The effect of Co complexes with a Schiff base ligand on the electrochemical corrosion behavior of 316 L SS in 0.1 M H<sub>2</sub>SO<sub>4</sub> at 25℃ has been investigated at various inhibito...The effect of Co complexes with a Schiff base ligand on the electrochemical corrosion behavior of 316 L SS in 0.1 M H<sub>2</sub>SO<sub>4</sub> at 25℃ has been investigated at various inhibitor concentration using electrochemical techniques (impedance spectroscopy (EIS), polarization curves). Corrosion measurements indicate that Co complex act as moderately inhibitors. Results revealed that increasing the concentration of Co complex increases the corresponding IE% values till 100 ppm. Co complex acts as mixed type inhibitors with predominant effect on the anodic dissolution of iron. Adsorption studies showed that the process follows Langmuir adsorption isotherm.展开更多
A new ab initio potential energy surface of the Ne-CO complex is developed using single and double excitation coupled-cluster theory with noniterative treatment of triple excitations [CCSD（T）]. The potential has a m...A new ab initio potential energy surface of the Ne-CO complex is developed using single and double excitation coupled-cluster theory with noniterative treatment of triple excitations [CCSD（T）]. The potential has a minimum value of -49.396 cm-1 at Re = 6.40α0 with approximately T-shaped geometry （θe=82.5°）. Bound state energies are calculated up to J = 12. The theoretically predicted transition frequencies and spectroscopic constants are in good agreement with the available experimental results.展开更多
The title compound, [Co(C16H10N2S4)2(H2O)4](C14H9N2O4)2(1,C16H10N2S4=4-pyridine-tetrathiafulvalene-4-pyridine and C14 H9 N2 O4 = 4-(4-carboxyphenyl)diazenyl)benzoate),has been successfully synthesized under hydrotherm...The title compound, [Co(C16H10N2S4)2(H2O)4](C14H9N2O4)2(1,C16H10N2S4=4-pyridine-tetrathiafulvalene-4-pyridine and C14 H9 N2 O4 = 4-(4-carboxyphenyl)diazenyl)benzoate),has been successfully synthesized under hydrothermal conditions. The structure was determined by elemental analyses and single-crystal X-ray diffraction analysis. Moreover, the conductivity property of compound 1 was investigated. Compound 1 crystallizes in triclinic system, space group P1 with a = 6.4006(3), b = 7.1818(4), c = 33.0932(14) ?, α = 89.261(4), β = 86.530(3), γ = 66.642(4)°, V =1393.90(12) ?3, Z = 1, C60 H46 N8 O12 S8 Co, M3 r = 1386.46, Dc = 1.652 g/cm, μ = 0.684 mm-1 and F(000) = 713. The final R = 0.0411 and wR = 0.0810 for 3936 observed reflections with I > 2σ(I).Compound 1 contains one-half of the complex cation with the CoI I ion located on an inversion center,and one 4-(4-carboxyphenyl)diazenyl)benzoate counter anion. The Co atom has a N2 O4 octahedral coordination. Complex 1 forms a three-dimensional supramolecular network and a semiconducting behavior is observed with srt= 0.04 S·cm-1.展开更多
The coordination complex of Co（Ⅲ） based on a macrocyclic triamine ligand 1,4-diacetate-1,4,7-triazacyclodecane （L） has been synthesized and characterized. The metal cation is bonded with three nitrogen atoms and ...The coordination complex of Co（Ⅲ） based on a macrocyclic triamine ligand 1,4-diacetate-1,4,7-triazacyclodecane （L） has been synthesized and characterized. The metal cation is bonded with three nitrogen atoms and two oxygen atoms of L and one chloride ion to form a distorted octahedral geometry. This complex coordinated with macrocyclic ligand possesses large pore volume that will be contributed to observe high H2 adsorption. With respect to the first-principles electronic structure calculations, the feasibility to store hydrogen in the complex is explored. Indeed, the complex has shown a very high total H2 adsorption of 7.2 wt% （wt% = （weight of adsorbed H2）/（weight of host material））, with a binding energy of 0.03 eV/H2展开更多
Several silica-supported poly-γ-aminopropylsiloxane-monometal and bimetal complexes (Si-NH_2-M,M = Cu or Co ; Si-NH_2-Cu-M', M' =Co, Sn, Mn, Ni or Fe) have been prepared. Their catalytic properties for oxidat...Several silica-supported poly-γ-aminopropylsiloxane-monometal and bimetal complexes (Si-NH_2-M,M = Cu or Co ; Si-NH_2-Cu-M', M' =Co, Sn, Mn, Ni or Fe) have been prepared. Their catalytic properties for oxidative ethoxycarbonylation of aniline to ethyl phenylcarbamate have been investigated.The catalytic reaction was carried out under relatively mild conditions. The catalyst Si-NH_2-Cu-CO had high activity and selectivity, and the turn-over number (molar of aniline converted/molar of metal in Si-NH_2-Cu-CO added) could amount to 450 under the conditions: 150℃ , 4 MPa (CO/O_2 =3) and 40 hours.The results of XPS and IR indicated that the coordination bonds were formed between nitrogen and metals in Si-NH2-Cu, Si-NH_2-Co and Si-NH_2-Cu-Co, and the coordination pattern was not single. In the oxidative ethoxycarbonylation of aniline to ethyl phenylcarbamate, the catalytic property of Si-NH_2-Cu-CO bimetallic complex was better than Si-NH_2-Cu or Si-NH_2-Co monometatlic complex. This indicated that there as synergistic action between different metals in the bimetallic complex.展开更多
In this research, the absorbance and luminescence response of two osmium(II) phenathrane (phen) carbonyl complexes to various DNA, heparin and i-carrageenan polyanions were studied. The [Os(phen)<sub>2</sub&g...In this research, the absorbance and luminescence response of two osmium(II) phenathrane (phen) carbonyl complexes to various DNA, heparin and i-carrageenan polyanions were studied. The [Os(phen)<sub>2</sub>CO(L)]<sup>2+</sup> complexes with L either a 4-phenyl pyridine (4-phpy) or phenyl imidazole (phimd) group exhibit moderate luminescent intensity in the visible region, their intensities are highly altered by the addition of DNA and other polyanion samples. These luminescent responses to polyanions were also compared with the [Ru(phen)<sub>3</sub>]<sup>2+</sup> complex. In ethanol solution, the presence of polyanions significantly enhanced the luminescent emission intensity of [Os(phen)<sub>2</sub>CO(L)]<sup>2+</sup> complexes with a blue shift. While the polyanions all showed emission enhancement on the highly lumi-nescent [Ru(phen)<sub>3</sub>]<sup>2+</sup> complex in ethanol solution with a red spectra shift. The [Os(phen)<sub>2</sub>CO(L)] <sup>2+</sup> with (phimd) ligand has the lowest emission in ethanol solution, its intensity can be enhanced up to 11 times in the presence of DNA polyanions. This enhancement for all the complexes in ethanol is mainly due to their electrostatic interaction with the anion sites and with some degree of ligand intercalation into the polyanion hydrophobic structure which reduced the solvent quenching of the complexes. The blue shift of the (4-phpy) and particularly (phimd) Os(II)CO complexes indicate an insertion of the (4-phpy) or (phimd) group into the polymer chains. The two new Os(II)CO complexes has great potential to be used as luminescence sensors for DNA and polyanion detection in the low micro molar range with high sensitivity.展开更多
A novel imidazole derivative with functional group and π-conjugated system, 1- [trans-4-（4-diethylaminostyryl）phenyl]imidazole （abbreviated as L）, and its Con complex （COCl2L4）2 （Co2C168H184N24Cl4, Mr = 2799....A novel imidazole derivative with functional group and π-conjugated system, 1- [trans-4-（4-diethylaminostyryl）phenyl]imidazole （abbreviated as L）, and its Con complex （COCl2L4）2 （Co2C168H184N24Cl4, Mr = 2799.05 ） have been synthesized and the crystal structure of the latter was determined by X-ray diffraction. The crystal is of triclinic, space group PI with a = 8.823（3）, b = 18.799（7）, c =23.065（9） A, α = 77.349（6）, β = 83.128（7）, ）, γ= 80.942（3）°, V = 3671.5（12） A^3, Z = 1, Dc = 1.266 g/cm^3,/z = 0.361 mm^-1 F（000） = 1482, the final R = 0.0587 and wR = 0.1284 for 6562 observed reflections with I 〉 2σ（I）. In the molecular structure of （COCl2L4）2, there are two crystallographically unique units. The Co^Ⅱ atoms are six-coordinated by four N atoms from four imidazole ligands （L） and two Cl atoms to form a distorted octahedral geometry. The optical properties of complex （COCl2L4）2 have been experimentally studied.展开更多
Two new coordination polymers [Co（oba）（mbix）]2n·nH2O （1） and [Mn（Hoba）2（H2O）2]n （2） （H2oba = 4,4＇-oxydibenzoic acid, mbix = 1,3-bis（imidazol-1-ylmethyl）benzene） have been successfully synthesized...Two new coordination polymers [Co（oba）（mbix）]2n·nH2O （1） and [Mn（Hoba）2（H2O）2]n （2） （H2oba = 4,4＇-oxydibenzoic acid, mbix = 1,3-bis（imidazol-1-ylmethyl）benzene） have been successfully synthesized under hydrothermal conditions. Their structures have been determined by elemental analyses, IR spectroscopy, UV and single-crystal X-ray diffraction analysis. The intermolecular hydrogen bonding and π-π stacking interactions extend the complexes into a 3D supramolecular structure.展开更多
Two new complexes[Mn(DHTA)(PLQ)]_(n)(1)and{[Co_(2)(DHTA)(phen)_(2)(H_(2)O)_(6)]·DHTA}_(n)(2)(H_(2)DHTA=2,5-dihydroxy-1,4-benzenedicarboxylic acid,PLQ=1,10-phenanthroline-5,6-quinone,phen=1,10-phenanthroline)have ...Two new complexes[Mn(DHTA)(PLQ)]_(n)(1)and{[Co_(2)(DHTA)(phen)_(2)(H_(2)O)_(6)]·DHTA}_(n)(2)(H_(2)DHTA=2,5-dihydroxy-1,4-benzenedicarboxylic acid,PLQ=1,10-phenanthroline-5,6-quinone,phen=1,10-phenanthroline)have been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,fluorescence spectrum,single-crystal and power X-ray diffraction.Complex 1 exhibits a two-dimensional(2 D)network,which was stabilized through O–H···O hydrogen bonding interactions.Complex 2 shows a zero-dimensional structure,which was further extended into a three-dimensional supramolecular structure through O–H···O hydrogen bonds andπ-πinteractions.展开更多
A new cobalt(Ⅱ) complex with tridentate ligand 2, 6-bis (benzimidazol- 2-yl)pyridine has been synthesized by microwave irradiation method and characterized by elemental analysis, electrochemical and spectral methods....A new cobalt(Ⅱ) complex with tridentate ligand 2, 6-bis (benzimidazol- 2-yl)pyridine has been synthesized by microwave irradiation method and characterized by elemental analysis, electrochemical and spectral methods. The binding of the complex with calf thymus DNA has also been investigated by absorption and fluorescence spectra.展开更多
The cobalt（II） complex with （quinolin-8-yloxy）acetate, [CoCl（C11H8NO3）]n （1）, has been prepared via the solvothermal method and characterized by IR, elemental analysis, UV- Vis diffuse-reflection spectra and s...The cobalt（II） complex with （quinolin-8-yloxy）acetate, [CoCl（C11H8NO3）]n （1）, has been prepared via the solvothermal method and characterized by IR, elemental analysis, UV- Vis diffuse-reflection spectra and single-crystal X-ray diffraction analysis. Complex 1 is a novel carboxylate-bridged one-dimensional helical cobalt（II） polymer, and the Co（II） centre exhibits an approximately square pyramidal CoClNO3 coordination geometry. It crystallizes in monoclinic, space group P21/n, with a = 9.1594（10）, b = 6.8864（7）, c = 17.290（2） , β = 102.629（3）o, C11H8ClCoNO3, Mr = 296.56, V = 1064.2（2） 3, Z = 4, Dc = 1.851 g/cm3, F（000） = 596, μ = 1.856 mm-1, the final R = 0.0308 and wR = 0.0807. Interestingly, the chain complexes are assembled to form two-dimensional networks through intermolecular face-to-face π-π stacking interactions with the centroid-to-centroid distance of 3.559（1） and the dihedral angle of 8.4（1）° between the aromatic rings.展开更多
A new 4-chlorobenzoic acid bridge Co（Ⅱ ） complex [[Co2（2,2＇-bpy）2（μ-L）e（L）2（μ-H2O）] （HL = 4-chlorobenzoic acid） has been obtained by hydrothermal synthesis, and X-ray single-crystal diffraction analysi...A new 4-chlorobenzoic acid bridge Co（Ⅱ ） complex [[Co2（2,2＇-bpy）2（μ-L）e（L）2（μ-H2O）] （HL = 4-chlorobenzoic acid） has been obtained by hydrothermal synthesis, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group C2/c with a = 22.537（5）, b = 16.212（3）, c = 15.306（3） A, β= 124.37（3）°, V= 4616.1（16）A3, Mr = 1070.45, Dc = 1.540 g/cm3, Z = 4, p = 1.012 mm-1, F（000） = 2176, the final R = 0.0338 and wR= 0.0810. The title complex is composed of dinuclear [Co2（2,2＇-bpy）2（μ-L）2（L）2（μ-HaO）] molecules. Each Co（Ⅱ ） atom is coordinated by two nitrogen atoms from one 2,2’-bipyridine ligand, three oxygen atoms from three 4-chlorobenzoic ions and another oxygen atom from one water molecule. The two Co（Ⅱ） atoms are connected by two 4-chlorobenzoic ions and one bridged water molecule. The dinuclear molecules are interlinked by hydrogen bond and π-π stacking interactions into a three-dimensional supramolecular network.展开更多
The synthesis, characterization of five ditopic or tritopic crown compounds were reported in this paper together with the preparation of the corresponding hetero-dinuclear and hetero-trinuclear complexes with differen...The synthesis, characterization of five ditopic or tritopic crown compounds were reported in this paper together with the preparation of the corresponding hetero-dinuclear and hetero-trinuclear complexes with different metal cations.展开更多
Novel 4-Chloro-2-[(1-phenyl-1H-tetrazol-5-ylimino)-methyl] phenol (Cl-PTMP) and its transition metal complexes were synthesized and characterized by FT-IR, 1H-NMR, UV-Vis spectroscopy, Mass spectrometry, TGA and SEM. ...Novel 4-Chloro-2-[(1-phenyl-1H-tetrazol-5-ylimino)-methyl] phenol (Cl-PTMP) and its transition metal complexes were synthesized and characterized by FT-IR, 1H-NMR, UV-Vis spectroscopy, Mass spectrometry, TGA and SEM. The pH-metric technique was applied to get an insight of the number of dissociable protons and protonation sites in candidate compound. The pH-Metric studies were also carried out in presence of metal ions to establish the formation of corresponding metal complexes in solution. Further, the metal ligand compositions of Cu (II) and Co (II) complexes were determined spectrophotometrically by employing Job’s continuous variation method. To know the molecular properties in title imine compound suitable for metal ion coordination, the computational studies were carried out by employing HyperChem 7.5 tools. The energies of HOMO and LUMO frontier orbitals and their electron density contour maps were generated with geometry optimized molecule. Biological activity of Cl-PTMP and its metal complexes was investigated by disc diffusion method.展开更多
A series of rare earth complexes Tb_(1-x)Eu_x(MAA)_3phen(x=0.00, 0.01, 0.03, 0.05, 0.07, 0.09, 0.10, 0.30, and 0.50) were synthesized with MAA as the first ligand and phen as the second ligand. The complexes were char...A series of rare earth complexes Tb_(1-x)Eu_x(MAA)_3phen(x=0.00, 0.01, 0.03, 0.05, 0.07, 0.09, 0.10, 0.30, and 0.50) were synthesized with MAA as the first ligand and phen as the second ligand. The complexes were characterized by means of FT-IR, thermogravimetry-differential scanning calorimetry (TG-DSC), XRD, UV absorption spectra, and photoluminescence spectra (PL). The results show that the luminescence intensity of Eu^(3+)increases as Tb^(3+) transfer the absorbed energy to Eu^(3+) in the complexes. The emission of Tb^(3+) at 545 nm is observed and increasing with x decreasing. When x=0.01, the luminescence intensity reaches the maximum value, and the emission intensity of Tb 3+ at 545 nm and Eu^(3+) at 614 nm are almost equal. It realizes the co-luminescence of Eu^(3+) and Tb^(3+) . We can obtain complexes with different colors by adjusting the ratio of Eu^(3+) to Tb^(3+) .展开更多
Co（Ⅱ）-salen was encapsulated in MIL- 100（Cr） metal organic framework by ＂ship in a bottle＂ to synthesize a new electrocatalyst, Cosalen@MIL- 100（Cr）. The material was characterized by XRD, FT-IR, UV-Vis and N...Co（Ⅱ）-salen was encapsulated in MIL- 100（Cr） metal organic framework by ＂ship in a bottle＂ to synthesize a new electrocatalyst, Cosalen@MIL- 100（Cr）. The material was characterized by XRD, FT-IR, UV-Vis and N2-adsorption. The Cosalen@MIL-100（Cr） modified glassy carbon electrode exhibits a well-defined reduction peak at the potential of -0.21 V toward the oxygen reduction reaction （ORR） by cyclic voltam- metry （CV） in pH = 6.84 phosphate buffer. Almost 400 mV positive shift of potential at Cosalen@MIL-100（Cr） modified electrode for ORR compared with that at bare glassy carbon, indicates that Cosalen@MIL-100（Cr） possesses excellent electrocatalytic activity. The transferred number of electrons for ORR was determined by chronocoulometry. The result suggests that the introduction of Co（II）-salen complex into MOF increases the electrocatalytic activity via a four-electron reduction pathway. Furthermore, this electrocatalyst exhibits good stability and reproducibility.展开更多
The Co（II） complex I and ammonium salt II were synthesized from the direct reaction of 1,2-ethylenediamine and cobaltous acetate tetrahydrate and manganese acetate tetrahydrate in anhydrous ethanol. Treatment of N,N...The Co（II） complex I and ammonium salt II were synthesized from the direct reaction of 1,2-ethylenediamine and cobaltous acetate tetrahydrate and manganese acetate tetrahydrate in anhydrous ethanol. Treatment of N,N＇-bis（salicylidene）ethylenediamine with Cu（OAc）2·H2O results in the formation of Cu（II） complex III. C14H37CoNaO8 （I）： triclinic, space group P1, a = 8.6296（12）, b = 12.0291（17）, c = 12.1108（17） A, α = 75.335（2）, β = 69.991（2）, γ = 72.248（2）°, V= 1109.4（3） A3, Z = 2, ρcaloa = 1.342 g/cm3, the final R= 0.0342 for 4817 observed reflections with I 〉 2σ（I） and Rw = 0.1263 for all data. C6H16N204 （II）： space group P1, a = 5.5513（10）, b = 5.5589（11）, c = 7.4437（14） A, α = 94.332（4）, β = 104.497（4）, γ = 103.487（4）°,V= 214.06（7） A3, Z = 1, ρcalcd = 1.398 g/cm3, the final R = 0.0431 for 829 observed reflections with I〉 2σ（I） and Rw = 0.1263 for all data. C14H37CuN40 （III）, space group P21/n, a = 9.050（9）, b = 18.434（17）, c = 11.659（11） A, β = 107.134（19）°, V= 1859（3） A3, Z = 4, ρcalcd =1.443 g/cm3, the final R = 0.0616 for 3308 observed reflections （O 〉 2σ（I）） and Rw = 0.1229 for all data. Their structures were all determined by X-ray diffraction, elemental analysis and IR.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
The geometries of van der Waals complex CO 2...CO were optimized at DFT and second order Moller Plesset perturbation(MP2) levels with the large basis set, three stable structures were found. The most stable structu...The geometries of van der Waals complex CO 2...CO were optimized at DFT and second order Moller Plesset perturbation(MP2) levels with the large basis set, three stable structures were found. The most stable structure has a T shape geometry in which the CO lies along the C 2 axis of CO 2, with the two C atoms direct contact and R (C...C)=0 3227 nm. The corresponding energies of the most stable structure were calculated by means of MP2, MP4D, MP4DQ, MP4SDTQ, MP4SDQ, CCSD and CCSD(T) methods. The BSSE(basis set superposition error) was eliminated by the Boys Bernardi counterpoise correction(CP) method. According to thermodynamics data, van der Waals complex CO 2...CO can be found at a low temperature and/or a high pressure. There is a little charge transferred between the two interacted subunits. In the most stable structure, CO 2 is the acceptor and CO is the donor.展开更多
文摘The effect of Co complexes with a Schiff base ligand on the electrochemical corrosion behavior of 316 L SS in 0.1 M H<sub>2</sub>SO<sub>4</sub> at 25℃ has been investigated at various inhibitor concentration using electrochemical techniques (impedance spectroscopy (EIS), polarization curves). Corrosion measurements indicate that Co complex act as moderately inhibitors. Results revealed that increasing the concentration of Co complex increases the corresponding IE% values till 100 ppm. Co complex acts as mixed type inhibitors with predominant effect on the anodic dissolution of iron. Adsorption studies showed that the process follows Langmuir adsorption isotherm.
文摘A new ab initio potential energy surface of the Ne-CO complex is developed using single and double excitation coupled-cluster theory with noniterative treatment of triple excitations [CCSD（T）]. The potential has a minimum value of -49.396 cm-1 at Re = 6.40α0 with approximately T-shaped geometry （θe=82.5°）. Bound state energies are calculated up to J = 12. The theoretically predicted transition frequencies and spectroscopic constants are in good agreement with the available experimental results.
基金supported by the National Natural Science Foundation of China(21372136)Ningbo Natural Science Foundation 2015A610126
文摘The title compound, [Co(C16H10N2S4)2(H2O)4](C14H9N2O4)2(1,C16H10N2S4=4-pyridine-tetrathiafulvalene-4-pyridine and C14 H9 N2 O4 = 4-(4-carboxyphenyl)diazenyl)benzoate),has been successfully synthesized under hydrothermal conditions. The structure was determined by elemental analyses and single-crystal X-ray diffraction analysis. Moreover, the conductivity property of compound 1 was investigated. Compound 1 crystallizes in triclinic system, space group P1 with a = 6.4006(3), b = 7.1818(4), c = 33.0932(14) ?, α = 89.261(4), β = 86.530(3), γ = 66.642(4)°, V =1393.90(12) ?3, Z = 1, C60 H46 N8 O12 S8 Co, M3 r = 1386.46, Dc = 1.652 g/cm, μ = 0.684 mm-1 and F(000) = 713. The final R = 0.0411 and wR = 0.0810 for 3936 observed reflections with I > 2σ(I).Compound 1 contains one-half of the complex cation with the CoI I ion located on an inversion center,and one 4-(4-carboxyphenyl)diazenyl)benzoate counter anion. The Co atom has a N2 O4 octahedral coordination. Complex 1 forms a three-dimensional supramolecular network and a semiconducting behavior is observed with srt= 0.04 S·cm-1.
基金the Natural Science Foundation of Science and Technology Bureau of Shaanxi Province (No. 2011JM6005)the Special Foundation of Shaanxi Province Education Bureau (No. 10JK548)National Natural Science Foundation for Young Scholars (No.81001669)
文摘The coordination complex of Co（Ⅲ） based on a macrocyclic triamine ligand 1,4-diacetate-1,4,7-triazacyclodecane （L） has been synthesized and characterized. The metal cation is bonded with three nitrogen atoms and two oxygen atoms of L and one chloride ion to form a distorted octahedral geometry. This complex coordinated with macrocyclic ligand possesses large pore volume that will be contributed to observe high H2 adsorption. With respect to the first-principles electronic structure calculations, the feasibility to store hydrogen in the complex is explored. Indeed, the complex has shown a very high total H2 adsorption of 7.2 wt% （wt% = （weight of adsorbed H2）/（weight of host material））, with a binding energy of 0.03 eV/H2
文摘Several silica-supported poly-γ-aminopropylsiloxane-monometal and bimetal complexes (Si-NH_2-M,M = Cu or Co ; Si-NH_2-Cu-M', M' =Co, Sn, Mn, Ni or Fe) have been prepared. Their catalytic properties for oxidative ethoxycarbonylation of aniline to ethyl phenylcarbamate have been investigated.The catalytic reaction was carried out under relatively mild conditions. The catalyst Si-NH_2-Cu-CO had high activity and selectivity, and the turn-over number (molar of aniline converted/molar of metal in Si-NH_2-Cu-CO added) could amount to 450 under the conditions: 150℃ , 4 MPa (CO/O_2 =3) and 40 hours.The results of XPS and IR indicated that the coordination bonds were formed between nitrogen and metals in Si-NH2-Cu, Si-NH_2-Co and Si-NH_2-Cu-Co, and the coordination pattern was not single. In the oxidative ethoxycarbonylation of aniline to ethyl phenylcarbamate, the catalytic property of Si-NH_2-Cu-CO bimetallic complex was better than Si-NH_2-Cu or Si-NH_2-Co monometatlic complex. This indicated that there as synergistic action between different metals in the bimetallic complex.
文摘In this research, the absorbance and luminescence response of two osmium(II) phenathrane (phen) carbonyl complexes to various DNA, heparin and i-carrageenan polyanions were studied. The [Os(phen)<sub>2</sub>CO(L)]<sup>2+</sup> complexes with L either a 4-phenyl pyridine (4-phpy) or phenyl imidazole (phimd) group exhibit moderate luminescent intensity in the visible region, their intensities are highly altered by the addition of DNA and other polyanion samples. These luminescent responses to polyanions were also compared with the [Ru(phen)<sub>3</sub>]<sup>2+</sup> complex. In ethanol solution, the presence of polyanions significantly enhanced the luminescent emission intensity of [Os(phen)<sub>2</sub>CO(L)]<sup>2+</sup> complexes with a blue shift. While the polyanions all showed emission enhancement on the highly lumi-nescent [Ru(phen)<sub>3</sub>]<sup>2+</sup> complex in ethanol solution with a red spectra shift. The [Os(phen)<sub>2</sub>CO(L)] <sup>2+</sup> with (phimd) ligand has the lowest emission in ethanol solution, its intensity can be enhanced up to 11 times in the presence of DNA polyanions. This enhancement for all the complexes in ethanol is mainly due to their electrostatic interaction with the anion sites and with some degree of ligand intercalation into the polyanion hydrophobic structure which reduced the solvent quenching of the complexes. The blue shift of the (4-phpy) and particularly (phimd) Os(II)CO complexes indicate an insertion of the (4-phpy) or (phimd) group into the polymer chains. The two new Os(II)CO complexes has great potential to be used as luminescence sensors for DNA and polyanion detection in the low micro molar range with high sensitivity.
基金This work was supported by the National Natural Science Foundation of China (50532030, 50335050, and 50325311) and Education Committee of Anhui Province (2006KJ158B)
文摘A novel imidazole derivative with functional group and π-conjugated system, 1- [trans-4-（4-diethylaminostyryl）phenyl]imidazole （abbreviated as L）, and its Con complex （COCl2L4）2 （Co2C168H184N24Cl4, Mr = 2799.05 ） have been synthesized and the crystal structure of the latter was determined by X-ray diffraction. The crystal is of triclinic, space group PI with a = 8.823（3）, b = 18.799（7）, c =23.065（9） A, α = 77.349（6）, β = 83.128（7）, ）, γ= 80.942（3）°, V = 3671.5（12） A^3, Z = 1, Dc = 1.266 g/cm^3,/z = 0.361 mm^-1 F（000） = 1482, the final R = 0.0587 and wR = 0.1284 for 6562 observed reflections with I 〉 2σ（I）. In the molecular structure of （COCl2L4）2, there are two crystallographically unique units. The Co^Ⅱ atoms are six-coordinated by four N atoms from four imidazole ligands （L） and two Cl atoms to form a distorted octahedral geometry. The optical properties of complex （COCl2L4）2 have been experimentally studied.
基金supported by the Science and Technology Development Project of Jilin Provincial Science & Technology Department(201205080)the Science and Technology Research Projects of the Education Office of Jilin Province(No.2013.384)
文摘Two new coordination polymers [Co（oba）（mbix）]2n·nH2O （1） and [Mn（Hoba）2（H2O）2]n （2） （H2oba = 4,4＇-oxydibenzoic acid, mbix = 1,3-bis（imidazol-1-ylmethyl）benzene） have been successfully synthesized under hydrothermal conditions. Their structures have been determined by elemental analyses, IR spectroscopy, UV and single-crystal X-ray diffraction analysis. The intermolecular hydrogen bonding and π-π stacking interactions extend the complexes into a 3D supramolecular structure.
基金supported by the Science and Technology development plan of Jilin Province(2015052006JH)
文摘Two new complexes[Mn(DHTA)(PLQ)]_(n)(1)and{[Co_(2)(DHTA)(phen)_(2)(H_(2)O)_(6)]·DHTA}_(n)(2)(H_(2)DHTA=2,5-dihydroxy-1,4-benzenedicarboxylic acid,PLQ=1,10-phenanthroline-5,6-quinone,phen=1,10-phenanthroline)have been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,fluorescence spectrum,single-crystal and power X-ray diffraction.Complex 1 exhibits a two-dimensional(2 D)network,which was stabilized through O–H···O hydrogen bonding interactions.Complex 2 shows a zero-dimensional structure,which was further extended into a three-dimensional supramolecular structure through O–H···O hydrogen bonds andπ-πinteractions.
文摘A new cobalt(Ⅱ) complex with tridentate ligand 2, 6-bis (benzimidazol- 2-yl)pyridine has been synthesized by microwave irradiation method and characterized by elemental analysis, electrochemical and spectral methods. The binding of the complex with calf thymus DNA has also been investigated by absorption and fluorescence spectra.
基金Supported by the Science and Technology Foundation of Ministry of Development of China (2010-K6-8)Science Foundation of Suzhou University of Science and Technology
文摘The cobalt（II） complex with （quinolin-8-yloxy）acetate, [CoCl（C11H8NO3）]n （1）, has been prepared via the solvothermal method and characterized by IR, elemental analysis, UV- Vis diffuse-reflection spectra and single-crystal X-ray diffraction analysis. Complex 1 is a novel carboxylate-bridged one-dimensional helical cobalt（II） polymer, and the Co（II） centre exhibits an approximately square pyramidal CoClNO3 coordination geometry. It crystallizes in monoclinic, space group P21/n, with a = 9.1594（10）, b = 6.8864（7）, c = 17.290（2） , β = 102.629（3）o, C11H8ClCoNO3, Mr = 296.56, V = 1064.2（2） 3, Z = 4, Dc = 1.851 g/cm3, F（000） = 596, μ = 1.856 mm-1, the final R = 0.0308 and wR = 0.0807. Interestingly, the chain complexes are assembled to form two-dimensional networks through intermolecular face-to-face π-π stacking interactions with the centroid-to-centroid distance of 3.559（1） and the dihedral angle of 8.4（1）° between the aromatic rings.
基金supported by the Science and Technology Bureau of Jinhua City (No. 2003-01-179)
文摘A new 4-chlorobenzoic acid bridge Co（Ⅱ ） complex [[Co2（2,2＇-bpy）2（μ-L）e（L）2（μ-H2O）] （HL = 4-chlorobenzoic acid） has been obtained by hydrothermal synthesis, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group C2/c with a = 22.537（5）, b = 16.212（3）, c = 15.306（3） A, β= 124.37（3）°, V= 4616.1（16）A3, Mr = 1070.45, Dc = 1.540 g/cm3, Z = 4, p = 1.012 mm-1, F（000） = 2176, the final R = 0.0338 and wR= 0.0810. The title complex is composed of dinuclear [Co2（2,2＇-bpy）2（μ-L）2（L）2（μ-HaO）] molecules. Each Co（Ⅱ ） atom is coordinated by two nitrogen atoms from one 2,2’-bipyridine ligand, three oxygen atoms from three 4-chlorobenzoic ions and another oxygen atom from one water molecule. The two Co（Ⅱ） atoms are connected by two 4-chlorobenzoic ions and one bridged water molecule. The dinuclear molecules are interlinked by hydrogen bond and π-π stacking interactions into a three-dimensional supramolecular network.
基金the National Natural Science Foundation of China (29872034) and the Natural Science Foundation of Henan Province for the financi
文摘The synthesis, characterization of five ditopic or tritopic crown compounds were reported in this paper together with the preparation of the corresponding hetero-dinuclear and hetero-trinuclear complexes with different metal cations.
文摘Novel 4-Chloro-2-[(1-phenyl-1H-tetrazol-5-ylimino)-methyl] phenol (Cl-PTMP) and its transition metal complexes were synthesized and characterized by FT-IR, 1H-NMR, UV-Vis spectroscopy, Mass spectrometry, TGA and SEM. The pH-metric technique was applied to get an insight of the number of dissociable protons and protonation sites in candidate compound. The pH-Metric studies were also carried out in presence of metal ions to establish the formation of corresponding metal complexes in solution. Further, the metal ligand compositions of Cu (II) and Co (II) complexes were determined spectrophotometrically by employing Job’s continuous variation method. To know the molecular properties in title imine compound suitable for metal ion coordination, the computational studies were carried out by employing HyperChem 7.5 tools. The energies of HOMO and LUMO frontier orbitals and their electron density contour maps were generated with geometry optimized molecule. Biological activity of Cl-PTMP and its metal complexes was investigated by disc diffusion method.
基金supported by the National Defense Fundamental Research of China(No.6134502-1)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘A series of rare earth complexes Tb_(1-x)Eu_x(MAA)_3phen(x=0.00, 0.01, 0.03, 0.05, 0.07, 0.09, 0.10, 0.30, and 0.50) were synthesized with MAA as the first ligand and phen as the second ligand. The complexes were characterized by means of FT-IR, thermogravimetry-differential scanning calorimetry (TG-DSC), XRD, UV absorption spectra, and photoluminescence spectra (PL). The results show that the luminescence intensity of Eu^(3+)increases as Tb^(3+) transfer the absorbed energy to Eu^(3+) in the complexes. The emission of Tb^(3+) at 545 nm is observed and increasing with x decreasing. When x=0.01, the luminescence intensity reaches the maximum value, and the emission intensity of Tb 3+ at 545 nm and Eu^(3+) at 614 nm are almost equal. It realizes the co-luminescence of Eu^(3+) and Tb^(3+) . We can obtain complexes with different colors by adjusting the ratio of Eu^(3+) to Tb^(3+) .
基金supported by the Program for New Century Excellent Talents in University(NCET-04-0270)the National Basic Research Program of China(2011CB201301)
文摘Co（Ⅱ）-salen was encapsulated in MIL- 100（Cr） metal organic framework by ＂ship in a bottle＂ to synthesize a new electrocatalyst, Cosalen@MIL- 100（Cr）. The material was characterized by XRD, FT-IR, UV-Vis and N2-adsorption. The Cosalen@MIL-100（Cr） modified glassy carbon electrode exhibits a well-defined reduction peak at the potential of -0.21 V toward the oxygen reduction reaction （ORR） by cyclic voltam- metry （CV） in pH = 6.84 phosphate buffer. Almost 400 mV positive shift of potential at Cosalen@MIL-100（Cr） modified electrode for ORR compared with that at bare glassy carbon, indicates that Cosalen@MIL-100（Cr） possesses excellent electrocatalytic activity. The transferred number of electrons for ORR was determined by chronocoulometry. The result suggests that the introduction of Co（II）-salen complex into MOF increases the electrocatalytic activity via a four-electron reduction pathway. Furthermore, this electrocatalyst exhibits good stability and reproducibility.
文摘The Co（II） complex I and ammonium salt II were synthesized from the direct reaction of 1,2-ethylenediamine and cobaltous acetate tetrahydrate and manganese acetate tetrahydrate in anhydrous ethanol. Treatment of N,N＇-bis（salicylidene）ethylenediamine with Cu（OAc）2·H2O results in the formation of Cu（II） complex III. C14H37CoNaO8 （I）： triclinic, space group P1, a = 8.6296（12）, b = 12.0291（17）, c = 12.1108（17） A, α = 75.335（2）, β = 69.991（2）, γ = 72.248（2）°, V= 1109.4（3） A3, Z = 2, ρcaloa = 1.342 g/cm3, the final R= 0.0342 for 4817 observed reflections with I 〉 2σ（I） and Rw = 0.1263 for all data. C6H16N204 （II）： space group P1, a = 5.5513（10）, b = 5.5589（11）, c = 7.4437（14） A, α = 94.332（4）, β = 104.497（4）, γ = 103.487（4）°,V= 214.06（7） A3, Z = 1, ρcalcd = 1.398 g/cm3, the final R = 0.0431 for 829 observed reflections with I〉 2σ（I） and Rw = 0.1263 for all data. C14H37CuN40 （III）, space group P21/n, a = 9.050（9）, b = 18.434（17）, c = 11.659（11） A, β = 107.134（19）°, V= 1859（3） A3, Z = 4, ρcalcd =1.443 g/cm3, the final R = 0.0616 for 3308 observed reflections （O 〉 2σ（I）） and Rw = 0.1229 for all data. Their structures were all determined by X-ray diffraction, elemental analysis and IR.
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(No.2 99730 2 2 ) the Foundation for Key Teachers inuniversity of State Ministry of Education of China and the Natural Science Foundation of Shandong Province.
文摘The geometries of van der Waals complex CO 2...CO were optimized at DFT and second order Moller Plesset perturbation(MP2) levels with the large basis set, three stable structures were found. The most stable structure has a T shape geometry in which the CO lies along the C 2 axis of CO 2, with the two C atoms direct contact and R (C...C)=0 3227 nm. The corresponding energies of the most stable structure were calculated by means of MP2, MP4D, MP4DQ, MP4SDTQ, MP4SDQ, CCSD and CCSD(T) methods. The BSSE(basis set superposition error) was eliminated by the Boys Bernardi counterpoise correction(CP) method. According to thermodynamics data, van der Waals complex CO 2...CO can be found at a low temperature and/or a high pressure. There is a little charge transferred between the two interacted subunits. In the most stable structure, CO 2 is the acceptor and CO is the donor.
