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2015 Volume 31 Issue 5
2015, (5): 857-864
doi: 10.11862/CJIC.2015.148
Abstract:
Three metal-organic frameworks, namely [PrL(HL)(H2O)2]·H2O (1), Er(H0.5L)2 (2), and [CoL(H2O)2]·H2O (3) (H2L=5-(1H-imidazol-1-yl)isophthalic acid), have been synthesized under hydrothermal condition. Single crystal X-ray diffraction indicates that all the three complexes belong to the monoclinic space group P21/c. The Pr3+ ions in 1 are nine-coordinated, while the Er3+ ions in 2 and Co2+ ions in 3 are both six-coordinated. In the lanthanide complex 1 and 2, the nitrogen atom does not coordinate with any metal ions. Complex 1 shows a 2D folding framework, while complex 2 exhibits a 3D network. In the transition metal complex 3, the nitrogen atom coordinates with Co2+, which helps to form a flat 2D framework. Complex 1 and 3 are further packed into 3D framework by the intermolecular π-π interactions. All the three complexes display good thermal stability.
Three metal-organic frameworks, namely [PrL(HL)(H2O)2]·H2O (1), Er(H0.5L)2 (2), and [CoL(H2O)2]·H2O (3) (H2L=5-(1H-imidazol-1-yl)isophthalic acid), have been synthesized under hydrothermal condition. Single crystal X-ray diffraction indicates that all the three complexes belong to the monoclinic space group P21/c. The Pr3+ ions in 1 are nine-coordinated, while the Er3+ ions in 2 and Co2+ ions in 3 are both six-coordinated. In the lanthanide complex 1 and 2, the nitrogen atom does not coordinate with any metal ions. Complex 1 shows a 2D folding framework, while complex 2 exhibits a 3D network. In the transition metal complex 3, the nitrogen atom coordinates with Co2+, which helps to form a flat 2D framework. Complex 1 and 3 are further packed into 3D framework by the intermolecular π-π interactions. All the three complexes display good thermal stability.
2015, (5): 865-872
doi: 10.11862/CJIC.2015.142
Abstract:
Based on cis-[Ru(dpq)2Cl2]·2H2O (dpq=dipyrido[3,2-d:2',3'-f]quinoxaline) and 5,5'-di(1-(triethylamm-onio)methyl)-2,2'-dipyridyl cation ligand (L), the complex [Ru(dpq)2L](PF6)4 was synthesized and structurally characterized. The interactions of the complex with different G-quadruplexes were investigated. FRET melting assay proved that the complex bonds more strongly to h-telo than to promoters, such as c-myc and bcl2. CD studies show that Ru(Ⅱ) complex can induce the formation of parallel G-quadruplex of h-telo in the absence of Na+ or K+. Results of absorption and emission titration indicated that the complex has a higher DNA affinity with h-telo in K+ buffer than in Na+ buffer.
Based on cis-[Ru(dpq)2Cl2]·2H2O (dpq=dipyrido[3,2-d:2',3'-f]quinoxaline) and 5,5'-di(1-(triethylamm-onio)methyl)-2,2'-dipyridyl cation ligand (L), the complex [Ru(dpq)2L](PF6)4 was synthesized and structurally characterized. The interactions of the complex with different G-quadruplexes were investigated. FRET melting assay proved that the complex bonds more strongly to h-telo than to promoters, such as c-myc and bcl2. CD studies show that Ru(Ⅱ) complex can induce the formation of parallel G-quadruplex of h-telo in the absence of Na+ or K+. Results of absorption and emission titration indicated that the complex has a higher DNA affinity with h-telo in K+ buffer than in Na+ buffer.
2015, (5): 873-879
doi: 10.11862/CJIC.2015.140
Abstract:
The cathode material Li1.2Ni0.13Co0.13Mn0.54O2 was synthesized by sol-gel method modified by glucose as carbon source. The structure, morphology and electrochemical performances of the as-prepared sample was studied by methods of XRD, SEM, EDS, BET, Laser Particle Size Analysis, cyclic voltammetry, galvanostatic charge-discharge and AC impedance. Test results showed that the distribution of particles became uniform and the sizes became smaller for the modification by glucose. The D50 decreased from 11.56 to 9.94 μm. The specific surface area nearly doubled. The initial discharge specific capacity at 0.2C reached 183.4 mAh·g-1 and 211.6 mAh·g-1 after been activated by 0.05C for blank and compared groups, respectively. The capacity at 2C retained 62.2% and 77.6% of that at 0.2C for the two samples, respectively. After 50 cycles at 1C, the discharge specific capacities retained 133.3 mAh·g-1 and 173.6 mAh·g-1, and the capacity retention rates were 95.1% and 100% for the two samples, respectively. The initial irreversible capacity loss was reduced for the modification by glucose. The rate performance and cycle stability were obviously improved. The impedance of charge transfer and Warburg, and dispersion effect of the electric double layer were decreased. The crystal structure of the sample stayed unchanged.
The cathode material Li1.2Ni0.13Co0.13Mn0.54O2 was synthesized by sol-gel method modified by glucose as carbon source. The structure, morphology and electrochemical performances of the as-prepared sample was studied by methods of XRD, SEM, EDS, BET, Laser Particle Size Analysis, cyclic voltammetry, galvanostatic charge-discharge and AC impedance. Test results showed that the distribution of particles became uniform and the sizes became smaller for the modification by glucose. The D50 decreased from 11.56 to 9.94 μm. The specific surface area nearly doubled. The initial discharge specific capacity at 0.2C reached 183.4 mAh·g-1 and 211.6 mAh·g-1 after been activated by 0.05C for blank and compared groups, respectively. The capacity at 2C retained 62.2% and 77.6% of that at 0.2C for the two samples, respectively. After 50 cycles at 1C, the discharge specific capacities retained 133.3 mAh·g-1 and 173.6 mAh·g-1, and the capacity retention rates were 95.1% and 100% for the two samples, respectively. The initial irreversible capacity loss was reduced for the modification by glucose. The rate performance and cycle stability were obviously improved. The impedance of charge transfer and Warburg, and dispersion effect of the electric double layer were decreased. The crystal structure of the sample stayed unchanged.
2015, (5): 880-887
doi: 10.11862/CJIC.2015.128
Abstract:
Highly-dispersed LiFePO4/C composite with micro-leaf structure was synthesized by a facile citric acid-assisted hydrothermal method in this study. Crystal structure and morphology of samples were investigated by XRD, FTIR, SEM, HR-TEM and selected area electron diffraction (SAED). The characterization results indicate that citric acid accelerates the formation of leaf-like LiFePO4/C composite. The as-prepared leaf-like LiFePO4/C composite with an enlarged (010) plane has high dispersibility. By comparing the electrochemical properties of the LiFePO4/C particles in our study, the LiFePO4/C micro-leaves exhibit larger discharge capacity and better rate performance, which deliver a discharge capacity of 158 mAh·g-1 at 0.1C and 126 mAh·g-1 at 5C. The enhanced performance perhaps is attributed to the reduced Li-ion diffusion paths along the [010] direction and larger Li-ion diffusion coefficient.
Highly-dispersed LiFePO4/C composite with micro-leaf structure was synthesized by a facile citric acid-assisted hydrothermal method in this study. Crystal structure and morphology of samples were investigated by XRD, FTIR, SEM, HR-TEM and selected area electron diffraction (SAED). The characterization results indicate that citric acid accelerates the formation of leaf-like LiFePO4/C composite. The as-prepared leaf-like LiFePO4/C composite with an enlarged (010) plane has high dispersibility. By comparing the electrochemical properties of the LiFePO4/C particles in our study, the LiFePO4/C micro-leaves exhibit larger discharge capacity and better rate performance, which deliver a discharge capacity of 158 mAh·g-1 at 0.1C and 126 mAh·g-1 at 5C. The enhanced performance perhaps is attributed to the reduced Li-ion diffusion paths along the [010] direction and larger Li-ion diffusion coefficient.
2015, (5): 888-894
doi: 10.11862/CJIC.2015.137
Abstract:
In the mixed-solution of ethanol and water, the monodisperse strontium titanate (STO) nanocrys-tallines were synthesized by hydrothermal method. The powder X-ray diffraction (XRD) patterns results revealed that the nanocrystallines crystallized in the cubic phase, and the crystallization of the products became more significant with the reaction continuing. The particle size of about 70 nm and cubic morphology were further evidenced by the scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The growth process of the nanocrystallines was studied by SEM, TEM, high resolution transmission electron microscopy (HRTEM) and electron diffraction(ED) spectroscopy in detail. The results have discovered that as follow: first, the nucleus of STO was produced by the diffusion reaction between the precursors; then, the nuclei orientedly attached by each other and the nanoparticle-aggregation came into being; last, the nanoparticle-aggregations were converted into the single crystallines of STO under Ostwald ripening mechanisms. The growth process of “diffusion reaction—oriented attachment—Ostwald ripening” has discovered the formation mechanism of STO nanocrystalline. The results of kinetics modeling with Johnson-Mehl-Avrami(JMA) equation show that the diffusion reaction is dominant at the early stage and the active energy is 15.79 kJ·mol-1.
In the mixed-solution of ethanol and water, the monodisperse strontium titanate (STO) nanocrys-tallines were synthesized by hydrothermal method. The powder X-ray diffraction (XRD) patterns results revealed that the nanocrystallines crystallized in the cubic phase, and the crystallization of the products became more significant with the reaction continuing. The particle size of about 70 nm and cubic morphology were further evidenced by the scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The growth process of the nanocrystallines was studied by SEM, TEM, high resolution transmission electron microscopy (HRTEM) and electron diffraction(ED) spectroscopy in detail. The results have discovered that as follow: first, the nucleus of STO was produced by the diffusion reaction between the precursors; then, the nuclei orientedly attached by each other and the nanoparticle-aggregation came into being; last, the nanoparticle-aggregations were converted into the single crystallines of STO under Ostwald ripening mechanisms. The growth process of “diffusion reaction—oriented attachment—Ostwald ripening” has discovered the formation mechanism of STO nanocrystalline. The results of kinetics modeling with Johnson-Mehl-Avrami(JMA) equation show that the diffusion reaction is dominant at the early stage and the active energy is 15.79 kJ·mol-1.
2015, (5): 895-900
doi: 10.11862/CJIC.2015.133
Abstract:
Acolloidal method was used to synthesize Mn-doped CdS/ZnS core/shell nanocrystals, and the film containing these nanosrystals was sandwiched between two Ta2O5 layers to get an AC-driven thin film electroluminescent(EL) device. Its EL spectrum is dependent on the location of Mn dopants. The ELintensity increased with the temperature, and then decreased with the further rise of temperature.
Acolloidal method was used to synthesize Mn-doped CdS/ZnS core/shell nanocrystals, and the film containing these nanosrystals was sandwiched between two Ta2O5 layers to get an AC-driven thin film electroluminescent(EL) device. Its EL spectrum is dependent on the location of Mn dopants. The ELintensity increased with the temperature, and then decreased with the further rise of temperature.
2015, (5): 901-907
doi: 10.11862/CJIC.2015.124
Abstract:
Density functional theory was applied to study the structure and vibratioanl spectra of framework titanium located in the 10-membered ring channel of Ti-MWW. The calculations were carried out at B3LYP/6-31G(d,p) level of theory based on the 36Tcluster models, leading to the results that the [Ti(OSi)4] species prefer to locate at the T3 site. The stretching vibrations correlated to [Ti(OSi)4] occur between 924~987 cm-1, including three vibrational modes as the collection of asymmetric stretching motions of four Ti-O-Si centred on tetrahedral Ti(Ⅳ) center, in which the strongest band at 958 cm-1 is attributed to the Ti-specific vibrational frequency. The 960 cm-1 band is absent from the Ti-species at the T2 and T8 sites. Adsorption of H2O on Ti(OSi)4 has no influence on the 960 cm-1 band. The hydrolysis of [Ti(OSi)4] resulted in [Ti(OSi)3OH], showing the Ti-specific vibrational frequency shifted to 969 cm-1. In addition, we also explored the structures and vibrational spetra of framework boron and hydroxyl nest. The calculated frequencies are in good agreement with the reported experimental values.
Density functional theory was applied to study the structure and vibratioanl spectra of framework titanium located in the 10-membered ring channel of Ti-MWW. The calculations were carried out at B3LYP/6-31G(d,p) level of theory based on the 36Tcluster models, leading to the results that the [Ti(OSi)4] species prefer to locate at the T3 site. The stretching vibrations correlated to [Ti(OSi)4] occur between 924~987 cm-1, including three vibrational modes as the collection of asymmetric stretching motions of four Ti-O-Si centred on tetrahedral Ti(Ⅳ) center, in which the strongest band at 958 cm-1 is attributed to the Ti-specific vibrational frequency. The 960 cm-1 band is absent from the Ti-species at the T2 and T8 sites. Adsorption of H2O on Ti(OSi)4 has no influence on the 960 cm-1 band. The hydrolysis of [Ti(OSi)4] resulted in [Ti(OSi)3OH], showing the Ti-specific vibrational frequency shifted to 969 cm-1. In addition, we also explored the structures and vibrational spetra of framework boron and hydroxyl nest. The calculated frequencies are in good agreement with the reported experimental values.
2015, (5): 908-914
doi: 10.11862/CJIC.2015.109
Abstract:
Two trialkyltin carboxylates [n-Bu3Sn(O2CC8H7)]n (1) and Cy3Sn(O2CC8H7)·MeOH (2) were synthesized by the reactions of cinnamic acid with bis(tributyltin) oxide and tricyclohexyltin hydroxide, respectively. Their structures were characterized by IR, 1H and 13C NMR, elemental analysis and X-ray crystal diffraction. The crystal of complex 1 belongs to monoclinic system, space group P21/c, a=1.05381(2) nm, b=1.85066(4) nm, c=2.49500(5) nm, β=106.3460(10)°, V=4.66918(16) nm3, Z=4, Dc=1.244 g·cm-3, μ(Mo Kα)=1.103 mm-1, F(000)= 1808, R1=0.0519, wR2=0.1320. The crystal of complex 2 belongs to triclinic system, space group P1, a=1.3388(3) nm, b=1.4926(4) nm, c=1.7884(5) nm, α=67.066(14)°, β=69.631(15)°, γ=63.938(14)°, V=2.8882(13) nm3, Z=4, Dc=1.259 g·cm-3, μ(Mo Kα)=0.908 mm-1, F(000)=1144, R1=0.0506, wR2=0.1102. The central tin atoms of two complexes are aberrant trigonal bipyramidal configurations with five coordination, and a 1Dinfinite chain of 1 is bridged by carboxyl Oatoms, while a 2D network of 2 is generated by O-H…O hydrogen bonds and π-π effects. Moreover, the preliminary tests showed that complex 1 displayed stronger than carboplatin in vitro anti-tumor activity against five human tumor cell lines, Colo205, HepG2, MCF-7, Hela and NCI-H460, and had higher medicinal value than complex 2. Thermogravimetric analysis shows the complexes were stable up to 145 or 190 ℃, respectively.
Two trialkyltin carboxylates [n-Bu3Sn(O2CC8H7)]n (1) and Cy3Sn(O2CC8H7)·MeOH (2) were synthesized by the reactions of cinnamic acid with bis(tributyltin) oxide and tricyclohexyltin hydroxide, respectively. Their structures were characterized by IR, 1H and 13C NMR, elemental analysis and X-ray crystal diffraction. The crystal of complex 1 belongs to monoclinic system, space group P21/c, a=1.05381(2) nm, b=1.85066(4) nm, c=2.49500(5) nm, β=106.3460(10)°, V=4.66918(16) nm3, Z=4, Dc=1.244 g·cm-3, μ(Mo Kα)=1.103 mm-1, F(000)= 1808, R1=0.0519, wR2=0.1320. The crystal of complex 2 belongs to triclinic system, space group P1, a=1.3388(3) nm, b=1.4926(4) nm, c=1.7884(5) nm, α=67.066(14)°, β=69.631(15)°, γ=63.938(14)°, V=2.8882(13) nm3, Z=4, Dc=1.259 g·cm-3, μ(Mo Kα)=0.908 mm-1, F(000)=1144, R1=0.0506, wR2=0.1102. The central tin atoms of two complexes are aberrant trigonal bipyramidal configurations with five coordination, and a 1Dinfinite chain of 1 is bridged by carboxyl Oatoms, while a 2D network of 2 is generated by O-H…O hydrogen bonds and π-π effects. Moreover, the preliminary tests showed that complex 1 displayed stronger than carboplatin in vitro anti-tumor activity against five human tumor cell lines, Colo205, HepG2, MCF-7, Hela and NCI-H460, and had higher medicinal value than complex 2. Thermogravimetric analysis shows the complexes were stable up to 145 or 190 ℃, respectively.
2015, (5): 915-922
doi: 10.11862/CJIC.2015.127
Abstract:
To improve the inhibitory selectivity and explore the substitution effect of the Schiff base ligands on the inhibitory effect of the complex against the PTPs, three Cu(Ⅱ) complexes, [Cu(X-pimp)2] (X-pimp=2-((4-X-phenylimino)methyl) phenol), X=Cl, Br, and Acetyl), were prepared and characterized by X-ray, EA, IR, UV-Vis and ESI-MS. Taking [Cu(Cl-pimp)2] complex as an example, the solution species distribution with different pH values and the main existing form under the pH neutral condition were investigated using both the pHpotentiometric and UV titrations, indicating that the ration of Cl-pimp ligand and Cu(Ⅱ) ion in the complex was 2:1 in an aqueous solution and [Cu(Cl-pimp)2H-1]- is the main existing form in the pHneutral condition. Then the inhibitory activities of these complexes against above-mentioned protein tyrosine phosphatase 1B(PTP1B), T-cell protein tyrosine phosphatase(TCPTP), Src homology phosphatase 1 (SHP-1), and Src homology phosphates 2 (SHP-2) was evaluated using IC50 values. The results revealed that these three complexes showed similar inhibitory behaviours, i.e. potent effect against PTP1B and TCPTP (0.20 μmol·L-150 <0.31 μmol·L-1), the relatively lower effect against SHP-1 (2.7 μmol·L-1 < IC50 <4.7 μmol·L-1), while negligible effect against SHP-2 (IC50 >100 μmol·L-1), which indicated that the type of substituents on the papa position of phenylimino of the Schiff base ligand did not influence the inhibitory effect of the complexes against PTPs obviously. However, comparing the current results to that of the above-mentioned previous work, we can find that the change in the position of the substituents may change the selectivity of inhibitory effect of the complexes against PTPs. The interactions between the complexes and PTPs were studied using [Cu(Cl-pimp)2] and PTP1B as the representatives. The kinetics assays showed that the complex inhibited PTP1B in a non-competitive mode and the inhibition constant was calculated to be 0.35 μmol·L-1. The fluorescence titration revealed that the complex bound to PTp1B with the molar ration of 1:1 and the binding constant of 9.3×106 L·mol-1. We infer that the [Cu(Cl-pimp)2] complex may bind firmly to inactive area of PTP1B and indirectly lead to the structural changes to the active center, which inhibits the activity of PTP1B.
To improve the inhibitory selectivity and explore the substitution effect of the Schiff base ligands on the inhibitory effect of the complex against the PTPs, three Cu(Ⅱ) complexes, [Cu(X-pimp)2] (X-pimp=2-((4-X-phenylimino)methyl) phenol), X=Cl, Br, and Acetyl), were prepared and characterized by X-ray, EA, IR, UV-Vis and ESI-MS. Taking [Cu(Cl-pimp)2] complex as an example, the solution species distribution with different pH values and the main existing form under the pH neutral condition were investigated using both the pHpotentiometric and UV titrations, indicating that the ration of Cl-pimp ligand and Cu(Ⅱ) ion in the complex was 2:1 in an aqueous solution and [Cu(Cl-pimp)2H-1]- is the main existing form in the pHneutral condition. Then the inhibitory activities of these complexes against above-mentioned protein tyrosine phosphatase 1B(PTP1B), T-cell protein tyrosine phosphatase(TCPTP), Src homology phosphatase 1 (SHP-1), and Src homology phosphates 2 (SHP-2) was evaluated using IC50 values. The results revealed that these three complexes showed similar inhibitory behaviours, i.e. potent effect against PTP1B and TCPTP (0.20 μmol·L-1
2015, (5): 923-929
doi: 10.11862/CJIC.2015.122
Abstract:
Two complexes [Cu(L1)Cl2]·0.5C2H5OH (1) and Co(L1)Cl2 (2) (L1=1,4-bis((1H-pyrazol-1-yl)methyl)benzene) were designed and synthesized in the anhydrous ethanol system. The spectrum and structural characters of the two complexes were analyzed by elemental analysis, IR spectrum, thermogravimetric analysis, powder X-ray diffraction and single crystal X-ray diffraction analysis. The structural analysis shows that the coordination numbers of metal in complexes 1 and 2 are five and four to form square pyramidal and distorted tetrahedron geometry, respectively, and ligand L1 is in bidentate coordination mode. In addition, complexes 1 and 2 had the mimic catalytic activity during brominating reaction process.
Two complexes [Cu(L1)Cl2]·0.5C2H5OH (1) and Co(L1)Cl2 (2) (L1=1,4-bis((1H-pyrazol-1-yl)methyl)benzene) were designed and synthesized in the anhydrous ethanol system. The spectrum and structural characters of the two complexes were analyzed by elemental analysis, IR spectrum, thermogravimetric analysis, powder X-ray diffraction and single crystal X-ray diffraction analysis. The structural analysis shows that the coordination numbers of metal in complexes 1 and 2 are five and four to form square pyramidal and distorted tetrahedron geometry, respectively, and ligand L1 is in bidentate coordination mode. In addition, complexes 1 and 2 had the mimic catalytic activity during brominating reaction process.
2015, (5): 930-938
doi: 10.11862/CJIC.2015.149
Abstract:
The composite adsorption materials modified by wispy nanostructure γ-AlOOH or γ-Al2O3 were prepared via one-step hydrothermal method by using crystalline aluminum chloride (AlCl3·6H2O) as the resource of aluminum, sodium dodecylbenzenesulfonate (SDBS) as template and diatomite as the substrate. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis/differential scanning calorimetry (TG/DSC), and N2 adsorption-desorption measurement. The adsorption capacity for Cs+ and Pb2+ of the samples were investigated. It was found that the samples showed superb adsorption properties for Cs+ and Pb2+. The maximal removal efficiency of the γ-AlOOH/diatomite and γ-Al2O3/diatomite for Cs+ were 98.9 and 99.6%, respectively, and the maximum adsorption capacities for Pb2+ were 357.1 and 416.7 mg·g-1, respectively. Both of the adsorption models for Pb2+ were consistent with the Langmuir adsorption model.
The composite adsorption materials modified by wispy nanostructure γ-AlOOH or γ-Al2O3 were prepared via one-step hydrothermal method by using crystalline aluminum chloride (AlCl3·6H2O) as the resource of aluminum, sodium dodecylbenzenesulfonate (SDBS) as template and diatomite as the substrate. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis/differential scanning calorimetry (TG/DSC), and N2 adsorption-desorption measurement. The adsorption capacity for Cs+ and Pb2+ of the samples were investigated. It was found that the samples showed superb adsorption properties for Cs+ and Pb2+. The maximal removal efficiency of the γ-AlOOH/diatomite and γ-Al2O3/diatomite for Cs+ were 98.9 and 99.6%, respectively, and the maximum adsorption capacities for Pb2+ were 357.1 and 416.7 mg·g-1, respectively. Both of the adsorption models for Pb2+ were consistent with the Langmuir adsorption model.
2015, (5): 939-946
doi: 10.11862/CJIC.2015.108
Abstract:
We use ammonium molybdate, bismuth nitrate and silver nitrate as raw materials, hexadecyl trimethyl ammonium bromide(CTAB) as auxiliary surfactant to synthesize photocatalyst Ag2O-Bi2MoO6 via hydrothermal method. The photocatalyst was characterized by XRD, SEM and UV-Vis spectroscopy. The photocatalytic oxidation of fulvic acid in water was performed over the catalyst. The results show that the surface of pure bismuth molybdate is smooth while on the surface of Ag2O-Bi2MoO6 there are some well-distributed small grains. The XRD pattern of Ag2O-Bi2MoO6 shows diffraction peaks of Ag2O. Compared with the pure sample, Ag2O-Bi2MoO6 has much higher photocatalytic activity under visible light, and when its doping level is 1.5%, it shows the highest activity. The best catalyst concentration is 0.6 g·L-1. The decrease in pH value of the solvent and initial concentration of fulvic acid will promote the removal of fulvic acid. The degradation process of fulvic acid conforms the first order kinetics, and the fitting equation is y=-0.0195x. A Photobacterium phosphoreum toxicity test results show that the toxicity of the 2 h photocatalytic degradation product is reduced by about 90% compared to the un-degraded fulvic acid.
We use ammonium molybdate, bismuth nitrate and silver nitrate as raw materials, hexadecyl trimethyl ammonium bromide(CTAB) as auxiliary surfactant to synthesize photocatalyst Ag2O-Bi2MoO6 via hydrothermal method. The photocatalyst was characterized by XRD, SEM and UV-Vis spectroscopy. The photocatalytic oxidation of fulvic acid in water was performed over the catalyst. The results show that the surface of pure bismuth molybdate is smooth while on the surface of Ag2O-Bi2MoO6 there are some well-distributed small grains. The XRD pattern of Ag2O-Bi2MoO6 shows diffraction peaks of Ag2O. Compared with the pure sample, Ag2O-Bi2MoO6 has much higher photocatalytic activity under visible light, and when its doping level is 1.5%, it shows the highest activity. The best catalyst concentration is 0.6 g·L-1. The decrease in pH value of the solvent and initial concentration of fulvic acid will promote the removal of fulvic acid. The degradation process of fulvic acid conforms the first order kinetics, and the fitting equation is y=-0.0195x. A Photobacterium phosphoreum toxicity test results show that the toxicity of the 2 h photocatalytic degradation product is reduced by about 90% compared to the un-degraded fulvic acid.
2015, (5): 947-953
doi: 10.11862/CJIC.2015.121
Abstract:
Three-dimensionally(3D) ordered macro-mesoporous silica monolith was prepared via a facile dual-templating technique using self-made poly-(methyl methacrylate) (PMMA) colloidal crystal and triblockcopolymer P123 as templates. The pore structure, surface features of as-prepared samples were characterized by SEM, TEM, low-angle XRD and N2 adsorption and desorption techniques. The results show that these highly ordered macro-mesoporous silica monoliths have a macropore of about 200 nm, narrowly distributed mesopores (3.5 nm), and high surface area (>550 m2·g-1). These results also indicate that the 3D ordered macro-mesoporous silica monolith with network or layered structure can be prepared controllably by facilely tailoring and controlling the self-assembly process of PMMA colloidal crystal template. The formation mechanism of the 3D ordered macro-mesoporous composites was also proposed.
Three-dimensionally(3D) ordered macro-mesoporous silica monolith was prepared via a facile dual-templating technique using self-made poly-(methyl methacrylate) (PMMA) colloidal crystal and triblockcopolymer P123 as templates. The pore structure, surface features of as-prepared samples were characterized by SEM, TEM, low-angle XRD and N2 adsorption and desorption techniques. The results show that these highly ordered macro-mesoporous silica monoliths have a macropore of about 200 nm, narrowly distributed mesopores (3.5 nm), and high surface area (>550 m2·g-1). These results also indicate that the 3D ordered macro-mesoporous silica monolith with network or layered structure can be prepared controllably by facilely tailoring and controlling the self-assembly process of PMMA colloidal crystal template. The formation mechanism of the 3D ordered macro-mesoporous composites was also proposed.
2015, (5): 954-960
doi: 10.11862/CJIC.2015.139
Abstract:
Alow toxicity and biodegradable polymetic temlplating route to ordered mesoporous and super-micorporous silica materials is reported. By grafting stearic acid on Jeffamine ED2003 (H2N-(PO)l(EO)m(PO)n-NH2, l+n=6, m=39), a polyether amide polymeric surfactant was obtained, which has the ability of self-assembly in aqueous solution, named ED2003-fa-18. Using ED2003-fa-18 as a template, tetraethyl orthosilicate (TEOS) as inorganic silicon source, the ordered mesoporous and super-microporous silica microspheres were hydrothermally synthesized under acidic conditions at mild temperature. The resulting materials were characterized by powder X-ray diffraction (XRD), nitrogen sorption, infrared spectroscopy (IR), 1H NMR, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The influence of the templating concentration on the pore size and morphologies of the resulting materials has been investigated. The results show that the well-ordered mesoporous and super-microporous silica materials have been successfully synthesized. As the templating concentration (from 1wt% to 7wt%) increased, the pore diameter decreased obviously from mesoporous range to supermicroporous range. SEM photographs show that the as-synthesized silica materials were spherical nanoparticles of 20~30 nm, and these nanoparticles further agglomerated and formed a densely packed microspheres of 2~4 μm. In addition, ordered pore structures can be observed by the transmission electron microscopy (TEM).
Alow toxicity and biodegradable polymetic temlplating route to ordered mesoporous and super-micorporous silica materials is reported. By grafting stearic acid on Jeffamine ED2003 (H2N-(PO)l(EO)m(PO)n-NH2, l+n=6, m=39), a polyether amide polymeric surfactant was obtained, which has the ability of self-assembly in aqueous solution, named ED2003-fa-18. Using ED2003-fa-18 as a template, tetraethyl orthosilicate (TEOS) as inorganic silicon source, the ordered mesoporous and super-microporous silica microspheres were hydrothermally synthesized under acidic conditions at mild temperature. The resulting materials were characterized by powder X-ray diffraction (XRD), nitrogen sorption, infrared spectroscopy (IR), 1H NMR, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The influence of the templating concentration on the pore size and morphologies of the resulting materials has been investigated. The results show that the well-ordered mesoporous and super-microporous silica materials have been successfully synthesized. As the templating concentration (from 1wt% to 7wt%) increased, the pore diameter decreased obviously from mesoporous range to supermicroporous range. SEM photographs show that the as-synthesized silica materials were spherical nanoparticles of 20~30 nm, and these nanoparticles further agglomerated and formed a densely packed microspheres of 2~4 μm. In addition, ordered pore structures can be observed by the transmission electron microscopy (TEM).
2015, (5): 961-967
doi: 10.11862/CJIC.2015.131
Abstract:
The immobilized catalysts with double-acid active sites were synthesized by loading ionic liquids (ILs) on MCM-41 with different Si/Al molar ratios. The catalysts were characterized by XRD, FTIR, N2 adsorption-desorption, thermogravimetric analysis and TEM, and the activities of catalysts were investigated by the transesterification of soybean oil with methanol for biodiesel synthesis as the probe reaction. The results demonstrated that the ionic liquids were successfully immobilized on the mesoporous molecular sieves. The catalysts could maintain their mesoporous structure and showed good catalytic performance in transesterification. The biodiesel yield was more than 90% under the condition of 30% ILs-loading, methanol to oil molar ratio of 36:1 and temperature at 140 ℃ for 5 h. The beneficial acid environment was created for the active component ILs by introducing Al to MCM-41, which greatly improved the catalytic performance of ILs. The ILs immobilized catalysts exhibited much higher activities in transesterification than the homogeneous ILs, and the ILs immobilized catalyst still yielded about 88% after four cycles.
The immobilized catalysts with double-acid active sites were synthesized by loading ionic liquids (ILs) on MCM-41 with different Si/Al molar ratios. The catalysts were characterized by XRD, FTIR, N2 adsorption-desorption, thermogravimetric analysis and TEM, and the activities of catalysts were investigated by the transesterification of soybean oil with methanol for biodiesel synthesis as the probe reaction. The results demonstrated that the ionic liquids were successfully immobilized on the mesoporous molecular sieves. The catalysts could maintain their mesoporous structure and showed good catalytic performance in transesterification. The biodiesel yield was more than 90% under the condition of 30% ILs-loading, methanol to oil molar ratio of 36:1 and temperature at 140 ℃ for 5 h. The beneficial acid environment was created for the active component ILs by introducing Al to MCM-41, which greatly improved the catalytic performance of ILs. The ILs immobilized catalysts exhibited much higher activities in transesterification than the homogeneous ILs, and the ILs immobilized catalyst still yielded about 88% after four cycles.
2015, (5): 968-974
doi: 10.11862/CJIC.2015.141
Abstract:
Four meso-substituted iron(Ⅳ) corroles having different number of pentafluorophenylor phenyl groups were synthesized and characterized by UV-Vis, NMR and MS. The catalytic styrene oxidation by these iron corroles using tert-butyl hydroperoxide (TBHP), iodosylbenzene (PhIO), hydrogen peroxide(H2O2) in acetonitrile was investigated. The effect of imidazole as axial ligand on the catalytic oxidation was also examined. The results indicate that the yields of the products depend on oxidants, catalysts and axial ligand. For TBHP, benzaldehyde is the major product. Styrene epoxide is the major product when using PhIOoxidant. All iron(Ⅳ) corroles studied cannot effectively catalyze styrene oxidation by using H2O2. Four iron corroles exhibit different activity order when using different oxidants, and the catalytic process may involve free radical and Fe(Ⅴ)-oxocorrole species. The axial coordination of F15C-Feby imidazole gives 1:2 complexes. Also, axial ligand imidazole has different effect on the oxidation product distribution when using different oxidants.
Four meso-substituted iron(Ⅳ) corroles having different number of pentafluorophenylor phenyl groups were synthesized and characterized by UV-Vis, NMR and MS. The catalytic styrene oxidation by these iron corroles using tert-butyl hydroperoxide (TBHP), iodosylbenzene (PhIO), hydrogen peroxide(H2O2) in acetonitrile was investigated. The effect of imidazole as axial ligand on the catalytic oxidation was also examined. The results indicate that the yields of the products depend on oxidants, catalysts and axial ligand. For TBHP, benzaldehyde is the major product. Styrene epoxide is the major product when using PhIOoxidant. All iron(Ⅳ) corroles studied cannot effectively catalyze styrene oxidation by using H2O2. Four iron corroles exhibit different activity order when using different oxidants, and the catalytic process may involve free radical and Fe(Ⅴ)-oxocorrole species. The axial coordination of F15C-Feby imidazole gives 1:2 complexes. Also, axial ligand imidazole has different effect on the oxidation product distribution when using different oxidants.
2015, (5): 975-980
doi: 10.11862/CJIC.2015.090
Abstract:
By incorporating a phosphine donor within a thiosemicarbazone moiety to enhance the coordinated ability of the chelators, a cobalt complex Co-NSP (HNSP: 4-[2-(2-diphenylphosphino-benzylidene) thiosemicar-bohydrazone]benzenesulfonate) was obtained as the proton reduction catalyst for light driven H2 evolution in homogeneous environment with fluorescein as the photosensitizer. The presence of NSP tridentate chelator benefits the formation of low oxidized species to increase the catalytic efficiency, and the incorporation of a sulfonate group enhances the water solubility of the catalyst. The amount of H2 generation in 12 h photolysis maximizes in the presence of sacrificial reagent NEt3 at pHvalue of 11.0. The initial TOF (turnover frequency) is about 200 mol H2 per mole catalyst per hour with the turnover number (TON) about 2000 mol H2 per mole of catalyst.
By incorporating a phosphine donor within a thiosemicarbazone moiety to enhance the coordinated ability of the chelators, a cobalt complex Co-NSP (HNSP: 4-[2-(2-diphenylphosphino-benzylidene) thiosemicar-bohydrazone]benzenesulfonate) was obtained as the proton reduction catalyst for light driven H2 evolution in homogeneous environment with fluorescein as the photosensitizer. The presence of NSP tridentate chelator benefits the formation of low oxidized species to increase the catalytic efficiency, and the incorporation of a sulfonate group enhances the water solubility of the catalyst. The amount of H2 generation in 12 h photolysis maximizes in the presence of sacrificial reagent NEt3 at pHvalue of 11.0. The initial TOF (turnover frequency) is about 200 mol H2 per mole catalyst per hour with the turnover number (TON) about 2000 mol H2 per mole of catalyst.
2015, (5): 981-988
doi: 10.11862/CJIC.2015.125
Abstract:
By using a rigid tetrapodal carboxylate linker 4,4',4",4"'-silanetetrayltetrabenzoic acid (H4L), two open-framework coordination polymers, namely, [CoL][NH2(CH3)2]2·2.25H2O (1) and [Co3L2]H3O]2·4DMA (2) (DMA=N, N-Dimethylacetamide), were solvothermally synthesized and structurally characterized. The crystal structure analyses indicate that both compounds crystallize in orthorhombic system. The unit cell parameters for compound 1 are space group Pbca, a=2.2702(2) nm, b=1.4565(7) nm, c=2.8264(7) nm, and for compound 2, space group Pnna, a=2.6982(3) nm, b=2.1882(2) nm, c=1.3821(9) nm. Compound 1 is a 3D framework built on tetrahedral Co units and a 4-connecting ligand Lto give a 4-connected sra structure. Compound 2 is a 3D 2-nodal (4,8)-connected alb network with small 1D channels built from a trinuclear {Co3(COO)8} unit and a 4-connected tetrahedral Lligand. The structure diversity of H4L-based MOFs is discussed.
By using a rigid tetrapodal carboxylate linker 4,4',4",4"'-silanetetrayltetrabenzoic acid (H4L), two open-framework coordination polymers, namely, [CoL][NH2(CH3)2]2·2.25H2O (1) and [Co3L2]H3O]2·4DMA (2) (DMA=N, N-Dimethylacetamide), were solvothermally synthesized and structurally characterized. The crystal structure analyses indicate that both compounds crystallize in orthorhombic system. The unit cell parameters for compound 1 are space group Pbca, a=2.2702(2) nm, b=1.4565(7) nm, c=2.8264(7) nm, and for compound 2, space group Pnna, a=2.6982(3) nm, b=2.1882(2) nm, c=1.3821(9) nm. Compound 1 is a 3D framework built on tetrahedral Co units and a 4-connecting ligand Lto give a 4-connected sra structure. Compound 2 is a 3D 2-nodal (4,8)-connected alb network with small 1D channels built from a trinuclear {Co3(COO)8} unit and a 4-connected tetrahedral Lligand. The structure diversity of H4L-based MOFs is discussed.
2015, (5): 989-1002
doi: 10.11862/CJIC.2015.120
Abstract:
Four kinds of support materials, i.e. a thermally stable material La2O3-Al2O3(LA), three oxygen storage materials CeO2-ZrO2-La2O3-Al2O3(CZLA), CeO2-ZrO2-La2O3+La2O3-Al2O3(CZL+LA) and CeO2-ZrO2-La2O3(CZL) with ceria content of 15%, 33% and 47%, respectively, were prepared by co-precipitation. The corresponding Pd-only catalysts Pd/LA, Pd/CZLA, Pd/CZL+LA and Pd/CZL were obtained by wet-impregnation and further fabricated as three-way catalysts in a monolith form. The support materials were characterized by low temperature nitrogen adsorption-desorption and H2-temperature programmed reduction (H2-TPR). The catalysts were characterized by H2-TPR and XPS, and were evaluated with a simulated automobile exhaust in terms of the relationships of three way performance with the air/fuel operation window and with temperatures. The results indicate that the support material CZLA integrates the advantages of ceria-based and alumina-based materials effectively thus having superior textural property, thermal stability and reduction property. Additionally, Pd/CZLA catalyst shows little difference in low temperature reducibility, surface elemental distribution and elemental oxidation states before and after aging treatment. As a result, Pd/CZLA exhibits the widest air/fuel operation window and the lowest light-off temperature among the four catalysts, especially after aging treatment, the light-off temperature of C3H8, NOx and CO is 370 ℃, 257 ℃, 223 ℃, respectively. Then material CZLA is the most suitable support for Pd-only three-way catalyst compared with the other three supports.
Four kinds of support materials, i.e. a thermally stable material La2O3-Al2O3(LA), three oxygen storage materials CeO2-ZrO2-La2O3-Al2O3(CZLA), CeO2-ZrO2-La2O3+La2O3-Al2O3(CZL+LA) and CeO2-ZrO2-La2O3(CZL) with ceria content of 15%, 33% and 47%, respectively, were prepared by co-precipitation. The corresponding Pd-only catalysts Pd/LA, Pd/CZLA, Pd/CZL+LA and Pd/CZL were obtained by wet-impregnation and further fabricated as three-way catalysts in a monolith form. The support materials were characterized by low temperature nitrogen adsorption-desorption and H2-temperature programmed reduction (H2-TPR). The catalysts were characterized by H2-TPR and XPS, and were evaluated with a simulated automobile exhaust in terms of the relationships of three way performance with the air/fuel operation window and with temperatures. The results indicate that the support material CZLA integrates the advantages of ceria-based and alumina-based materials effectively thus having superior textural property, thermal stability and reduction property. Additionally, Pd/CZLA catalyst shows little difference in low temperature reducibility, surface elemental distribution and elemental oxidation states before and after aging treatment. As a result, Pd/CZLA exhibits the widest air/fuel operation window and the lowest light-off temperature among the four catalysts, especially after aging treatment, the light-off temperature of C3H8, NOx and CO is 370 ℃, 257 ℃, 223 ℃, respectively. Then material CZLA is the most suitable support for Pd-only three-way catalyst compared with the other three supports.
2015, (5): 1003-1009
doi: 10.11862/CJIC.2015.126
Abstract:
Formamidine lead iodine becomes extremely promising for its highly thermal stability and narrow band gap. In this work, we have employed a hydroxyl iodine lead precursor to replace lead chloride and lead iodide to fabricate a pure phase formamidine lead iodine perovskite in mesoscopic solar cells based on the one-step solution processing method and then studied the effect of annealing temperature on the material crystallinity, the morphology of capping layer and devices efficiency etc. Compared with the traditional solution processing methods, the hydroxyl iodine lead derived formamidine lead iodine film delivers an improved textured structure and thermal stability. As a result, a short circuit photocurrent density of 18.6 mA·cm-2, an open circuit voltage of 0.67 mV, fill factor of 0.47, and a power conversion efficiency of 5.8% are achieved under the simulated AM 1.5G one sun illumination.
Formamidine lead iodine becomes extremely promising for its highly thermal stability and narrow band gap. In this work, we have employed a hydroxyl iodine lead precursor to replace lead chloride and lead iodide to fabricate a pure phase formamidine lead iodine perovskite in mesoscopic solar cells based on the one-step solution processing method and then studied the effect of annealing temperature on the material crystallinity, the morphology of capping layer and devices efficiency etc. Compared with the traditional solution processing methods, the hydroxyl iodine lead derived formamidine lead iodine film delivers an improved textured structure and thermal stability. As a result, a short circuit photocurrent density of 18.6 mA·cm-2, an open circuit voltage of 0.67 mV, fill factor of 0.47, and a power conversion efficiency of 5.8% are achieved under the simulated AM 1.5G one sun illumination.
2015, (5): 1010-1018
doi: 10.11862/CJIC.2015.129
Abstract:
Hollow spindle-shaped CuO/Cu2(OH)2CO3 composites were fabricated via a templateless hydrothermal route with Cu2(OH)3NO3 as the precursor. XRD measurements and TEM observations reveal that the as-prepared CuO/Cu2(OH)2CO3 is hollow spindle-shaped with size of 1~2 μm. HRTEM image indicates that the shell of each particle is highly dispersive mixtures of nanoscale CuO and Cu2(OH)2CO3. Time dependent experiments disclose that the formation of hollow spindle-shaped CuO/Cu2(OH)2CO3 composites particles is driven by self-transformation and Ostwald ripening. The gas sensing performances were investigated with ethanol and acetone as the target gases. The as-prepared hollow CuO/Cu2(OH)2CO3 composites exhibit improved gas sensing properties in comparison with the commercial CuO powders, which can be ascribed to the decreased grain-to-grain contacts of the highly dispersive mixtures.
Hollow spindle-shaped CuO/Cu2(OH)2CO3 composites were fabricated via a templateless hydrothermal route with Cu2(OH)3NO3 as the precursor. XRD measurements and TEM observations reveal that the as-prepared CuO/Cu2(OH)2CO3 is hollow spindle-shaped with size of 1~2 μm. HRTEM image indicates that the shell of each particle is highly dispersive mixtures of nanoscale CuO and Cu2(OH)2CO3. Time dependent experiments disclose that the formation of hollow spindle-shaped CuO/Cu2(OH)2CO3 composites particles is driven by self-transformation and Ostwald ripening. The gas sensing performances were investigated with ethanol and acetone as the target gases. The as-prepared hollow CuO/Cu2(OH)2CO3 composites exhibit improved gas sensing properties in comparison with the commercial CuO powders, which can be ascribed to the decreased grain-to-grain contacts of the highly dispersive mixtures.
2015, (5): 1019-1026
doi: 10.11862/CJIC.2015.135
Abstract:
Abenzohydrazone compound N'-(2-hydroxy-5-methoxybenzylidene)-4-dimethylaminobenzohydrazide (H2L) was prepared. Reaction of H2L and acetylhydroxamic acid (HAHA) with VO(acac)2 in methanol gave complex [VOL(AHA)]. Both H2L and the oxovanadium complex were characterized by elemental analysis, IR and UV-Vis spectra, and single crystal X-ray diffraction. The benzohydrazone ligand, in its dianionic form, coordinates to Vatom through the phenolate oxygen, imino nitrogen and enolate oxygen. The acetohydroxamic acid coordintes to Vatom through the carbonyl oxygen and deprotonated hydroxyl oxygen. The Vatom is in octahedral coordination. H2L, HAHAand the oxovanadium(Ⅴ) complex were tested for their urease inhibitory activities. The inhibition rate at concentration of 100 μmol·L-1 on Helicobacter pylori urease is 63% for the oxovanadium complex. The IC50 value for the complex is 45 μmol·L-1. Molecular docking study was performed to study the inhibition.
Abenzohydrazone compound N'-(2-hydroxy-5-methoxybenzylidene)-4-dimethylaminobenzohydrazide (H2L) was prepared. Reaction of H2L and acetylhydroxamic acid (HAHA) with VO(acac)2 in methanol gave complex [VOL(AHA)]. Both H2L and the oxovanadium complex were characterized by elemental analysis, IR and UV-Vis spectra, and single crystal X-ray diffraction. The benzohydrazone ligand, in its dianionic form, coordinates to Vatom through the phenolate oxygen, imino nitrogen and enolate oxygen. The acetohydroxamic acid coordintes to Vatom through the carbonyl oxygen and deprotonated hydroxyl oxygen. The Vatom is in octahedral coordination. H2L, HAHAand the oxovanadium(Ⅴ) complex were tested for their urease inhibitory activities. The inhibition rate at concentration of 100 μmol·L-1 on Helicobacter pylori urease is 63% for the oxovanadium complex. The IC50 value for the complex is 45 μmol·L-1. Molecular docking study was performed to study the inhibition.
2015, (5): 1027-1033
doi: 10.11862/CJIC.2015.147
Abstract:
[Hg(C32H28N4O)](CH3COO)(PF6)2 (1) and [NiCl(C30H28N6O)]PF6 (2) have been synthesized based on1,1'-bisbenzyl-3,3'-oxybis(ethane-2,1-diyl)-dibenzimidazolium-dihexafluorophosphate ligand (L1) and 1,1'-bis (pyridine-2-ylmethyl)-3,3'-oxybis(ethane-2,1-diyl)-dibenzimidazolium-dihexafluorophosphate ligand (L2) and structurally characterized. The complex 1 is a rare three valence state mercury NHC and crystallizes in the P21/c space group with monoclinic crystal system. The complex 2 crystallizes in the P21/n space group with monoclinic crystal system. There are O-H…F, C-H…F, C-H…Cl, C-H…π, P-F…π hydrogen bonds interactions and π…π stacking interactions contributing to 3D supramolecular structure of 1 and 2.
[Hg(C32H28N4O)](CH3COO)(PF6)2 (1) and [NiCl(C30H28N6O)]PF6 (2) have been synthesized based on1,1'-bisbenzyl-3,3'-oxybis(ethane-2,1-diyl)-dibenzimidazolium-dihexafluorophosphate ligand (L1) and 1,1'-bis (pyridine-2-ylmethyl)-3,3'-oxybis(ethane-2,1-diyl)-dibenzimidazolium-dihexafluorophosphate ligand (L2) and structurally characterized. The complex 1 is a rare three valence state mercury NHC and crystallizes in the P21/c space group with monoclinic crystal system. The complex 2 crystallizes in the P21/n space group with monoclinic crystal system. There are O-H…F, C-H…F, C-H…Cl, C-H…π, P-F…π hydrogen bonds interactions and π…π stacking interactions contributing to 3D supramolecular structure of 1 and 2.
2015, (5): 1034-1040
doi: 10.11862/CJIC.2015.123
Abstract:
A green-light emitting iridium(Ⅱ) complex Ir(dfbppy)2(acac) with 2-(3-(2',4'-difluorophenyl)phenyl)pyridine (Hdfbppy) as C^N ligands and 2,4-pentanedione (Hacac) as an ancillary ligand was designed and synthesized for phosphorescent organic light emitting diodes, and its photophysical and electroluminescent properties were investigated. The title complex exhibits a peak emission at 520 nm, a high PL quantum yield of 71%, and a relatively short phosphorescence emission lifetime of 381 ns in CH2Cl2 at room temperature. An organic light-emitting diode using this complex with 4,4'-N,N'-dicarbazolylbiphenyl (CBP) as the host shows a green color with CIE coordinates of (0.33, 0.62), accompanied by a rather excellent performance with a maximum luminance of 68324 cd·m-2 at 7.2 V, the luminous and power efficiencies are 53 cd·A-1 and 37 lm·W-1, respectively.
A green-light emitting iridium(Ⅱ) complex Ir(dfbppy)2(acac) with 2-(3-(2',4'-difluorophenyl)phenyl)pyridine (Hdfbppy) as C^N ligands and 2,4-pentanedione (Hacac) as an ancillary ligand was designed and synthesized for phosphorescent organic light emitting diodes, and its photophysical and electroluminescent properties were investigated. The title complex exhibits a peak emission at 520 nm, a high PL quantum yield of 71%, and a relatively short phosphorescence emission lifetime of 381 ns in CH2Cl2 at room temperature. An organic light-emitting diode using this complex with 4,4'-N,N'-dicarbazolylbiphenyl (CBP) as the host shows a green color with CIE coordinates of (0.33, 0.62), accompanied by a rather excellent performance with a maximum luminance of 68324 cd·m-2 at 7.2 V, the luminous and power efficiencies are 53 cd·A-1 and 37 lm·W-1, respectively.
2015, (5): 1041-1048
doi: 10.11862/CJIC.2015.130
Abstract:
Two heteronuclear/homonuclear coordination polymers {[MnSm2(INAIP)4(H2O)4]·2H2O}n (1) and{[Sm(INAIP)(HINAIP)]·2H2O}n (2), where H2INAIP=5-(isonicotinamido)isophthalic acid, were synthesized in a pot and their crystal structures were determined by X-ray diffraction analysis. Complex 1 crystallizes in the triclinic system, space group P1 with a=1.0188(5) nm, b=1.08386(6) nm, c=1.38721(8) nm, V=1.475(14) nm3, Z=1, Dc=1.802 g·cm-3, μ=2.271 mm-1, F(000)=793, Rint=0.0105, R1=0.0512, wR2=0.1319. Complex 2 is of monoclinic system, space group P21/c with a=1.34305(18) nm, b=1.3765(17) nm, c=1.62408(15) nm, V=2.7028(6) nm3, Z=4, Dc=1.861 g·cm-3, μ=2.251 mm-1, F(000)=1500, Rint=0.0514, R1=0.0322, wR2=0.0887. In complex 1, the 2D Sm-carboxylate layer is linked by Mn-Nand Mn-Ointeraction into complicated 3D framework. However, for complex 2, the central Sm(Ⅱ) atom is eight-coordinated by eight carboxylate oxygen atoms. The molecules are connected to form a 2D bilayer structure bridged by 5-(isonicotinamido)isophthalic acid. Furthermore, complex 1 shows adsorption behavior of CO2 with almost no N2 uptake, and the luminescent property of complexes 1 and 2 has also been investigated.
Two heteronuclear/homonuclear coordination polymers {[MnSm2(INAIP)4(H2O)4]·2H2O}n (1) and{[Sm(INAIP)(HINAIP)]·2H2O}n (2), where H2INAIP=5-(isonicotinamido)isophthalic acid, were synthesized in a pot and their crystal structures were determined by X-ray diffraction analysis. Complex 1 crystallizes in the triclinic system, space group P1 with a=1.0188(5) nm, b=1.08386(6) nm, c=1.38721(8) nm, V=1.475(14) nm3, Z=1, Dc=1.802 g·cm-3, μ=2.271 mm-1, F(000)=793, Rint=0.0105, R1=0.0512, wR2=0.1319. Complex 2 is of monoclinic system, space group P21/c with a=1.34305(18) nm, b=1.3765(17) nm, c=1.62408(15) nm, V=2.7028(6) nm3, Z=4, Dc=1.861 g·cm-3, μ=2.251 mm-1, F(000)=1500, Rint=0.0514, R1=0.0322, wR2=0.0887. In complex 1, the 2D Sm-carboxylate layer is linked by Mn-Nand Mn-Ointeraction into complicated 3D framework. However, for complex 2, the central Sm(Ⅱ) atom is eight-coordinated by eight carboxylate oxygen atoms. The molecules are connected to form a 2D bilayer structure bridged by 5-(isonicotinamido)isophthalic acid. Furthermore, complex 1 shows adsorption behavior of CO2 with almost no N2 uptake, and the luminescent property of complexes 1 and 2 has also been investigated.
2015, (5): 1049-1054
doi: 10.11862/CJIC.2015.140
Abstract:
Reactions of aryl-substituted indenyl ligands (R=Ph (1), 4-tolyl (2), 4-chlorophenyl (3), 4-methoxy-phenyl (4), 2-thienyl (5)) with Ru3(CO)12 in refluxing toluene or xylene gave the responding dinuclear metal carbonyl complexes [(η5-C9H6R)Ru(CO)]2(μ-CO)2 (R=Ph (6), 4-tolyl (7), 4-chlorophenyl (8), 4-methoxyphenyl (9), 2-thienyl (10)), respectively. These complexes have been characterized by elemental analysis, IR, and 1H NMR spectroscopy. The molecular structures of 6, 7 and 10 were determined by X-ray diffraction analysis.
Reactions of aryl-substituted indenyl ligands (R=Ph (1), 4-tolyl (2), 4-chlorophenyl (3), 4-methoxy-phenyl (4), 2-thienyl (5)) with Ru3(CO)12 in refluxing toluene or xylene gave the responding dinuclear metal carbonyl complexes [(η5-C9H6R)Ru(CO)]2(μ-CO)2 (R=Ph (6), 4-tolyl (7), 4-chlorophenyl (8), 4-methoxyphenyl (9), 2-thienyl (10)), respectively. These complexes have been characterized by elemental analysis, IR, and 1H NMR spectroscopy. The molecular structures of 6, 7 and 10 were determined by X-ray diffraction analysis.
2015, (5): 1055-1062
doi: 10.11862/CJIC.2015.134
Abstract:
A Schiff base chelating ligand containing oxime group, 1-(4-{[(E)-5-chloro-2-hydroxybenzylidene]amino}phenyl)ethanone O-benzyloxime (HL, C15H16N2O) and its Cu(Ⅱ) complex ([CuL2]) have been synthesized and characterized by elemental analyses, IR spectra, UV-Vis spectra and X-ray single crystal diffraction method. In the crystal structure of HL, the intermolecular Cl…Cl halogen bonding interaction links a pair of HL molecules to form a dimer unit with the Cl…Cl distance of 0.3459(3) nm, and every dimer further links four other adjacent dimer units into an infinite 3D supramolecular networks structure containing 1D rectangle channels by intermolecular C-H…π interactions. The structure of the Cu(Ⅱ) complex is a mononuclear, consists of one Cu(Ⅱ) atoms, two bidentate L- units. The Cu(Ⅱ) atom is in a square-planar geometry. And each Cu(Ⅱ) complex molecule links four other molecules into an infinite 2D layer supramolecular structure by intermolecular C-H…π interactions. This linkage is further stabilized by π…π stacking interactions with the centroid-centroid distances of 0.3689(3) nm.
A Schiff base chelating ligand containing oxime group, 1-(4-{[(E)-5-chloro-2-hydroxybenzylidene]amino}phenyl)ethanone O-benzyloxime (HL, C15H16N2O) and its Cu(Ⅱ) complex ([CuL2]) have been synthesized and characterized by elemental analyses, IR spectra, UV-Vis spectra and X-ray single crystal diffraction method. In the crystal structure of HL, the intermolecular Cl…Cl halogen bonding interaction links a pair of HL molecules to form a dimer unit with the Cl…Cl distance of 0.3459(3) nm, and every dimer further links four other adjacent dimer units into an infinite 3D supramolecular networks structure containing 1D rectangle channels by intermolecular C-H…π interactions. The structure of the Cu(Ⅱ) complex is a mononuclear, consists of one Cu(Ⅱ) atoms, two bidentate L- units. The Cu(Ⅱ) atom is in a square-planar geometry. And each Cu(Ⅱ) complex molecule links four other molecules into an infinite 2D layer supramolecular structure by intermolecular C-H…π interactions. This linkage is further stabilized by π…π stacking interactions with the centroid-centroid distances of 0.3689(3) nm.
2015, (5): 1063-1070
doi: 10.11862/CJIC.2015.143
Abstract:
Two coordination polymers {[Ag2(ELBA)(4,4'-bipy)2(NO3)]·2H2O}n (1) and [Ag2(ELBA)2(2,2'-bipy)]n (2) were synthesized by evaporation methods using 2,4-dichlorophenoxyacetic acid(ELBA), 4,4'-dipyridyl(4,4'-bipy), 2,2'-dipyridyl(2,2'-bipy) and AgNO3. The complexes were characterized by elemental analysis, FT-IR, thermo-gravimetrie analysis (TGA) and X-ray single-crystal structure analysis, and fluorescence properties of the complex 2 have been studied. As a result, complexes 1 and 2 are one-dimensional structure. Among others, in complex 1, Ag(Ⅰ) ion is surrounded by two nitrogen atoms from two bipy ligands form an infinite chain, and adjacent Ag-bipy chains produce “rungs” of a ladder by silver ions contacts. And in compound 2, the similar S-shape one-dimensional infinite chain is obtained by Ag…Ag interactions. Hydrogen bonding and π…π interactions were observed in these complexes.
Two coordination polymers {[Ag2(ELBA)(4,4'-bipy)2(NO3)]·2H2O}n (1) and [Ag2(ELBA)2(2,2'-bipy)]n (2) were synthesized by evaporation methods using 2,4-dichlorophenoxyacetic acid(ELBA), 4,4'-dipyridyl(4,4'-bipy), 2,2'-dipyridyl(2,2'-bipy) and AgNO3. The complexes were characterized by elemental analysis, FT-IR, thermo-gravimetrie analysis (TGA) and X-ray single-crystal structure analysis, and fluorescence properties of the complex 2 have been studied. As a result, complexes 1 and 2 are one-dimensional structure. Among others, in complex 1, Ag(Ⅰ) ion is surrounded by two nitrogen atoms from two bipy ligands form an infinite chain, and adjacent Ag-bipy chains produce “rungs” of a ladder by silver ions contacts. And in compound 2, the similar S-shape one-dimensional infinite chain is obtained by Ag…Ag interactions. Hydrogen bonding and π…π interactions were observed in these complexes.
