Three novel Zn（II） complexes,[Zn4L1Cl4]-3H2O（1）,[Zn4L2Cl4]-2DMF（2） and[Zn4L^3Cl4]H2O（3）,have been synthesized and structurally characterized.In these complexes,interesting 32-membered dodecadentate macrocyclic...Three novel Zn（II） complexes,[Zn4L1Cl4]-3H2O（1）,[Zn4L2Cl4]-2DMF（2） and[Zn4L^3Cl4]H2O（3）,have been synthesized and structurally characterized.In these complexes,interesting 32-membered dodecadentate macrocyclic ligands were generated in situ by ＇2 ＋ 2＇ type condensation reactions between a tetraamine and various dialdehydes.All the complexes are isostructurally tetranuclear Zn（Ⅱ） complexes,containing endogenous alkoxo and phenoxo bridges.Applications of the macrocyclic ligands as Zn^2＋ sensors have been investigated.Take H4L^1 for example,it exhibits a 4-fold fluorescence enhancement upon the addition of 2 equiv.of Zn^2＋ in MeOH.展开更多
The process of obtaining of high quality Mn-Zn,Mn-Cu and Mn-Cu-Zn alloy coatings from complexing ligands--citrate,EDTA(ethylene diaminetetra acetic acid)and nitrilotriacetic acid solutions was studied.Factors affectin...The process of obtaining of high quality Mn-Zn,Mn-Cu and Mn-Cu-Zn alloy coatings from complexing ligands--citrate,EDTA(ethylene diaminetetra acetic acid)and nitrilotriacetic acid solutions was studied.Factors affecting stability of solutions containing ligand or ligands and influence of electrolysis parameters:electrolyte composition,pH,cathodic current density on chemical composition of the obtained coatings,on their current efficiency,morphology and structure were investigated.展开更多
The title complex was obtained by reactions of [Mo(CO)_3(MeCN)_3] with [CuBr(pySH)(PPh_3)_2]or directly with pySH and PPh_3. The latter method can be used to synthesize the corresponding tungsten complex [W_2(CO)_4(μ...The title complex was obtained by reactions of [Mo(CO)_3(MeCN)_3] with [CuBr(pySH)(PPh_3)_2]or directly with pySH and PPh_3. The latter method can be used to synthesize the corresponding tungsten complex [W_2(CO)_4(μ-pyS)_2(PPh_3)_2].The molecular structure of the title compound was determined by X-ray diffraction method.展开更多
The title complex[Zn_2L(C_5H_7N_2)_2(C_5H_7N_2·HClO_4)_2](L=1,2-di(3', 5'-dimethylpyrazolyl) formylhydrazine and C_5H_7N_2= 3 , 5 dimethylpyrazole anion) has been synthesized by template reaction, in whic...The title complex[Zn_2L(C_5H_7N_2)_2(C_5H_7N_2·HClO_4)_2](L=1,2-di(3', 5'-dimethylpyrazolyl) formylhydrazine and C_5H_7N_2= 3 , 5 dimethylpyrazole anion) has been synthesized by template reaction, in which carbonhydrazine, 2, 4-pentanedione and zinc perchlorate hexahydrate were used as the original materials. The crystals of complex with formula C_(32)H_(46)N_(14)O_(10)Cl_2Zn_2 (Mr=988.46) are triclinic,space group P1,a= 8.275 (2),b=11.523 (3),c= 12.872(5), a=69. 90(3),β= 69.79 (2), γ=83. 52 (2)°,V=1081.6(6),Z=1,Dc=1.524g/cm￣3,μ=13.265cm￣(-1),F (000)=510. The final refinement is converged with R= 0.057. The results indicate that in one complex molecule there are three kinds of pyrazole rings all directly coordinated to the central Zn atom; and each zinc atom possesses a five-coordinated polyhedron.展开更多
Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of...Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of montmorillonite （MT） by ion exchange and coordination reaction of L with the Tb^3＋ ion existing in the interlayer space of Tb-MT respectively. The obtained luminescent supramolecular composite materials, [ TbL （NO3） ]^2＋-MT and [TbL]^3＋-MT were characterized by elemental analysis, XRD, FT-IR, UV-vis and thermal analysis. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalated materials with regular layered structure, good thermal stability and the interlayer spacing （d001） approximates to the size of the complex ions which are located in the interlayer space of MT in the form of a monolayer.展开更多
Four novel palladium（（Ⅱ）） complexes coordinated by phosphorus atoms from both 3,5-disubstituted-1H- 1,2,4-diazaphospholes in monodentate fashion were developed as efficient catalyst for the Mizoroki- Heck reactio...Four novel palladium（（Ⅱ）） complexes coordinated by phosphorus atoms from both 3,5-disubstituted-1H- 1,2,4-diazaphospholes in monodentate fashion were developed as efficient catalyst for the Mizoroki- Heck reaction of aryl halides with electron-deficient olefins. The coupling reaction of awl halide bearig different functional groups with olefin derivatives took place and the corresponding products were isolated in good to excellent yields under optimal conditions. The procedure exhibits good functional group tolerance and wide substrate scope. This Mizoroki-Heck reaction was further achieved using Pd（OAc）2 and 3,5-di-isopropyl-1H-1,2,4-diazaphospholes as combined catalyst, which provide the convenient and alternative method in organic synthesis展开更多
In this study, novel mono/di-nuclear Cu（p-2-bmb）（OH）（Cl O4）（1） and Co2（p-2-bmb）2Cl4（2）（p-2-bmb = 1-（（2-（pyridin-2-yl）-benzoimidazol-1-yl）methyl）-1H-benzotriazole） complexes with the nitrogen hetero...In this study, novel mono/di-nuclear Cu（p-2-bmb）（OH）（Cl O4）（1） and Co2（p-2-bmb）2Cl4（2）（p-2-bmb = 1-（（2-（pyridin-2-yl）-benzoimidazol-1-yl）methyl）-1H-benzotriazole） complexes with the nitrogen heterocyclic benzimidazole-based ligand were synthesized and characterized. The two complexes showed antiproliferative effects in various carcinoma cell lines, especially complex 1 in the SMMC7721 tumor cell line. Complex 1 was also able to pass through the cell membrane and enter the nucleus and mitochondrion. An analysis of in vitro chemical nuclease activity revealed that complex 1 partially intercalated to calf thymus DNA and exhibited strong unwinding activity against p BR322 superhelical plasmid DNA. The comet assay and flow cytometry analysis confirmed that 1 caused extensive DNA damage and arrested SMMC7721 tumor cells at G2/M phase of the cell cycle, leading to loss of mitochondrial membrane potential and apoptosis. These results suggest that these benzimidazole-based metal complexes could be potential anti-cancer agents.展开更多
One new Zn（Ⅱ） complex [Zn2（cptpy）2（tzba）（H2O）]·H2O（1, Hcptpy = 4-（4-carboxyphenyl）-2,2＇：4＇,4＇＇-terpyridine（Hcptpy）, H_2tzba = 4-（tetrazol-5-yl）benzenecarboxylic acid） has been synthesized an...One new Zn（Ⅱ） complex [Zn2（cptpy）2（tzba）（H2O）]·H2O（1, Hcptpy = 4-（4-carboxyphenyl）-2,2＇：4＇,4＇＇-terpyridine（Hcptpy）, H_2tzba = 4-（tetrazol-5-yl）benzenecarboxylic acid） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction techniques. It is formulated as C52H36O8N10Zn2, crystallizes in monoclinic system, space group P21/c with α = 15.1599（13）, b = 28.083（2）, c = 10.9039（9） A, b = 97.517（8）o. V = 4602.3（6） A^3, Z = 4, Mr = 1059.68, Dc = 1.529 g/cm^3, F（000） = 2168 and μ = 1.112 mm^-1. The final R = 0.0831 and wR = 0.2143 for 8458 observed reflections with I 〉 2s（I）. The assembly of polyfunctional organic ligands Hcptpy and H_2tzba with Zn（II） atoms resulting in a rare example of double-edge ladders, which is further extended into a 3D supramolecular network via O–H…O/N hydrogen bonds. In addition, thermal gravimetric analysis（TGA） and PXRD patterns for 1 were studied. Photo luminescent property of 1 was also investigated.展开更多
Copper complexing ligands concentration (C C) and conditional stability constant of the sea surface microlayer (SML) and subsurface layer (SSL) samples, collected from Daya Bay of Guangdong Province and Jiaozhou Bay o...Copper complexing ligands concentration (C C) and conditional stability constant of the sea surface microlayer (SML) and subsurface layer (SSL) samples, collected from Daya Bay of Guangdong Province and Jiaozhou Bay of Shandong Province, were determined by anodic stripping voltammetry (ASV) technique. C C of Daya Bay in the SML ranged from 6.19×10-7 to 3.52×10-7 mol/L. C C of Jiaozhou Bay in the SML ranged from 5.30×10-7 to 3.03×10-7 mol/L in August 1998 and from 3.46×10-7 to 1.36×10-7 mol/L in May 2000. The C C concentrations were higher in all surface microlayer samples, compared with corresponding subsurface samples. The average enrichment factors of copper complexation in the SML observed above were 1.58, 1.41 and 1.56, respectively. The enrichment of C C concentration in the microlayer demonstrated that organic ligands had certain buffer action on the toxicity of the enriched trace metals in the same layer. Conditional stability constants of the SML in Jiaozhou Bay were lower than those of the SSL; however, it showed just opposite for Daya Bay. BOD (biological oxygen demand) and COD (chemical oxygen demand) indicated the organic matter content, also showed enriched in the SML. C C had an obvious relationship with BOD or COD.展开更多
Copper complexing ligand concentrations in the Daya Bay, Qingdao coast, Jiaozhou Bay, South China Sea and Huanghe Estuary waters were determined by the anodic stripping voltammetry technique. The distribution regulari...Copper complexing ligand concentrations in the Daya Bay, Qingdao coast, Jiaozhou Bay, South China Sea and Huanghe Estuary waters were determined by the anodic stripping voltammetry technique. The distribution regularity and the relationship with other parameters were discussed. The results were as follows： Copper complexing ligand concentrations of the South China Sea were a little higher than those of other sea areas, and they were apparently higher than those of the ocean. Compared with the subsurface layer （SSL） in the sea surface microlayer copper complexing ligand concentrations showed an enrichment phenomenon, of which the mechanism is similar to dissolved organic matter. The metal complexing ligand concentration profiles of the South China Sea showed that the value in the sea surface was the highest, then it decreased with depth accruing, and a higher value appeared at the bottom. Copper complex- ing ligand concentrations were higher than those of cadmium and lead. Ligands in each sea area exhibited a complicated property. In short, the distribution regularity of copper complexing ligand concentrations in China＇s coastal waters was consistent with that of other regions in the world. Meanwhile, the positive relationship between the copper complexing ligand concentrations and biological oxygen demand, chemical oxygen demand, dissolved organic carbon, and viscosity were found clearly.展开更多
The photoluminescent (PL) and electroluminescent (EL) properties of a series of ligand emitting rare earth complexes (including Y^(3+), La^(3+), Gd^(3+) and Lu^(3+)) were systematically studied. These complexes have t...The photoluminescent (PL) and electroluminescent (EL) properties of a series of ligand emitting rare earth complexes (including Y^(3+), La^(3+), Gd^(3+) and Lu^(3+)) were systematically studied. These complexes have the same anionic ligand, 1-phenyl-3-methyl-4-isobutyryl-5-pyrazoloneate (PMIP), and three neutral ligands, triphenyl phosphine oxide (TPPO), 2, 2′-dipyridine (Bipy) and phenanthroline (Phen). Measured with 60 nm thin film of these complexes vaporized in vacuum on quartz substrates, a good regularity in the PL properties was observed. For rational comparison, the same structural EL devices based on these complexes, ITO/PVK (40 nm)/the complex (80 nm)/Mg: Ag (200 nm)/Ag (100 nm), were fabricated. Excluding the exciplex emission happens, the EL luminance usually increases with the increasing of PL efficiency.展开更多
Reaction of Cu(ClO4)2'6H2O with tripodal ligand tri s (2-benzi nd dazol yl methyl ) aInine(ntb) and sodium isonicotinate (Iso) yielded a mononuclear complex lCu(ntb)(lso)]ClO4.3.5H2O. Thestructure has been establi...Reaction of Cu(ClO4)2'6H2O with tripodal ligand tri s (2-benzi nd dazol yl methyl ) aInine(ntb) and sodium isonicotinate (Iso) yielded a mononuclear complex lCu(ntb)(lso)]ClO4.3.5H2O. Thestructure has been established by X-ray crystallography The Cu (Ⅱ) atom is in a distorted trigonalbipyranddal environment with three benzimindazole N atoms of ntb defining the equatorial plane, oneandne N atom of ntb, and one O atom of the carboxylate group of isonicotinate occupying the axialpositions.展开更多
The copper complex Cu（C12H9N2O3）2 has been synthesized by the reaction of furaldehyde salicylylhydrazone （Hfs） and copper acetylacetonate and characterized by X-ray crystal diffraction and spectroscopic studies. T...The copper complex Cu（C12H9N2O3）2 has been synthesized by the reaction of furaldehyde salicylylhydrazone （Hfs） and copper acetylacetonate and characterized by X-ray crystal diffraction and spectroscopic studies. The crystal crystallizes in space group P211n with a = 5.9765（3）, b = 15.7196（9）, c = 12.0514（6）A,β= 101.618（3）^o, V = 1109.0（1）A^3, C24H18CuN4O6, Mr = 521.96, Z = 2, Dc = 1.563 g/cm^3, μ = 1.035 mm^-1, F（000） = 534, R = 0.0373 and wR = 0.1058 for 2283 observed reflections （I 〉 2σ（I））. The copper atom has a square-planar CuN2O2 coordination and should be in an octahedral coordination if considering Cu-O （phenol） with distances of 2.796（2）A as weak bonds. The neighboring copper complex molecules are linked together by these weak Cu-O （phenol） bonds, resulting in an extended 1D chain. The title compound exhibits paramagnetic property and fluorescence behavior at room temperature supported by the EPR and fluorescence spectra.展开更多
<span style="font-family:Verdana;">Coordination compounds of 2-amino-3-methylbutanoic acid were synthesized with chromium(III) and oxovanadium(IV) ions. M:L;1:2. Adducts of these complexes using 1,10-p...<span style="font-family:Verdana;">Coordination compounds of 2-amino-3-methylbutanoic acid were synthesized with chromium(III) and oxovanadium(IV) ions. M:L;1:2. Adducts of these complexes using 1,10-phenantroline and ethylenediamine were further synthesized, M:L, (1:2). These compounds were characterized using electronic, infra-red spectrophotometry, magnetic susceptibility measurement and percentage metal analyses. The zones of inhibition and minimum inhibitory concentrations of the compounds against eight microbes were studied. The results obtained indicated an octahedral geometry for the Cr(III) complexes, indicative of additional coordination of two water molecules. On the other hand a square pyramid geometry was obtained for the binary oxovanadium complex and its 1,10-phenantroline adduct. However</span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">,</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;"> for the oxovanadium ethylenediamine adduct a distorted octahedral geometry was proposed. The result for the antibacterial studies indicated that both mixed ligand complexes of 1,10-phenantroline exhibited good antibacterial activity, and in some cases better activity than the standard, streptomycin.</span></span></span>展开更多
A ditopic ligand bpy-cyclam(L)and its heterometallo-binuclear complex Ru(bpy)_2(bpy-cyclam-Ni)(ClO_4)_43H_2O(3)designed for use in the catalytic photoreduction of carbon dioxide have been newly synthesized and charact...A ditopic ligand bpy-cyclam(L)and its heterometallo-binuclear complex Ru(bpy)_2(bpy-cyclam-Ni)(ClO_4)_43H_2O(3)designed for use in the catalytic photoreduction of carbon dioxide have been newly synthesized and characterized.The protonation constants of L were also determined.展开更多
<span style="font-family:Verdana;">Coordination compounds of 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="fo...<span style="font-family:Verdana;">Coordination compounds of 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one with </span><span style="font-family:Verdana;">iron(III), cobat(III) and chromium(III) were synthesized with M:L (1:2)</span><span style="font-family:Verdana;">. Mixed ligand coordination compounds of 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one and 1,2-diaminocyclohexane using the same metal ions were also synthesized </span><b><span style="font-family:Verdana;">M:L1</span></b><span style="font-family:Verdana;">:</span><b><span style="font-family:Verdana;">L2</span></b><span style="font-family:Verdana;"> (1:1:1) where </span><b><span style="font-family:Verdana;">L1</span></b><span style="font-family:Verdana;"> is 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one and </span><b><span style="font-family:Verdana;">L2</span></b><span style="font-family:Verdana;"> is 1,2-diaminocyclohexane. The coordination compounds obtained were characterized using electronic and infrared spectral analyses, magnetic susceptibility and percentage metal analysis. They were also evaluated for their cytotoxic and antioxidant activities. The result obtained suggested that octahedral geometry was obtained for all the compounds, as a result of additional two molecules of the solvent coordinated to the metal ions. Both the primary and secondary ligands coordinated in a bidentate fashion. The synthesized compounds exhibited moderate cytotoxicity, although none was as active as the standard. The cobalt(III) mixed ligand complex elicited the highest activity. The synthesized compounds all exhibited good to moderate antioxidant activity.</span>展开更多
Co(II) and Cr(III) metal complexes of Schiff bases were synthesized from the condensation reaction between 4-(dimethylamino)benzaldehyde and 4-amino-3-hydroxy-naphthalene-1-sulfonic acid. Their structures were investi...Co(II) and Cr(III) metal complexes of Schiff bases were synthesized from the condensation reaction between 4-(dimethylamino)benzaldehyde and 4-amino-3-hydroxy-naphthalene-1-sulfonic acid. Their structures were investigated by elemental analysis, molar conductance measurements, infrared spectroscopy, electronic spectroscopy, and 1HNMR spectroscopy. The elemental analysis data suggested a 1:1 [M:L] ratio for the complexes. The molar conductance measurements of the complexes indicate their electrolytic nature in DMSO as a solvent. The absorption bands in the electronic spectra verified an octahedral environment around the metal ions in the complexes.展开更多
A rapid method is applied to analyze conjugated organic ligands bridged binuclear ruthenium complexes by electrospray ionization-tandem mass spectrometry (ESI MSn).Fragmentation pattern be discussed.
One new polyoxometalate （POM）-based inorganic-organic hybrid [Cdn3~HPO4）（Hbpp）（H20）2]{CdII[P4_ Mo6028H3.s（OH）312}.（H4tpb）.7H20 （1） （bpp = 1,3-bis-（4-pyridyl）propane, tpb = 1,2,4,5-tetra（4-pyridyl）- b...One new polyoxometalate （POM）-based inorganic-organic hybrid [Cdn3~HPO4）（Hbpp）（H20）2]{CdII[P4_ Mo6028H3.s（OH）312}.（H4tpb）.7H20 （1） （bpp = 1,3-bis-（4-pyridyl）propane, tpb = 1,2,4,5-tetra（4-pyridyl）- benzene） constructed from reduced molybdophosphate [P4Mo6028H3.5（OH）3]s＇5- （P4Mo6）, trinuclear Cdn-phosphate-Hbpp fragment and protonated tpb has been hydrothermally synthesized and structurally characterized by IR, elemental analyses and single crystal X-ray diffraction. The complex 1 crystallizes in the monoclinic system with the space group P21]c and cell parameters of a=15.672（12）A, b=23.839（19）A, c=27.654（2）,~, fl=115.850（10）~, V=9297.9（12） ~3, Z=4, R1 ~0.0534 and wR2 ~0.1135. In complex 1, the P4Mo6 units are bridged by CdII ions to form the classic sandwich-type [Cd（P4Mo6）2] dimers, which are further connected into a two dimensional network via the trinuclear Cdn subunits. The tpb is synthesized in situ from the bpp ligands and connects the adjacent 2D layers into a 3D supramolecular framework through hydrogen bonding interactions. The electrochemical and fluorescent properties of complex 1 have been investigated.展开更多
The deprotonated derivative pyridine-2-thiolato （PyS<sup>-</sup>） of pyridine-2-thione （PySH）is a potentially amibidentate or multi-functional donor which coordinates toward transitionmetals with eithe...The deprotonated derivative pyridine-2-thiolato （PyS<sup>-</sup>） of pyridine-2-thione （PySH）is a potentially amibidentate or multi-functional donor which coordinates toward transitionmetals with either the exocyclic S or heterocyclic N atom or both atoms to form differentcoordination modes. We have recently reported the synthesis and crystal structure ofthe first dinuclear molybdenum complex with doubly-bridging PyS ligands [Mo<sub>2</sub>（CO）<sub>4</sub>（μ-PyS）<sub>2</sub>（PPh<sub>3</sub>）<sub>2</sub>]which was obtained from the reaction of [Mo（CO）<sub>3</sub>（CH<sub>3</sub>CN）<sub>3</sub>]展开更多
基金financially supported by NSFC,the Program for Professor of Special Appointment(Eastern Scholar) at Shanghai Institutions of Higher Learning,Program for New Century Excellent Talents in University(No.NCET-11-0638)Innovation Program of Shanghai Municipal Education Commission,the Fundamental Research Funds for the Central Universities(No.WK1013002)+1 种基金SRFDP(No.20100074110015)S.W.Ng is grateful for support by the University of Malaya(No.UM.C/625/1/H1R/033/10)
文摘Three novel Zn（II） complexes,[Zn4L1Cl4]-3H2O（1）,[Zn4L2Cl4]-2DMF（2） and[Zn4L^3Cl4]H2O（3）,have been synthesized and structurally characterized.In these complexes,interesting 32-membered dodecadentate macrocyclic ligands were generated in situ by ＇2 ＋ 2＇ type condensation reactions between a tetraamine and various dialdehydes.All the complexes are isostructurally tetranuclear Zn（Ⅱ） complexes,containing endogenous alkoxo and phenoxo bridges.Applications of the macrocyclic ligands as Zn^2＋ sensors have been investigated.Take H4L^1 for example,it exhibits a 4-fold fluorescence enhancement upon the addition of 2 equiv.of Zn^2＋ in MeOH.
文摘The process of obtaining of high quality Mn-Zn,Mn-Cu and Mn-Cu-Zn alloy coatings from complexing ligands--citrate,EDTA(ethylene diaminetetra acetic acid)and nitrilotriacetic acid solutions was studied.Factors affecting stability of solutions containing ligand or ligands and influence of electrolysis parameters:electrolyte composition,pH,cathodic current density on chemical composition of the obtained coatings,on their current efficiency,morphology and structure were investigated.
文摘The title complex was obtained by reactions of [Mo(CO)_3(MeCN)_3] with [CuBr(pySH)(PPh_3)_2]or directly with pySH and PPh_3. The latter method can be used to synthesize the corresponding tungsten complex [W_2(CO)_4(μ-pyS)_2(PPh_3)_2].The molecular structure of the title compound was determined by X-ray diffraction method.
文摘The title complex[Zn_2L(C_5H_7N_2)_2(C_5H_7N_2·HClO_4)_2](L=1,2-di(3', 5'-dimethylpyrazolyl) formylhydrazine and C_5H_7N_2= 3 , 5 dimethylpyrazole anion) has been synthesized by template reaction, in which carbonhydrazine, 2, 4-pentanedione and zinc perchlorate hexahydrate were used as the original materials. The crystals of complex with formula C_(32)H_(46)N_(14)O_(10)Cl_2Zn_2 (Mr=988.46) are triclinic,space group P1,a= 8.275 (2),b=11.523 (3),c= 12.872(5), a=69. 90(3),β= 69.79 (2), γ=83. 52 (2)°,V=1081.6(6),Z=1,Dc=1.524g/cm￣3,μ=13.265cm￣(-1),F (000)=510. The final refinement is converged with R= 0.057. The results indicate that in one complex molecule there are three kinds of pyrazole rings all directly coordinated to the central Zn atom; and each zinc atom possesses a five-coordinated polyhedron.
文摘Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of montmorillonite （MT） by ion exchange and coordination reaction of L with the Tb^3＋ ion existing in the interlayer space of Tb-MT respectively. The obtained luminescent supramolecular composite materials, [ TbL （NO3） ]^2＋-MT and [TbL]^3＋-MT were characterized by elemental analysis, XRD, FT-IR, UV-vis and thermal analysis. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalated materials with regular layered structure, good thermal stability and the interlayer spacing （d001） approximates to the size of the complex ions which are located in the interlayer space of MT in the form of a monolayer.
基金Financial support from Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(No. 2015157)Teaching Reform Project of Shanxi Normal University(No. SD2014JGKT-52)Undergraduate Training Programs for Innovation and Entrepreneurship of Modern College of Arts and Sciences, Shanxi Normal University(No. WL2015CXCY-YJ-26)
文摘Four novel palladium（（Ⅱ）） complexes coordinated by phosphorus atoms from both 3,5-disubstituted-1H- 1,2,4-diazaphospholes in monodentate fashion were developed as efficient catalyst for the Mizoroki- Heck reaction of aryl halides with electron-deficient olefins. The coupling reaction of awl halide bearig different functional groups with olefin derivatives took place and the corresponding products were isolated in good to excellent yields under optimal conditions. The procedure exhibits good functional group tolerance and wide substrate scope. This Mizoroki-Heck reaction was further achieved using Pd（OAc）2 and 3,5-di-isopropyl-1H-1,2,4-diazaphospholes as combined catalyst, which provide the convenient and alternative method in organic synthesis
基金supported by the National Natural Science Foundation of China (Nos. 21371046, 21401041)
文摘In this study, novel mono/di-nuclear Cu（p-2-bmb）（OH）（Cl O4）（1） and Co2（p-2-bmb）2Cl4（2）（p-2-bmb = 1-（（2-（pyridin-2-yl）-benzoimidazol-1-yl）methyl）-1H-benzotriazole） complexes with the nitrogen heterocyclic benzimidazole-based ligand were synthesized and characterized. The two complexes showed antiproliferative effects in various carcinoma cell lines, especially complex 1 in the SMMC7721 tumor cell line. Complex 1 was also able to pass through the cell membrane and enter the nucleus and mitochondrion. An analysis of in vitro chemical nuclease activity revealed that complex 1 partially intercalated to calf thymus DNA and exhibited strong unwinding activity against p BR322 superhelical plasmid DNA. The comet assay and flow cytometry analysis confirmed that 1 caused extensive DNA damage and arrested SMMC7721 tumor cells at G2/M phase of the cell cycle, leading to loss of mitochondrial membrane potential and apoptosis. These results suggest that these benzimidazole-based metal complexes could be potential anti-cancer agents.
基金supported by the National Natural Science Foundation of China(Nos.21273101 and 21302082)Foundation for Science&Technology Innovation Talents in Henan province(Nos.2014HASTIT014 and 164100510012)+1 种基金Tackle Key Problem of Science and Technology Project of Henan Province,(No.14210 231 0483)Ministry of Science and Technology of China(973 Project,No.2014CB660804)
文摘One new Zn（Ⅱ） complex [Zn2（cptpy）2（tzba）（H2O）]·H2O（1, Hcptpy = 4-（4-carboxyphenyl）-2,2＇：4＇,4＇＇-terpyridine（Hcptpy）, H_2tzba = 4-（tetrazol-5-yl）benzenecarboxylic acid） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction techniques. It is formulated as C52H36O8N10Zn2, crystallizes in monoclinic system, space group P21/c with α = 15.1599（13）, b = 28.083（2）, c = 10.9039（9） A, b = 97.517（8）o. V = 4602.3（6） A^3, Z = 4, Mr = 1059.68, Dc = 1.529 g/cm^3, F（000） = 2168 and μ = 1.112 mm^-1. The final R = 0.0831 and wR = 0.2143 for 8458 observed reflections with I 〉 2s（I）. The assembly of polyfunctional organic ligands Hcptpy and H_2tzba with Zn（II） atoms resulting in a rare example of double-edge ladders, which is further extended into a 3D supramolecular network via O–H…O/N hydrogen bonds. In addition, thermal gravimetric analysis（TGA） and PXRD patterns for 1 were studied. Photo luminescent property of 1 was also investigated.
基金Supported by subproject of the China’s "Ninth Five Year Plan" Scientific Research Project No. 97-926-04-03 the Natural Science Foundation of China (No. 40076020, 40376022) the Doctoral Research Program of Higher Education (No. 98042304) and KZ95T-04-04-04 Fund.
文摘Copper complexing ligands concentration (C C) and conditional stability constant of the sea surface microlayer (SML) and subsurface layer (SSL) samples, collected from Daya Bay of Guangdong Province and Jiaozhou Bay of Shandong Province, were determined by anodic stripping voltammetry (ASV) technique. C C of Daya Bay in the SML ranged from 6.19×10-7 to 3.52×10-7 mol/L. C C of Jiaozhou Bay in the SML ranged from 5.30×10-7 to 3.03×10-7 mol/L in August 1998 and from 3.46×10-7 to 1.36×10-7 mol/L in May 2000. The C C concentrations were higher in all surface microlayer samples, compared with corresponding subsurface samples. The average enrichment factors of copper complexation in the SML observed above were 1.58, 1.41 and 1.56, respectively. The enrichment of C C concentration in the microlayer demonstrated that organic ligands had certain buffer action on the toxicity of the enriched trace metals in the same layer. Conditional stability constants of the SML in Jiaozhou Bay were lower than those of the SSL; however, it showed just opposite for Daya Bay. BOD (biological oxygen demand) and COD (chemical oxygen demand) indicated the organic matter content, also showed enriched in the SML. C C had an obvious relationship with BOD or COD.
基金supported by the National"Ninth Five-Year Plan"Scientific Research Project of China under contract No.979260403the National"Tenth Five-Year Plan"Scientific Research Project of China under contract No.2001CB409700+1 种基金the National Natural Science Foundation of China under contract Nos 40076020 and 40376022National Natural Science Special Key Foundation of China under contract No.40490263.
文摘Copper complexing ligand concentrations in the Daya Bay, Qingdao coast, Jiaozhou Bay, South China Sea and Huanghe Estuary waters were determined by the anodic stripping voltammetry technique. The distribution regularity and the relationship with other parameters were discussed. The results were as follows： Copper complexing ligand concentrations of the South China Sea were a little higher than those of other sea areas, and they were apparently higher than those of the ocean. Compared with the subsurface layer （SSL） in the sea surface microlayer copper complexing ligand concentrations showed an enrichment phenomenon, of which the mechanism is similar to dissolved organic matter. The metal complexing ligand concentration profiles of the South China Sea showed that the value in the sea surface was the highest, then it decreased with depth accruing, and a higher value appeared at the bottom. Copper complex- ing ligand concentrations were higher than those of cadmium and lead. Ligands in each sea area exhibited a complicated property. In short, the distribution regularity of copper complexing ligand concentrations in China＇s coastal waters was consistent with that of other regions in the world. Meanwhile, the positive relationship between the copper complexing ligand concentrations and biological oxygen demand, chemical oxygen demand, dissolved organic carbon, and viscosity were found clearly.
文摘The photoluminescent (PL) and electroluminescent (EL) properties of a series of ligand emitting rare earth complexes (including Y^(3+), La^(3+), Gd^(3+) and Lu^(3+)) were systematically studied. These complexes have the same anionic ligand, 1-phenyl-3-methyl-4-isobutyryl-5-pyrazoloneate (PMIP), and three neutral ligands, triphenyl phosphine oxide (TPPO), 2, 2′-dipyridine (Bipy) and phenanthroline (Phen). Measured with 60 nm thin film of these complexes vaporized in vacuum on quartz substrates, a good regularity in the PL properties was observed. For rational comparison, the same structural EL devices based on these complexes, ITO/PVK (40 nm)/the complex (80 nm)/Mg: Ag (200 nm)/Ag (100 nm), were fabricated. Excluding the exciplex emission happens, the EL luminance usually increases with the increasing of PL efficiency.
文摘Reaction of Cu(ClO4)2'6H2O with tripodal ligand tri s (2-benzi nd dazol yl methyl ) aInine(ntb) and sodium isonicotinate (Iso) yielded a mononuclear complex lCu(ntb)(lso)]ClO4.3.5H2O. Thestructure has been established by X-ray crystallography The Cu (Ⅱ) atom is in a distorted trigonalbipyranddal environment with three benzimindazole N atoms of ntb defining the equatorial plane, oneandne N atom of ntb, and one O atom of the carboxylate group of isonicotinate occupying the axialpositions.
基金This work was financially supported by the NNSFC (No. 20431010 and 20171012)
文摘The copper complex Cu（C12H9N2O3）2 has been synthesized by the reaction of furaldehyde salicylylhydrazone （Hfs） and copper acetylacetonate and characterized by X-ray crystal diffraction and spectroscopic studies. The crystal crystallizes in space group P211n with a = 5.9765（3）, b = 15.7196（9）, c = 12.0514（6）A,β= 101.618（3）^o, V = 1109.0（1）A^3, C24H18CuN4O6, Mr = 521.96, Z = 2, Dc = 1.563 g/cm^3, μ = 1.035 mm^-1, F（000） = 534, R = 0.0373 and wR = 0.1058 for 2283 observed reflections （I 〉 2σ（I））. The copper atom has a square-planar CuN2O2 coordination and should be in an octahedral coordination if considering Cu-O （phenol） with distances of 2.796（2）A as weak bonds. The neighboring copper complex molecules are linked together by these weak Cu-O （phenol） bonds, resulting in an extended 1D chain. The title compound exhibits paramagnetic property and fluorescence behavior at room temperature supported by the EPR and fluorescence spectra.
文摘<span style="font-family:Verdana;">Coordination compounds of 2-amino-3-methylbutanoic acid were synthesized with chromium(III) and oxovanadium(IV) ions. M:L;1:2. Adducts of these complexes using 1,10-phenantroline and ethylenediamine were further synthesized, M:L, (1:2). These compounds were characterized using electronic, infra-red spectrophotometry, magnetic susceptibility measurement and percentage metal analyses. The zones of inhibition and minimum inhibitory concentrations of the compounds against eight microbes were studied. The results obtained indicated an octahedral geometry for the Cr(III) complexes, indicative of additional coordination of two water molecules. On the other hand a square pyramid geometry was obtained for the binary oxovanadium complex and its 1,10-phenantroline adduct. However</span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">,</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;"> for the oxovanadium ethylenediamine adduct a distorted octahedral geometry was proposed. The result for the antibacterial studies indicated that both mixed ligand complexes of 1,10-phenantroline exhibited good antibacterial activity, and in some cases better activity than the standard, streptomycin.</span></span></span>
文摘A ditopic ligand bpy-cyclam(L)and its heterometallo-binuclear complex Ru(bpy)_2(bpy-cyclam-Ni)(ClO_4)_43H_2O(3)designed for use in the catalytic photoreduction of carbon dioxide have been newly synthesized and characterized.The protonation constants of L were also determined.
文摘<span style="font-family:Verdana;">Coordination compounds of 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one with </span><span style="font-family:Verdana;">iron(III), cobat(III) and chromium(III) were synthesized with M:L (1:2)</span><span style="font-family:Verdana;">. Mixed ligand coordination compounds of 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one and 1,2-diaminocyclohexane using the same metal ions were also synthesized </span><b><span style="font-family:Verdana;">M:L1</span></b><span style="font-family:Verdana;">:</span><b><span style="font-family:Verdana;">L2</span></b><span style="font-family:Verdana;"> (1:1:1) where </span><b><span style="font-family:Verdana;">L1</span></b><span style="font-family:Verdana;"> is 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one and </span><b><span style="font-family:Verdana;">L2</span></b><span style="font-family:Verdana;"> is 1,2-diaminocyclohexane. The coordination compounds obtained were characterized using electronic and infrared spectral analyses, magnetic susceptibility and percentage metal analysis. They were also evaluated for their cytotoxic and antioxidant activities. The result obtained suggested that octahedral geometry was obtained for all the compounds, as a result of additional two molecules of the solvent coordinated to the metal ions. Both the primary and secondary ligands coordinated in a bidentate fashion. The synthesized compounds exhibited moderate cytotoxicity, although none was as active as the standard. The cobalt(III) mixed ligand complex elicited the highest activity. The synthesized compounds all exhibited good to moderate antioxidant activity.</span>
文摘Co(II) and Cr(III) metal complexes of Schiff bases were synthesized from the condensation reaction between 4-(dimethylamino)benzaldehyde and 4-amino-3-hydroxy-naphthalene-1-sulfonic acid. Their structures were investigated by elemental analysis, molar conductance measurements, infrared spectroscopy, electronic spectroscopy, and 1HNMR spectroscopy. The elemental analysis data suggested a 1:1 [M:L] ratio for the complexes. The molar conductance measurements of the complexes indicate their electrolytic nature in DMSO as a solvent. The absorption bands in the electronic spectra verified an octahedral environment around the metal ions in the complexes.
文摘A rapid method is applied to analyze conjugated organic ligands bridged binuclear ruthenium complexes by electrospray ionization-tandem mass spectrometry (ESI MSn).Fragmentation pattern be discussed.
基金Financial supports of this research by the National Natural Science Foundation of China(Nos.21171025 and 21101015)New Century Excellent Talents in University(No.NCET-09-0853)+1 种基金Natural Science Foundation of Liaoning Province(No.201102003)Program of Innovative Research Team in University of Liaoning Province(No.LT2012020)
文摘One new polyoxometalate （POM）-based inorganic-organic hybrid [Cdn3~HPO4）（Hbpp）（H20）2]{CdII[P4_ Mo6028H3.s（OH）312}.（H4tpb）.7H20 （1） （bpp = 1,3-bis-（4-pyridyl）propane, tpb = 1,2,4,5-tetra（4-pyridyl）- benzene） constructed from reduced molybdophosphate [P4Mo6028H3.5（OH）3]s＇5- （P4Mo6）, trinuclear Cdn-phosphate-Hbpp fragment and protonated tpb has been hydrothermally synthesized and structurally characterized by IR, elemental analyses and single crystal X-ray diffraction. The complex 1 crystallizes in the monoclinic system with the space group P21]c and cell parameters of a=15.672（12）A, b=23.839（19）A, c=27.654（2）,~, fl=115.850（10）~, V=9297.9（12） ~3, Z=4, R1 ~0.0534 and wR2 ~0.1135. In complex 1, the P4Mo6 units are bridged by CdII ions to form the classic sandwich-type [Cd（P4Mo6）2] dimers, which are further connected into a two dimensional network via the trinuclear Cdn subunits. The tpb is synthesized in situ from the bpp ligands and connects the adjacent 2D layers into a 3D supramolecular framework through hydrogen bonding interactions. The electrochemical and fluorescent properties of complex 1 have been investigated.
文摘The deprotonated derivative pyridine-2-thiolato （PyS<sup>-</sup>） of pyridine-2-thione （PySH）is a potentially amibidentate or multi-functional donor which coordinates toward transitionmetals with either the exocyclic S or heterocyclic N atom or both atoms to form differentcoordination modes. We have recently reported the synthesis and crystal structure ofthe first dinuclear molybdenum complex with doubly-bridging PyS ligands [Mo<sub>2</sub>（CO）<sub>4</sub>（μ-PyS）<sub>2</sub>（PPh<sub>3</sub>）<sub>2</sub>]which was obtained from the reaction of [Mo（CO）<sub>3</sub>（CH<sub>3</sub>CN）<sub>3</sub>]
