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2013 Volume 29 Issue 12
2013, 29(12): 2509-2513
doi: 10.3969/j.issn.1001-4861.2013.00.399
Abstract:
In this paper, La2O3 doped with varied Ce3+ concentrations were synthesized via hydrothermal co-precipitation followed by high temperature calcined process in H2/N2 atmosphere. Three new peaks show up at 698, 650 and 558 in 17O solid state NMR spectra due to Ce3+ doping. The intensies of these peaks increase with Ce3+ concentration. According to the resonant frequencies and the intensities, the peaks at around 698 and 650, and 558 are assigned to four-coordinated OCeLa3 and six-coordinated OCeLa5 species, respectively. The results show that 17O solid-state NMR spectroscopy can be used to study rare earth doped oxides for applicable functional materials.
In this paper, La2O3 doped with varied Ce3+ concentrations were synthesized via hydrothermal co-precipitation followed by high temperature calcined process in H2/N2 atmosphere. Three new peaks show up at 698, 650 and 558 in 17O solid state NMR spectra due to Ce3+ doping. The intensies of these peaks increase with Ce3+ concentration. According to the resonant frequencies and the intensities, the peaks at around 698 and 650, and 558 are assigned to four-coordinated OCeLa3 and six-coordinated OCeLa5 species, respectively. The results show that 17O solid-state NMR spectroscopy can be used to study rare earth doped oxides for applicable functional materials.
2013, 29(12): 2514-2520
doi: 10.3969/j.issn.1001-4861.2013.00.344
Abstract:
Ru-doped SnO2 semiconductor is a significant component of titanium based oxide acid-resistant anode. Using the first-principle method based on the density functional theory, crystal cells were built, which include SnO2 and variety proportions of Ru-doped SnO2, and electronic structures of Sn1-xRuxO2 semiconductor (x=0, 1/16, 1/12, 1/8, 1/6, 1/4, 1/2) were calculated after geometry optimization. Lattice parameters, electron density, band structure, and density of states are discussed. The results show that the corresponding lattice parameters reduce linearly with composition and the errors between calculated and experimental values of that are within 4%; in addition, the number of electrons filled at the bottom of the conduction band increases after doping, resulting in the strengthening of the conductivity of the solid solution after doping of Ru. The results provide a theoretical basis for the development and application of the Sn1-xRuxO2 solid solutions electrode.
Ru-doped SnO2 semiconductor is a significant component of titanium based oxide acid-resistant anode. Using the first-principle method based on the density functional theory, crystal cells were built, which include SnO2 and variety proportions of Ru-doped SnO2, and electronic structures of Sn1-xRuxO2 semiconductor (x=0, 1/16, 1/12, 1/8, 1/6, 1/4, 1/2) were calculated after geometry optimization. Lattice parameters, electron density, band structure, and density of states are discussed. The results show that the corresponding lattice parameters reduce linearly with composition and the errors between calculated and experimental values of that are within 4%; in addition, the number of electrons filled at the bottom of the conduction band increases after doping, resulting in the strengthening of the conductivity of the solid solution after doping of Ru. The results provide a theoretical basis for the development and application of the Sn1-xRuxO2 solid solutions electrode.
2013, 29(12): 2521-2527
doi: 10.3969/j.issn.1001-4861.2013.00.387
Abstract:
A novel coordination polymer, [Zn3(BTCA)2(4,4'-bipy)2](1) (BTCAH3=5-bromobenzene-1,2,4-tricarboxylic acid, 4,4'-bipy=4,4'-bipyridine) has been synthesized utilizing Zn(OAc)2·2H2O, the rigid 5-bromobenzene-1,2,4-tricarboxylic acid and 4,4'-bipy under the hydrothermal reaction. Compound 1 was characterized by infrared spectroscopy, elemental analysis, thermogravimetric analysis and single crystal X-ray diffraction analysis. In 1, the Zn(Ⅱ) ions are linked through the carboxylate oxygen atoms of the BTCA3- anions, forming a three-dimensional framework structure with 3-nodal and 4-connected net with Schläfli symbol of (4·7·84)2(4·74·8)2(74·82). The 4,4'-bipy ligand coordinates the Zn(Ⅱ) ions in the framework. In addition, the thermal stability and luminescent properties of Compound 1 were also investigated in this paper. CCDC: 811925.
A novel coordination polymer, [Zn3(BTCA)2(4,4'-bipy)2](1) (BTCAH3=5-bromobenzene-1,2,4-tricarboxylic acid, 4,4'-bipy=4,4'-bipyridine) has been synthesized utilizing Zn(OAc)2·2H2O, the rigid 5-bromobenzene-1,2,4-tricarboxylic acid and 4,4'-bipy under the hydrothermal reaction. Compound 1 was characterized by infrared spectroscopy, elemental analysis, thermogravimetric analysis and single crystal X-ray diffraction analysis. In 1, the Zn(Ⅱ) ions are linked through the carboxylate oxygen atoms of the BTCA3- anions, forming a three-dimensional framework structure with 3-nodal and 4-connected net with Schläfli symbol of (4·7·84)2(4·74·8)2(74·82). The 4,4'-bipy ligand coordinates the Zn(Ⅱ) ions in the framework. In addition, the thermal stability and luminescent properties of Compound 1 were also investigated in this paper. CCDC: 811925.
2013, 29(12): 2528-2534
doi: 10.3969/j.issn.1001-4861.2013.00.396
Abstract:
A fluorescent probe of PET mechanism, NBD-Py, was constructed by coupling fluorophore NBD-NH2 with a proton receptor N-(4-pyridylmethyl) ethylene diamine. This probe displays the pH decrease-induced emission enhancement in pH range from 5.0 to 8.5, with a pKa of 6.48. This sensing behavior is reversible and not interfered by normal intracellular metal cations such as Na+, K+, Ca2+, Mg2+ and other transition metal cations. Comparison between the pH sensing behaviors of NBD-Py and its analogue without the N-(4-pyridyl)methyl group disclosed that the pyridylmethyl group is essential its pH sensing ability for weak acidic and near neutral pH, which is important for cell biology. Confocal imaging in HeLa cells confirmed the pHi imaging ability and the lysosome-targetability of NBD-Py, which is valuable for lysosome cell biology.
A fluorescent probe of PET mechanism, NBD-Py, was constructed by coupling fluorophore NBD-NH2 with a proton receptor N-(4-pyridylmethyl) ethylene diamine. This probe displays the pH decrease-induced emission enhancement in pH range from 5.0 to 8.5, with a pKa of 6.48. This sensing behavior is reversible and not interfered by normal intracellular metal cations such as Na+, K+, Ca2+, Mg2+ and other transition metal cations. Comparison between the pH sensing behaviors of NBD-Py and its analogue without the N-(4-pyridyl)methyl group disclosed that the pyridylmethyl group is essential its pH sensing ability for weak acidic and near neutral pH, which is important for cell biology. Confocal imaging in HeLa cells confirmed the pHi imaging ability and the lysosome-targetability of NBD-Py, which is valuable for lysosome cell biology.
2013, 29(12): 2535-2542
doi: 10.3969/j.issn.1001-4861.2013.00.402
Abstract:
Novel CdS photocatalytic nanomaterials were synthesized by a simple "one-pot" hydrothermal biomolecule-assisted method using glutathione (GSH) as the sulfur source and structure-directing reagent. HRTEM, FESEM, XRD, UV-Vis, PL, BET and photo-stimulated surface reaction technology were used to investigate the surface structure, photo absorption property and photocatalytic performance of CdS. Results show that various morphologies of CdS photocatalysts, such as solid nanospheres (s-CdS), hollow nanospheres (h-CdS) and nanorods (r-CdS), were obtained. The photocatalytic activity of s-CdS was superior to that of h-CdS and r-CdS under visible light. The excellent photocatalytic activity of s-CdS was ascribed to the small sizes of subnanocrystallites, which make it easy for photoinduced electrons and holes on the solid sphere to migrate to the surface and react with water and the sacrificial agent quickly.
Novel CdS photocatalytic nanomaterials were synthesized by a simple "one-pot" hydrothermal biomolecule-assisted method using glutathione (GSH) as the sulfur source and structure-directing reagent. HRTEM, FESEM, XRD, UV-Vis, PL, BET and photo-stimulated surface reaction technology were used to investigate the surface structure, photo absorption property and photocatalytic performance of CdS. Results show that various morphologies of CdS photocatalysts, such as solid nanospheres (s-CdS), hollow nanospheres (h-CdS) and nanorods (r-CdS), were obtained. The photocatalytic activity of s-CdS was superior to that of h-CdS and r-CdS under visible light. The excellent photocatalytic activity of s-CdS was ascribed to the small sizes of subnanocrystallites, which make it easy for photoinduced electrons and holes on the solid sphere to migrate to the surface and react with water and the sacrificial agent quickly.
2013, 29(12): 2543-2548
doi: 10.3969/j.issn.1001-4861.2013.00.371
Abstract:
Silicon carbide nanowires were synthesized by mixing formaldehyde resin carbon and nanometer silicon dioxide (atomic Si/C ratio, 1∶1) under cell voltage of 2.0 V in molten CaCl2 at 900 ℃. The morphology, structure and chemical composition of the samples prepared by electro-reduction method were characterized by field-emission scanning electron microscopy (FE-SEM), transmission electronic microscope (TEM), High-resolution transmission electron microscopy (HRTEM) coupled with electron energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and laser Raman spectroscopy. The results reveal that silicon carbide nanowires are crystalline with a cube structure, the diameter is distributed from 4 nm to 13 nm and the length is generally several micrometers. Two broad photoluminescence (PL) peaks at the center wavelength of about 415 nm and 534 nm were observed at room temperature. The formation mechanism of the SiC nanowires is also discussed.
Silicon carbide nanowires were synthesized by mixing formaldehyde resin carbon and nanometer silicon dioxide (atomic Si/C ratio, 1∶1) under cell voltage of 2.0 V in molten CaCl2 at 900 ℃. The morphology, structure and chemical composition of the samples prepared by electro-reduction method were characterized by field-emission scanning electron microscopy (FE-SEM), transmission electronic microscope (TEM), High-resolution transmission electron microscopy (HRTEM) coupled with electron energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and laser Raman spectroscopy. The results reveal that silicon carbide nanowires are crystalline with a cube structure, the diameter is distributed from 4 nm to 13 nm and the length is generally several micrometers. Two broad photoluminescence (PL) peaks at the center wavelength of about 415 nm and 534 nm were observed at room temperature. The formation mechanism of the SiC nanowires is also discussed.
2013, 29(12): 2549-2554
doi: 10.3969/j.issn.1001-4861.2013.00.403
Abstract:
Carbon fiber (CF) was coated with TiO2 layer by sol-dipping method using CuSO4 as dopant. The prepared samples were characterized by X-ray diffraction (XRD), scanning electronic microscopy (SEM) and transmission electron microscopy (TEM). The SEM/TEM results show that the prepared CuSO4-TiO2 layer is uniformly and compactly. The thickness of the coating layer is increased from 45 nm to 185 nm. XRD results show that prepared layer is composited by anatase TiO2. The oxidation resistant properties of the carbon fibers were studied using isothermal oxidation experimental. Compared with TiO2 coated carbon fiber, the complete decomposition temperature of the CuSO4-TiO2 coated carbon fiber is increased from 667 ℃ to 800 ℃. The oxidation activation energy of TiO2 coating carbon fiber and CuSO4-TiO2 coating carbon fiber are 118.390 kJ· mol-1, 152.562 kJ·mol-1, respectively. The improvement of oxidation resistant of the CuSO4-TiO2 coated carbon fiber is attributed to the CuSO4 liquid sinter effect on the TiO2 layer.
Carbon fiber (CF) was coated with TiO2 layer by sol-dipping method using CuSO4 as dopant. The prepared samples were characterized by X-ray diffraction (XRD), scanning electronic microscopy (SEM) and transmission electron microscopy (TEM). The SEM/TEM results show that the prepared CuSO4-TiO2 layer is uniformly and compactly. The thickness of the coating layer is increased from 45 nm to 185 nm. XRD results show that prepared layer is composited by anatase TiO2. The oxidation resistant properties of the carbon fibers were studied using isothermal oxidation experimental. Compared with TiO2 coated carbon fiber, the complete decomposition temperature of the CuSO4-TiO2 coated carbon fiber is increased from 667 ℃ to 800 ℃. The oxidation activation energy of TiO2 coating carbon fiber and CuSO4-TiO2 coating carbon fiber are 118.390 kJ· mol-1, 152.562 kJ·mol-1, respectively. The improvement of oxidation resistant of the CuSO4-TiO2 coated carbon fiber is attributed to the CuSO4 liquid sinter effect on the TiO2 layer.
2013, 29(12): 2555-2560
doi: 10.3969/j.issn.1001-4861.2013.00.345
Abstract:
A zinc(Ⅱ) complex [Zn2(L) Cl3]2[ZnCl4]·CH3CN·CH3OH·3H2O (L=1,1,4,7,7-Pentakis (2-pyridyl-methyl) diethylenetriamine) has been synthesized and structurally characterized, and its catalytic activity was investigated by using p-nitrophenyl phosphate (PNPP) as the substrate. The results showed that one zinc(Ⅱ)) of the complex was coordinated in a distorted trigonal-bipyramidal geometry, and the coordination geometry around another zinc(Ⅱ) was distorted octahedron. Its catalytic hydrolysis of PNPP was consistent with Michaelis-Mentent model. Several kinetic parameters Vmax, Km and Kcat were examined under different conditions, and maximal catalytic activity of zinc(Ⅱ) complex was observed at a temperature of 30 ℃ and pH=8.0. CCDC: 921868.
A zinc(Ⅱ) complex [Zn2(L) Cl3]2[ZnCl4]·CH3CN·CH3OH·3H2O (L=1,1,4,7,7-Pentakis (2-pyridyl-methyl) diethylenetriamine) has been synthesized and structurally characterized, and its catalytic activity was investigated by using p-nitrophenyl phosphate (PNPP) as the substrate. The results showed that one zinc(Ⅱ)) of the complex was coordinated in a distorted trigonal-bipyramidal geometry, and the coordination geometry around another zinc(Ⅱ) was distorted octahedron. Its catalytic hydrolysis of PNPP was consistent with Michaelis-Mentent model. Several kinetic parameters Vmax, Km and Kcat were examined under different conditions, and maximal catalytic activity of zinc(Ⅱ) complex was observed at a temperature of 30 ℃ and pH=8.0. CCDC: 921868.
2013, 29(12): 2561-2567
doi: 10.3969/j.issn.1001-4861.2013.00.382
Abstract:
Mercury(Ⅱ) complex with tris [(p-hydroxybenzaldehyde)ethyl]amine has been synthesized and characterized. The crystal and molecular structures of the complex was determined by singlecrystal X-ray diffraction. The interaction of complex with calf thymus DNA was investigated by UV-Vis、fluorescence spectrum and viscosity measurements. Results suggest that complex can bind to DNA via intercalation mode. CCDC: 952313, L; 843072, complex.
Mercury(Ⅱ) complex with tris [(p-hydroxybenzaldehyde)ethyl]amine has been synthesized and characterized. The crystal and molecular structures of the complex was determined by singlecrystal X-ray diffraction. The interaction of complex with calf thymus DNA was investigated by UV-Vis、fluorescence spectrum and viscosity measurements. Results suggest that complex can bind to DNA via intercalation mode. CCDC: 952313, L; 843072, complex.
2013, 29(12): 2568-2574
doi: 10.3969/j.issn.1001-4861.2013.00.401
Abstract:
A novel hybrid compound [CuCl(H2O)4)][CuCl(H2O)(Phen)][{(CuPhen)2Cl2}2(bdc)]2[P2W18O62]·5H2O(1) (Phen=1,10-phenanthroline and bdc=1,4-benzenedicarboxylate), containing multinuclear CuⅡ complex cations, has been obtained in hydrothermal conditions and characterized by IR, elemental, thermogravimetric, electrochemical and single-crystal X-ray diffraction analysis. The main structural feature to this compound is the copper-Phen complex moieties which compose new tetranuclear copper-Phen complex cation [{(CuPhen)2Cl2}2(bdc)]2+ bridged by Cl and bdc ligands. Furthermore, a Compound 1-modiffied carbon paste electrode (1-CPE) displays the good electrocatalytic activity toward the reduction of nitrite. CCDC: 952036.
A novel hybrid compound [CuCl(H2O)4)][CuCl(H2O)(Phen)][{(CuPhen)2Cl2}2(bdc)]2[P2W18O62]·5H2O(1) (Phen=1,10-phenanthroline and bdc=1,4-benzenedicarboxylate), containing multinuclear CuⅡ complex cations, has been obtained in hydrothermal conditions and characterized by IR, elemental, thermogravimetric, electrochemical and single-crystal X-ray diffraction analysis. The main structural feature to this compound is the copper-Phen complex moieties which compose new tetranuclear copper-Phen complex cation [{(CuPhen)2Cl2}2(bdc)]2+ bridged by Cl and bdc ligands. Furthermore, a Compound 1-modiffied carbon paste electrode (1-CPE) displays the good electrocatalytic activity toward the reduction of nitrite. CCDC: 952036.
2013, 29(12): 2575-2581
doi: 10.3969/j.issn.1001-4861.2013.00.388
Abstract:
The effect of impregnation sequence on the surface structure and catalytic performance of CuCe/AC (Activated carbon) (by adding rare earth Ce promoter to Cu/AC) catalyst was studied for gas-phase oxidative carbonylation of methanol to dimethyl carbonate. The active component content, surface dispersion and valence state of as-prepared catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H2-temperature programmed reduction(H2-TPR), High resolution transmission electron microscope (HR-TEM). The results show that Ce promoter plays a key role for active component Cu to disperse on the surface of activated carbon in CuCe/AC catalyst prepared by co-impregnation. The Cu components are difficult to be reduced and difficult to contact with reactant molecules for CuCe/AC catalyst prepared by first impregnation with Cu and then with Ce because part of Cu components are covered by Ce impregnation leading to the decrease of catalytic activity. For CuCe/AC catalyst prepared by first impregnation with Ce and then with Cu, the Ce and Cu components interact with each other, resulting in an optimal catalytic performance because of a more uniform dispersion of Cu (0) and Cu(Ⅰ) species on the surface of the catalyst. The space time yield and selectivity of dimethyl carbonate are 142 mg·g-1·h-1 and 85%, respectively.
The effect of impregnation sequence on the surface structure and catalytic performance of CuCe/AC (Activated carbon) (by adding rare earth Ce promoter to Cu/AC) catalyst was studied for gas-phase oxidative carbonylation of methanol to dimethyl carbonate. The active component content, surface dispersion and valence state of as-prepared catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H2-temperature programmed reduction(H2-TPR), High resolution transmission electron microscope (HR-TEM). The results show that Ce promoter plays a key role for active component Cu to disperse on the surface of activated carbon in CuCe/AC catalyst prepared by co-impregnation. The Cu components are difficult to be reduced and difficult to contact with reactant molecules for CuCe/AC catalyst prepared by first impregnation with Cu and then with Ce because part of Cu components are covered by Ce impregnation leading to the decrease of catalytic activity. For CuCe/AC catalyst prepared by first impregnation with Ce and then with Cu, the Ce and Cu components interact with each other, resulting in an optimal catalytic performance because of a more uniform dispersion of Cu (0) and Cu(Ⅰ) species on the surface of the catalyst. The space time yield and selectivity of dimethyl carbonate are 142 mg·g-1·h-1 and 85%, respectively.
2013, 29(12): 2582-2586
doi: 10.3969/j.issn.1001-4861.2013.00.362
Abstract:
Silver doped hydroxyapatite antimicrobial powders were synthesized by one-step reaction, then it was used for preparing antibacterial ceramic. The experimental results show that there was a significant linear correlation between silver content of HA and quantity of silver nitrate at hydrothermal condition. The XRD patterns and TEM photos indicate that HA and Ag-HA have the same crystal structure, and Ca2+ in HA crystals is displaced by Ag+ and AgxCa1-x(PO4)6(OH)2 was produced at hydrothermal condition. The length of Ag-HA antimicrobial powders increases with the increase of content of Ag+ in Ag-HA. Ag-HA antimicrobial powders went from sticks to whisker when the contents of Ag+ in Ag-HA exceeds 1.5%. 4.50% Ag-HA was selected as antimicrobial powders, an antibacterial rate of antibacterial ceramic is above 99.9%. and at this point, the mass fraction of Ag3PO4 in antimicrobial tglazes is 0.56%, which was far below 2wt%~4wt% of Ag3PO4 in antimicrobial tglazes of ongoing research. This technology can not only reduce the cost of producing antibacterial ceramic, but also meet JC/T 897-2002 demands for antibacterial properties of antibacterial ceramic.
Silver doped hydroxyapatite antimicrobial powders were synthesized by one-step reaction, then it was used for preparing antibacterial ceramic. The experimental results show that there was a significant linear correlation between silver content of HA and quantity of silver nitrate at hydrothermal condition. The XRD patterns and TEM photos indicate that HA and Ag-HA have the same crystal structure, and Ca2+ in HA crystals is displaced by Ag+ and AgxCa1-x(PO4)6(OH)2 was produced at hydrothermal condition. The length of Ag-HA antimicrobial powders increases with the increase of content of Ag+ in Ag-HA. Ag-HA antimicrobial powders went from sticks to whisker when the contents of Ag+ in Ag-HA exceeds 1.5%. 4.50% Ag-HA was selected as antimicrobial powders, an antibacterial rate of antibacterial ceramic is above 99.9%. and at this point, the mass fraction of Ag3PO4 in antimicrobial tglazes is 0.56%, which was far below 2wt%~4wt% of Ag3PO4 in antimicrobial tglazes of ongoing research. This technology can not only reduce the cost of producing antibacterial ceramic, but also meet JC/T 897-2002 demands for antibacterial properties of antibacterial ceramic.
2013, 29(12): 2587-2594
doi: 10.3969/j.issn.1001-4861.2013.00.391
Abstract:
Two high-nitrogen energetic salts were prepared by reacting 3,6-dihydrazino-1,2,4,5-tetrazine (DHT) and perchloric acid or nitric acid aqueous solution. Their structures have been determined by using X-ray single crystal diffraction method. (DHT)(NO3)2 (1) belongs to monoclinic, C2/c space group, a=1.300 0(6) nm, b= 0.834 9(3) nm, c=1.018 7(5) nm, β=118.89(5)°, Z=4; (DHT)(ClO4)2(2) belongs to orthorhombic, P21212 space group, a=0.980 4(4) nm, b=1.074 7(4) nm, c=0.532 5(2) nm, Z=2. The thermal decomposition was investigated with DSC and TG-DTG measurement. The non-isothermal kinetic parameters of the first exothermic process were studied by applying Kissingers, Ozawa-Doyles and Starinks methods. The critical temperature of thermal explosion and sensitivity properties also have been fully investigated. We can come to the conclusion that the two salts have potential application in sensitive energetic material area. CCDC: 884111, 1; 884112, 2.
Two high-nitrogen energetic salts were prepared by reacting 3,6-dihydrazino-1,2,4,5-tetrazine (DHT) and perchloric acid or nitric acid aqueous solution. Their structures have been determined by using X-ray single crystal diffraction method. (DHT)(NO3)2 (1) belongs to monoclinic, C2/c space group, a=1.300 0(6) nm, b= 0.834 9(3) nm, c=1.018 7(5) nm, β=118.89(5)°, Z=4; (DHT)(ClO4)2(2) belongs to orthorhombic, P21212 space group, a=0.980 4(4) nm, b=1.074 7(4) nm, c=0.532 5(2) nm, Z=2. The thermal decomposition was investigated with DSC and TG-DTG measurement. The non-isothermal kinetic parameters of the first exothermic process were studied by applying Kissingers, Ozawa-Doyles and Starinks methods. The critical temperature of thermal explosion and sensitivity properties also have been fully investigated. We can come to the conclusion that the two salts have potential application in sensitive energetic material area. CCDC: 884111, 1; 884112, 2.
2013, 29(12): 2595-2602
doi: 10.3969/j.issn.1001-4861.2013.00.393
Abstract:
Three mononuclear complexes, formulated as [ZnL2]·4H2O(1), [CuL2]·4H2O(2) and [FeL2]·4H2O(3) (LH=[2,2'∶6',2"-terpyridine]-4'-carboxylic acid), have been synthesized under the solvothermal conditions and characterized by elemental analysis, IR spectral, and single-crystal and powder X-ray diffraction methods. Complexes 1~3 are isomorphous structures and they crystallize in the tetragonal space group I42d. The ligand shows a tridentate chelating mode where the deprotonated carboxylate unit is free of coordinative bond. Three-dimensional supramolecular networks are observed in 1~3, which are sustained by π-π stacking and hydrogen bonding interactions. In addition, the solid-state luminescence spectrum of zinc(Ⅱ) complex 1 reveals strong blue photoluminescence at room temperature. CCDC: 925947, 1; 925948, 2; 925949, 3.
Three mononuclear complexes, formulated as [ZnL2]·4H2O(1), [CuL2]·4H2O(2) and [FeL2]·4H2O(3) (LH=[2,2'∶6',2"-terpyridine]-4'-carboxylic acid), have been synthesized under the solvothermal conditions and characterized by elemental analysis, IR spectral, and single-crystal and powder X-ray diffraction methods. Complexes 1~3 are isomorphous structures and they crystallize in the tetragonal space group I42d. The ligand shows a tridentate chelating mode where the deprotonated carboxylate unit is free of coordinative bond. Three-dimensional supramolecular networks are observed in 1~3, which are sustained by π-π stacking and hydrogen bonding interactions. In addition, the solid-state luminescence spectrum of zinc(Ⅱ) complex 1 reveals strong blue photoluminescence at room temperature. CCDC: 925947, 1; 925948, 2; 925949, 3.
2013, 29(12): 2603-2608
doi: 10.3969/j.issn.1001-4861.2013.00.366
Abstract:
A sandwich-type polyoxometalate compound built on sandwich-type polyoxoanion {Ni4(H2O)2(PW9O34)2}10-, ethlyenediamine(en) and Ni(Ⅱ) cation, [Ni(en)2]2[{Ni(en)2}{Ni(en)2H2O}2{(PW9O34)2Ni4(H2O)2}]·16H2O(1), has been hydrothermally synthesized and characterized by IR spectrum, single crystal X-ray diffraction analysis, TG/DTG and electrochemical studies. The sandwich polyoxoanions are linked by [Ni(en)2]2+ cations to form a 1D linear structure and the multiform hydrogen bonds in the compound form a 3D supramolecular framework. CCDC: 917320.
A sandwich-type polyoxometalate compound built on sandwich-type polyoxoanion {Ni4(H2O)2(PW9O34)2}10-, ethlyenediamine(en) and Ni(Ⅱ) cation, [Ni(en)2]2[{Ni(en)2}{Ni(en)2H2O}2{(PW9O34)2Ni4(H2O)2}]·16H2O(1), has been hydrothermally synthesized and characterized by IR spectrum, single crystal X-ray diffraction analysis, TG/DTG and electrochemical studies. The sandwich polyoxoanions are linked by [Ni(en)2]2+ cations to form a 1D linear structure and the multiform hydrogen bonds in the compound form a 3D supramolecular framework. CCDC: 917320.
2013, 29(12): 2609-2614
doi: 10.3969/j.issn.1001-4861.2013.00.360
Abstract:
A novel tetranuclear M4[2×2] square grid complex [ZN4(HL)4](ClO4)4·2MeCN·2MeOH(H2L=1,5-bis(1-(pyridine-2-yl)ethylidene)carbonhydrazide) was constructed via self-assembly using Schiff base ligand based on carbohydrazone derivative. The complex was characterized by elemental analyses, IR spectra, UV-Vis absorption spectra and single crystal X-ray diffraction. Single crystal structure analysis showed that all mental atoms have N4O2 distorted octahedral coordination spheres and four ligands are monodeprotonated with four enolyl oxygen atoms direct bridging the Zn ions to form a tetranuclear [2×2] square grid complex. Furthermore, the fluorescent spectra analysis indicated the tetranuclear Zn(Ⅱ)4 complex exhibits intense fluorescence emission band at around 530 nm in the solid state. CCDC: 922042.
A novel tetranuclear M4[2×2] square grid complex [ZN4(HL)4](ClO4)4·2MeCN·2MeOH(H2L=1,5-bis(1-(pyridine-2-yl)ethylidene)carbonhydrazide) was constructed via self-assembly using Schiff base ligand based on carbohydrazone derivative. The complex was characterized by elemental analyses, IR spectra, UV-Vis absorption spectra and single crystal X-ray diffraction. Single crystal structure analysis showed that all mental atoms have N4O2 distorted octahedral coordination spheres and four ligands are monodeprotonated with four enolyl oxygen atoms direct bridging the Zn ions to form a tetranuclear [2×2] square grid complex. Furthermore, the fluorescent spectra analysis indicated the tetranuclear Zn(Ⅱ)4 complex exhibits intense fluorescence emission band at around 530 nm in the solid state. CCDC: 922042.
2013, 29(12): 2615-2622
doi: 10.3969/j.issn.1001-4861.2013.00.377
Abstract:
Nanocrystalline magnetite (Fe3O4) and Ni-doped magnetites (NixFe3-xO4, x=0.1, 0.3, and 0.6) were prepared by a modified coprecipitation procedure, and their surface properties and application for the removal of Pb(Ⅱ) ions from aqueous solutions were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen physical adsorption, potentiometric titrations and batch adsorption experiments. Results show that all the samples are single-phase crystalline nanoparticles with an approximately spherical shape. Compared to Fe3O4, the particle size, the pHpzc value and the surface charge at pH=5.0 for NixFe3-xO4 nanoparticles are decreased; and the pore volume, specific surface area (SSA), surface fractal dimension and the content of surface hydroxyls are increased. Langmuir correlation coefficients for Pb(Ⅱ) adsorption on the samples are fairly high (R2=0.9942~0.9858) and they follow the order: Fe3O4>Ni0.1Fe2.9O4>Ni0.3Fe2.7O4=Ni0.6Fe2.4O4, and those of Freundlich model are relatively low (R2=0.9813~0.9477) and the order is opposite to Langmuirs. At pH=5.0, Langmuir adsorption capacities (qmax) of Fe3O4, Ni0.1Fe2.9O4, Ni0.3Fe2.7O4 and Ni0.6Fe2.4O4 are 6.02, 6.68, 7.29, and 8.34 mg·g-1, respectively. Compared to Fe3O4, NixFe3-xO4 nanoparticles with a high content of Ni have a higher adsorption capacity for the Pb(Ⅱ) ions in aqueous solutions.
Nanocrystalline magnetite (Fe3O4) and Ni-doped magnetites (NixFe3-xO4, x=0.1, 0.3, and 0.6) were prepared by a modified coprecipitation procedure, and their surface properties and application for the removal of Pb(Ⅱ) ions from aqueous solutions were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen physical adsorption, potentiometric titrations and batch adsorption experiments. Results show that all the samples are single-phase crystalline nanoparticles with an approximately spherical shape. Compared to Fe3O4, the particle size, the pHpzc value and the surface charge at pH=5.0 for NixFe3-xO4 nanoparticles are decreased; and the pore volume, specific surface area (SSA), surface fractal dimension and the content of surface hydroxyls are increased. Langmuir correlation coefficients for Pb(Ⅱ) adsorption on the samples are fairly high (R2=0.9942~0.9858) and they follow the order: Fe3O4>Ni0.1Fe2.9O4>Ni0.3Fe2.7O4=Ni0.6Fe2.4O4, and those of Freundlich model are relatively low (R2=0.9813~0.9477) and the order is opposite to Langmuirs. At pH=5.0, Langmuir adsorption capacities (qmax) of Fe3O4, Ni0.1Fe2.9O4, Ni0.3Fe2.7O4 and Ni0.6Fe2.4O4 are 6.02, 6.68, 7.29, and 8.34 mg·g-1, respectively. Compared to Fe3O4, NixFe3-xO4 nanoparticles with a high content of Ni have a higher adsorption capacity for the Pb(Ⅱ) ions in aqueous solutions.
2013, 29(12): 2623-2630
doi: 10.3969/j.issn.1001-4861.2013.00.381
Abstract:
Employing solvothermal method, two new lanthanide sulfates [Tb2(SO4)5][(CH3)2NH2]4(1) and [Y2(SO4)5][(CH3)2NH2]4(2) with two-dimensional layered structures have been synthesized and characterized by single-crystal XRD, ICP, IR and TGA. Both of the two compounds crystallize in the triclinic space group p1. Crystal data for 1, a=0.988 7(3) nm, b=1.106 1(3) nm, c=1.535 4(4) nm, α=70.45(4)°, β=75.12(3)°, γ=67.11(3)°, Z=2. For 2, a=0.9816(5) nm, b=1.100 1(5) nm, c=1.528 6(8) nm, α=70.44(6)°, β=75.45(6)°, γ=67.48(6)°, Z=2. Crystal structure analysis reveals that both of the inorganic frameworks of Compound 1 and 2 have layered two-dimensional architectures which are formed by two types of double stranded chains and 12-membered rings (12MRs). The solid state luminescent properties of compounds 1 were investigated and it displays a typical luminescent property of Tb3+ with excitation wavelength at 369 nm. CCDC: 941147, 1; 941148 2.
Employing solvothermal method, two new lanthanide sulfates [Tb2(SO4)5][(CH3)2NH2]4(1) and [Y2(SO4)5][(CH3)2NH2]4(2) with two-dimensional layered structures have been synthesized and characterized by single-crystal XRD, ICP, IR and TGA. Both of the two compounds crystallize in the triclinic space group p1. Crystal data for 1, a=0.988 7(3) nm, b=1.106 1(3) nm, c=1.535 4(4) nm, α=70.45(4)°, β=75.12(3)°, γ=67.11(3)°, Z=2. For 2, a=0.9816(5) nm, b=1.100 1(5) nm, c=1.528 6(8) nm, α=70.44(6)°, β=75.45(6)°, γ=67.48(6)°, Z=2. Crystal structure analysis reveals that both of the inorganic frameworks of Compound 1 and 2 have layered two-dimensional architectures which are formed by two types of double stranded chains and 12-membered rings (12MRs). The solid state luminescent properties of compounds 1 were investigated and it displays a typical luminescent property of Tb3+ with excitation wavelength at 369 nm. CCDC: 941147, 1; 941148 2.
2013, 29(12): 2631-2636
doi: 10.3969/j.issn.1001-4861.2013.00.392
Abstract:
Tetragonal phase NaYW2O8∶Ln3+(Ln=Yb/Er and Eu) microcrystals were synthesized using a hydrothermal method and a subsequent calcination treatment. The effect of pH value of the reaction solutions on the phase composition, morphologies, and luminescence properties of NaYW2O8∶Ln3+ microcrystals was investigated. Upconversion luminescence tuning of NaYW2O8∶Er3+/Yb3+ under 980 nm excitation was achieved by adjusting the crystal structure and morphology of samples. The upconversion luminescence mechanism was also investigated. In the excitation spectra monitored at 618 nm of NaYW2O8∶Eu3+, the intensity ratio of the charge transfer bands of the Eu3+-O2- and W6+-O2- transitions to the f-f shell transitions of Eu3+ ions changed with the structure and morphology of the sample. Under 254 and 396 nm excitation, the 5D0→7F1, 5D0→7F2, 5D0→7F3, and 5D0→7F4 emissions were observed. For the sample prepared at pH=12, the 5D0→7F1 emission was split into two sub-bands.
Tetragonal phase NaYW2O8∶Ln3+(Ln=Yb/Er and Eu) microcrystals were synthesized using a hydrothermal method and a subsequent calcination treatment. The effect of pH value of the reaction solutions on the phase composition, morphologies, and luminescence properties of NaYW2O8∶Ln3+ microcrystals was investigated. Upconversion luminescence tuning of NaYW2O8∶Er3+/Yb3+ under 980 nm excitation was achieved by adjusting the crystal structure and morphology of samples. The upconversion luminescence mechanism was also investigated. In the excitation spectra monitored at 618 nm of NaYW2O8∶Eu3+, the intensity ratio of the charge transfer bands of the Eu3+-O2- and W6+-O2- transitions to the f-f shell transitions of Eu3+ ions changed with the structure and morphology of the sample. Under 254 and 396 nm excitation, the 5D0→7F1, 5D0→7F2, 5D0→7F3, and 5D0→7F4 emissions were observed. For the sample prepared at pH=12, the 5D0→7F1 emission was split into two sub-bands.
2013, 29(12): 2637-2642
doi: 10.3969/j.issn.1001-4861.2013.00.397
Abstract:
Hexagonal tungsten oxide (h-WO3) was synthesized by an ionic liquid (1-methyl-3-ethyl imidazole bromide (Emim+Br-)) -assisted hydrothermal method at 180 ℃ for 21 h. The as-synthesized products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray spectroscopy (EDS). The results show that the morphologies of WO3 are controlled by the amount of Emim+Br-. In 0.5 g Emim+Br--added solution, the product is h-WO3 nanorod bundles composed of uniform WO3 nanorods with average diameter of 25 nm and length of 200~300 nm. The formation mechanism of h-WO3 nanorod bundles is proposed according to the experimental results.
Hexagonal tungsten oxide (h-WO3) was synthesized by an ionic liquid (1-methyl-3-ethyl imidazole bromide (Emim+Br-)) -assisted hydrothermal method at 180 ℃ for 21 h. The as-synthesized products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray spectroscopy (EDS). The results show that the morphologies of WO3 are controlled by the amount of Emim+Br-. In 0.5 g Emim+Br--added solution, the product is h-WO3 nanorod bundles composed of uniform WO3 nanorods with average diameter of 25 nm and length of 200~300 nm. The formation mechanism of h-WO3 nanorod bundles is proposed according to the experimental results.
2013, 29(12): 2643-2648
doi: 10.3969/j.issn.1001-4861.2013.00.400
Abstract:
A new copper(Ⅱ) complex [Cu2(DMSO)2(ODPA)4]·2DMSO (DMSO=dimethyl sulfoxide, ODPA=N-Phthaloylglycinate) was synthesized and characterized by single-crystal X-ray diffraction. The complex crystallizes in the triclinic system, space group P1, with cell parameters: a=10.361(2) nm, b=11.273(2) nm, c=12.126(2) nm, β=81.765(3)°, cell volume; V=1 383.6(4) nm3, number of molecules inside the cell: Z=1, Dc=1.508 g·cm-3, the final R=0.075 0 and wR2=0.192 7. The interaction of the complex with DNA was studied by UV spectroscopy, EtBr fluoescent probe and DNA cleavage. The results indicate that the complex could interact with DNA by partial intercalative mode. The agarose gel electrophoresis studies revealed that the complex can cleave pBR322 DNA to Form Ⅱ. CCDC: 937398.
A new copper(Ⅱ) complex [Cu2(DMSO)2(ODPA)4]·2DMSO (DMSO=dimethyl sulfoxide, ODPA=N-Phthaloylglycinate) was synthesized and characterized by single-crystal X-ray diffraction. The complex crystallizes in the triclinic system, space group P1, with cell parameters: a=10.361(2) nm, b=11.273(2) nm, c=12.126(2) nm, β=81.765(3)°, cell volume; V=1 383.6(4) nm3, number of molecules inside the cell: Z=1, Dc=1.508 g·cm-3, the final R=0.075 0 and wR2=0.192 7. The interaction of the complex with DNA was studied by UV spectroscopy, EtBr fluoescent probe and DNA cleavage. The results indicate that the complex could interact with DNA by partial intercalative mode. The agarose gel electrophoresis studies revealed that the complex can cleave pBR322 DNA to Form Ⅱ. CCDC: 937398.
2013, 29(12): 2649-2654
doi: 10.3969/j.issn.1001-4861.2013.00.404
Abstract:
[CoCl0.5(H2O)0.5(HDPPZC)2](PW12O40)0.5·3.5H2O (1) has been synthesized under hydrothermal conditions using HDPPZC (dipyrido[3,2-a∶2',3'-c]-phenazine-2-carboxylic acid) as a neutral organic ligand. Compound 1 has been characterized by single-crystal X-ray diffraction, elemental analysis, UV-Vis spectrum and thermogravimetric analysis (TGA). It crystallizes in triclinic, space group P1 with a=1.036 0(2) nm, b=1.564 0(3) nm, c=1.656 0(3) nm, α=80.99(3)°, β=84.93(3)°, γ=85.44(3)°, V=2.633 9(9) nm3, Z=1. Single-crystal X-ray diffraction analysis reveals that compounds 1 consists of a discrete dinuclear, linked by hydrogen bonding and π-π stacking interactions into 2D supramolecular framework. Furthermore, we studied the Rhodamine B (RhB) photodegration process by Compound 1 as the catalyst. CCDC: 968312.
[CoCl0.5(H2O)0.5(HDPPZC)2](PW12O40)0.5·3.5H2O (1) has been synthesized under hydrothermal conditions using HDPPZC (dipyrido[3,2-a∶2',3'-c]-phenazine-2-carboxylic acid) as a neutral organic ligand. Compound 1 has been characterized by single-crystal X-ray diffraction, elemental analysis, UV-Vis spectrum and thermogravimetric analysis (TGA). It crystallizes in triclinic, space group P1 with a=1.036 0(2) nm, b=1.564 0(3) nm, c=1.656 0(3) nm, α=80.99(3)°, β=84.93(3)°, γ=85.44(3)°, V=2.633 9(9) nm3, Z=1. Single-crystal X-ray diffraction analysis reveals that compounds 1 consists of a discrete dinuclear, linked by hydrogen bonding and π-π stacking interactions into 2D supramolecular framework. Furthermore, we studied the Rhodamine B (RhB) photodegration process by Compound 1 as the catalyst. CCDC: 968312.
2013, 29(12): 2655-2665
doi: 10.3969/j.issn.1001-4861.2013.00.389
Abstract:
Two coordination polymers based on 4-[(8-hydroxy-5-quinolinyl)azo]-benzenesulfonic acid(H2L), namely [CuL(en)]·0.5H2O (1) and [CuL2][Cu(en)2]·2H2O (2)(en=ethylenediamine) have been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction, infrared (IR) spectra, elemental analysis, powder X-ray diffractions (PXRD) and thermogravimetric analysis (TGA). compounds 1 and 2 are connected into three-dimensional (3D) supramolecular networks by both hydrogen bonding and π…π interactions. In addition, their fluorescent properties have been investigated. CCDC: 881778, 1; 889463, 2.
Two coordination polymers based on 4-[(8-hydroxy-5-quinolinyl)azo]-benzenesulfonic acid(H2L), namely [CuL(en)]·0.5H2O (1) and [CuL2][Cu(en)2]·2H2O (2)(en=ethylenediamine) have been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction, infrared (IR) spectra, elemental analysis, powder X-ray diffractions (PXRD) and thermogravimetric analysis (TGA). compounds 1 and 2 are connected into three-dimensional (3D) supramolecular networks by both hydrogen bonding and π…π interactions. In addition, their fluorescent properties have been investigated. CCDC: 881778, 1; 889463, 2.
2013, 29(12): 2666-2672
doi: 10.3969/j.issn.1001-4861.2013.00.398
Abstract:
Reactions of ligand 4-[(1H-imidazol-4-yl)methylamino]benzoic acid (H2L) with transition metal salts led to the formation of three complexes [M(HL)2(H2O)2](M(Ⅱ)=Mn(Ⅱ)(1), Cd(Ⅱ)(2), Cu(Ⅱ)(3)) under different conditions. The single crystal X-ray diffraction analyses revealed that three complexes crystallized in the same triclinic space group P1 are isomorphous and isostructural, and the molecules are further connected by hydrogen bonds interactions resulting in formation of 3D structures. Thermal stability and electrochemistry properties of complexes were also investigated. CCDC: 945340, 1; 945338, 2; 945339, 3.
Reactions of ligand 4-[(1H-imidazol-4-yl)methylamino]benzoic acid (H2L) with transition metal salts led to the formation of three complexes [M(HL)2(H2O)2](M(Ⅱ)=Mn(Ⅱ)(1), Cd(Ⅱ)(2), Cu(Ⅱ)(3)) under different conditions. The single crystal X-ray diffraction analyses revealed that three complexes crystallized in the same triclinic space group P1 are isomorphous and isostructural, and the molecules are further connected by hydrogen bonds interactions resulting in formation of 3D structures. Thermal stability and electrochemistry properties of complexes were also investigated. CCDC: 945340, 1; 945338, 2; 945339, 3.
2013, 29(12): 2673-2677
doi: 10.3969/j.issn.1001-4861.2013.00.390
Abstract:
The complex [Nd(HINAIP)(INAIP)(H2O)2]n·nH2O was obtained by hydrothermal assembly of Nd(Ⅲ) salt with a 5-(isonicotinamido) isophthalic acid(H2INAIP) and its crystal structure was determined by X-ray single-crystal diffraction. It is of triclinic, P1 space group space group. Single-crystal X-ray diffraction analysis revealed that the HINAIP- and INAIP2- ligands connect Nd(Ⅲ)-carboxylate chains to form 2D layers in complex 1. Finally, It was extended to 3D supramolecular structures by H-bonding interactions. The complex was characterized by TG, IR, UV and near IR fluorescence spectra. CCDC: 958122.
The complex [Nd(HINAIP)(INAIP)(H2O)2]n·nH2O was obtained by hydrothermal assembly of Nd(Ⅲ) salt with a 5-(isonicotinamido) isophthalic acid(H2INAIP) and its crystal structure was determined by X-ray single-crystal diffraction. It is of triclinic, P1 space group space group. Single-crystal X-ray diffraction analysis revealed that the HINAIP- and INAIP2- ligands connect Nd(Ⅲ)-carboxylate chains to form 2D layers in complex 1. Finally, It was extended to 3D supramolecular structures by H-bonding interactions. The complex was characterized by TG, IR, UV and near IR fluorescence spectra. CCDC: 958122.
2013, 29(12): 2678-2682
doi: 10.3969/j.issn.1001-4861.2013.00.394
Abstract:
[CdL(H2O)(NO3)]NO3·CH3COCH3(1) (L=N-methyl-N-phenyl-2-(quinolin-8-yloxy)acetamide), was synth-esized and characterized by X-ray diffraction. In complex 1, the Cd(Ⅱ) center is coordinated with two O atoms and one N atom from one ligand L, two O atoms from two mono-dentate nitrate anions and one O atom from one water molecule, possessing a distorted octahedral coordination geometry. In the crystal, intramolecular O-H…O hydrogen bonds between the coordinated water molecules and free nitrate O atoms link the complexes into chains along the a axis. In CH3CN solution, both ligand L and complex 1 exhibit emission band at 390 nm. However, the emission intensity of 1 is much lower than that of the ligand L. CCDC: 958121.
[CdL(H2O)(NO3)]NO3·CH3COCH3(1) (L=N-methyl-N-phenyl-2-(quinolin-8-yloxy)acetamide), was synth-esized and characterized by X-ray diffraction. In complex 1, the Cd(Ⅱ) center is coordinated with two O atoms and one N atom from one ligand L, two O atoms from two mono-dentate nitrate anions and one O atom from one water molecule, possessing a distorted octahedral coordination geometry. In the crystal, intramolecular O-H…O hydrogen bonds between the coordinated water molecules and free nitrate O atoms link the complexes into chains along the a axis. In CH3CN solution, both ligand L and complex 1 exhibit emission band at 390 nm. However, the emission intensity of 1 is much lower than that of the ligand L. CCDC: 958121.
2013, 29(12): 2683-2687
doi: 10.3969/j.issn.1001-4861.2013.00.358
Abstract:
A new zinc(Ⅱ) complex Zn (2-PMBBA)2(Phen) with 2-(p-methylbenzoyl) benzoic acid (2-PMBBA) and 1, 10-phenanthroline (Phen) as ligands has been synthesized. Crystal data for this complex are as follows: orthorhombic, space group Pccn, a=1.371 6(4) nm, b=1.336 8(4) nm, c=1.928 7(5) nm, V=3.536 4(17) nm3, Dc=1.360 g·cm-3, Z=4, μ(Mo Kα)=0.746 mm-1, F(000)=1 496, final discrepancy factors R1=0.0358, wR2=0.086 1. In the title complex, it is less common that the central Zn(Ⅱ) ion is in a four-coordinated distorted tetrahedron coordination environment. The electrochemical, magnetic and fluorescent properties of the title complex were investigated. The results show that its electron transfer is irreversible in the cyclic voltammetric reaction corresponding to Zn(Ⅱ)/Zn(0), and it exhibits diamagnetic property in the temperature range of 300~7 K. In addition, it can give off fluorescent emission bands at around 450 and 472 nm, respectively, with the excitation wavelength of 224 nm. CCDC: 926215.
A new zinc(Ⅱ) complex Zn (2-PMBBA)2(Phen) with 2-(p-methylbenzoyl) benzoic acid (2-PMBBA) and 1, 10-phenanthroline (Phen) as ligands has been synthesized. Crystal data for this complex are as follows: orthorhombic, space group Pccn, a=1.371 6(4) nm, b=1.336 8(4) nm, c=1.928 7(5) nm, V=3.536 4(17) nm3, Dc=1.360 g·cm-3, Z=4, μ(Mo Kα)=0.746 mm-1, F(000)=1 496, final discrepancy factors R1=0.0358, wR2=0.086 1. In the title complex, it is less common that the central Zn(Ⅱ) ion is in a four-coordinated distorted tetrahedron coordination environment. The electrochemical, magnetic and fluorescent properties of the title complex were investigated. The results show that its electron transfer is irreversible in the cyclic voltammetric reaction corresponding to Zn(Ⅱ)/Zn(0), and it exhibits diamagnetic property in the temperature range of 300~7 K. In addition, it can give off fluorescent emission bands at around 450 and 472 nm, respectively, with the excitation wavelength of 224 nm. CCDC: 926215.
2013, 29(12): 2688-2694
doi: 10.3969/j.issn.1001-4861.2013.00.373
Abstract:
A new organotin complex [PH3Sn(O2CC14H9)(CH3OH)]2·CH3OH has been synthesized by the reaction of triphenyltin hydroxide with 9-anthroic acid in methanol. It was characterized by IR, 1H and 13C NMR, elemental analysis and X-ray crystal diffraction. Crystal structure shows a distorted trigonal bipyramidal configuration with five-coordination for the central tin atom. In the crystal, O-H…O hydrogen-bond interactions exist between the methanol O atom and the carbonyl O atom in an adjacent complex molecule, and between the neighboring methanol O atoms, resulting in the formation of a 1D S-shaped chain. Due to the C-H…π interactions between anthryl-H and anthracene ring, the obtained chain is further linked to form 1D ladderlike structure. Finally, a 2D network has been generated by the C-H…π interactions between methyl-H and benzene ring in the neighbouring 1D ladderlike chains. Fluorescence spectra of the complex reveals a strong emission band at 460 nm when excited with 360 nm radiation at room temperature. Thermogravimetric analysis shows that the complex is stable up to 240 ℃. The stability of the complex, the orbital energies and composition characteristics of some frontier molecular orbitals have been investigated at LANL2DZ level with G03W software. CCDC: 899826.
A new organotin complex [PH3Sn(O2CC14H9)(CH3OH)]2·CH3OH has been synthesized by the reaction of triphenyltin hydroxide with 9-anthroic acid in methanol. It was characterized by IR, 1H and 13C NMR, elemental analysis and X-ray crystal diffraction. Crystal structure shows a distorted trigonal bipyramidal configuration with five-coordination for the central tin atom. In the crystal, O-H…O hydrogen-bond interactions exist between the methanol O atom and the carbonyl O atom in an adjacent complex molecule, and between the neighboring methanol O atoms, resulting in the formation of a 1D S-shaped chain. Due to the C-H…π interactions between anthryl-H and anthracene ring, the obtained chain is further linked to form 1D ladderlike structure. Finally, a 2D network has been generated by the C-H…π interactions between methyl-H and benzene ring in the neighbouring 1D ladderlike chains. Fluorescence spectra of the complex reveals a strong emission band at 460 nm when excited with 360 nm radiation at room temperature. Thermogravimetric analysis shows that the complex is stable up to 240 ℃. The stability of the complex, the orbital energies and composition characteristics of some frontier molecular orbitals have been investigated at LANL2DZ level with G03W software. CCDC: 899826.
2013, 29(12): 2695-2703
doi: 10.3969/j.issn.1001-4861.2013.00.386
Abstract:
The synthesis and thermal stabilities, spectroscopic and electrochemical properties for a series of platinum(Ⅱ) metalloporphyrin dimer complexes with aliphatic chain of different lengths [-O(CH2)nO-] have been studied. Although dimeric porphyrin ligands and platinum(Ⅱ) complexes display nearly the same absorption spectra in the concentration range from 10-7 to 10-4 mol·dm-3, these ligands and their complexes show concentration-dependent emission when the length of aliphatic chain is beyond four carbon atoms. At elevated concentration of the ligands and complexes, the emission spectra show obvious red-shifts. For complex Pt2C6(OPTPP)2 and Pt2C10(OPTPP)2, the emission maxima at 652 nm are red-shifted to 676 and 681 nm at concentrations >10-4 mol·dm-3. Emission spectra of the sublimate films of complexes also display similar red-shifts: 43 nm for Pt2C6(OPTPP)2 and 53 nm for Pt2C10(OPTPP)2. The concentration-dependent emission indicates that there are intramolecular π-π interactions in porphyrin dimers and platinum(Ⅱ) metalloporphyrins.
The synthesis and thermal stabilities, spectroscopic and electrochemical properties for a series of platinum(Ⅱ) metalloporphyrin dimer complexes with aliphatic chain of different lengths [-O(CH2)nO-] have been studied. Although dimeric porphyrin ligands and platinum(Ⅱ) complexes display nearly the same absorption spectra in the concentration range from 10-7 to 10-4 mol·dm-3, these ligands and their complexes show concentration-dependent emission when the length of aliphatic chain is beyond four carbon atoms. At elevated concentration of the ligands and complexes, the emission spectra show obvious red-shifts. For complex Pt2C6(OPTPP)2 and Pt2C10(OPTPP)2, the emission maxima at 652 nm are red-shifted to 676 and 681 nm at concentrations >10-4 mol·dm-3. Emission spectra of the sublimate films of complexes also display similar red-shifts: 43 nm for Pt2C6(OPTPP)2 and 53 nm for Pt2C10(OPTPP)2. The concentration-dependent emission indicates that there are intramolecular π-π interactions in porphyrin dimers and platinum(Ⅱ) metalloporphyrins.
2013, 29(12): 2704-2708
doi: 10.3969/j.issn.1001-4861.2013.00.395
Abstract:
A new complex [Cd(H2O)2(DNBA)(Im)2](DNBA)·H2O has been synthesized by H2DNBA and Im with Cd(Ⅱ), where H2DNBA =3,5-dinitrobenzoic acid, Im=imidazole. The crystal belongs to orthorhombic system, space group Ccc2. The cell parameters are: a=1.324 99(4) nm, b=1.516 01(5) nm, c=2.789 22(8) nm; V=5.602 7(3) nm3, Dc=1.719 g·cm-3, Z=8, μ=0.866 mm-1, F(000)=2 912, final discrepancy factors R1=0.058 3, wR2=0.146 4. There are two mononuclear Cd(Ⅱ) complexes in the asymmetric unit of the compound, and where the two Cd(Ⅱ) ions are in the same coordination number. In addition, the luminescent property of 1 is also discussed in the liquid state at room temperature. CCDC: 952035.
A new complex [Cd(H2O)2(DNBA)(Im)2](DNBA)·H2O has been synthesized by H2DNBA and Im with Cd(Ⅱ), where H2DNBA =3,5-dinitrobenzoic acid, Im=imidazole. The crystal belongs to orthorhombic system, space group Ccc2. The cell parameters are: a=1.324 99(4) nm, b=1.516 01(5) nm, c=2.789 22(8) nm; V=5.602 7(3) nm3, Dc=1.719 g·cm-3, Z=8, μ=0.866 mm-1, F(000)=2 912, final discrepancy factors R1=0.058 3, wR2=0.146 4. There are two mononuclear Cd(Ⅱ) complexes in the asymmetric unit of the compound, and where the two Cd(Ⅱ) ions are in the same coordination number. In addition, the luminescent property of 1 is also discussed in the liquid state at room temperature. CCDC: 952035.
2013, 29(12): 2709-2713
doi: 10.3969/j.issn.1001-4861.2013.00.372
Abstract:
Reaction of dimethylammonium chloride with mercuric chloride in aqueous solution yielded one novel organic-inorganic hybrid compound (C2H8N)[Hg2Cl5](1). X-ray structure determination reveals that complex 1 shows a one-dimensional chloride-bridged [Hg2Cl5]n anionic chain structure along the b axis. Each Hg(Ⅱ) ion is coordinated with four chloride ions. Temperature-dependent dielectric constant of 1 shows no distinct anomalies, suggesting no phase transition occurred in the measured temperature range 80~298 K. CCDC: 880350.
Reaction of dimethylammonium chloride with mercuric chloride in aqueous solution yielded one novel organic-inorganic hybrid compound (C2H8N)[Hg2Cl5](1). X-ray structure determination reveals that complex 1 shows a one-dimensional chloride-bridged [Hg2Cl5]n anionic chain structure along the b axis. Each Hg(Ⅱ) ion is coordinated with four chloride ions. Temperature-dependent dielectric constant of 1 shows no distinct anomalies, suggesting no phase transition occurred in the measured temperature range 80~298 K. CCDC: 880350.
