model (R 2=0.999) was proved to fit the equilibrium data much better than the Freundlich isotherm model (R 2=0.918).The monolayer adsorption capacity of dried activated sludge for zinc(Ⅱ) was found to be 17.86 mg/g at pH of 5 and 25°C.The kinetic data were tested using pseudo firstand second-order models.The results suggested that the pseudo second-order model (R 2 > 0.999) was better for the description of the adsorption behavior of zinc(Ⅱ) onto the dried activated sludge.Fourier transform infrared spectral analysis showed that the dominant mechanism of zinc(Ⅱ) biosorption onto the dried activated sludge was the binding between amide groups and zinc ions.

Separation of indium (Ⅲ), gallium (Ⅲ), and zinc (Ⅱ) with Levextrel resin containing di(2-ethylhexyl) phosphoric acid (CL-P204): Part I. Selection of separation conditions

A kind of Levextrel resin separation process was developed for separation of indium (Ⅲ), gallium (Ⅲ), and zinc (Ⅱ) from aqueous sulfate solution with Levextrel resin containing di(2-ethylhexyl) phosphoric acid (CL-P204). The aim of the research is to collect preliminary results for a pilot-scale production. Properties of adsorbing indium (Ⅲ), gallium (Ⅲ),and zinc (Ⅱ) from sulfate solution with the Levextrel resin were first studied by batch operation and column operation. The optimum pH, adsorption capacities and concentrations of stripping agents for indium (Ⅲ), gallim (Ⅲ) were tested. The separation order of indium (Ⅲ), gallim (Ⅲ), and zinc (Ⅱ) from sulfate solution with CL-P204 Levextrel resin was found that indium (Ⅲ) could be first separated by adsorbing at the acidity of 1.0 mol/L whereas gallium (Ⅲ) and zinc (Ⅱ) could not, and they were adsorbed together by adsorbing at pH = 2.8, then separated from each other by stripping with 0.1 and 0.5mol/L hydrochloric acid, respectively. The recoveries of three metal ions were all higher than 99%. The cyclic properties of this resin are well.

Hydrothermal Synthesis and Crystal Structure of a New 2D Zinc(Ⅱ) Coordination Polymer with 2-Aminoethanesulfonic Acid

A new 2D Zn(Ⅱ) coordination polymer [Zn(TAU)2]n (1, HTAU=2-aminoethane- sulfonic acid) constructed by 2-aminoethanesulfonic acid ligand has been hydrothermally synthesized by the reaction of Zn(CH3COO)2 and 2-aminoethanesulfonic acid with a 1:2 mole ratio and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy and thermogravimetric analysis. Crystal structural analysis reveals it crystallizes in monoclinic, space group P21/c with a=8.672(4), b=6.523(3), c=9.134(5) , β=115.441(5)°, V=466.6(4) 3, Mr=313.65, Z=2, Dc=2.232 Mg·m-3, F(000) =320, μ(MoKα)=3.091 mm-1, the final R=0.0358 and wR=0.0919 for 2026 observed reflections with Ⅰ > 2σ(Ⅰ). In the structure, each zinc(Ⅱ) ion is coordinated in a slightly distorted octahedron, and each μ3-TAU– acts as a bridge to bond three neighboring Zn(Ⅱ) ions to form an infinite 2D network structure.

Theoretical Investigation on the Second-order Nonlinear Optical Properties of Chiral Amino Acid Zinc(Ⅱ) Porphyrins

Static second-order nonlinear optical effects of amino acid zinc(II) porphyrins 1, 2, 3 and 4 were calculated by the TDHF/PM3 method based on the molecular structures optimized at the semiempirical PM3 quantum chemistry level, showing due to the cancellation of symmetric center, these amino acid zinc(II) porphyrins exhibit second order nonlinear optical response. The analysis of β components indicated that these amino acid zinc(II) porphyrins are of multipola- rizabilities, and they may be ascribed as the “mixture” of octupolar and dipoar molecules with ||βJ=3||/||βJ=1|| ≈ 5. It is found that there are no significant differences between the static β values of non-chiral and chiral amino acid zinc(II) porphyrins. However, the βxyz component, which is quite important to quadratic macroscopic χ (2) susceptibility of chiral material, is increased significantly with the increase of side chain group of amino acids.

Some Hybrid Systems of Chiral Schiff Base Zn(II) Complexes and Photochromic Spiropyrans for Environmental Ion Sensing

This is a review article including our recent results and some previous photo functional hybrid system having potential applications for environmental ion sensing. We have prepared several new and known chiral Schiff base Zn(II) complexes and measured (and also calculated) absorption and fluorescence spectra for sole complexes. After assembling hybrid systems with 1,3,3-trime- thylindolino-6’-nitrobenzopyrylospiran (SP) in methanol solutions, we measured spectral changes before and after alternate irradiation of UV and visible light. Intensity of fluorescence spectra for pale yellow Zn(II) complexes (λem = 450 nm, λex = 270 and 360 nm) was quenched by colorless SP (λem = 533 nm, λex = 612 nm). After UV light irradiation to form purple merocyanine (MC), photoisomerization resulted in changes of the intensity of absorption spectra as well as fluorescence spectra. Thus the hybrid systems could successfully act as molecular logic circuit by input (excitation by light) and output (intensity of fluorescence peaks). Moreover, we investigated concentration dependence of doped Zn(II) and Cu(II) ions to confirm quenching of intensity of fluorescence peaks by Zn(II) and Cu(II) MC complexes for metal ion sensing in solutions.

Synthesis and Crystal Structure of a Zinc(Ⅱ)Complex with 2,2'-Diphenic Acid and Benzimidazole Ligands

A new complex [Zn1.5(dpa)1.5(bim)]2n(dpa = 2,2-diphenic acid,bim = benzimida-zole)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 C2/c with a = 18.773(8),b = 16.560(7),c = 16.417(9),β = 94.737(9)o,V = 5086(4)3,C56H36N4O12Zn3,Mr = 1153.00,Dc = 1.506 g/cm3,μ(MoKα)= 1.472 mm1,F(000)= 2344,Z = 4,the final R = 0.0573 and wR = 0.1164 for 2968 observed reflections(I > 2σ(I)).It exhibits a one-dimensional chain-like structure and shows luminescent property in the blue region.

A Novel Luminescent Zinc(Ⅱ) Coordination Polymer with 2D → 3D Polythreaded Motif

A new zinc(Ⅱ) compound, [Zn(BTA)(UCA)]n(1, HBTA = 1,2,3-benzotriazole, HUCA = 4-imidazoleacrylic acid), has been synthesized via the hydrothermal reactions of Zn(OAC)2·2H2O, HBTA and HUCA. The crystal structure is of monoclinic, space group P21/c with a = 7.450(3), b = 18.911(8), c = 9.198(4) ?, β = 94.317(8)°, V = 1292.2(9) ?3, C12H9N5O2 Zn, Mr = 320.63, Z = 4, Dc = 1.648 g/cm3, F(000) = 648, μ = 1.909 mm-1, R = 0.0255 and w R = 0.0655 for 2104 observed reflections(I > 2σ(I)). Single-crystal X-ray diffraction analysis revealed that compound 1 features a two-dimensional(2D) layered framework based on benzotriazole controlled dinuclear [Zn2(BTA)2] subunits. Furthermore, these 2D layers are threaded into a 3D supramolecular framework via the direction of intermolecular hydrogen bonds and π...π interactions. In addition, the thermal stability and fluorescence property of compound 1 were also investigated.

Synthesis,Crystal Structure,Spectroscopic Property and Redox Behavior of Zinc(Ⅱ) Complexes Containing Oligoaniline-functionalized Terpyridine Ligands

Two novel mono-nuclear zinc(Ⅱ) complexes with oligoaniline-functionalized terpyridine ligands have been synthesized and verified by 1H-NMR,13C-NMR,Elemental Analysis (EA) and X-ray Diffraction (XRD). The UV-vis spectra show the ligand-centered (LC) π-π* transitions and intra-ligand charge transfer (1ILCT) transitions,and the 1ILCT band red-shifts with the increasing number of aromatic amine groups in the ligands. Complex [Zn(L1)2](PF6)2 with an aromatic amine group in ligand shows a strong emission peak at 523 nm in the MeCN solution at 293 K and a blue-shifted band at 517 nm in the alcoholic glass at 77 K. However,for complex [Zn(L2)2](PF6)2 containing aniline dimer modified ligand,no apparent emission can be observed in the MeCN solution at room temperature due to a PET non-radiative decay pathway. Both of them show multiplicate redox processes based on oligoaniline and terpyridine units. The shifts of redox potentials also reflect the D-A interactions between the oligoaniline units and [Zn(TPY)2]2+ core.

Batch Studies for Sorption of Ga(III), Cu(II), Ni(II) and Zn(II) Ions onto Synthetic Polymeric Resins

Poly(acrylamide-acrylic acid-dimethyl amino ethylmethacrylate), p(AM-AA-DMAEM) and Poly(acrylamide-acrylic acid)-ethylene diamine tetracetic acid disodium, p(AM-AA)-EDTANa2 were prepared by gamma radiation-induced template polymerization technique. The prepared polymeric materials were used for the sorption of Ga(III), Cu(II), Ni(II) and Zn(II) in aqueous solution. The effect of pH, weight of resins, metal ion concentrations and contact time on the sorption of these metal ions were studied.

乳化液膜提取工业废水中多种共存金属离子的研究

同时提取多种重金属离子的实际应用意义较大,本实验利用正交实验法确定了从模拟工业废水中提取三种离子的最佳膜配方,同时考察了其他条件对多种重金属离子萃取率和乳液膜破乳率的影响。经一级液膜萃取,Cu(Ⅱ)、Zn(Ⅱ)、Cd(Ⅱ)三种离子萃取率均到达98%以上,实验结果较好。

二正丁基二硫代氨基甲酸锌配合物的量子化学研究

The geometric configurations of binuclear Zinc( complex Zn2[(n-Bu)2NCSS]4 and the ligand Na[(n-Bu)2 NCSS] have been optimized by B3LYP quantum chemical method. The electronic structures have been performed by density functional theory at B3LYP/6-31G* level. The electronic spectrums of the complex and ligand were calculated by ZINDO/S-CIS method. It is indicated from the calculation that: (1) The coordination effect of bridging ligand is bigger than that of chelating one, and the bridging ligands also translate more charge to Zn than the chelating one. (2) The calculated results about electronic spectrums are similarly to experimental measurement, and farther explain that absorption band at λ=267 nm of complex is assigned to two n → π* transitions :one arising from the bridging ligands and the another mainly arising from the chelating ligands;but absorption band at λ=236 nm of complex is assigned to π → π* transition which the electron mainly translates from the bridging ligands to the chelating ligands. (3) By consideration of delocalization and polar effects in coordination, the charge transfer from ligand to metal decreases the π-π and p-π conjugation effects in the chromophore group NCS2 and to increase the energy needed for the π → π* and n → π* transitions, and results in the absorption bands shifting towards the short wavelength direction.