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-c...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.展开更多
The title complex [ZN8II(4-APha)8(CH3COO)8(CH3CH2OH)2]n (1, 4-APha = 4-ami- nophenylhydroxamic acid) has been prepared under solvothermal conditions. It has been characterized by X-ray single-crystal diffracti...The title complex [ZN8II(4-APha)8(CH3COO)8(CH3CH2OH)2]n (1, 4-APha = 4-ami- nophenylhydroxamic acid) has been prepared under solvothermal conditions. It has been characterized by X-ray single-crystal diffraction, IR and elemental analysis. The crystal belongs to the monoclinic system, space group C2/c with a = 39.074(4), b = 9.9645(8), c=38.846(3) A, β = 136.438°, V= 10423.1(14) A3, C84H118N16O39Zn8, Mr = 2498.90, Z = 4, Dc = 1.592 g/cm3,μ= 1.900 mm-1, F(000) = 5144, the final R = 0.1036 and wR = 0.2953. This complex possesses a 3-D structure which is constructed from 1-D chain motifs linked by the 4-APha" ligands. The luminescent property of the title complex has been investigated.展开更多
Unlike natural organic matter(NOM), wastewater organic matter(WWOM) from wastewater treatment plant effluents has not been extensively studied with respect to complexation reactions with heavy metals such as copper or...Unlike natural organic matter(NOM), wastewater organic matter(WWOM) from wastewater treatment plant effluents has not been extensively studied with respect to complexation reactions with heavy metals such as copper or zinc. In this study, organic matter from surface waters and a wastewater treatment plant effluent were concentrated by reverse osmosis(RO) method. The samples were treated in the laboratory to remove trace metals and major cations. The zinc complexing properties of both NOM and the WWOM were studied by square wave anodic stripping voltammetry(SWASV). Experimental data were compared to predictions using the Windermere Humic Aqueous Model(WHAM) Version VI. We found that the zinc binding of WWOM was much stronger than that of NOM and not well predicted by WHAM. This suggests that in natural water bodies that receive wastewater treatment plant effluents the ratio of WWOM to NOM must be taken into account in order to accurately predict free zinc activities.展开更多
Using N-P-acetamidobenzenesulfonyl-glycine acid (abbreviated as abglyH2) as a ligand, two zinc(II) complexes [Zn(abglyH)2(bipy)2(H2O)2], (1) and {[Znz(abgly)2(bipy)2(H2O)2]. 2(H2O)}n (2) (bipy =...Using N-P-acetamidobenzenesulfonyl-glycine acid (abbreviated as abglyH2) as a ligand, two zinc(II) complexes [Zn(abglyH)2(bipy)2(H2O)2], (1) and {[Znz(abgly)2(bipy)2(H2O)2]. 2(H2O)}n (2) (bipy = 4,4'-bipyridine) have been synthesized under mild conditions and characterized by IR, elemental analysis and X-ray diffraction analysis. Complex 1 is a monomeric compound, which is further assembled by intermolecular hydrogen bonds and π-π interactions into a 3-D supramolecular network. Complex 2 adopts a one-dimensional double chain structure and is further linked by hydrogen bonds to form a 2-D structure. Fluorescent analysis shows that complex 1 has an emissive maximum at 337 nm and complex 2 exhibits an emissive maximum at 339 nm in the solution state at room temperature.展开更多
Fluorescent mesoporous silica nanoparticles functionalized with carboxyl group(Znq-CMSCOOH) were successfully synthesized by in situ formation route of 8-hydroxyquinolinate zinc complexes in channels of mesoporous sil...Fluorescent mesoporous silica nanoparticles functionalized with carboxyl group(Znq-CMSCOOH) were successfully synthesized by in situ formation route of 8-hydroxyquinolinate zinc complexes in channels of mesoporous silica nanoparticles and post-grafting of carboxyl group on the surface. Moreover,the particle size and structural properties of Znq-CMS-COOH were characterized by transmission electron microscopy(TEM),field emission scanning electron microscopy(FE-SEM),dynamic light scattering(DLS),Fourier transform infrared spectroscopy(FT-IR),UV-vis spectrometer, fluorescence spectrometer and nitrogen adsorption-desorption measurements. The obtained results suggest that the Znq-CMS-COOH presents the uniform spherical shape with the mean diameter of about 85 nm and the obvious wormhole arrangement mesoporous. In addition, the Znq-CMS-COOH possesses green fluorescence with the emission peaks at 495 nm. So the Znq-CMS-COOH, which is beneficial to further modification and tracing, might be a great potential carrier for applying in drug delivery system in the future.展开更多
Two zinc complexes, [Zn(MPIP)Cl2](1) and [Zn(EPIP)Cl2](2), where MPIP = 1-(methoxymethyl)-3-(pyridin-2-yl)imidazo[1,5-a]pyridine and EPIP = 1-(ethoxymethyl)-3-(pyridin-2-yl)imidazo[1,5-a]pyridine, were synthesized und...Two zinc complexes, [Zn(MPIP)Cl2](1) and [Zn(EPIP)Cl2](2), where MPIP = 1-(methoxymethyl)-3-(pyridin-2-yl)imidazo[1,5-a]pyridine and EPIP = 1-(ethoxymethyl)-3-(pyridin-2-yl)imidazo[1,5-a]pyridine, were synthesized under solvothermal conditions. The etheric ligand MPIP was formed in situ via metal ligand reaction between(3-(pyridin-2-yl)imidazo[1,5-a]pyridin-1-yl)methanol(HPIPM) and methanol solvent. Similarly, the ligand EPIP was generated in situ from the reaction of HPIPM with ethanol solvent. The structures of 1 and 2 were characterized by X-ray single-crystal diffraction analysis. They are four-coordinated mononuclear complexes, and the ZnII ion of 1 and 2 displays distorted tetrahedral geometry. The photoluminescent properties of 1 and 2 were investigated. Strong emissions were observed for both 1 and 2, which were ascribed as the intraligand(π-π*) fluorescent transitions. This paper provides a simple and efficient method for the synthesis of etheric compounds.展开更多
A zinc complex, [Zn(iso)_2(H_2O)_4](iso=C_6H_4NO_2^-), was synthesized and characterized by elemental analysis, thermal analysis and IR spectrum studies. The crystal structure of the complex was determined by X-ray di...A zinc complex, [Zn(iso)_2(H_2O)_4](iso=C_6H_4NO_2^-), was synthesized and characterized by elemental analysis, thermal analysis and IR spectrum studies. The crystal structure of the complex was determined by X-ray diffraction. The crystal crystallizes in the triclinic system, molecular formula ZnC12H16N2O8, Mr=381.64, space group P with a = 6.338(1), b =6.919(1), c=9.277(1), α=96.28(1), β=104.91(1), γ=112.85(1)°, V=352.12(9)?3, Z=1, Dc=1.80g?cm-3 and F(000)=196, μ =1.791mm-1. The crystal structure was solved by direct methods for final R=0.0204 and Rw=0.0542 for 1258 observed reflections with [Fo>4σ(Fo)]. The crystal structure reveals that zinc ion is trans-octahedral with two pyridyl nitrogens and two aque oxygens at the equational positions and two aqua oxygens at the axial positions. The complex forms a three-dimensional network through intermolecular hydrogen bonds.展开更多
The title complex is a new binuclear Zn(Ⅱ) with chelate ligand of Schiff base containing S and N atom.The complex crystallizes in the orthorhombicspace group Pccn,with a=12.338(9),b=16.666(8),c=17.503(6),V=3599(6),Mr...The title complex is a new binuclear Zn(Ⅱ) with chelate ligand of Schiff base containing S and N atom.The complex crystallizes in the orthorhombicspace group Pccn,with a=12.338(9),b=16.666(8),c=17.503(6),V=3599(6),Mr=723.52,Z=4,Dx=1.34 g/cm3,μ=15.22 cm-1,F(000)=1488.The structure was solved by direct methods and the final R=0.078.The crystal consists of discrete molecules with symmetric center at the center of the fourmembered ring consisting of two Zn atoms and two O atoms.展开更多
The self-assembly of clusters in inorganic systems is an interesting subject. The self-assembly of big molecules has been well established in biological systems. In addition, the coordination chemistry of metal-sulfur...The self-assembly of clusters in inorganic systems is an interesting subject. The self-assembly of big molecules has been well established in biological systems. In addition, the coordination chemistry of metal-sulfur-nitrogen cluster complexes has been a very active and attracting field for many years as a result of the novelty and versatility of the crystal structures and reactivities of such clusters, as well as their potential applications as the models for the active sites in non-heme proteins. At the same time, there is currently considerable interest in the formation of metal complexes with heterocyclic ligands because of the diverse characteristics of ligands and their consequential wide range of applications.展开更多
A convenient colorimetric approach for visual detection of melamine in raw milk was realized by using gold nanoparticles(AuNPs)stabilized by an unsymmetrical terpyridyl zinc complex with a thymine fragment at one term...A convenient colorimetric approach for visual detection of melamine in raw milk was realized by using gold nanoparticles(AuNPs)stabilized by an unsymmetrical terpyridyl zinc complex with a thymine fragment at one terminal and a quaternary ammonium salt at the other.Even without pre-addition of melamine or relative additives,obvious color change from red to blue was observed by naked eye in the presence of trace amount of melamine,which was attributed to the alternation of aggregation state of AuNPs caused by the selective binding between the thymine fragment and melamine via triple hydrogenbonding interactions.Remarkably,the detection limit for melamine was as low as 2.4 ppb,providing a highly sensitive and efficient approach for the visual detection of melamine.展开更多
The title complex was prepared from self-assembly reaction of La(NO3)3(6H2O, Zn(NO3)2(6H2O, m-cyanobenzoic acid (m-CNC6H4COOH) and pyridine (Py) in refluxing ethanol and its structure was determined by single-...The title complex was prepared from self-assembly reaction of La(NO3)3(6H2O, Zn(NO3)2(6H2O, m-cyanobenzoic acid (m-CNC6H4COOH) and pyridine (Py) in refluxing ethanol and its structure was determined by single-crystal X-ray diffraction. Crystallographic data: C94H62N12La2O22Zn2, Mr = 2120.12, triclinic space group P, a = 13.2219(5), b = 13.2713(5), c = 14.1987(6) ?, (???69.156(1), ( = 84.034(1), ( = 89.400(1) (, V = 2314.9(2) ?3, Z = 1, Dc = 1.521 g/cm3, F(000) = 1060, ( (MoK() = 14.94 cm-1, the final R = 0.043 and wR = 0.117 for 6381 unique reflections with I > 2((I). Crystal structure determination shows that the neighboring lanthanum(III) and zinc(II) ions are bridged by three bidentate m-cyanobenzonate ligands in the syn-syn fashion to form a pair of dinuclear [LaZn(m-CNC6H4COO)3(Py)(C2H5OH)] subunits, being linked together by two bidentate and two tridentate m-cyanobenzonate groups in the syn-syn and syn-anti modes, respectively, to construct a tetranuclear La-Zn complex [La2Zn2(m-CNC6H4COO)10(Py)2(C2H5OH)2].展开更多
A series of anilido-imine zinc complexes ortho-C6H4(CH:NAr)(NAr)ZnEt[Ar=2,6-Me2C6H3(2a); Ar=2,6-Et2C6H3(2b)] was synthesized, characterized and used as catalysts for the ring-opening polymerization of L-lacti...A series of anilido-imine zinc complexes ortho-C6H4(CH:NAr)(NAr)ZnEt[Ar=2,6-Me2C6H3(2a); Ar=2,6-Et2C6H3(2b)] was synthesized, characterized and used as catalysts for the ring-opening polymerization of L-lactide in the presence of benzyl alcohol. The effects of the structures of catalysts and reaction conditions on the reactivity were investigated. The polymerization of L-lactide initiated by each of these complexes was found to take place with a controlled manner.展开更多
A novel zinc(II) complex, Zn(IBT)2 (1, H1BT = 5-(4-((1H-imidazol-1-yl)methyl)- phenyl)-2H-tetrazole) has been synthesized with Zn(NO3)2·6H2O, 4-(imidazol-l-ylmethyl)benzonnitrile (IBN) and NaN3 ...A novel zinc(II) complex, Zn(IBT)2 (1, H1BT = 5-(4-((1H-imidazol-1-yl)methyl)- phenyl)-2H-tetrazole) has been synthesized with Zn(NO3)2·6H2O, 4-(imidazol-l-ylmethyl)benzonnitrile (IBN) and NaN3 by the hydrothermal method, and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Crystallographic data for 1: C22H18N12Zn, Mr = 515.85, orthorhombic, Pbcn, a = 16.0567(15), b = 9.5316(9), c = 14.6107(14) A, V= 2236.1(4) A3, Z= 4, Dc = 1.532 g/cm3,μ = 1.138 mm-1, F(000) = 1056, R = 0.0350 and wR = 0.0888 for 1438 observed reflections (I 〉 2σ(I)) and the goodness-of-fit S = 1.002 on F2. The crystal structural analysis revealed that complex 1 exhibits a rare two-dimensional homochiral wave-like layer structure. In addition, the photoluminescence of complex 1 was studied in the solid state at room temperature together with its theoretical analysis.展开更多
The title complex [bis(dien)zinc(Ⅱ)] zinc(Ⅱ) tetrachloride was synthesized and characterized by X-ray single-crystal diffraction, elemental analysis, electric conductivity, IR and electronic spectra. The compo...The title complex [bis(dien)zinc(Ⅱ)] zinc(Ⅱ) tetrachloride was synthesized and characterized by X-ray single-crystal diffraction, elemental analysis, electric conductivity, IR and electronic spectra. The compound crystallizes in the tetragonal system, space group I^-4 with a = 10.250(3), b = 10.250(3), c = 9.054(2) V = 951.2(5)A^3, Mr = 486.95, Z = 2, F(000) = 504, Dc = 1.700 g/cm&3,μ = 3.083 mm^-1, λ. = 0.71073A, the final R = 0.0226 and wR = 0.0642. The symmetric crystal smacture consists of a zinc complex cation [Zn(dien)2]^2+ and a zinc tetrachloride aniOn [ZnC14]^2-, forming a three, dimensional framework through intrmnolecular and intermolecular hydrogen bonds.展开更多
A new zinc(II)complex of formula[ZnCl2(L1)2](1)[L1=2‐(2‐thienyl)‐1‐(2‐thienylmethyl)‐1Hbenzimidazole]was synthesized and fully characterized by nuclear magnetic resonance and infrared spectroscopy,elemental anal...A new zinc(II)complex of formula[ZnCl2(L1)2](1)[L1=2‐(2‐thienyl)‐1‐(2‐thienylmethyl)‐1Hbenzimidazole]was synthesized and fully characterized by nuclear magnetic resonance and infrared spectroscopy,elemental analysis,electrospray ionization high‐resolution mass spectrometry,and thermogravimetric analysis.The molecular structure was confirmed by single‐crystal X‐ray diffraction.Complex1consists of mononuclear tetrahedral zinc(II)units with a locked geometry resulting from weak intramolecular S···?and?–?interligand interactions.The benzimidazole ligand and its zinc(II)complex were readily obtained through a simple synthetic route.The catalytic activity of1was investigated in the coupling of carbon dioxide with epoxides to produce cyclic carbonates,and a series of parameters were evaluated.The complex efficiently catalyzed the transformation of various epoxides under solvent‐free conditions,with good conversions,turnover numbers,and turnover frequencies.展开更多
Reaction of sulfonylated binaphthol [2-hydroxy-2'-tosyloxy-l,l-binaphthyl (la, Ts-Binol) or 2-hydroxy-2'- (phenylsulfonyloxy)-l,l-binaphthyl (lb, Ps-Binol)] with 1 equiv, of ZnEt2 afforded zinc complexes [(Ys...Reaction of sulfonylated binaphthol [2-hydroxy-2'-tosyloxy-l,l-binaphthyl (la, Ts-Binol) or 2-hydroxy-2'- (phenylsulfonyloxy)-l,l-binaphthyl (lb, Ps-Binol)] with 1 equiv, of ZnEt2 afforded zinc complexes [(Ys-Binol)ZnEt]2 (2a) and [(Ps-Binol)ZnEt]2 (2b). Further reaction of zinc complexes 2a and 2b with benzyl alco- hol (BnOH) gave the zinc benzyloxide [(Ts-Binol)2Zn2(OBn)2]2 (3a) and [(Ps-Binol)2Znz(OBn)2]2 (3b). Alterna- tively, the zinc benzyloxides 3a and 3b could also be obtained by reaction of compound la or lb with Zn(OBn)2 (in situ reaction of ZnEt2 and BnOH). The complexes were fully characterized by elemental analyses and spectroscopic analyses, and complexes 2a, 2b and 3a were further characterized by single-crystal X-ray analyses. The catalytic activities of these zinc complexes towards ring-opening polymerization of ε-caprolactone and D,L-lactide were studied.展开更多
Reaction of Zn(ClO4)2·6H2O with septadentate 2,6-bis[bis(2-benzimidazolylme-thyl)amino methyl]-4-methylphenol (Hbbap) and sodium isonicotinate yielded a dinuclear zinc complex[Zn2(bbap) (Iso) (Hiso)] (ClO4)2·...Reaction of Zn(ClO4)2·6H2O with septadentate 2,6-bis[bis(2-benzimidazolylme-thyl)amino methyl]-4-methylphenol (Hbbap) and sodium isonicotinate yielded a dinuclear zinc complex[Zn2(bbap) (Iso) (Hiso)] (ClO4)2·[Zn2 (bbap) (Iso) (H2O)] (ClO4)2·4H2O(1a·1b·4H2O). Hiso isisonicotinic acid and Iso is isonicotinate anion. The structure has been established by X-raycrystallography and shows that the two zinc ions are bridged by the phenoxy unit of bbap- ligand,and the presence of unusual monodentate O-coordination of carboxylate group from isonicotinicacid. The coordination geometry around the zinc ion is approximately trigonal bipyramidal.展开更多
The reaction of bidentate N,N-dimethylaniline-arylamido ligands,o-C6H4NMe2(CH2NHAr)(Ar =Ph,1a;2,6-Me2C6H3,1b; 2,6-Et2C6H3,1c; 2,6-ipr2C6H3,1d) with ZnEt2 yields the complexes o-C6H4(NMe2)(CH2NAr)ZnEt (2a-2d)...The reaction of bidentate N,N-dimethylaniline-arylamido ligands,o-C6H4NMe2(CH2NHAr)(Ar =Ph,1a;2,6-Me2C6H3,1b; 2,6-Et2C6H3,1c; 2,6-ipr2C6H3,1d) with ZnEt2 yields the complexes o-C6H4(NMe2)(CH2NAr)ZnEt (2a-2d),respectively.All the complexes were characterized by 1H and 13C NMR spectroscopy and elemental analyses.It was found that all the zinc complexes were efficient catalysts for the ring-opening polymerization of L-lactide in the presence of benzyl alcohol with good molecular weight control and narrow polydispersity.展开更多
Two new ternary complexes [Zη(3-aba)2(phen)]·2.58H2O 1 and {[Cd(3-aba)- (phen)2]·(NO3)·(1.5H2O) }n 2 (3-aba = 3-aminobenzoic acid anion, phen = 1,10-phenanthroline) were synthesized and c...Two new ternary complexes [Zη(3-aba)2(phen)]·2.58H2O 1 and {[Cd(3-aba)- (phen)2]·(NO3)·(1.5H2O) }n 2 (3-aba = 3-aminobenzoic acid anion, phen = 1,10-phenanthroline) were synthesized and characterized by elemental analysis, IR, UV spectrum and X-ray diffraction. Complex 1 crystallizes in the rhombohedral system, space group R3 with a = 3.5733(3), b = 3.5733(3), c = 1.1231(2) nm; V= 12.419(3) nm^3, C26H25.17NaO6.58Zn, Mr= 564.37, Z= 18, F(000) = 5253, μ= 0.937 mm^-1, Dc = 1.358 g/cm^3, R = 0.0668 and wR = 0.1690 for 2424 observed reflections (I〉 2σ(I)). Complex 2 belongs to the tetragonal system, space group P4/ncc with a = 2.88451(10), b = 2.88451(10), c = 1.55571(11) nm, V= 12.9441(11) nm^3, C31H25CdN6O6.50, Mr = 697.97, Z = 16, F(000) = 5648,μ=0.727 mm^-1, Dc= 1.433 g/cm^3, R = 0.0607 and wR = 0.1742 for 3468 observed reflections (I 〉 2σ(I)). Complex 1 displays a mononuclear structure. The carboxylate group of 3-aminobenzoic acid anion coordinates to Zn(Ⅱ) in a chelating bidentate mode, and the nitrogen atom of the ligand does not involve in coordination. Complex 2 exhibits a one-dimensional chain structure with 3-aminobenzoic acid anion coordinating to Cd(Ⅱ) in a μ2-bridging mode through its nitrogen atom and one of its oxygen atoms.展开更多
A novel 1,2,3-triazolyl-containing ligand (H2L) with long donor arms extending from the central pyridyl linker was synthesized by click cycloaddition of 2,6-bis(azidomethyl)pyri- line and 2-((prop-2-yn-1-yl(pyr...A novel 1,2,3-triazolyl-containing ligand (H2L) with long donor arms extending from the central pyridyl linker was synthesized by click cycloaddition of 2,6-bis(azidomethyl)pyri- line and 2-((prop-2-yn-1-yl(pyridin-2-ylmethyl)amino)methyl)phenol. Further treatment of the igand H2L with zinc(II) perchlorate in the presence of triethylaminc, followed by anion exchange vith Na[BPh4], provided a dinuclear zinc(II) complex [Zn2L][BPh4]E-2DMF (1). Complex 1 crystallizes in monoclinic, space group P21 with a = 10.4873(4), b = 14.9078(5), c = 25.8620(9) A, = 94.566(2)°, V = 4030.5(2) A3, Z = 2,μ= 0.657 mm-1, Dc = 1.324 Mg/m3, T = 296(2) K, C93H91N13B2O4Zn2, Mr = 1607.19, F(000) = 1684, S = 0.958, R = 0.0271 and wR = 0.0607. In the tructurc of cation, the phenolate oxygen atoms of ligand act as the bridging nodes to form a hombic Zn2(OAr)2 core.展开更多
基金The project was supported by the Education Office of Jilin Province (No. 0047)
文摘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.
基金Supported by Department of Education of Shaanxi Province(2013JK0664)
文摘The title complex [ZN8II(4-APha)8(CH3COO)8(CH3CH2OH)2]n (1, 4-APha = 4-ami- nophenylhydroxamic acid) has been prepared under solvothermal conditions. It has been characterized by X-ray single-crystal diffraction, IR and elemental analysis. The crystal belongs to the monoclinic system, space group C2/c with a = 39.074(4), b = 9.9645(8), c=38.846(3) A, β = 136.438°, V= 10423.1(14) A3, C84H118N16O39Zn8, Mr = 2498.90, Z = 4, Dc = 1.592 g/cm3,μ= 1.900 mm-1, F(000) = 5144, the final R = 0.1036 and wR = 0.2953. This complex possesses a 3-D structure which is constructed from 1-D chain motifs linked by the 4-APha" ligands. The luminescent property of the title complex has been investigated.
文摘Unlike natural organic matter(NOM), wastewater organic matter(WWOM) from wastewater treatment plant effluents has not been extensively studied with respect to complexation reactions with heavy metals such as copper or zinc. In this study, organic matter from surface waters and a wastewater treatment plant effluent were concentrated by reverse osmosis(RO) method. The samples were treated in the laboratory to remove trace metals and major cations. The zinc complexing properties of both NOM and the WWOM were studied by square wave anodic stripping voltammetry(SWASV). Experimental data were compared to predictions using the Windermere Humic Aqueous Model(WHAM) Version VI. We found that the zinc binding of WWOM was much stronger than that of NOM and not well predicted by WHAM. This suggests that in natural water bodies that receive wastewater treatment plant effluents the ratio of WWOM to NOM must be taken into account in order to accurately predict free zinc activities.
基金Supported by the NNSFC (Nos. 20471046 and 20771054)Henan Tackle Key Problem of Science and Technology (Nos. 072102270030 and 072102270034)
文摘Using N-P-acetamidobenzenesulfonyl-glycine acid (abbreviated as abglyH2) as a ligand, two zinc(II) complexes [Zn(abglyH)2(bipy)2(H2O)2], (1) and {[Znz(abgly)2(bipy)2(H2O)2]. 2(H2O)}n (2) (bipy = 4,4'-bipyridine) have been synthesized under mild conditions and characterized by IR, elemental analysis and X-ray diffraction analysis. Complex 1 is a monomeric compound, which is further assembled by intermolecular hydrogen bonds and π-π interactions into a 3-D supramolecular network. Complex 2 adopts a one-dimensional double chain structure and is further linked by hydrogen bonds to form a 2-D structure. Fluorescent analysis shows that complex 1 has an emissive maximum at 337 nm and complex 2 exhibits an emissive maximum at 339 nm in the solution state at room temperature.
基金Fund by the National Natural Science Foundation of China(No.8120119)
文摘Fluorescent mesoporous silica nanoparticles functionalized with carboxyl group(Znq-CMSCOOH) were successfully synthesized by in situ formation route of 8-hydroxyquinolinate zinc complexes in channels of mesoporous silica nanoparticles and post-grafting of carboxyl group on the surface. Moreover,the particle size and structural properties of Znq-CMS-COOH were characterized by transmission electron microscopy(TEM),field emission scanning electron microscopy(FE-SEM),dynamic light scattering(DLS),Fourier transform infrared spectroscopy(FT-IR),UV-vis spectrometer, fluorescence spectrometer and nitrogen adsorption-desorption measurements. The obtained results suggest that the Znq-CMS-COOH presents the uniform spherical shape with the mean diameter of about 85 nm and the obvious wormhole arrangement mesoporous. In addition, the Znq-CMS-COOH possesses green fluorescence with the emission peaks at 495 nm. So the Znq-CMS-COOH, which is beneficial to further modification and tracing, might be a great potential carrier for applying in drug delivery system in the future.
基金Supported by the Natural Science Foundation of Shaanxi Province(2018JM2055,2018JQ2079,2018JQ2040)
文摘Two zinc complexes, [Zn(MPIP)Cl2](1) and [Zn(EPIP)Cl2](2), where MPIP = 1-(methoxymethyl)-3-(pyridin-2-yl)imidazo[1,5-a]pyridine and EPIP = 1-(ethoxymethyl)-3-(pyridin-2-yl)imidazo[1,5-a]pyridine, were synthesized under solvothermal conditions. The etheric ligand MPIP was formed in situ via metal ligand reaction between(3-(pyridin-2-yl)imidazo[1,5-a]pyridin-1-yl)methanol(HPIPM) and methanol solvent. Similarly, the ligand EPIP was generated in situ from the reaction of HPIPM with ethanol solvent. The structures of 1 and 2 were characterized by X-ray single-crystal diffraction analysis. They are four-coordinated mononuclear complexes, and the ZnII ion of 1 and 2 displays distorted tetrahedral geometry. The photoluminescent properties of 1 and 2 were investigated. Strong emissions were observed for both 1 and 2, which were ascribed as the intraligand(π-π*) fluorescent transitions. This paper provides a simple and efficient method for the synthesis of etheric compounds.
文摘A zinc complex, [Zn(iso)_2(H_2O)_4](iso=C_6H_4NO_2^-), was synthesized and characterized by elemental analysis, thermal analysis and IR spectrum studies. The crystal structure of the complex was determined by X-ray diffraction. The crystal crystallizes in the triclinic system, molecular formula ZnC12H16N2O8, Mr=381.64, space group P with a = 6.338(1), b =6.919(1), c=9.277(1), α=96.28(1), β=104.91(1), γ=112.85(1)°, V=352.12(9)?3, Z=1, Dc=1.80g?cm-3 and F(000)=196, μ =1.791mm-1. The crystal structure was solved by direct methods for final R=0.0204 and Rw=0.0542 for 1258 observed reflections with [Fo>4σ(Fo)]. The crystal structure reveals that zinc ion is trans-octahedral with two pyridyl nitrogens and two aque oxygens at the equational positions and two aqua oxygens at the axial positions. The complex forms a three-dimensional network through intermolecular hydrogen bonds.
文摘The title complex is a new binuclear Zn(Ⅱ) with chelate ligand of Schiff base containing S and N atom.The complex crystallizes in the orthorhombicspace group Pccn,with a=12.338(9),b=16.666(8),c=17.503(6),V=3599(6),Mr=723.52,Z=4,Dx=1.34 g/cm3,μ=15.22 cm-1,F(000)=1488.The structure was solved by direct methods and the final R=0.078.The crystal consists of discrete molecules with symmetric center at the center of the fourmembered ring consisting of two Zn atoms and two O atoms.
基金Supported by the National Natural Science Foundation of China(Nos. 20476011 and 20371007).
文摘The self-assembly of clusters in inorganic systems is an interesting subject. The self-assembly of big molecules has been well established in biological systems. In addition, the coordination chemistry of metal-sulfur-nitrogen cluster complexes has been a very active and attracting field for many years as a result of the novelty and versatility of the crystal structures and reactivities of such clusters, as well as their potential applications as the models for the active sites in non-heme proteins. At the same time, there is currently considerable interest in the formation of metal complexes with heterocyclic ligands because of the diverse characteristics of ligands and their consequential wide range of applications.
基金Financial support from the State General Administration of the People’s Republic of China for Quality Supervision and Inspection and Quarantine(No.2016QK122)the Science and Technology Projects of Jiangxi Province(No.20181BBH80007)+1 种基金Shanghai Institute of Quality Inspection and Technical Researchthe Department of Chemistry,Fudan University。
文摘A convenient colorimetric approach for visual detection of melamine in raw milk was realized by using gold nanoparticles(AuNPs)stabilized by an unsymmetrical terpyridyl zinc complex with a thymine fragment at one terminal and a quaternary ammonium salt at the other.Even without pre-addition of melamine or relative additives,obvious color change from red to blue was observed by naked eye in the presence of trace amount of melamine,which was attributed to the alternation of aggregation state of AuNPs caused by the selective binding between the thymine fragment and melamine via triple hydrogenbonding interactions.Remarkably,the detection limit for melamine was as low as 2.4 ppb,providing a highly sensitive and efficient approach for the visual detection of melamine.
基金the Natural Science Foundation of China, Fujian Province and Chinese Academy of Sciences.
文摘The title complex was prepared from self-assembly reaction of La(NO3)3(6H2O, Zn(NO3)2(6H2O, m-cyanobenzoic acid (m-CNC6H4COOH) and pyridine (Py) in refluxing ethanol and its structure was determined by single-crystal X-ray diffraction. Crystallographic data: C94H62N12La2O22Zn2, Mr = 2120.12, triclinic space group P, a = 13.2219(5), b = 13.2713(5), c = 14.1987(6) ?, (???69.156(1), ( = 84.034(1), ( = 89.400(1) (, V = 2314.9(2) ?3, Z = 1, Dc = 1.521 g/cm3, F(000) = 1060, ( (MoK() = 14.94 cm-1, the final R = 0.043 and wR = 0.117 for 6381 unique reflections with I > 2((I). Crystal structure determination shows that the neighboring lanthanum(III) and zinc(II) ions are bridged by three bidentate m-cyanobenzonate ligands in the syn-syn fashion to form a pair of dinuclear [LaZn(m-CNC6H4COO)3(Py)(C2H5OH)] subunits, being linked together by two bidentate and two tridentate m-cyanobenzonate groups in the syn-syn and syn-anti modes, respectively, to construct a tetranuclear La-Zn complex [La2Zn2(m-CNC6H4COO)10(Py)2(C2H5OH)2].
基金Supported by the National Natural Science Foundation of China(No.21104026).
文摘A series of anilido-imine zinc complexes ortho-C6H4(CH:NAr)(NAr)ZnEt[Ar=2,6-Me2C6H3(2a); Ar=2,6-Et2C6H3(2b)] was synthesized, characterized and used as catalysts for the ring-opening polymerization of L-lactide in the presence of benzyl alcohol. The effects of the structures of catalysts and reaction conditions on the reactivity were investigated. The polymerization of L-lactide initiated by each of these complexes was found to take place with a controlled manner.
基金supported by the National Natural Science Foundation of China (No. 20971004, 21171008)the Natural Science Foundation of Anhui Provincial Educational Commission (No. KJ2010A2229)the Outstanding Youth Foundation of Anhui Provincial Education Commission (No. 2010SQRL108ZD)
文摘A novel zinc(II) complex, Zn(IBT)2 (1, H1BT = 5-(4-((1H-imidazol-1-yl)methyl)- phenyl)-2H-tetrazole) has been synthesized with Zn(NO3)2·6H2O, 4-(imidazol-l-ylmethyl)benzonnitrile (IBN) and NaN3 by the hydrothermal method, and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Crystallographic data for 1: C22H18N12Zn, Mr = 515.85, orthorhombic, Pbcn, a = 16.0567(15), b = 9.5316(9), c = 14.6107(14) A, V= 2236.1(4) A3, Z= 4, Dc = 1.532 g/cm3,μ = 1.138 mm-1, F(000) = 1056, R = 0.0350 and wR = 0.0888 for 1438 observed reflections (I 〉 2σ(I)) and the goodness-of-fit S = 1.002 on F2. The crystal structural analysis revealed that complex 1 exhibits a rare two-dimensional homochiral wave-like layer structure. In addition, the photoluminescence of complex 1 was studied in the solid state at room temperature together with its theoretical analysis.
基金This project was supported by the Foundation of Science Committee of Jiangsu Province (BK2005045)Natural Science Foundation of Jiangsu Provincial Educational Commission (02KJD150014, 03KJD150031)the Foundation of Science Committee of Huaihai Institute of Technology (Z2006005)
文摘The title complex [bis(dien)zinc(Ⅱ)] zinc(Ⅱ) tetrachloride was synthesized and characterized by X-ray single-crystal diffraction, elemental analysis, electric conductivity, IR and electronic spectra. The compound crystallizes in the tetragonal system, space group I^-4 with a = 10.250(3), b = 10.250(3), c = 9.054(2) V = 951.2(5)A^3, Mr = 486.95, Z = 2, F(000) = 504, Dc = 1.700 g/cm&3,μ = 3.083 mm^-1, λ. = 0.71073A, the final R = 0.0226 and wR = 0.0642. The symmetric crystal smacture consists of a zinc complex cation [Zn(dien)2]^2+ and a zinc tetrachloride aniOn [ZnC14]^2-, forming a three, dimensional framework through intrmnolecular and intermolecular hydrogen bonds.
文摘A new zinc(II)complex of formula[ZnCl2(L1)2](1)[L1=2‐(2‐thienyl)‐1‐(2‐thienylmethyl)‐1Hbenzimidazole]was synthesized and fully characterized by nuclear magnetic resonance and infrared spectroscopy,elemental analysis,electrospray ionization high‐resolution mass spectrometry,and thermogravimetric analysis.The molecular structure was confirmed by single‐crystal X‐ray diffraction.Complex1consists of mononuclear tetrahedral zinc(II)units with a locked geometry resulting from weak intramolecular S···?and?–?interligand interactions.The benzimidazole ligand and its zinc(II)complex were readily obtained through a simple synthetic route.The catalytic activity of1was investigated in the coupling of carbon dioxide with epoxides to produce cyclic carbonates,and a series of parameters were evaluated.The complex efficiently catalyzed the transformation of various epoxides under solvent‐free conditions,with good conversions,turnover numbers,and turnover frequencies.
文摘Reaction of sulfonylated binaphthol [2-hydroxy-2'-tosyloxy-l,l-binaphthyl (la, Ts-Binol) or 2-hydroxy-2'- (phenylsulfonyloxy)-l,l-binaphthyl (lb, Ps-Binol)] with 1 equiv, of ZnEt2 afforded zinc complexes [(Ys-Binol)ZnEt]2 (2a) and [(Ps-Binol)ZnEt]2 (2b). Further reaction of zinc complexes 2a and 2b with benzyl alco- hol (BnOH) gave the zinc benzyloxide [(Ts-Binol)2Zn2(OBn)2]2 (3a) and [(Ps-Binol)2Znz(OBn)2]2 (3b). Alterna- tively, the zinc benzyloxides 3a and 3b could also be obtained by reaction of compound la or lb with Zn(OBn)2 (in situ reaction of ZnEt2 and BnOH). The complexes were fully characterized by elemental analyses and spectroscopic analyses, and complexes 2a, 2b and 3a were further characterized by single-crystal X-ray analyses. The catalytic activities of these zinc complexes towards ring-opening polymerization of ε-caprolactone and D,L-lactide were studied.
文摘Reaction of Zn(ClO4)2·6H2O with septadentate 2,6-bis[bis(2-benzimidazolylme-thyl)amino methyl]-4-methylphenol (Hbbap) and sodium isonicotinate yielded a dinuclear zinc complex[Zn2(bbap) (Iso) (Hiso)] (ClO4)2·[Zn2 (bbap) (Iso) (H2O)] (ClO4)2·4H2O(1a·1b·4H2O). Hiso isisonicotinic acid and Iso is isonicotinate anion. The structure has been established by X-raycrystallography and shows that the two zinc ions are bridged by the phenoxy unit of bbap- ligand,and the presence of unusual monodentate O-coordination of carboxylate group from isonicotinicacid. The coordination geometry around the zinc ion is approximately trigonal bipyramidal.
基金Supported by the National Natural Science Foundation of China(No.21104026).
文摘The reaction of bidentate N,N-dimethylaniline-arylamido ligands,o-C6H4NMe2(CH2NHAr)(Ar =Ph,1a;2,6-Me2C6H3,1b; 2,6-Et2C6H3,1c; 2,6-ipr2C6H3,1d) with ZnEt2 yields the complexes o-C6H4(NMe2)(CH2NAr)ZnEt (2a-2d),respectively.All the complexes were characterized by 1H and 13C NMR spectroscopy and elemental analyses.It was found that all the zinc complexes were efficient catalysts for the ring-opening polymerization of L-lactide in the presence of benzyl alcohol with good molecular weight control and narrow polydispersity.
基金This work was supported by the Natural Science Foundation of Guangxi Province (No. 0229004)
文摘Two new ternary complexes [Zη(3-aba)2(phen)]·2.58H2O 1 and {[Cd(3-aba)- (phen)2]·(NO3)·(1.5H2O) }n 2 (3-aba = 3-aminobenzoic acid anion, phen = 1,10-phenanthroline) were synthesized and characterized by elemental analysis, IR, UV spectrum and X-ray diffraction. Complex 1 crystallizes in the rhombohedral system, space group R3 with a = 3.5733(3), b = 3.5733(3), c = 1.1231(2) nm; V= 12.419(3) nm^3, C26H25.17NaO6.58Zn, Mr= 564.37, Z= 18, F(000) = 5253, μ= 0.937 mm^-1, Dc = 1.358 g/cm^3, R = 0.0668 and wR = 0.1690 for 2424 observed reflections (I〉 2σ(I)). Complex 2 belongs to the tetragonal system, space group P4/ncc with a = 2.88451(10), b = 2.88451(10), c = 1.55571(11) nm, V= 12.9441(11) nm^3, C31H25CdN6O6.50, Mr = 697.97, Z = 16, F(000) = 5648,μ=0.727 mm^-1, Dc= 1.433 g/cm^3, R = 0.0607 and wR = 0.1742 for 3468 observed reflections (I 〉 2σ(I)). Complex 1 displays a mononuclear structure. The carboxylate group of 3-aminobenzoic acid anion coordinates to Zn(Ⅱ) in a chelating bidentate mode, and the nitrogen atom of the ligand does not involve in coordination. Complex 2 exhibits a one-dimensional chain structure with 3-aminobenzoic acid anion coordinating to Cd(Ⅱ) in a μ2-bridging mode through its nitrogen atom and one of its oxygen atoms.
基金Financially supported by the Education Department of Jiangxi Province(GJJ13106)
文摘A novel 1,2,3-triazolyl-containing ligand (H2L) with long donor arms extending from the central pyridyl linker was synthesized by click cycloaddition of 2,6-bis(azidomethyl)pyri- line and 2-((prop-2-yn-1-yl(pyridin-2-ylmethyl)amino)methyl)phenol. Further treatment of the igand H2L with zinc(II) perchlorate in the presence of triethylaminc, followed by anion exchange vith Na[BPh4], provided a dinuclear zinc(II) complex [Zn2L][BPh4]E-2DMF (1). Complex 1 crystallizes in monoclinic, space group P21 with a = 10.4873(4), b = 14.9078(5), c = 25.8620(9) A, = 94.566(2)°, V = 4030.5(2) A3, Z = 2,μ= 0.657 mm-1, Dc = 1.324 Mg/m3, T = 296(2) K, C93H91N13B2O4Zn2, Mr = 1607.19, F(000) = 1684, S = 0.958, R = 0.0271 and wR = 0.0607. In the tructurc of cation, the phenolate oxygen atoms of ligand act as the bridging nodes to form a hombic Zn2(OAr)2 core.