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 dos...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.展开更多
The new coordination polymer formulated as [Zn(bim)2]?H2O)1.67 (Hbim = benzimidazole, bim = benzimidazolate) has been synthesized and shown by single-crystal structural analysis to be a three-dimensional network with ...The new coordination polymer formulated as [Zn(bim)2]?H2O)1.67 (Hbim = benzimidazole, bim = benzimidazolate) has been synthesized and shown by single-crystal structural analysis to be a three-dimensional network with the 4264 sodalite topology, constructed by tetrahedral building blocks, [Zn(bim)4]2-. Each sodalite cage defined by the 24 zinc atoms at the apexes centers hosts 10 water molecules (ca. 18% occupancy).展开更多
We report a fast in situ seeding approach based on zinc（II） porphyrin （ZnP） under white light irradiation, leading to uniform spherical platinum nanodendrites with tunable sizes. The platinum nanodendrites exhibit...We report a fast in situ seeding approach based on zinc（II） porphyrin （ZnP） under white light irradiation, leading to uniform spherical platinum nanodendrites with tunable sizes. The platinum nanodendrites exhibit significantly improved electrocatalytic activities toward oxygen reduction reaction （ORR） and methanol oxidation reaction （MOR） compared with commercial platinum black.展开更多
A kind of Levextrel resin separation process was developed for separation ofindium (III), gallium (III), and zinc (II) from aqueous sulfate solution with Levextrel resincontaining di(2-ethylhexyl) phosphoric acid (CL-...A kind of Levextrel resin separation process was developed for separation ofindium (III), gallium (III), and zinc (II) from aqueous sulfate solution with Levextrel resincontaining di(2-ethylhexyl) phosphoric acid (CL-P 204). The aim of the research is to collectpreliminary 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 batchoperation and column operation. The optimum pH, adsorption capacities and concentrations ofstripping agents for indium (III), gallium (III) were tested. The separation order of indium (III),gallium (III), and zinc (II) from sulfate solution with CL-P 204 Levextrel resin was found thatindium (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 separatedfrom each other by stripping with 0.1 and 0.5 mol/L hydrochloric acid, respectively. The recoveriesof three metal ions were all higher than 99 percent. The cyclic properties of this resin are well.展开更多
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 analy...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.展开更多
A double-T-shaped ligand （H4BPTC） and bis（2-benzimidazole）alkanes as the spacers have been firstly used to direct the assembly of a 2D coordination polymer with wavy parquet network topology, [Zn（BPTC）0.5（H2C2...A double-T-shaped ligand （H4BPTC） and bis（2-benzimidazole）alkanes as the spacers have been firstly used to direct the assembly of a 2D coordination polymer with wavy parquet network topology, [Zn（BPTC）0.5（H2C2EIm）（H2O）]n （1, C24H18ZnN4O5, Mr = 507.79, H4BPTC = biphenyl-3,3＇,4,4＇-tetracarboxylic acid, H2C2EIm = 2,2＇-（1,2-ethanediyl）-bis（1H-benzi- midazole）, which was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/n with a = 1.1844（5）, b = 1.4019（5）, c = 1.4026（5） nm, β = 108.359（5）°, V = 2.2104（15） nm3, Z = 4, Dc = 1.526 g/cm3, μ（MoKα） = 1.156 mm-1, F（000） = 1040, S = 1.038, the final R = 0.0427 and wR = 0.0793 for 3834 reflections with I 2σ（I）. The compound units are linked through BPTC ligands into a wavilness parquet 2D layer and further connected into a 3D framework via π-π packing interactions between the adjacent H2C2EIm ligands and weak N-H…O hydrogen bonding between uncoordinated carboxylate and the nitrogen atoms of H2C2EIm as well as the free water molecules.展开更多
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 tem...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.展开更多
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 s...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.展开更多
2,4-Bis(3,5-dimethylpyrazol-1-yl)-6-methoxyl-1,3,5-triazine(bpt) has been synthesized by using a new, simple and general method with high yields. Reactions of bpt with Ni(ClO4)2·6H2O and Zn(ClO4)2·6H2O in me...2,4-Bis(3,5-dimethylpyrazol-1-yl)-6-methoxyl-1,3,5-triazine(bpt) has been synthesized by using a new, simple and general method with high yields. Reactions of bpt with Ni(ClO4)2·6H2O and Zn(ClO4)2·6H2O in methanol gave mononuclear complex [Ni(bpt)2]· (ClO4)2·H2O and ternary complex [Zn(mpt)2(dmp)](ClO4)2 respectively, where mpt (2,4-dimethoxy-6-(3,5-dimethyl- pyrazol-1-yl)-1,3,5-triazine) and dmp(3,5-dimethylpyrazole) are the alcoholysis products of bpt in the presence of Zn2+ ion. A possible mechanism for this catalytic reaction was proposed. X-ray crystal structure for ligand bpt, Ni and Zn complexes are reported. The protonated form of the ligand bpt crystallizes as its perchlorate salt including one molecule of water, [Hbpt·H2O·ClO4]. The proton is located on one pyrazole N-atom. [Hbpt·H2O·ClO4], in which [Hbpt]+ is in cis-cis conformation, are packed in slipped stacks of approximately parallel layers. The Π -Π overlap interactions between the non-protonized pyrazoles of the adjacent layers give a zigzag arrangement of the planar aromatic [Hbpt]+ molecules. In [Ni(bpt)2](ClO4)2·H2O, bpt are meridionally three-coordinated with Ni2+. The coordination sphere around Ni2+ is a slightly distorted square bipyramid, where four pyrazole nitrogen atoms occupy the basal positions and two triazine nitrogen atoms the apical one. In [Zn(mpt)2(dmp)](ClO4)2, the Zn atom is coordinated with a pair of bidentate mpt ligands and one monodentate dmp ligand, forming a distorted trigonal bipyramid, where the two triazine nitrogen atoms of mpt and one nitrogen atom of dmp occupy the basal positions, and the two pyrazole nitrogen atoms of mpt the apical one.展开更多
The structures of [Cu(S_2CN(CH_2)_4)_2] (1) and [Zn_2(S_2CN-(CH_2)_4)_4] (2) have been determined by X-ray crystallography analysis. They are all isomorphous and triclinic, space group of P1, with Z=1. The lattice p...The structures of [Cu(S_2CN(CH_2)_4)_2] (1) and [Zn_2(S_2CN-(CH_2)_4)_4] (2) have been determined by X-ray crystallography analysis. They are all isomorphous and triclinic, space group of P1, with Z=1. The lattice parameters of compound 1 is: a=0.63483(2) nm, b=0.74972(3) nm, c=0.78390(1) nm, α=75.912(2)°, β=78.634(2)° and γ=86.845(2)°; compound 2: a=0.78707(6) nm, b=0.79823(6) nm, c=1.23246(9) nm, α=74.813(2)°, β=73.048(2)° and γ=88.036(2)°. The copper atom is located on a crystallographic inversion center and zinc atom lies across centers of symmetry. The Cu(II) ion has a square-planar geometry while Zn(II) has a distorted tetrahedral geometry. The thermal gravity (TG) data indicate that no structural transitions in the two compounds were abserved and the decomposition products can adsorb gas. Also they all have a high thermal stability.展开更多
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 chemi...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.展开更多
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...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.展开更多
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...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.展开更多
A zinc(II) complex [Zn(bdc)(py)·H 2O] n (bdc=1,4-benzenedicarboxylate, py=pyridine) has been prepared and characterized. Single crystal X-ray diffraction analysis reveals that the complex crystallizes in the mo...A zinc(II) complex [Zn(bdc)(py)·H 2O] n (bdc=1,4-benzenedicarboxylate, py=pyridine) has been prepared and characterized. Single crystal X-ray diffraction analysis reveals that the complex crystallizes in the monoclinic space group P2 1/n with a=0.84823(3), b=0.91440(3), c=1.65141(2) nm, β=91.243(2)°, V=1.28057(6) nm 3, Z=4. The coordination geometry at each Zn(II) center is a distorted tetrahedron. Two independent bdc ligands in a herringbone pattern link alternatively four-coordinated Zn(II) centers into a one-dimensional polymeric chain. Hydrogen bonds among coordinated water molecules and uncoordinated oxygen atoms of two independent bdc ligands from different polymeric chains extend one-dimensional polymeric chains into a three-dimensional structure.展开更多
基金supported by the National Natural Science Foundation of China (No. 50778066)the National Science and Technology Support Program of China(No. 2006BAJ04A13)+1 种基金the Program for New Century Excellent Talents in University from the Ministry of Education of China (No. NCET-08-0181)the China Postdoctoral Science Foundation (No. 200801338)
文摘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.
基金supported by the National Natural Science Foundation of China(Grant No.20131020)the Ministry of Education of China(Grant No.01134).
文摘The new coordination polymer formulated as [Zn(bim)2]?H2O)1.67 (Hbim = benzimidazole, bim = benzimidazolate) has been synthesized and shown by single-crystal structural analysis to be a three-dimensional network with the 4264 sodalite topology, constructed by tetrahedral building blocks, [Zn(bim)4]2-. Each sodalite cage defined by the 24 zinc atoms at the apexes centers hosts 10 water molecules (ca. 18% occupancy).
基金Acknowledgements This work was partially supported by the National Basic Research Program （973 Program） of China （No. 2012CB215500）, the National High-tech R＆D Program（863 Program） of China （No. 2011AA11A273）, and the National Natural Science Foundation of China （NSFC, Nos. 21003114 and 21103163）. The authors thank Professor John A. Shelnutt at Georgia University, USA for fruitful discussions.
文摘We report a fast in situ seeding approach based on zinc（II） porphyrin （ZnP） under white light irradiation, leading to uniform spherical platinum nanodendrites with tunable sizes. The platinum nanodendrites exhibit significantly improved electrocatalytic activities toward oxygen reduction reaction （ORR） and methanol oxidation reaction （MOR） compared with commercial platinum black.
文摘A kind of Levextrel resin separation process was developed for separation ofindium (III), gallium (III), and zinc (II) from aqueous sulfate solution with Levextrel resincontaining di(2-ethylhexyl) phosphoric acid (CL-P 204). The aim of the research is to collectpreliminary 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 batchoperation and column operation. The optimum pH, adsorption capacities and concentrations ofstripping agents for indium (III), gallium (III) were tested. The separation order of indium (III),gallium (III), and zinc (II) from sulfate solution with CL-P 204 Levextrel resin was found thatindium (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 separatedfrom each other by stripping with 0.1 and 0.5 mol/L hydrochloric acid, respectively. The recoveriesof three metal ions were all higher than 99 percent. The cyclic properties of this resin are well.
基金supported by the Science and Technology Research Projects of the Education Department of Jilin Province (No. 2011. 459)
文摘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.
基金supported by the research grant of Phytochemistry Key Laboratory of Shaanxi Province(No.11JS006,11JS007)the Scientific Research Fund of shaanxi Provincial Education Department(No.11JK0603)
文摘A double-T-shaped ligand （H4BPTC） and bis（2-benzimidazole）alkanes as the spacers have been firstly used to direct the assembly of a 2D coordination polymer with wavy parquet network topology, [Zn（BPTC）0.5（H2C2EIm）（H2O）]n （1, C24H18ZnN4O5, Mr = 507.79, H4BPTC = biphenyl-3,3＇,4,4＇-tetracarboxylic acid, H2C2EIm = 2,2＇-（1,2-ethanediyl）-bis（1H-benzi- midazole）, which was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/n with a = 1.1844（5）, b = 1.4019（5）, c = 1.4026（5） nm, β = 108.359（5）°, V = 2.2104（15） nm3, Z = 4, Dc = 1.526 g/cm3, μ（MoKα） = 1.156 mm-1, F（000） = 1040, S = 1.038, the final R = 0.0427 and wR = 0.0793 for 3834 reflections with I 2σ（I）. The compound units are linked through BPTC ligands into a wavilness parquet 2D layer and further connected into a 3D framework via π-π packing interactions between the adjacent H2C2EIm ligands and weak N-H…O hydrogen bonding between uncoordinated carboxylate and the nitrogen atoms of H2C2EIm as well as the free water molecules.
文摘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.
基金Supported by the Science and Technology Research Projects of the Education Office of Jilin Province (No. 2009. 272)
文摘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.
基金the National Natural Science Foundation of China (Grant No. 29671034) and Natural Science Foundation of Guangdong Province (Grant Nos. 990128,974174).
文摘2,4-Bis(3,5-dimethylpyrazol-1-yl)-6-methoxyl-1,3,5-triazine(bpt) has been synthesized by using a new, simple and general method with high yields. Reactions of bpt with Ni(ClO4)2·6H2O and Zn(ClO4)2·6H2O in methanol gave mononuclear complex [Ni(bpt)2]· (ClO4)2·H2O and ternary complex [Zn(mpt)2(dmp)](ClO4)2 respectively, where mpt (2,4-dimethoxy-6-(3,5-dimethyl- pyrazol-1-yl)-1,3,5-triazine) and dmp(3,5-dimethylpyrazole) are the alcoholysis products of bpt in the presence of Zn2+ ion. A possible mechanism for this catalytic reaction was proposed. X-ray crystal structure for ligand bpt, Ni and Zn complexes are reported. The protonated form of the ligand bpt crystallizes as its perchlorate salt including one molecule of water, [Hbpt·H2O·ClO4]. The proton is located on one pyrazole N-atom. [Hbpt·H2O·ClO4], in which [Hbpt]+ is in cis-cis conformation, are packed in slipped stacks of approximately parallel layers. The Π -Π overlap interactions between the non-protonized pyrazoles of the adjacent layers give a zigzag arrangement of the planar aromatic [Hbpt]+ molecules. In [Ni(bpt)2](ClO4)2·H2O, bpt are meridionally three-coordinated with Ni2+. The coordination sphere around Ni2+ is a slightly distorted square bipyramid, where four pyrazole nitrogen atoms occupy the basal positions and two triazine nitrogen atoms the apical one. In [Zn(mpt)2(dmp)](ClO4)2, the Zn atom is coordinated with a pair of bidentate mpt ligands and one monodentate dmp ligand, forming a distorted trigonal bipyramid, where the two triazine nitrogen atoms of mpt and one nitrogen atom of dmp occupy the basal positions, and the two pyrazole nitrogen atoms of mpt the apical one.
基金ProjectsupportedbytheKeyProjectofEducationalAdministrationofShandongProvince (No .J0 1C0 5 )andtheOutstandingAdult YoungScien tificResearchEncouragingFoundationofShandongProvince (No .O1BS18)
文摘The structures of [Cu(S_2CN(CH_2)_4)_2] (1) and [Zn_2(S_2CN-(CH_2)_4)_4] (2) have been determined by X-ray crystallography analysis. They are all isomorphous and triclinic, space group of P1, with Z=1. The lattice parameters of compound 1 is: a=0.63483(2) nm, b=0.74972(3) nm, c=0.78390(1) nm, α=75.912(2)°, β=78.634(2)° and γ=86.845(2)°; compound 2: a=0.78707(6) nm, b=0.79823(6) nm, c=1.23246(9) nm, α=74.813(2)°, β=73.048(2)° and γ=88.036(2)°. The copper atom is located on a crystallographic inversion center and zinc atom lies across centers of symmetry. The Cu(II) ion has a square-planar geometry while Zn(II) has a distorted tetrahedral geometry. The thermal gravity (TG) data indicate that no structural transitions in the two compounds were abserved and the decomposition products can adsorb gas. Also they all have a high thermal stability.
基金This work was supported by the NNSFC (20476034 NSFC/HKUST43)+1 种基金 NSF of Guangdong Province (000489) and SRF for ROCS State Education Ministry.
文摘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.
基金Supported by the Natural Science Foundation of Henan Province (No. 102300410221)the Natural Science Foundation of Nanyang Normal University (No. ZX2010012)Project supported by the Young Core Instructor from the Education Commission of Henan Province
文摘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.
基金Supported by the foundation for Dr of Jianggangshan University (JZ10044)the NSF of Guangxi Province (No. 0832090)the NSF of the Education Committee of Guangxi Province (No. 201012MS203)
文摘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.
基金ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .2 982 5 10 3) ,theNaturalScienceFoundation (No .8982 0 0 3)ofFujianProvinceandChineseAcademyofSciences
文摘A zinc(II) complex [Zn(bdc)(py)·H 2O] n (bdc=1,4-benzenedicarboxylate, py=pyridine) has been prepared and characterized. Single crystal X-ray diffraction analysis reveals that the complex crystallizes in the monoclinic space group P2 1/n with a=0.84823(3), b=0.91440(3), c=1.65141(2) nm, β=91.243(2)°, V=1.28057(6) nm 3, Z=4. The coordination geometry at each Zn(II) center is a distorted tetrahedron. Two independent bdc ligands in a herringbone pattern link alternatively four-coordinated Zn(II) centers into a one-dimensional polymeric chain. Hydrogen bonds among coordinated water molecules and uncoordinated oxygen atoms of two independent bdc ligands from different polymeric chains extend one-dimensional polymeric chains into a three-dimensional structure.
