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2017 Volume 33 Issue 4
2017, 33(4): 529-542
doi: 10.11862/CJIC.2017.063
Abstract:
The copper (Ⅱ) complexes with quinolones and aromatic amines has been flourishing and become an important research field of bioinorganic chemistry, since the complexes can be used as chemical nucleases, SOD mimics and antibacterial agents, etc. Based on the studies of authors' laboratory, the research progress on the structure, chemical nuclease activity, SOD simulation and antibacterial action of this kind of copper (Ⅱ) complexes is reviewed. Moreover, with these described above as basis, some related suggestions are given.
The copper (Ⅱ) complexes with quinolones and aromatic amines has been flourishing and become an important research field of bioinorganic chemistry, since the complexes can be used as chemical nucleases, SOD mimics and antibacterial agents, etc. Based on the studies of authors' laboratory, the research progress on the structure, chemical nuclease activity, SOD simulation and antibacterial action of this kind of copper (Ⅱ) complexes is reviewed. Moreover, with these described above as basis, some related suggestions are given.
2017, 33(4): 543-549
doi: 10.11862/CJIC.2017.044
Abstract:
The white LED with advantages of high brightness, small volume, long service life, high efficiency, energy saving and green environmental protection arouses wide attention. But currently most of the phosphors used in white LED also owns some drawbacks such as low luminous efficiency, poor color rendering index, high color temperature, high cost. However, red phosphors can obviously improve the luminous efficacy and color rendering index of the white LED, so the red phosphors in white LED play an important role in improving its color rendering index modulation. In recent years, red phosphors have been deeply studied and a lot of new type red phosphors have been reported. This paper introduces the red line emission phosphors doped by Eu3+, the band red emission phosphors doped by Eu2+, and emphatically introduces the narrow band red emission phosphors doped by Eu2+. The development of Eu doped red phosphors, the methods to improve the deficiency of the phosphor, as well as the recent frontier and development tendency of red phosphors are also introduced.
The white LED with advantages of high brightness, small volume, long service life, high efficiency, energy saving and green environmental protection arouses wide attention. But currently most of the phosphors used in white LED also owns some drawbacks such as low luminous efficiency, poor color rendering index, high color temperature, high cost. However, red phosphors can obviously improve the luminous efficacy and color rendering index of the white LED, so the red phosphors in white LED play an important role in improving its color rendering index modulation. In recent years, red phosphors have been deeply studied and a lot of new type red phosphors have been reported. This paper introduces the red line emission phosphors doped by Eu3+, the band red emission phosphors doped by Eu2+, and emphatically introduces the narrow band red emission phosphors doped by Eu2+. The development of Eu doped red phosphors, the methods to improve the deficiency of the phosphor, as well as the recent frontier and development tendency of red phosphors are also introduced.
2017, 33(4): 550-559
doi: 10.11862/CJIC.2017.069
Abstract:
Three binuclear iron (Ⅱ) imidazole Schiff-base complexes were constructed by one-pot multicomponent assembly of di (imidazole aldehyde)(A~C), 2-aminoethyl (ethyl) amine (D) and Fe (OTf)2 under solvent-free grinding conditions. X-ray crystallography revealed that the three complexes crystallized in different space groups of Cmca for 1, P21/c for 2~3. And the molecular structures of 1~3 all display Fe2L2 arrangement. In complexes 1~3, two ligand strands wrap around two Fe2+ ions and the Fe2+ ions are coordinated to chelating moieties from two imidazole nitrogen atoms and four amine nitrogen atoms, resulting in the pseudo octahedral FeN6 coordination geometry. Taking advantage of the facile approach above, we then investigated the discrimination abilities of the multicomponent assembly process under the solvent-free condition when different components were mixed together (a mixture of D, two kinds of di (imidazole aldehyde) of A~C and Fe (OTf)2). In this assemble system, combinations[D+A+B+Fe2+] or[D+A+C+Fe2+] adopt narcissistic self-sorting with only two species, while social self-sorting took place in the combination[D+B+C+Fe2+] forming the single heteromer 4, which was composed of two different ligands and exhibited Fe2LL' arrangement. The structure of 4 was further verified by the X-ray analysis by preparing the single crystal of the heteromer 4. To compare the efficiency of solvent-free grinding solid self-sorting against the solution self-sorting, the conventional solution-based self-sorting reactions were also performed using the same starting materials with equal amount. In consequence of the complexity of 1H NMR peaks of mixture, the selectivity is poor in solution. Overall, compared with self-sorting in solution, the solvent-free grinding self-sorting is more efficient due to the certain restrictions of molecular movement.
Three binuclear iron (Ⅱ) imidazole Schiff-base complexes were constructed by one-pot multicomponent assembly of di (imidazole aldehyde)(A~C), 2-aminoethyl (ethyl) amine (D) and Fe (OTf)2 under solvent-free grinding conditions. X-ray crystallography revealed that the three complexes crystallized in different space groups of Cmca for 1, P21/c for 2~3. And the molecular structures of 1~3 all display Fe2L2 arrangement. In complexes 1~3, two ligand strands wrap around two Fe2+ ions and the Fe2+ ions are coordinated to chelating moieties from two imidazole nitrogen atoms and four amine nitrogen atoms, resulting in the pseudo octahedral FeN6 coordination geometry. Taking advantage of the facile approach above, we then investigated the discrimination abilities of the multicomponent assembly process under the solvent-free condition when different components were mixed together (a mixture of D, two kinds of di (imidazole aldehyde) of A~C and Fe (OTf)2). In this assemble system, combinations[D+A+B+Fe2+] or[D+A+C+Fe2+] adopt narcissistic self-sorting with only two species, while social self-sorting took place in the combination[D+B+C+Fe2+] forming the single heteromer 4, which was composed of two different ligands and exhibited Fe2LL' arrangement. The structure of 4 was further verified by the X-ray analysis by preparing the single crystal of the heteromer 4. To compare the efficiency of solvent-free grinding solid self-sorting against the solution self-sorting, the conventional solution-based self-sorting reactions were also performed using the same starting materials with equal amount. In consequence of the complexity of 1H NMR peaks of mixture, the selectivity is poor in solution. Overall, compared with self-sorting in solution, the solvent-free grinding self-sorting is more efficient due to the certain restrictions of molecular movement.
2017, 33(4): 560-568
doi: 10.11862/CJIC.2017.075
Abstract:
A electron-donating bidentate ligands of isocyano-compounds were designed and synthesized, which could formed a series of aza-isocyanide heteroleptic copper photosensitizers 4a~4h with 1, 10-phenanthroline derivatives as N ligands. The photosensitive activities of this copper complexes were studied in water reduction system, and the turnover number (TON) of hydrogen evolution was up to 168 with bis (2-isocyanophenyl) sulfane as isocyanide ligand and 1, 10-phenanthroline with 2, 9-disubstitutes as N ligand. After the photophysical and photoelectric properties of these copper complexes were studied, a preliminary explanation and discussion of the structure-activity relationship and the mechanism of photocatalytic hydrogen evolution from water were carried out.
A electron-donating bidentate ligands of isocyano-compounds were designed and synthesized, which could formed a series of aza-isocyanide heteroleptic copper photosensitizers 4a~4h with 1, 10-phenanthroline derivatives as N ligands. The photosensitive activities of this copper complexes were studied in water reduction system, and the turnover number (TON) of hydrogen evolution was up to 168 with bis (2-isocyanophenyl) sulfane as isocyanide ligand and 1, 10-phenanthroline with 2, 9-disubstitutes as N ligand. After the photophysical and photoelectric properties of these copper complexes were studied, a preliminary explanation and discussion of the structure-activity relationship and the mechanism of photocatalytic hydrogen evolution from water were carried out.
2017, 33(4): 569-575
doi: 10.11862/CJIC.2017.065
Abstract:
A facile method was used for synthesis of triangular silver nanoprisms by the photo-mediated methods, which was a considerably simple procedure and relatively low requirements for instruments. Effects of lighting time, the amount of sodium citrate and OH- ions on the yield, uniformity and stability of triangular silver nanoprisms were investigated. The obtained triangular silver nanoprisms were also characterized by TEM and UV-Vis spectra. The optimized photo-mediated prepared conditions for triangular silver nanoprisms were as follows:lighting for 3.5 h, nAgNO3:nNa3C6H5O7:nNaBH4=1:10:0.8, and cOH-=0.125 mol·L-1. The results of TEM showed that triangular silver nanoprisms were successfully obtained with a diameter distribution of 70~80 nm. The photo-mediated method was good for the synthesis of monodisperse high-quality triangular silver nanoprisms than the direct chemical reduction route. Results of antimicrobial activities showed that silver nanoprisms had better antibacterial activity against S. Aureus and E. Coli than spherical particles.
A facile method was used for synthesis of triangular silver nanoprisms by the photo-mediated methods, which was a considerably simple procedure and relatively low requirements for instruments. Effects of lighting time, the amount of sodium citrate and OH- ions on the yield, uniformity and stability of triangular silver nanoprisms were investigated. The obtained triangular silver nanoprisms were also characterized by TEM and UV-Vis spectra. The optimized photo-mediated prepared conditions for triangular silver nanoprisms were as follows:lighting for 3.5 h, nAgNO3:nNa3C6H5O7:nNaBH4=1:10:0.8, and cOH-=0.125 mol·L-1. The results of TEM showed that triangular silver nanoprisms were successfully obtained with a diameter distribution of 70~80 nm. The photo-mediated method was good for the synthesis of monodisperse high-quality triangular silver nanoprisms than the direct chemical reduction route. Results of antimicrobial activities showed that silver nanoprisms had better antibacterial activity against S. Aureus and E. Coli than spherical particles.
2017, 33(4): 576-582
doi: 10.11862/CJIC.2017.077
Abstract:
The Cu-SiO2 composite films were first prepared by electrochemical sol-gel method at-0.9 V from Cu2+-SiO2 tranparent composite sol which was prepared by using CuSO4·5H2O and tetraethoxysilane as precursors. Then, Cu-SiO2 composite films were transformed into Cu2O-SiO2 and CuO-SiO2 composite films by thermal treatment at 250 and 450℃, respectively. The compostion, morphology and thickness of the two composited films were characterized by X-ray diffraction (XRD) and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX) and step profiler, respectively. In addition, the linear and nonlinear optical properties were measured by using UV-Vis spectrum and Z-scan methods. It was found that the optical properties of these composite films were influenced by the Cu content, the forms of Cu element (i.e. CuO or Cu2O) and particle size of CuO or Cu2O in the films. The optical band gaps of Cu2O-SiO2 and CuO-SiO2 composite films were respectively 2.67 and 2.54 eV, and the third-order nonlinear susceptibilities (χ(3)) were 2.31×10-6 and 1.36×10-6 esu, respectively.
The Cu-SiO2 composite films were first prepared by electrochemical sol-gel method at-0.9 V from Cu2+-SiO2 tranparent composite sol which was prepared by using CuSO4·5H2O and tetraethoxysilane as precursors. Then, Cu-SiO2 composite films were transformed into Cu2O-SiO2 and CuO-SiO2 composite films by thermal treatment at 250 and 450℃, respectively. The compostion, morphology and thickness of the two composited films were characterized by X-ray diffraction (XRD) and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX) and step profiler, respectively. In addition, the linear and nonlinear optical properties were measured by using UV-Vis spectrum and Z-scan methods. It was found that the optical properties of these composite films were influenced by the Cu content, the forms of Cu element (i.e. CuO or Cu2O) and particle size of CuO or Cu2O in the films. The optical band gaps of Cu2O-SiO2 and CuO-SiO2 composite films were respectively 2.67 and 2.54 eV, and the third-order nonlinear susceptibilities (χ(3)) were 2.31×10-6 and 1.36×10-6 esu, respectively.
2017, 33(4): 583-588
doi: 10.11862/CJIC.2017.072
Abstract:
With CMK-3 mesoporous carbon as support Pt/CMK-3, Pt/CMK-3-US, Pt/CMK-3-HNO3 and Pt/CMK-3-CTAB were synthesized by traditional impregnation method, ultrasound assisted impregnation method, treating support with HNO3 and surfactant assisted impregnation method respectively. Catalysts were characterized and their catalytic performances were evaluated. Characterizations including XRD, BET, SEM, TEM and H2-TPR results showed that the dispersion of Pt in Pt/CMK-3 is the worst, Pt can disperse well in Pt/CMK-3-HNO3 and Pt/CMK-3-CTAB, however, HNO3 may destroy the pore structure of CMK-3, and the surface properties of CMK-3 in Pt/CMK-3-HNO3 and Pt/CMK-3-CTAB have obvious changes. Only the ultrasound assisted impregnation method can improve the dispersion of Pt based on the maintenance of the pore structure and surface properties of CMK-3, the particle size of Pt is about 3 nm. The catalytic activity and selectivity of Pt/CMK-3-US were higher than Pt/CMK-3, and much higher than Pt/CMK-3-HNO3 and Pt/CMK-3-CTAB. Conversion of naphthalene is over 98% and the selectivity for dekalin is more than 95%.
With CMK-3 mesoporous carbon as support Pt/CMK-3, Pt/CMK-3-US, Pt/CMK-3-HNO3 and Pt/CMK-3-CTAB were synthesized by traditional impregnation method, ultrasound assisted impregnation method, treating support with HNO3 and surfactant assisted impregnation method respectively. Catalysts were characterized and their catalytic performances were evaluated. Characterizations including XRD, BET, SEM, TEM and H2-TPR results showed that the dispersion of Pt in Pt/CMK-3 is the worst, Pt can disperse well in Pt/CMK-3-HNO3 and Pt/CMK-3-CTAB, however, HNO3 may destroy the pore structure of CMK-3, and the surface properties of CMK-3 in Pt/CMK-3-HNO3 and Pt/CMK-3-CTAB have obvious changes. Only the ultrasound assisted impregnation method can improve the dispersion of Pt based on the maintenance of the pore structure and surface properties of CMK-3, the particle size of Pt is about 3 nm. The catalytic activity and selectivity of Pt/CMK-3-US were higher than Pt/CMK-3, and much higher than Pt/CMK-3-HNO3 and Pt/CMK-3-CTAB. Conversion of naphthalene is over 98% and the selectivity for dekalin is more than 95%.
2017, 33(4): 589-594
doi: 10.11862/CJIC.2017.071
Abstract:
Two di-n-butyltin compounds with μ3-O bridging the framework, [(μ3-O)(n-Bu2Sn)2(O2CR)2]2(R=4-(t-Bu)-C6H5 (1), (3-Me-4-NH2)-C6H4 (2)), were obtained by microwave-assisted solvothermal reaction of di-n-butyltin oxide precursor with the aromatic acid in methanol environments, which have been structurally characterized by elemental analysis, IR and NMR (1H, 13C and 119Sn) spectra and X-ray crystallography diffraction analyses. This compound was of a centrosymmetric dimer structure mode with a four-membered central endo-cyclic Sn2O2 unit in which the bridging oxygen atoms were tri-coordinated. Each bridging oxygen atom also connects with an exo-cyclic tin atom. The endo-cyclic and exo-cyclic tin atoms all were five-coordinated with distorted trigonal bipyramid geometry. The compounds 1 and 2 have strong anti-tumor activity in vitro.
Two di-n-butyltin compounds with μ3-O bridging the framework, [(μ3-O)(n-Bu2Sn)2(O2CR)2]2(R=4-(t-Bu)-C6H5 (1), (3-Me-4-NH2)-C6H4 (2)), were obtained by microwave-assisted solvothermal reaction of di-n-butyltin oxide precursor with the aromatic acid in methanol environments, which have been structurally characterized by elemental analysis, IR and NMR (1H, 13C and 119Sn) spectra and X-ray crystallography diffraction analyses. This compound was of a centrosymmetric dimer structure mode with a four-membered central endo-cyclic Sn2O2 unit in which the bridging oxygen atoms were tri-coordinated. Each bridging oxygen atom also connects with an exo-cyclic tin atom. The endo-cyclic and exo-cyclic tin atoms all were five-coordinated with distorted trigonal bipyramid geometry. The compounds 1 and 2 have strong anti-tumor activity in vitro.
2017, 33(4): 595-600
doi: 10.11862/CJIC.2017.081
Abstract:
Carbon nanofibers (CNFs) was produced as load matrix and reactor based on the electrospinning technology and carbonization process, which is used as nanoreactor for the grouth and regulation of molybdenum disulfide (MoS2) nanosheets. Taking the advantage of high catalytic activity of MoS2 nanosheets, high specific surface area, good stability, and high electrical conductivity of carbon nanofibers (CNFs), we have investigated the electrocatalytic activity of MoS2/CNFs with different morphologies and structures for hydrogen evolution reaction (HER). A variety of analytical techniques were used to investigate the prepared hybrid nanomaterials. Meanwhile, MoS2/CNFs hybrid materials were used to study the electrocatalytic activity, and it is found that the MoS2/CNFs-10 with core-shell structure for HER has the best electrocatalytic activity with onset potential of 220 mV and Tafel slope of 110 mV·dec-1.
Carbon nanofibers (CNFs) was produced as load matrix and reactor based on the electrospinning technology and carbonization process, which is used as nanoreactor for the grouth and regulation of molybdenum disulfide (MoS2) nanosheets. Taking the advantage of high catalytic activity of MoS2 nanosheets, high specific surface area, good stability, and high electrical conductivity of carbon nanofibers (CNFs), we have investigated the electrocatalytic activity of MoS2/CNFs with different morphologies and structures for hydrogen evolution reaction (HER). A variety of analytical techniques were used to investigate the prepared hybrid nanomaterials. Meanwhile, MoS2/CNFs hybrid materials were used to study the electrocatalytic activity, and it is found that the MoS2/CNFs-10 with core-shell structure for HER has the best electrocatalytic activity with onset potential of 220 mV and Tafel slope of 110 mV·dec-1.
2017, 33(4): 601-606
doi: 10.11862/CJIC.2017.066
Abstract:
A bithiophene-fused BODIPY (SY) dye is synthesized via acid catalyzed condensation of thiophene substituted thienopyrrole and 4-N, N-dimethylaminobenzaldehyde, followed by treatment with boron trifluoride diethyl ether. The structure of SY has been characterized by 1H NMR, mass and elemental analysis. The absorption and emission bands of SY are centered at 654 nm and 689 nm in CH2Cl2, respectively. Fluorometric titration experiment shows that the fluorescence intensity is enhanced upon protonation of the electron donating N, N-dimethylamino group, suggesting that SY can be used as a NIR fluorescence probe for pH value.
A bithiophene-fused BODIPY (SY) dye is synthesized via acid catalyzed condensation of thiophene substituted thienopyrrole and 4-N, N-dimethylaminobenzaldehyde, followed by treatment with boron trifluoride diethyl ether. The structure of SY has been characterized by 1H NMR, mass and elemental analysis. The absorption and emission bands of SY are centered at 654 nm and 689 nm in CH2Cl2, respectively. Fluorometric titration experiment shows that the fluorescence intensity is enhanced upon protonation of the electron donating N, N-dimethylamino group, suggesting that SY can be used as a NIR fluorescence probe for pH value.
2017, 33(4): 607-614
doi: 10.11862/CJIC.2017.084
Abstract:
Cobaltosic sulfide (Co3S4) was synthesized by hydrothermal synthesis method. Combining the ball grinding mill and spray method, Co3S4 was prepared into counter electrode (CE) and fabricated dye-sensitized solar cells (DSCs) with the novel electrolyte Co2+/Co3+. The power conversion efficiency (PCE) obtained by the DSCs based on the pure Co3S4 CE was only 6.06%, which was much smaller than that of Pt (8.05%). To improve the catalytic activity of pure Co3S4, electrospun carbon nanofibers (ECs) were fabricated by the electrospun method and the composite of ECs supported cobaltosic sulfide (Co3S4/ECs) was synthesized by hydrothermal synthesis method. And the DSCs based on Co3S4/ECs CE achieved a high PCE of (8.22±0.08)%, which was a little higher than that of Pt (8.05%).
Cobaltosic sulfide (Co3S4) was synthesized by hydrothermal synthesis method. Combining the ball grinding mill and spray method, Co3S4 was prepared into counter electrode (CE) and fabricated dye-sensitized solar cells (DSCs) with the novel electrolyte Co2+/Co3+. The power conversion efficiency (PCE) obtained by the DSCs based on the pure Co3S4 CE was only 6.06%, which was much smaller than that of Pt (8.05%). To improve the catalytic activity of pure Co3S4, electrospun carbon nanofibers (ECs) were fabricated by the electrospun method and the composite of ECs supported cobaltosic sulfide (Co3S4/ECs) was synthesized by hydrothermal synthesis method. And the DSCs based on Co3S4/ECs CE achieved a high PCE of (8.22±0.08)%, which was a little higher than that of Pt (8.05%).
2017, 33(4): 615-622
doi: 10.11862/CJIC.2017.078
Abstract:
SiO2 microspheres with different diameters were prepared by Stober method, and the SiO2 microspheres were uniformly coated with ZrO2 by adsorption and hydrolysis of ZrOCl2. The ZrO2 hollow microspheres were then obtained after SiO2 was removed by hydrofluoric acid, and Au@ZrO2 hollow microspheres were finally prepared by deposition-precipitation (DP) method. Catalytic properties of Au@ZrO2 hollow microspheres in reduction of paranitroaniline were studied carefully. The research results indicate that the SiO2 microspheres have regular shape and good dispersity. The sizes and the surface areas of the ZrO2 hollow microspheres could be controlled effectively by the diameters of SiO2 microspheres. Compared to the solid microsphere Au@ZrO2, the Au@ZrO2 hollow microspheres showed good catalytic performance in reduction of p-nitroaniline, and p-nitroaniline was completely reduced to p-phenylenediamine in 7 min at 45℃.
SiO2 microspheres with different diameters were prepared by Stober method, and the SiO2 microspheres were uniformly coated with ZrO2 by adsorption and hydrolysis of ZrOCl2. The ZrO2 hollow microspheres were then obtained after SiO2 was removed by hydrofluoric acid, and Au@ZrO2 hollow microspheres were finally prepared by deposition-precipitation (DP) method. Catalytic properties of Au@ZrO2 hollow microspheres in reduction of paranitroaniline were studied carefully. The research results indicate that the SiO2 microspheres have regular shape and good dispersity. The sizes and the surface areas of the ZrO2 hollow microspheres could be controlled effectively by the diameters of SiO2 microspheres. Compared to the solid microsphere Au@ZrO2, the Au@ZrO2 hollow microspheres showed good catalytic performance in reduction of p-nitroaniline, and p-nitroaniline was completely reduced to p-phenylenediamine in 7 min at 45℃.
2017, 33(4): 623-629
doi: 10.11862/CJIC.2017.080
Abstract:
A series of porous Co1-xFexOy(0 ≤ x ≤ 1) nanorods were fabricated by a simple thermal decomposed of CoFe-NTA precursors and were served as oxygen evolving catalysts for water electrolysis in 1 mol·L-1 KOH solution. It was found that different Fe doping amounts have dramatically effects on the structure and electrocatalytic water oxidation activities and the 16%(n/n) Fe-doping sample exhibited the most excellent oxygen evolving activity. A lowered overpotential of 345 mV was achieved at a current density of 10 mA·cm-2 with a Tafel slope of 54 mV·dec-1 for the 16% Fe-doping sample, which suggest that it can be applied as low cost and efficient oxygen catalyst for water splitting.
A series of porous Co1-xFexOy(0 ≤ x ≤ 1) nanorods were fabricated by a simple thermal decomposed of CoFe-NTA precursors and were served as oxygen evolving catalysts for water electrolysis in 1 mol·L-1 KOH solution. It was found that different Fe doping amounts have dramatically effects on the structure and electrocatalytic water oxidation activities and the 16%(n/n) Fe-doping sample exhibited the most excellent oxygen evolving activity. A lowered overpotential of 345 mV was achieved at a current density of 10 mA·cm-2 with a Tafel slope of 54 mV·dec-1 for the 16% Fe-doping sample, which suggest that it can be applied as low cost and efficient oxygen catalyst for water splitting.
2017, 33(4): 630-636
doi: 10.11862/CJIC.2017.074
Abstract:
The Schiff base hmmpH2 (hmmpH2=2-[(2-hydroxyethylimino) methyl]-6-methoxyphenol) was synthesized by o-vanillin and ethanolamine. Complexes[Fe2(hmmp)2(hmmpH)2]·1.5CH3CN·0.5H2O (1) and[Co2Na ((hmmp)2(N3)2(CH3O)(CH3OH)2] (2) were synthesized by using hmmpH2 ligand. The Schiff base hmdbrpH2 (hmdbrpH2=2-[(2-hydroxyethylimino) methyl]-4, 6-dibromophenol) was synthesized by 3, 5-dibromosalicylaldehyde and ethanolamine. Complex[Mn(Ⅱ) Mn(Ⅲ)2(hmdbrp)2(O2CPh)4(CH3OH)2]·2CH3CN·2CH3OH (3) was synthesized by using hmdbrpH2 ligand. These complexes were fully characterized by elemental analysis and X-ray single crystal diffraction, and complexes 1 and 3 were also studied by magnetic investigation. The structural analysis indicates that in complex 1 two six-coordinated Fe(Ⅲ) ions are bridged by two alcoholic hydroxyl atoms to form a dimer structure. In complex 2, Co(Ⅲ) is six-coordinated with an octahedral coordination environment and the two Co(Ⅲ) ions are bridged by two O atoms from CH3OH constructing a binuclear complex. The complex 3 is a mixed valence trinuclear structure, with three Mn ions in linear array. Magnetic study indicates that the antiferromagnetic interaction exist between Fe(Ⅲ) ions in complex 1, and in complex 3 antiferromagnetic interactions exist between the Mn(Ⅱ) and Mn(Ⅲ) ions in the trinuclear manganese unit.
The Schiff base hmmpH2 (hmmpH2=2-[(2-hydroxyethylimino) methyl]-6-methoxyphenol) was synthesized by o-vanillin and ethanolamine. Complexes[Fe2(hmmp)2(hmmpH)2]·1.5CH3CN·0.5H2O (1) and[Co2Na ((hmmp)2(N3)2(CH3O)(CH3OH)2] (2) were synthesized by using hmmpH2 ligand. The Schiff base hmdbrpH2 (hmdbrpH2=2-[(2-hydroxyethylimino) methyl]-4, 6-dibromophenol) was synthesized by 3, 5-dibromosalicylaldehyde and ethanolamine. Complex[Mn(Ⅱ) Mn(Ⅲ)2(hmdbrp)2(O2CPh)4(CH3OH)2]·2CH3CN·2CH3OH (3) was synthesized by using hmdbrpH2 ligand. These complexes were fully characterized by elemental analysis and X-ray single crystal diffraction, and complexes 1 and 3 were also studied by magnetic investigation. The structural analysis indicates that in complex 1 two six-coordinated Fe(Ⅲ) ions are bridged by two alcoholic hydroxyl atoms to form a dimer structure. In complex 2, Co(Ⅲ) is six-coordinated with an octahedral coordination environment and the two Co(Ⅲ) ions are bridged by two O atoms from CH3OH constructing a binuclear complex. The complex 3 is a mixed valence trinuclear structure, with three Mn ions in linear array. Magnetic study indicates that the antiferromagnetic interaction exist between Fe(Ⅲ) ions in complex 1, and in complex 3 antiferromagnetic interactions exist between the Mn(Ⅱ) and Mn(Ⅲ) ions in the trinuclear manganese unit.
2017, 33(4): 637-643
doi: 10.11862/CJIC.2017.082
Abstract:
Photocatalytic reduction of nitrate and/or nitrite is performed using g-C3N4-TiO2 as photocatalytic cathode combined with electricity generating bio-anode. Effect on photocatalytic reduction of nitrate is investigated from hole scavenger, aeration conditions and biological anode, respectively, and the reduction mechanism is analyzed. The result shows that the system has the best removal efficiency with a biological anode and exposure to nitrogen, while hole scavenger has the least effect on photocatalytic reduction. The removal of nitrate is 72.57% and the concentration of nitrite (by-product) is 0.31 mg·L-1 after 210 min of reaction, while ammonia is not detected. The supported catalyst does not fall off and the catalyst activity remains essentially unchanged after repeated experiments, which means the catalyst and electrode can be reused.
Photocatalytic reduction of nitrate and/or nitrite is performed using g-C3N4-TiO2 as photocatalytic cathode combined with electricity generating bio-anode. Effect on photocatalytic reduction of nitrate is investigated from hole scavenger, aeration conditions and biological anode, respectively, and the reduction mechanism is analyzed. The result shows that the system has the best removal efficiency with a biological anode and exposure to nitrogen, while hole scavenger has the least effect on photocatalytic reduction. The removal of nitrate is 72.57% and the concentration of nitrite (by-product) is 0.31 mg·L-1 after 210 min of reaction, while ammonia is not detected. The supported catalyst does not fall off and the catalyst activity remains essentially unchanged after repeated experiments, which means the catalyst and electrode can be reused.
2017, 33(4): 644-650
doi: 10.11862/CJIC.2017.073
Abstract:
Tri (3, 5-difluorobenzyl) tin chloride (1) and tetra (o-chlorobenzyl) tin (2) have been synthesized. The crystal structures of the compounds were determined by X-ray diffraction. The crystal 1 belongs to monoclinic space group C2/c with a=1.858 33(11) nm, b=1.140 98(7) nm, c=2.690 06 (16) nm, β=109.288(10)°, V=5.383 6(6) nm3, Z=8, Dc=1.532 g·cm-3, μ(Mo Kα)=13.61 cm-1, F(000)=2 480, R1=0.085 1, wR2=0.168 1. The crystal 2 belongs to monoclinic space group P21/m with a=0.585 54(5) nm, b=1.969 74(18) nm, c=0.857 86(8) nm, β=95.204 0(10)°, V=0.985 34(15) nm3, Z=2, Dc=1.805 g·cm-3, μ(Mo Kα)=14.91 cm-1, F(000)=524, R1=0.0540, wR2=0.163 9. The tin atoms have a distorted tetrahedral geometry. The study on two compounds have been performed with quantum chemistry calculation. The stabilities, some frontier molecular orbital energies and composition characteristics of some frontier molecular orbital of the compound have been investigated. The thermal stability of the compounds were tested.
Tri (3, 5-difluorobenzyl) tin chloride (1) and tetra (o-chlorobenzyl) tin (2) have been synthesized. The crystal structures of the compounds were determined by X-ray diffraction. The crystal 1 belongs to monoclinic space group C2/c with a=1.858 33(11) nm, b=1.140 98(7) nm, c=2.690 06 (16) nm, β=109.288(10)°, V=5.383 6(6) nm3, Z=8, Dc=1.532 g·cm-3, μ(Mo Kα)=13.61 cm-1, F(000)=2 480, R1=0.085 1, wR2=0.168 1. The crystal 2 belongs to monoclinic space group P21/m with a=0.585 54(5) nm, b=1.969 74(18) nm, c=0.857 86(8) nm, β=95.204 0(10)°, V=0.985 34(15) nm3, Z=2, Dc=1.805 g·cm-3, μ(Mo Kα)=14.91 cm-1, F(000)=524, R1=0.0540, wR2=0.163 9. The tin atoms have a distorted tetrahedral geometry. The study on two compounds have been performed with quantum chemistry calculation. The stabilities, some frontier molecular orbital energies and composition characteristics of some frontier molecular orbital of the compound have been investigated. The thermal stability of the compounds were tested.
2017, 33(4): 651-658
doi: 10.11862/CJIC.2017.088
Abstract:
The urea-based pyridyl ligand L was synthesized from the reaction of 1, 3-Benzenediamine with 3-isocyanatopyridine in toluene heating to reflux. CdSO4·8H2O, ZnI2, HgI2 and HgCl2 reacted with L to give the complexes {[Cd (L)(SO4)(H2O)3]·H2O}n (1), {[Zn (L) I2]·2C2H5OH}n (2), {[Hg (L) I2]·2C2H5OH}n (3), [Hg (L) Cl2]·H2O (4), which were characterized by elemental analysis, FT-IR, single crystal X-ray diffraction and powder X-ray diffraction. Complex 1 forms a one-dimensional helix chain structure, complex 2 and complex 3 show a one-dimensional zigzag chain structure and complex 4 shows a 32-membered ring.
The urea-based pyridyl ligand L was synthesized from the reaction of 1, 3-Benzenediamine with 3-isocyanatopyridine in toluene heating to reflux. CdSO4·8H2O, ZnI2, HgI2 and HgCl2 reacted with L to give the complexes {[Cd (L)(SO4)(H2O)3]·H2O}n (1), {[Zn (L) I2]·2C2H5OH}n (2), {[Hg (L) I2]·2C2H5OH}n (3), [Hg (L) Cl2]·H2O (4), which were characterized by elemental analysis, FT-IR, single crystal X-ray diffraction and powder X-ray diffraction. Complex 1 forms a one-dimensional helix chain structure, complex 2 and complex 3 show a one-dimensional zigzag chain structure and complex 4 shows a 32-membered ring.
2017, 33(4): 659-663
doi: 10.11862/CJIC.2017.083
Abstract:
La0.1BixSr0.9-xTiO3(x=0, 0.05, 0.075, 0.1) ceramics were fabricated at 1 500℃ for 4 h in 5%H2+95%N2(V/V) reduction atmosphere. The phase composition, microstructure and thermoelectric properties were investigated. The results indicated that the main phase of the samples doped with Bi was SrTiO3, and trace Bi2O3 was observed when the Bi doping content is more than 0.075. The grain of the samples doped with Bi was fully developed, regularly shaped and combined closely, suggesting the good sintering effect of Bi2O3. Moreover, the electric conductivity and the absolute Seebeck coefficient of La0.1Sr0.9TiO3 ceramics increased obviously with the doping of Bi, indicating that the carrier concentration and carrier mobility were greatly improved by the Bi doping. The power factor of the sample with x=0.075 was maximum, which attained 692 μW·m-1·K-2 at 400℃. Though the thermal conductivity of the samples doped with Bi was higher than that of the sample without Bi, the ZT value of the sample with x=0.075 could still reach 0.172 at 500℃, which was increased by 130% compared with that of the sample without Bi.
La0.1BixSr0.9-xTiO3(x=0, 0.05, 0.075, 0.1) ceramics were fabricated at 1 500℃ for 4 h in 5%H2+95%N2(V/V) reduction atmosphere. The phase composition, microstructure and thermoelectric properties were investigated. The results indicated that the main phase of the samples doped with Bi was SrTiO3, and trace Bi2O3 was observed when the Bi doping content is more than 0.075. The grain of the samples doped with Bi was fully developed, regularly shaped and combined closely, suggesting the good sintering effect of Bi2O3. Moreover, the electric conductivity and the absolute Seebeck coefficient of La0.1Sr0.9TiO3 ceramics increased obviously with the doping of Bi, indicating that the carrier concentration and carrier mobility were greatly improved by the Bi doping. The power factor of the sample with x=0.075 was maximum, which attained 692 μW·m-1·K-2 at 400℃. Though the thermal conductivity of the samples doped with Bi was higher than that of the sample without Bi, the ZT value of the sample with x=0.075 could still reach 0.172 at 500℃, which was increased by 130% compared with that of the sample without Bi.
2017, 33(4): 664-672
doi: 10.11862/CJIC.2017.060
Abstract:
Two organic-inorganic hybrids, (DPASP)2[Zn (NCS)4]·2CH3OH (1) and {(DPASP)2[Cd (SCN)(NCS)3]·2CH3OH}n (2), have been facilely prepared from (E)-4-(4-(diphenylamino) styryl)-1-methylpyridinium iodide (DPASPI, DPASP=(E)-4-(4-(diphenylamino) styryl)-1-methylpyridinium) at gram scale. Their crystal structures have been confirmed by single-crystal X-ray diffraction analysis, which show that the hybrids 1 and 2 consist of organic pyridium cations and metal thiocyanato anions bearing different spacial structure through self-assembly processes. Furthermore, the interactions between the ions have been investigated by 1H NMR spectra. Finally, red photolumencent properties with enhanced quantum yields of hybrids 1 and 2 were investigated.
Two organic-inorganic hybrids, (DPASP)2[Zn (NCS)4]·2CH3OH (1) and {(DPASP)2[Cd (SCN)(NCS)3]·2CH3OH}n (2), have been facilely prepared from (E)-4-(4-(diphenylamino) styryl)-1-methylpyridinium iodide (DPASPI, DPASP=(E)-4-(4-(diphenylamino) styryl)-1-methylpyridinium) at gram scale. Their crystal structures have been confirmed by single-crystal X-ray diffraction analysis, which show that the hybrids 1 and 2 consist of organic pyridium cations and metal thiocyanato anions bearing different spacial structure through self-assembly processes. Furthermore, the interactions between the ions have been investigated by 1H NMR spectra. Finally, red photolumencent properties with enhanced quantum yields of hybrids 1 and 2 were investigated.
2017, 33(4): 673-678
doi: 10.11862/CJIC.2017.070
Abstract:
Four metal hybrid calix[4]arene coordination polymers:{[Cd (L)(tpa)]·3H2O}n (1), {[Zn2(L)2(tpa)2]·3H2O}n (2), {[Co (L)(oba)]·2DMA·0.5H2O}n (3) and {[Zn (L)(oba)]·DMA}n (4) (L=2-((1H-imidazol-1-yl) methyl)-6-(3-((1H-imidazol-1-yl) methyl)-5-tert-butyl-2-hydroxybenzyl)-4-tert-butylphenol, H2tpa=terephthalic acid, H2oba=4, 4'-oxy-bisbenzoic acid) have been successfully synthesized and characterized by elemental analysis, thermogravimetry, IR, the solid-sate UV-Vis spectra, single-crystal X-ray diffraction and PXRD. The single-crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the monoclinic system, space group P21/n while complexes 2, 3 and 4 crystallize in the triclinic, space group P1. Complexes 1, 2, 3 and 4 are one-dimensional coordination polymers, which are formed through 0D[M (N4O2C29H36)] (M=Zn, Co, Cd) metal hybrid calix[4]arene bridged H2tpa and H2oba ligands.
Four metal hybrid calix[4]arene coordination polymers:{[Cd (L)(tpa)]·3H2O}n (1), {[Zn2(L)2(tpa)2]·3H2O}n (2), {[Co (L)(oba)]·2DMA·0.5H2O}n (3) and {[Zn (L)(oba)]·DMA}n (4) (L=2-((1H-imidazol-1-yl) methyl)-6-(3-((1H-imidazol-1-yl) methyl)-5-tert-butyl-2-hydroxybenzyl)-4-tert-butylphenol, H2tpa=terephthalic acid, H2oba=4, 4'-oxy-bisbenzoic acid) have been successfully synthesized and characterized by elemental analysis, thermogravimetry, IR, the solid-sate UV-Vis spectra, single-crystal X-ray diffraction and PXRD. The single-crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the monoclinic system, space group P21/n while complexes 2, 3 and 4 crystallize in the triclinic, space group P1. Complexes 1, 2, 3 and 4 are one-dimensional coordination polymers, which are formed through 0D[M (N4O2C29H36)] (M=Zn, Co, Cd) metal hybrid calix[4]arene bridged H2tpa and H2oba ligands.
2017, 33(4): 679-684
doi: 10.11862/CJIC.2017.032
Abstract:
A novel method to prepare carbon nanorods through hydrothermal nanocasting method was presented using halloysite nanotubes (HNTs) as the template and polyvinyl alcohol (PVA) as the carbon source. This method involved in three steps, i.e. nanocasting PVA in HNTs, carbonization and etching removal of template. A series of characterization, such as XRD, FT-IR, SEM, TEM, Raman, XPS, SAED and N2 adsorption-desorption were used to detect the formation and structure of the as-prepared carbon nanorods (CNRs). The CNRs with a 1D rod-like structure were of high specific surface area (408 m2·g-1) and possessed typical mesoporous characterization.
A novel method to prepare carbon nanorods through hydrothermal nanocasting method was presented using halloysite nanotubes (HNTs) as the template and polyvinyl alcohol (PVA) as the carbon source. This method involved in three steps, i.e. nanocasting PVA in HNTs, carbonization and etching removal of template. A series of characterization, such as XRD, FT-IR, SEM, TEM, Raman, XPS, SAED and N2 adsorption-desorption were used to detect the formation and structure of the as-prepared carbon nanorods (CNRs). The CNRs with a 1D rod-like structure were of high specific surface area (408 m2·g-1) and possessed typical mesoporous characterization.
2017, 33(4): 685-691
doi: 10.11862/CJIC.2017.064
Abstract:
Two complexes[Ni (L1)2]·2H2O (1) and[Ni (L2)2]·2H2O (2) have been synthesized using the bezimidazole derived tridentate (NNO donor) potential Schiff base ligands HL1 and HL2, which are prepared from reaction of 2-aminoethyl-1H-benzimidazole with 5-chlorosalicylaldehyde and 5-bromosalicylaldehyde, respectively, and characterized by elemental analysis, FT-IR and UV-Vis spectroscopies and single crystal X-ray crystallography. In 1 and 2, each Ni(Ⅱ) has a distorted octahedral arrangement with a N4O2 donor set in trichelated fashion of the Schiff base ligands. Furthermore, the complex units in 1 and 2 are linked into 2D and 3D supramolecular networks by H-bonding in the solid state, respectively. The bioactivity studies showed that both the two complexes exhibit moderate to strong antibacterial activities against S. aureus (Gram-positive) and E. coli (Gram-negative) bacteria and were found more active than the corresponding Schiff base ligands.
Two complexes[Ni (L1)2]·2H2O (1) and[Ni (L2)2]·2H2O (2) have been synthesized using the bezimidazole derived tridentate (NNO donor) potential Schiff base ligands HL1 and HL2, which are prepared from reaction of 2-aminoethyl-1H-benzimidazole with 5-chlorosalicylaldehyde and 5-bromosalicylaldehyde, respectively, and characterized by elemental analysis, FT-IR and UV-Vis spectroscopies and single crystal X-ray crystallography. In 1 and 2, each Ni(Ⅱ) has a distorted octahedral arrangement with a N4O2 donor set in trichelated fashion of the Schiff base ligands. Furthermore, the complex units in 1 and 2 are linked into 2D and 3D supramolecular networks by H-bonding in the solid state, respectively. The bioactivity studies showed that both the two complexes exhibit moderate to strong antibacterial activities against S. aureus (Gram-positive) and E. coli (Gram-negative) bacteria and were found more active than the corresponding Schiff base ligands.
2017, 33(4): 692-698
doi: 10.11862/CJIC.2017.067
Abstract:
Four complexes[NiL2]·2CH3OH (1), [ZnL2]·CH3OH (2), [CdL2]·CH3CH2OH (3) and[Cu2L2Cl2] (4) (HL=4-methyl-1-((quinolin-8-yl) methylene)-thiosemicarbazide) have been synthesized and structurally determined by single-crystal X-ray diffraction. The results show that the structures of complexes 1~3 are quite similar. The metal ion in each complex with a distorted octahedron geometry is surrounded by two anionic thiosemicarbazone ligands with N4S2 donor set. However, complex 4 is binuclear, and each central Cu(Ⅱ) ion is coordinated by one independent neutral ligand HL and three chloride anions, two of which act as μ2-bridges. In addition, the fluorescence spectra indicate that the interactions of the complex es with DNA, particularly of the complex 4, are stronger than that of the ligand HL.
Four complexes[NiL2]·2CH3OH (1), [ZnL2]·CH3OH (2), [CdL2]·CH3CH2OH (3) and[Cu2L2Cl2] (4) (HL=4-methyl-1-((quinolin-8-yl) methylene)-thiosemicarbazide) have been synthesized and structurally determined by single-crystal X-ray diffraction. The results show that the structures of complexes 1~3 are quite similar. The metal ion in each complex with a distorted octahedron geometry is surrounded by two anionic thiosemicarbazone ligands with N4S2 donor set. However, complex 4 is binuclear, and each central Cu(Ⅱ) ion is coordinated by one independent neutral ligand HL and three chloride anions, two of which act as μ2-bridges. In addition, the fluorescence spectra indicate that the interactions of the complex es with DNA, particularly of the complex 4, are stronger than that of the ligand HL.
2017, 33(4): 699-704
doi: 10.11862/CJIC.2017.051
Abstract:
Two complexes, namely, [Cu2(L)2Br2]·CH3OH (1) and[Zn2(L)2(CH3COO)2]·2CH3OH (2) (HL=1-(3-ethylpyrazin-2-yl) ethylidene-4-phenylsemicarbazide) have been synthesized and characterized by single crystal X-ray diffraction, elemental analysis and IR spectroscopy. In complex 1, the center Cu(Ⅱ) ion with a distorted square pyramid coordination geometry is coordinated by one tridentate deprotonated semicarbazone with N2O donor set and two μ2-bridged bromide anions. The coordination geometry of the Zn(Ⅱ) ion in complex 2 is same as that of the Cu(Ⅱ) ion in complex 1, while with N2O3 donor set. In addition, two acetate anions in complex 2 exhibit different coordination modes, one of which is bidentate bridge (μ-OCO), while the other one is oxygen bridge (μ-O). In the methanol solution, both complexes exhibit the intra-ligand emission.
Two complexes, namely, [Cu2(L)2Br2]·CH3OH (1) and[Zn2(L)2(CH3COO)2]·2CH3OH (2) (HL=1-(3-ethylpyrazin-2-yl) ethylidene-4-phenylsemicarbazide) have been synthesized and characterized by single crystal X-ray diffraction, elemental analysis and IR spectroscopy. In complex 1, the center Cu(Ⅱ) ion with a distorted square pyramid coordination geometry is coordinated by one tridentate deprotonated semicarbazone with N2O donor set and two μ2-bridged bromide anions. The coordination geometry of the Zn(Ⅱ) ion in complex 2 is same as that of the Cu(Ⅱ) ion in complex 1, while with N2O3 donor set. In addition, two acetate anions in complex 2 exhibit different coordination modes, one of which is bidentate bridge (μ-OCO), while the other one is oxygen bridge (μ-O). In the methanol solution, both complexes exhibit the intra-ligand emission.
2017, 33(4): 705-712
doi: 10.11862/CJIC.2017.068
Abstract:
The Zn(Ⅱ) complex, [Zn (C14H8O4S)(ip)(H2O)] (1) (C14H8O4S=bis (2-carboxyphenyl) sulfide, ip=1H-imidazo[4, 5-f] [1, 10]phenanthroline) was prepared with 2, 2'-dithiosalicylic acid, ip and Zn (NO3)2·6H2O by in situ hydro-thermal reaction; while {[Co (C14H8O4S2)(im)2]·H2O}n (2) (C14H8O4S2=2, 2'-dithiosalicylate, im=imidazole) was synth-esized by mixing 2, 2'-dithiosalicylic acid, im and cobalt dinitrate; after that they were characterized by elemental analysis, thermal analysis, IR, fluorescent spectra analysis, XRD and X-ray single crystal diffraction. Complex 1 has a dinuclear structure, and the Zn(Ⅱ) ion is five-coordinated in a distorted trigonal bipyramidal geometry. Complex 2 has a one-dimensional chain structure, while the Co(Ⅱ) ion is six-coordinated to form a distorted octahedral configuration.
The Zn(Ⅱ) complex, [Zn (C14H8O4S)(ip)(H2O)] (1) (C14H8O4S=bis (2-carboxyphenyl) sulfide, ip=1H-imidazo[4, 5-f] [1, 10]phenanthroline) was prepared with 2, 2'-dithiosalicylic acid, ip and Zn (NO3)2·6H2O by in situ hydro-thermal reaction; while {[Co (C14H8O4S2)(im)2]·H2O}n (2) (C14H8O4S2=2, 2'-dithiosalicylate, im=imidazole) was synth-esized by mixing 2, 2'-dithiosalicylic acid, im and cobalt dinitrate; after that they were characterized by elemental analysis, thermal analysis, IR, fluorescent spectra analysis, XRD and X-ray single crystal diffraction. Complex 1 has a dinuclear structure, and the Zn(Ⅱ) ion is five-coordinated in a distorted trigonal bipyramidal geometry. Complex 2 has a one-dimensional chain structure, while the Co(Ⅱ) ion is six-coordinated to form a distorted octahedral configuration.
