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2015 Volume 31 Issue 8
2015, 31(8): 1467-1479
doi: 10.11862/CJIC.2015.209
Abstract:
Near-infrared (NIR) fluorescent dyes based-on boron difluoride dipyrromethene (BODIPY) are a new type of fluorescent dyes, which have been widely studied because of their excellent photophysical and photochemical properties and have become a newly-emerging hotspot in recent years. In this review article, we summarize the latest research progresses in the design, synthesis and application of near-infrared fluorescent BODIPYs, in addition their future research aspects and application perspectives are also prospected.
Near-infrared (NIR) fluorescent dyes based-on boron difluoride dipyrromethene (BODIPY) are a new type of fluorescent dyes, which have been widely studied because of their excellent photophysical and photochemical properties and have become a newly-emerging hotspot in recent years. In this review article, we summarize the latest research progresses in the design, synthesis and application of near-infrared fluorescent BODIPYs, in addition their future research aspects and application perspectives are also prospected.
2015, 31(8): 1480-1488
doi: 10.11862/CJIC.2015.221
Abstract:
By using a semi-rigid multidentate carboxylate linker 3,3',3"-(((2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene))tris(oxy))tribenzoic acid (H3L), four coordination polymers, namely, {[Cd3(L)2(H2O)2]·5DMF·6H2O}n (1), {[Co3(L)2(H2O)2]·2DMF·6H2O}n (2), {[Mn3(L)2(H2O)2]·3DMF·6H2O}n (3), {[Zn3(L)2(H2O)2]·5DMA·5H2O}n (4) were obtained and characterized by single crystal X-ray diffraction, thermogravimetric, elemental analysis, thermal analyses, IR spectra and fluorescence. Four compounds are isostructural with hourglass M3 clusters and L3- ligands as secondary building units (SBUs) to form a pumpkin-shaped metalorganic nanocage, and possess a three-connected node (3,3,6)-connected 3D network. Compounds 1 and 4 exhibited strong photoluminescent emissions at room temperature with a peak at 385 nm, owing to a ligand-centered excited state. The emission intensities of the compound 1 varied upon contact with different solvents or analytes, exhibiting selective emission quenching responses towards nitroaromatics. CCDC: 1041419, 1; 1041420, 2; 1041421, 2; 1041422, 4.
By using a semi-rigid multidentate carboxylate linker 3,3',3"-(((2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene))tris(oxy))tribenzoic acid (H3L), four coordination polymers, namely, {[Cd3(L)2(H2O)2]·5DMF·6H2O}n (1), {[Co3(L)2(H2O)2]·2DMF·6H2O}n (2), {[Mn3(L)2(H2O)2]·3DMF·6H2O}n (3), {[Zn3(L)2(H2O)2]·5DMA·5H2O}n (4) were obtained and characterized by single crystal X-ray diffraction, thermogravimetric, elemental analysis, thermal analyses, IR spectra and fluorescence. Four compounds are isostructural with hourglass M3 clusters and L3- ligands as secondary building units (SBUs) to form a pumpkin-shaped metalorganic nanocage, and possess a three-connected node (3,3,6)-connected 3D network. Compounds 1 and 4 exhibited strong photoluminescent emissions at room temperature with a peak at 385 nm, owing to a ligand-centered excited state. The emission intensities of the compound 1 varied upon contact with different solvents or analytes, exhibiting selective emission quenching responses towards nitroaromatics. CCDC: 1041419, 1; 1041420, 2; 1041421, 2; 1041422, 4.
2015, 31(8): 1489-1494
doi: 10.11862/CJIC.2015.224
Abstract:
The CaAl12O19:Mn4+ phosphors coated with amorphous SiO2 were prepared by means of sol-gel method and were characterized by XRD, TEM, EDS, FTIR and photoluminescence spectra. The X-ray diffraction results showed that the as-prepared powders appeared an amorphous silica feature wide peak around 22° which showing increasing intensity with increasing amount of coated SiO2. FTIR analysis found obvious Si-O-Si band of coated samples. The TEM demonstrated that the particle size was about 3~6 μm. After coated, the intensity of excitation and emission spectrum were reduced. It showed that the photostability of the 10% silica coated sample can be effectively improved with minimum loss of emission intensity. The temperature-dependent emission spectra of 50% silica coated and the uncoated samples were investigated from 80 to 400 K, the results found that an anti-quenching phenomenon that the emission intensities increased then decreased at increased temperature, and the coated samples has higher thermal activation energy compared with uncoated sample.
The CaAl12O19:Mn4+ phosphors coated with amorphous SiO2 were prepared by means of sol-gel method and were characterized by XRD, TEM, EDS, FTIR and photoluminescence spectra. The X-ray diffraction results showed that the as-prepared powders appeared an amorphous silica feature wide peak around 22° which showing increasing intensity with increasing amount of coated SiO2. FTIR analysis found obvious Si-O-Si band of coated samples. The TEM demonstrated that the particle size was about 3~6 μm. After coated, the intensity of excitation and emission spectrum were reduced. It showed that the photostability of the 10% silica coated sample can be effectively improved with minimum loss of emission intensity. The temperature-dependent emission spectra of 50% silica coated and the uncoated samples were investigated from 80 to 400 K, the results found that an anti-quenching phenomenon that the emission intensities increased then decreased at increased temperature, and the coated samples has higher thermal activation energy compared with uncoated sample.
2015, 31(8): 1495-1504
doi: 10.11862/CJIC.2015.233
Abstract:
A thioflavin T-based fluorescent chelator 5-amino-2-(benzo[d]thiazol-2-yl)phenol (FC-9) was synthesized and characterized. Its interaction with metal-Aβ aggregates and the change of morphology, conformation, cytotoxicity of the resulting Aβ aggregates were investigated. The results showed that FC-9 can not only recognize different Aβ40/Aβ42 aggregates but also disaggregate metal-Aβ40/Aβ42 aggregates. After the interaction between FC-9 and metal-Aβ40/Aβ42 aggregates, the morphology of aggregates changed from fibril to amorphousness, and their β-sheet conformation was also reduced. Moreover, the cell membrane penetration of FC-9 fulfilled common drug-like criteria, and it can inhibit cytotoxicity of the Cu-Aβ40 aggregates, indicating that it could have potential prospect in the treatment of Alzheimer disease. CCDC: 960540.
A thioflavin T-based fluorescent chelator 5-amino-2-(benzo[d]thiazol-2-yl)phenol (FC-9) was synthesized and characterized. Its interaction with metal-Aβ aggregates and the change of morphology, conformation, cytotoxicity of the resulting Aβ aggregates were investigated. The results showed that FC-9 can not only recognize different Aβ40/Aβ42 aggregates but also disaggregate metal-Aβ40/Aβ42 aggregates. After the interaction between FC-9 and metal-Aβ40/Aβ42 aggregates, the morphology of aggregates changed from fibril to amorphousness, and their β-sheet conformation was also reduced. Moreover, the cell membrane penetration of FC-9 fulfilled common drug-like criteria, and it can inhibit cytotoxicity of the Cu-Aβ40 aggregates, indicating that it could have potential prospect in the treatment of Alzheimer disease. CCDC: 960540.
2015, 31(8): 1505-1510
doi: 10.11862/CJIC.2015.225
Abstract:
Meso-SAPO-34 molecular sieve was synthesized with TPOAC and colloidal silica as the silica source, the total surface area is up to 649 m2·g-1. The ratio of TPOAC and silica sol was investigated, which affects external surface area of SAPO-34. The structure was determined by XRD, BET, SEM, NH3-TPD, results show that mesoporous SAPO-34 external surface area can be adjusted, more the defect position crystal appearance, reduce the amount of strong acid weak acid, a weak trend.Under the condition of the ration of TPOAC and silica sol was 3:2, reaction time was 10 days and the ratio of nAl2O3:nP2O5:nSi:nTEAOH:nH2O=1:0.9:0.5:2:60, the external surface area of synthetic mesoporous SAPO-34 reaches the maximum, the value is 100 m2·g-1.
Meso-SAPO-34 molecular sieve was synthesized with TPOAC and colloidal silica as the silica source, the total surface area is up to 649 m2·g-1. The ratio of TPOAC and silica sol was investigated, which affects external surface area of SAPO-34. The structure was determined by XRD, BET, SEM, NH3-TPD, results show that mesoporous SAPO-34 external surface area can be adjusted, more the defect position crystal appearance, reduce the amount of strong acid weak acid, a weak trend.Under the condition of the ration of TPOAC and silica sol was 3:2, reaction time was 10 days and the ratio of nAl2O3:nP2O5:nSi:nTEAOH:nH2O=1:0.9:0.5:2:60, the external surface area of synthetic mesoporous SAPO-34 reaches the maximum, the value is 100 m2·g-1.
2015, 31(8): 1511-1519
doi: 10.11862/CJIC.2015.216
Abstract:
The research of cytochrome C (Cyt C) reacting with NO donor drugs(proliNONOate) has been focused on electrochemistry and medical treatment, while the study about reacting with NO gas is ignored. The previous study usually concentrated on Q band changes, but the Soret band was hardly mentioned. In this paper, we studied the reaction of two states of Cyt C with NO gas and the dissociation process by Soret band and Q band spectra, using ultraviolet-visible absorption spectra, electron paramagnetic resonance (EPR) spectra, ultraviolet-visible time course absorption spectra and synchronous fluorescence. The spectroscopic data showed that, ferric cytochrome C(Fe(Ⅲ)-Cyt C) and ferrous cytochrome C(Fe(Ⅱ)-Cyt C) could react with NO to convert to cytochrome C coordination compound(Cyt C-NO) with different mechanisms. Fe(Ⅱ)-Cyt C reacting with NO generated Fe(Ⅲ)-Cyt C firstly, then it combined with NO, while Fe(Ⅲ)-Cyt C can combine with NO directly. However, Cyt C-NO is not a stable coordinated macromolecule. With a small amount of NO bubbled into the sample, Cyt C-NO dissociated rapidly with rate constant value of (0.005 07±0.001) s-1, which is one-tenth of Cyt C-NO with NO donor drugs; while under excessive NO gas condition, the dissociation process was prevented. According to the experimental data, the coordination mechanism of the reaction between Cyt C and NO is that gas molecule gets access into the cavity of Heme, making the separation of Fe-S and the formation of Fe-N. Cyt C can react with NO gas directly, the Cyt C-NO is more stable than that reacted with NO donor drugs, and the Soret band have an obvious change. These results will be significant for us to remit the oxidative stress in cells and detect the respiratory enzymes change which could monitor the cell apoptosis and some diseases by NO.
The research of cytochrome C (Cyt C) reacting with NO donor drugs(proliNONOate) has been focused on electrochemistry and medical treatment, while the study about reacting with NO gas is ignored. The previous study usually concentrated on Q band changes, but the Soret band was hardly mentioned. In this paper, we studied the reaction of two states of Cyt C with NO gas and the dissociation process by Soret band and Q band spectra, using ultraviolet-visible absorption spectra, electron paramagnetic resonance (EPR) spectra, ultraviolet-visible time course absorption spectra and synchronous fluorescence. The spectroscopic data showed that, ferric cytochrome C(Fe(Ⅲ)-Cyt C) and ferrous cytochrome C(Fe(Ⅱ)-Cyt C) could react with NO to convert to cytochrome C coordination compound(Cyt C-NO) with different mechanisms. Fe(Ⅱ)-Cyt C reacting with NO generated Fe(Ⅲ)-Cyt C firstly, then it combined with NO, while Fe(Ⅲ)-Cyt C can combine with NO directly. However, Cyt C-NO is not a stable coordinated macromolecule. With a small amount of NO bubbled into the sample, Cyt C-NO dissociated rapidly with rate constant value of (0.005 07±0.001) s-1, which is one-tenth of Cyt C-NO with NO donor drugs; while under excessive NO gas condition, the dissociation process was prevented. According to the experimental data, the coordination mechanism of the reaction between Cyt C and NO is that gas molecule gets access into the cavity of Heme, making the separation of Fe-S and the formation of Fe-N. Cyt C can react with NO gas directly, the Cyt C-NO is more stable than that reacted with NO donor drugs, and the Soret band have an obvious change. These results will be significant for us to remit the oxidative stress in cells and detect the respiratory enzymes change which could monitor the cell apoptosis and some diseases by NO.
2015, 31(8): 1520-1528
doi: 10.11862/CJIC.2015.196
Abstract:
The Phenyl-acetic acid furan-2-ylmethylene-hydrazide (H2L: C13H12N2O2) was synthesized from methyl phenylacetate, hydrazine hydrate and furfural, and then reacted with nickel chloride hexahydrate to form a complex Ni(HL)2 (1). The structures of H2L and 1 were determined by X-ray single crystal diffraction and element analysis.The X-ray single crystal diffraction showed that the crystal of H2L belonged to monoclinic system, space group P21/c with a=1.161 9(3) nm, b=1.359 8(3) nm, c=0.792 16(19) nm, β=109.307(4)° and the crystal of the complex 1 belonged to triclinic system, space group P1 with a=0.455 70(14) nm, b=1.094 7(3) nm, c=1.204 8(4) nm, β=98.302(5)°. Thermal gravity analyses were used to investigate the thermal stabilities of H2L and 1, and the apparent activation energy (Ea) of the decompositions were also calculated, and the results indicated that the complex 1 was more thermal stable than the ligand H2L. The microcalorimetric method was used to study the interactions of H2L and the complex 1 with calf thymus DNA (CT-DNA), and the experimental results showed that the enthalpy change (ΔH) of the complex 1 was greater than that of the ligand H2L, indicating that the complex 1 displayed stronger interaction with CT-DNA than the ligand H2L. CCDC: 909434, H2L; 949203, 1.
The Phenyl-acetic acid furan-2-ylmethylene-hydrazide (H2L: C13H12N2O2) was synthesized from methyl phenylacetate, hydrazine hydrate and furfural, and then reacted with nickel chloride hexahydrate to form a complex Ni(HL)2 (1). The structures of H2L and 1 were determined by X-ray single crystal diffraction and element analysis.The X-ray single crystal diffraction showed that the crystal of H2L belonged to monoclinic system, space group P21/c with a=1.161 9(3) nm, b=1.359 8(3) nm, c=0.792 16(19) nm, β=109.307(4)° and the crystal of the complex 1 belonged to triclinic system, space group P1 with a=0.455 70(14) nm, b=1.094 7(3) nm, c=1.204 8(4) nm, β=98.302(5)°. Thermal gravity analyses were used to investigate the thermal stabilities of H2L and 1, and the apparent activation energy (Ea) of the decompositions were also calculated, and the results indicated that the complex 1 was more thermal stable than the ligand H2L. The microcalorimetric method was used to study the interactions of H2L and the complex 1 with calf thymus DNA (CT-DNA), and the experimental results showed that the enthalpy change (ΔH) of the complex 1 was greater than that of the ligand H2L, indicating that the complex 1 displayed stronger interaction with CT-DNA than the ligand H2L. CCDC: 909434, H2L; 949203, 1.
2015, 31(8): 1529-1533
doi: 10.11862/CJIC.2015.207
Abstract:
Cd3Al2Ge3O12:Mn2+ afterglow phosphors were synthesized by the conventional solid-state reaction in this work, and the enhanced afterglow properties were observed with Zr4+ ions co-doping. The Cd3Al2Ge3O12:Mn2+, Zr4+ phosphors were characterized by using XRD, photoluminescence and thermoluminescence spectroscopy. The emission spectrum shows a broad emission band from 500 to 700 nm which is assigned to the 4T1(4G)→6A1(6S) transitions of Mn2+ ion. An energy transfer from the Cd3Al2Ge3O12 host to Mn2+ ions was observed. The center and the profile of the emission remain unchanged when co-doped with Zr4+ ions, but the introduction of Zr4+ ions improved the afterglow duration. Thermoluminescence spectra indicated that the introduction of Zr4+ into the host produces traps with suitable depth, resulting in the enhanced phosphorescence of Mn2+.
Cd3Al2Ge3O12:Mn2+ afterglow phosphors were synthesized by the conventional solid-state reaction in this work, and the enhanced afterglow properties were observed with Zr4+ ions co-doping. The Cd3Al2Ge3O12:Mn2+, Zr4+ phosphors were characterized by using XRD, photoluminescence and thermoluminescence spectroscopy. The emission spectrum shows a broad emission band from 500 to 700 nm which is assigned to the 4T1(4G)→6A1(6S) transitions of Mn2+ ion. An energy transfer from the Cd3Al2Ge3O12 host to Mn2+ ions was observed. The center and the profile of the emission remain unchanged when co-doped with Zr4+ ions, but the introduction of Zr4+ ions improved the afterglow duration. Thermoluminescence spectra indicated that the introduction of Zr4+ into the host produces traps with suitable depth, resulting in the enhanced phosphorescence of Mn2+.
2015, 31(8): 1534-1538
doi: 10.11862/CJIC.2015.138
Abstract:
o-Carborane reacts with n-butyllithium, sulfur powder and Me4CpCo(CO)I2 respectively to give the half-sandwich 16e carborane compound Me4CpCoS2C2B10H10 (1). The reaction of 1 with ferrocenyne ketone in dichloro-methane leads to the product {(Me4CpCoS2C2B10H10)[FcC(O)CHCCHCC(O)Fc]} (2) (Fc=ferrocenyl). 2 is a 1:2 adduct. The alkynone is twofold inserted into one Co-S bond of 2 in a head-tail mode. 1 and 2 have been characterized by IR, NMR, elemental analysis, mass spectrum and single-crystal X-ray diffraction analysis. CCDC: 1045890, 1; 1045891, 2.
o-Carborane reacts with n-butyllithium, sulfur powder and Me4CpCo(CO)I2 respectively to give the half-sandwich 16e carborane compound Me4CpCoS2C2B10H10 (1). The reaction of 1 with ferrocenyne ketone in dichloro-methane leads to the product {(Me4CpCoS2C2B10H10)[FcC(O)CHCCHCC(O)Fc]} (2) (Fc=ferrocenyl). 2 is a 1:2 adduct. The alkynone is twofold inserted into one Co-S bond of 2 in a head-tail mode. 1 and 2 have been characterized by IR, NMR, elemental analysis, mass spectrum and single-crystal X-ray diffraction analysis. CCDC: 1045890, 1; 1045891, 2.
2015, 31(8): 1539-1547
doi: 10.11862/CJIC.2015.214
Abstract:
The macropore alumina catalysis material FA-06 was prepared by nano self-assembly technique which has a pore volume of 1.39 cm3·g-1, a specific surface area of 297 m2·g-1, most probable pore size of 32.4 nm and a porosity of 81.85%. High concentration pore size distribution of 10~30 nm and 30~60 nm which percentages are 35.61% and 40.88%, respectively. GPC showed that the dispersion and relative molecular weight of RHP are controlled by the amount of PIBSA, which is the formation material of RHP, in order to control the pore sizes. From TEM and SEM, the results showed that the diameters of nano aluminum hydroxide rods are 250~300 nm, and the lengths are 600~800 nm. After calcinating at 550.0℃, the nano alumina rods had the diameter of 150~300 nm, the length of 400~600 nm. XRD results of burned nano self-assembly aluminum hydroxide showed that γ-Al2O3 be formed completely from three types of precursor of nano self-assembly aluminum hydroxide by burning process. Combining with data of TG, the γ-Al2O3 is formed completely due to the decomposition of pseudoboehmite at temperature of 605.0℃, and the total weight loss reaches 61.88%. Based on the above experimental results, the molecular self-assembly and nano self-assembly formation process of reverse supersoluble micelle, aluminum hydroxide and macropore alumina were simulated. Moreover, the formation mechanism of NSA of nano self-assembly macropore alumina with penetrable pores was presented.
The macropore alumina catalysis material FA-06 was prepared by nano self-assembly technique which has a pore volume of 1.39 cm3·g-1, a specific surface area of 297 m2·g-1, most probable pore size of 32.4 nm and a porosity of 81.85%. High concentration pore size distribution of 10~30 nm and 30~60 nm which percentages are 35.61% and 40.88%, respectively. GPC showed that the dispersion and relative molecular weight of RHP are controlled by the amount of PIBSA, which is the formation material of RHP, in order to control the pore sizes. From TEM and SEM, the results showed that the diameters of nano aluminum hydroxide rods are 250~300 nm, and the lengths are 600~800 nm. After calcinating at 550.0℃, the nano alumina rods had the diameter of 150~300 nm, the length of 400~600 nm. XRD results of burned nano self-assembly aluminum hydroxide showed that γ-Al2O3 be formed completely from three types of precursor of nano self-assembly aluminum hydroxide by burning process. Combining with data of TG, the γ-Al2O3 is formed completely due to the decomposition of pseudoboehmite at temperature of 605.0℃, and the total weight loss reaches 61.88%. Based on the above experimental results, the molecular self-assembly and nano self-assembly formation process of reverse supersoluble micelle, aluminum hydroxide and macropore alumina were simulated. Moreover, the formation mechanism of NSA of nano self-assembly macropore alumina with penetrable pores was presented.
2015, 31(8): 1548-1554
doi: 10.11862/CJIC.2015.208
Abstract:
Flower-like Mg3B2O6:Eu3+ hierarchical microspheres, with an average diameter of 2.0~2.5 μm, were successfully synthesized via a simple precipitation method using poly (vinyl pyrrolidone) as template and followed by a subsequent heat treatment. The structure, morphology, composition and photoluminescence (PL) properties of as-prepared and calcined samples were systematically characterized by XRD, SEM, TEM and PL spectra, respectively. The resultant products presented a strong characteristic of red emission at 612 nm corresponding to 5D0→7F2 of the Eu3+ transition under ultraviolet excitation at 393 nm, which may open a wide door for its applications especially in fluorescent lamps, display systems, and optoelectronic devices. Besides, we demonstrated the morphology, concentration of Eu3+ as well as calcination temperature had a great effect on the PL properties of the microspheres.
Flower-like Mg3B2O6:Eu3+ hierarchical microspheres, with an average diameter of 2.0~2.5 μm, were successfully synthesized via a simple precipitation method using poly (vinyl pyrrolidone) as template and followed by a subsequent heat treatment. The structure, morphology, composition and photoluminescence (PL) properties of as-prepared and calcined samples were systematically characterized by XRD, SEM, TEM and PL spectra, respectively. The resultant products presented a strong characteristic of red emission at 612 nm corresponding to 5D0→7F2 of the Eu3+ transition under ultraviolet excitation at 393 nm, which may open a wide door for its applications especially in fluorescent lamps, display systems, and optoelectronic devices. Besides, we demonstrated the morphology, concentration of Eu3+ as well as calcination temperature had a great effect on the PL properties of the microspheres.
2015, 31(8): 1555-1562
doi: 10.11862/CJIC.2015.192
Abstract:
A series of CuO-CeO2 (nCu:nCe=1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3) catalysts with different Cu/Ce molar ratios (nCu:nCe) were prepared by soft template hydrothermal method. The effect of nCu:nCe and preparation methods (soft template hydrothermal method and co-precipitation without template method) on CO catalytic oxidation performance was investigated, and the structure, reduction features and surface chemical states of the CuO-CeO2 catalysts were characterized by XRD, TEM, low temperature adsorption-desorption, temperature programmed reduction (H2-TPR) and XPS. The results show that with the increase of nCu:nCe, the CO catalytic oxidation activities of CuO-CeO2 catalysts increase firstly and then decrease. When the nCu:nCe is 5:5, the CO catalytic oxidation activity of the catalyst is more than 90% at 100℃. The large specific surface area, narrow pore structure distribution, high dispersion of active CuO species and the strong interaction between CuO and CeO2 of CuO-CeO2 catalyst prepared by soft template hydrothermal method are the main factors for its excellent CO catalytic oxidation activity.
A series of CuO-CeO2 (nCu:nCe=1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3) catalysts with different Cu/Ce molar ratios (nCu:nCe) were prepared by soft template hydrothermal method. The effect of nCu:nCe and preparation methods (soft template hydrothermal method and co-precipitation without template method) on CO catalytic oxidation performance was investigated, and the structure, reduction features and surface chemical states of the CuO-CeO2 catalysts were characterized by XRD, TEM, low temperature adsorption-desorption, temperature programmed reduction (H2-TPR) and XPS. The results show that with the increase of nCu:nCe, the CO catalytic oxidation activities of CuO-CeO2 catalysts increase firstly and then decrease. When the nCu:nCe is 5:5, the CO catalytic oxidation activity of the catalyst is more than 90% at 100℃. The large specific surface area, narrow pore structure distribution, high dispersion of active CuO species and the strong interaction between CuO and CeO2 of CuO-CeO2 catalyst prepared by soft template hydrothermal method are the main factors for its excellent CO catalytic oxidation activity.
2015, 31(8): 1563-1570
doi: 10.11862/CJIC.2015.206
Abstract:
Zeolite-zeolite composites composed of ZSM-5 and β zeolite crystals were synthesized by a two-step hydrothermal crystallization procedure (denoted as MFI/BEA), in which the mixture of pre-synthesized β zeolite was used as the nutrients for the growth of the post-synthesized ZSM-5 zeolite. The structural, crystalline, and textural properties of the as-synthesized materials, as well as the references ZSM-5 and β zeolite samples, were characterized by XRD, FTIR, in situ pyridine IR spectroscopy, NH3-TPD, nitrogen adsorption/desorption, TEM and SEM. The results displayed that the post-synthesized ZSM-5 zeolite unexpectedly grew within the β zeolite crystals, and the ratios of MFI/BEA in the as-synthesized zeolite-zeolite composites could be adjusted by controlling the second-step crystalline time. Catalytic performances of Co-β, Co-ZSM-5 and Co-MFI/BEA were investigated during the catalytic reduction of NO by methane in the presence of O2. As compared with the references Co-β and Co-ZSM-5, the zeolite-zeolite composites Co-MFI/BEA exhibited an excellent catalytic performance with a higher activity as well as a higher stability and an excellent sulfur-resistance.
Zeolite-zeolite composites composed of ZSM-5 and β zeolite crystals were synthesized by a two-step hydrothermal crystallization procedure (denoted as MFI/BEA), in which the mixture of pre-synthesized β zeolite was used as the nutrients for the growth of the post-synthesized ZSM-5 zeolite. The structural, crystalline, and textural properties of the as-synthesized materials, as well as the references ZSM-5 and β zeolite samples, were characterized by XRD, FTIR, in situ pyridine IR spectroscopy, NH3-TPD, nitrogen adsorption/desorption, TEM and SEM. The results displayed that the post-synthesized ZSM-5 zeolite unexpectedly grew within the β zeolite crystals, and the ratios of MFI/BEA in the as-synthesized zeolite-zeolite composites could be adjusted by controlling the second-step crystalline time. Catalytic performances of Co-β, Co-ZSM-5 and Co-MFI/BEA were investigated during the catalytic reduction of NO by methane in the presence of O2. As compared with the references Co-β and Co-ZSM-5, the zeolite-zeolite composites Co-MFI/BEA exhibited an excellent catalytic performance with a higher activity as well as a higher stability and an excellent sulfur-resistance.
2015, 31(8): 1571-1580
doi: 10.11862/CJIC.2015.186
Abstract:
Ni-Fe catalysts were prepared via the replacement reaction of NiCl2 by Fe and used for the selective hydrogenation of dinitrotoluene (DNT) in liquid phase. The influences of Ni/Fe molar ratio (nNi/nFe) on the surface properties and catalytic performance of Ni-Fe catalysts were investigated. The characterization results from XRD, Low temperature nitrogen adsorption -desorption, H2-TPD, XPS and TEM show that nNi/nFe has a significant effect on the surface properties of Ni-Fe catalysts. When nNi/nFe is 1:4, the effect of Fe inhibition on the oxidation of nickel is more apparent, the chemical adsorption of hydrogen is 0.16 mmol·g-1 and the dispersion of active species Ni achieves 23%. The performance of Ni-Fe catalysts is greatly improved. Under the optimized catalysts preparation conditions, the conversion of DNT (dinitrotoluene) and the selectivity of TDA (toluenediamine) could reach~100% and 99%, respectively. In addition, Ni-Zn Urushibara nickel catalysts and Ni-Fe catalysts have~the same catalytic hydrogenation~pathway but different catalytic reaction rate in a different reaction stages.
Ni-Fe catalysts were prepared via the replacement reaction of NiCl2 by Fe and used for the selective hydrogenation of dinitrotoluene (DNT) in liquid phase. The influences of Ni/Fe molar ratio (nNi/nFe) on the surface properties and catalytic performance of Ni-Fe catalysts were investigated. The characterization results from XRD, Low temperature nitrogen adsorption -desorption, H2-TPD, XPS and TEM show that nNi/nFe has a significant effect on the surface properties of Ni-Fe catalysts. When nNi/nFe is 1:4, the effect of Fe inhibition on the oxidation of nickel is more apparent, the chemical adsorption of hydrogen is 0.16 mmol·g-1 and the dispersion of active species Ni achieves 23%. The performance of Ni-Fe catalysts is greatly improved. Under the optimized catalysts preparation conditions, the conversion of DNT (dinitrotoluene) and the selectivity of TDA (toluenediamine) could reach~100% and 99%, respectively. In addition, Ni-Zn Urushibara nickel catalysts and Ni-Fe catalysts have~the same catalytic hydrogenation~pathway but different catalytic reaction rate in a different reaction stages.
2015, 31(8): 1581-1589
doi: 10.11862/CJIC.2015.198
Abstract:
The Cu-Ni co-modified TiO2-based photocatalytic system was fabricated using TiO2 nanoparticles as the main catalyst component by an impregnation process followed by a reduction procedure. The effect of Cu-Ni cocatalyst on the visible photocatalytic activity of TiO2 for phenol preparation was studied using benzene as the starting material and hydrogen peroxide as the oxidant. The action mechanism of Cu-Ni cocatalyst for the photocatalytic activity of TiO2 nanoparticles is discussed. The results show that the pure TiO2 nanoparticles do not have photocatalytic activity for the phenol production from benzene under visible light irradiation. In contrast, the photocatalytic activity of TiO2 nanoparticles can be enhanced obviously due to the introduction of Cu and Ni. The yield of phenol is 18% when the Cu-Ni co-modified TiO2 nanoparticles are used as a photocatalyst. Moreover, there exists noticeable synergistic effect between Cu and Ni. The Cu-Ni co-modified TiO2 nanoparticles exhibit much higher photocatalytic activity in comparison with that of the Cu or Ni alone modified ones due to the synergistic effect. These results imply that the cheap cocatalyst with outstanding performance than that of noble metals may be prepared by taking advantage of the synergistic effect between various metals.
The Cu-Ni co-modified TiO2-based photocatalytic system was fabricated using TiO2 nanoparticles as the main catalyst component by an impregnation process followed by a reduction procedure. The effect of Cu-Ni cocatalyst on the visible photocatalytic activity of TiO2 for phenol preparation was studied using benzene as the starting material and hydrogen peroxide as the oxidant. The action mechanism of Cu-Ni cocatalyst for the photocatalytic activity of TiO2 nanoparticles is discussed. The results show that the pure TiO2 nanoparticles do not have photocatalytic activity for the phenol production from benzene under visible light irradiation. In contrast, the photocatalytic activity of TiO2 nanoparticles can be enhanced obviously due to the introduction of Cu and Ni. The yield of phenol is 18% when the Cu-Ni co-modified TiO2 nanoparticles are used as a photocatalyst. Moreover, there exists noticeable synergistic effect between Cu and Ni. The Cu-Ni co-modified TiO2 nanoparticles exhibit much higher photocatalytic activity in comparison with that of the Cu or Ni alone modified ones due to the synergistic effect. These results imply that the cheap cocatalyst with outstanding performance than that of noble metals may be prepared by taking advantage of the synergistic effect between various metals.
2015, 31(8): 1590-1596
doi: 10.11862/CJIC.2015.174
Abstract:
Two vanadium(Ⅴ) complexes, [VOLL1] (1) and [VOLL2] (1) (L=N'-(3,5-dibromo-2-hydroxybenzylidene)-3-methylbenzohydrazide, L1=methylmaltol, L2=ethylmaltol), have been prepared. The complexes have been characte-rized by physico-chemical methods and single crystal X-ray determination. The V atom in each complex is coordinated by three donor atoms of L, two donor atoms of L1 or L2, and one oxo group, forming octahedral coordination. The complexes were administered intragastrically to both normal and alloxan-diabetic mices for two weeks. The biological activity results show that the complexes at doses of 10.0 and 20.0 mgV·kg-1, can significantly decrease the blood glucose level in alloxan-diabetic mices, but the blood glucose level in the treated normal mices was not altered. CCDC: 1059791, 1; 1059793, 2.
Two vanadium(Ⅴ) complexes, [VOLL1] (1) and [VOLL2] (1) (L=N'-(3,5-dibromo-2-hydroxybenzylidene)-3-methylbenzohydrazide, L1=methylmaltol, L2=ethylmaltol), have been prepared. The complexes have been characte-rized by physico-chemical methods and single crystal X-ray determination. The V atom in each complex is coordinated by three donor atoms of L, two donor atoms of L1 or L2, and one oxo group, forming octahedral coordination. The complexes were administered intragastrically to both normal and alloxan-diabetic mices for two weeks. The biological activity results show that the complexes at doses of 10.0 and 20.0 mgV·kg-1, can significantly decrease the blood glucose level in alloxan-diabetic mices, but the blood glucose level in the treated normal mices was not altered. CCDC: 1059791, 1; 1059793, 2.
2015, 31(8): 1597-1602
doi: 10.11862/CJIC.2015.217
Abstract:
Two complexes of Cd(Ⅱ) or Zn(Ⅱ) with L (L=tris(2-mercaptopyridyl)methane), Cd(L)4(NO3)2 (1) and Zn(L)4(ClO4)2 (2), have been synthesized and characterized. The cleavage of the C-S bonds of the ligand has been discovered and the cleavage mechanism has been studied by UV-Vis titration and GC-MS. The possible reaction mechanism has been proposed. Single crystal X-ray analyses show that the Cd and Zn atoms are all in a four-coordinated distorted tetrahedron environment. The intermolecular π-π stacking action extends the complex 1 to a 2D net work. CCDC: 627210, 1; 644051, 2.
Two complexes of Cd(Ⅱ) or Zn(Ⅱ) with L (L=tris(2-mercaptopyridyl)methane), Cd(L)4(NO3)2 (1) and Zn(L)4(ClO4)2 (2), have been synthesized and characterized. The cleavage of the C-S bonds of the ligand has been discovered and the cleavage mechanism has been studied by UV-Vis titration and GC-MS. The possible reaction mechanism has been proposed. Single crystal X-ray analyses show that the Cd and Zn atoms are all in a four-coordinated distorted tetrahedron environment. The intermolecular π-π stacking action extends the complex 1 to a 2D net work. CCDC: 627210, 1; 644051, 2.
2015, 31(8): 1603-1608
doi: 10.11862/CJIC.2015.215
Abstract:
Two complexes with pyrazine polycarboxylic acid, namely {[Cu2(pztc)(4,4'-bpy)(H2O)4]·6H2O}n (1), {(H2bpe)[Cd(pztc)(H2O)2]·2.5H2O}n (2), (H4pztc=pyrazine-2,3,5,6-tetracarboxylic acid, bpe=1,2-bis(4-pyridyl)ethane, 4,4'-bpy=4,4'-bipyridine), have been prepared by modifying the reaction conditions at room temperature and characterized by IR, elemental analysis, thermal gravimetric analysis, fluorescence measurement and single crystal X-ray diffraction analysis. The structures of two complexes are two-dimensional (2D) networks, but H4pztc has different connection modes in 1 and 2. Complex 2 shows good luminescence properties in solid state at room temperature. Electron Paramagnetic Resonance (EPR) spectra of complex 1 is studied. CCDC: 1039147, 1; 1039296, 2.
Two complexes with pyrazine polycarboxylic acid, namely {[Cu2(pztc)(4,4'-bpy)(H2O)4]·6H2O}n (1), {(H2bpe)[Cd(pztc)(H2O)2]·2.5H2O}n (2), (H4pztc=pyrazine-2,3,5,6-tetracarboxylic acid, bpe=1,2-bis(4-pyridyl)ethane, 4,4'-bpy=4,4'-bipyridine), have been prepared by modifying the reaction conditions at room temperature and characterized by IR, elemental analysis, thermal gravimetric analysis, fluorescence measurement and single crystal X-ray diffraction analysis. The structures of two complexes are two-dimensional (2D) networks, but H4pztc has different connection modes in 1 and 2. Complex 2 shows good luminescence properties in solid state at room temperature. Electron Paramagnetic Resonance (EPR) spectra of complex 1 is studied. CCDC: 1039147, 1; 1039296, 2.
2015, 31(8): 1609-1618
doi: 10.11862/CJIC.2015.213
Abstract:
Five helical coordination polymers {[Cu(Hbpma)(H2O)4]2(SO4)3·3.5H2O}n (1), {[Ni(Hbpma)(H2O)4]4(SO4)6·10.75H2O}n (2), {[Mn(Hbpma)(H2O)4](SO4)1.5·3H2O}n (3), {[Zn(Hbpma)(H2O)4]4(SO4)6·4H2O·4CH3OH}n (4) and {[Cu(Hbpma)2(H2O)2](SO4)2·9H2O}n (5) (bpma=N,N'-bis(3-pyridylmethyl)amine) were synthesized and structurally char-acterized. The single-crystal X-ray analyses indicate that complexes 1~4 crystallize in the one-dimensional chain structures and complex 5 shows the two-dimensional layer structure, in which the metal ions are bridged by the protonated bpma ligands. It is noted that the flexible bpma ligands with the trans-trans conformation lead to the pseudo-helical chains for complexes 1~2, the helical chains for complexes 3~4 and a helical layer for complex 5. The magnetic properties and the thermal behavior are investigated. CCDC: 966929, 1; 966932, 2; 966930, 3; 966931, 4; 1054736, 5.
Five helical coordination polymers {[Cu(Hbpma)(H2O)4]2(SO4)3·3.5H2O}n (1), {[Ni(Hbpma)(H2O)4]4(SO4)6·10.75H2O}n (2), {[Mn(Hbpma)(H2O)4](SO4)1.5·3H2O}n (3), {[Zn(Hbpma)(H2O)4]4(SO4)6·4H2O·4CH3OH}n (4) and {[Cu(Hbpma)2(H2O)2](SO4)2·9H2O}n (5) (bpma=N,N'-bis(3-pyridylmethyl)amine) were synthesized and structurally char-acterized. The single-crystal X-ray analyses indicate that complexes 1~4 crystallize in the one-dimensional chain structures and complex 5 shows the two-dimensional layer structure, in which the metal ions are bridged by the protonated bpma ligands. It is noted that the flexible bpma ligands with the trans-trans conformation lead to the pseudo-helical chains for complexes 1~2, the helical chains for complexes 3~4 and a helical layer for complex 5. The magnetic properties and the thermal behavior are investigated. CCDC: 966929, 1; 966932, 2; 966930, 3; 966931, 4; 1054736, 5.
2015, 31(8): 1619-1625
doi: 10.11862/CJIC.2015.220
Abstract:
A novel trinuclear copper(Ⅱ) complex, [Cu3L2(py)](ClO4)2·2THF (1) (H2L=(E)-3-[N,N-di(2-pyridylmethyl)aminomethyl]-2-hydroxyl-5-methylbenzaldehyde oxime, py=pyridine, THF=tetrahydrofuran), has been successfully synthesized and characterized. 1 crystallizes in monoclinic system with space group C2/c, a=2.969 0(7) nm, b=1.302 8(3) nm, c=2.057 4(9) nm, β=132.435(2)°, V=5.873(3) nm3, Z=4 with final R1=0.047 9. X-ray crystallography analysis reveals that 1 is a mixed-bridged (-N-O-/μ2-O-) linear tricopper(Ⅱ) complex with all the copper cations being five-coordinated by three N and two O atoms: the central Cu(Ⅱ) in a distorted trigonal bipyramidal configuration, whereas the peripheral Cu(Ⅱ) in a distorted square pyramidal arrangement. Magnetic susceptibility measurement indicates that there is a medium antiferromagnetic exchange coupling between the Cu(Ⅱ) ions with a J value of -33.3(5) cm-1. CCDC: 916132.
A novel trinuclear copper(Ⅱ) complex, [Cu3L2(py)](ClO4)2·2THF (1) (H2L=(E)-3-[N,N-di(2-pyridylmethyl)aminomethyl]-2-hydroxyl-5-methylbenzaldehyde oxime, py=pyridine, THF=tetrahydrofuran), has been successfully synthesized and characterized. 1 crystallizes in monoclinic system with space group C2/c, a=2.969 0(7) nm, b=1.302 8(3) nm, c=2.057 4(9) nm, β=132.435(2)°, V=5.873(3) nm3, Z=4 with final R1=0.047 9. X-ray crystallography analysis reveals that 1 is a mixed-bridged (-N-O-/μ2-O-) linear tricopper(Ⅱ) complex with all the copper cations being five-coordinated by three N and two O atoms: the central Cu(Ⅱ) in a distorted trigonal bipyramidal configuration, whereas the peripheral Cu(Ⅱ) in a distorted square pyramidal arrangement. Magnetic susceptibility measurement indicates that there is a medium antiferromagnetic exchange coupling between the Cu(Ⅱ) ions with a J value of -33.3(5) cm-1. CCDC: 916132.
2015, 31(8): 1626-1636
doi: 10.11862/CJIC.2015.212
Abstract:
Under the green and mild conditions, the hierarchical ZnO was fabricated by the secondary deposition with mixed two zinc salts (zinc source), ionic liquid (surfactant). The composition, structure, morphology, photoluminescence properties and photocatalytic activity of samples were characterized by XRD, IR, SEM, UV-Vis and PL, respectively. The influential factors on sample morphology, such as surfactant, the kind of anion and temperature, were discussed. The results indicate that surfactant has a significant regulation on the morphologies of as-prepared ZnO samples. Furthermore, the anion and temperature also play a critical role in the crystal structure and morphology of ZnO. In addition, all of as-prepared hierarchical ZnO show an excellent photocatalytic activity on methyl orange under UV lamp, where the sample-1 is slightly better than others.
Under the green and mild conditions, the hierarchical ZnO was fabricated by the secondary deposition with mixed two zinc salts (zinc source), ionic liquid (surfactant). The composition, structure, morphology, photoluminescence properties and photocatalytic activity of samples were characterized by XRD, IR, SEM, UV-Vis and PL, respectively. The influential factors on sample morphology, such as surfactant, the kind of anion and temperature, were discussed. The results indicate that surfactant has a significant regulation on the morphologies of as-prepared ZnO samples. Furthermore, the anion and temperature also play a critical role in the crystal structure and morphology of ZnO. In addition, all of as-prepared hierarchical ZnO show an excellent photocatalytic activity on methyl orange under UV lamp, where the sample-1 is slightly better than others.
2015, 31(8): 1637-1643
doi: 10.11862/CJIC.2015.195
Abstract:
Two silver(Ⅰ) complexes with heterocyclic thione, [AgCl(PPh3)2(BTZT)]2 (1) and [Ag(PPh3)2(BTZT)2](NO3)·CH3OH (2) (PPh3=triphenylphosphine; BTZT=benzothiazoline-2-thione) have been synthesized and characterized by IR, single-crystal X-ray diffraction, fluorescence spectrum and 1H NMR spectroscopy. Heterocyclic thiones possess chemically active groups -N(H)-C(=S)- in equilibrium with its thiol form. 1 and 2 are obtained by the reactions of AgCl or AgNO3 with PPh3 in the presence of 2-mercaptobenzothiazole (MBT) in mixed solvent (CH3OH/CH2Cl2). The complex 1 contains two same structures in each asymmetric unit, but there are different bond lengths and bond angles. Complex 2 is a simple mono-nuclear heteroleptic complex whose main structure links free CH3OH and NO3- anion by hydrogen bonding interactions. The red-shift of emission peak of 1~2 is derived from ligand-centered π-π* transition. CCDC: 1059719, 1; 1059720, 2.
Two silver(Ⅰ) complexes with heterocyclic thione, [AgCl(PPh3)2(BTZT)]2 (1) and [Ag(PPh3)2(BTZT)2](NO3)·CH3OH (2) (PPh3=triphenylphosphine; BTZT=benzothiazoline-2-thione) have been synthesized and characterized by IR, single-crystal X-ray diffraction, fluorescence spectrum and 1H NMR spectroscopy. Heterocyclic thiones possess chemically active groups -N(H)-C(=S)- in equilibrium with its thiol form. 1 and 2 are obtained by the reactions of AgCl or AgNO3 with PPh3 in the presence of 2-mercaptobenzothiazole (MBT) in mixed solvent (CH3OH/CH2Cl2). The complex 1 contains two same structures in each asymmetric unit, but there are different bond lengths and bond angles. Complex 2 is a simple mono-nuclear heteroleptic complex whose main structure links free CH3OH and NO3- anion by hydrogen bonding interactions. The red-shift of emission peak of 1~2 is derived from ligand-centered π-π* transition. CCDC: 1059719, 1; 1059720, 2.
2015, 31(8): 1644-1650
doi: 10.11862/CJIC.2015.218
Abstract:
A one-pot method was developed for synthesizing Magnesium-doped ZnO quantum dots (QDs) capped with (3-aminopropyl)triethoxysilane (APTES). The as-prepared quantum dots were characterized by XRD, TEM, UV-Vis, FL (fluorescent spectroscopy) and FTIR. The results show that the Mg-doped quantum dots exhibit greatly enhanced luminescent property and their quantum yield is increased from 11% for un-doped ZnO QDs to 33% for Mg-doped ZnO QDs at Mg-doping content of 30%. In addition, aqueous-stability is achieved by capping the Mg-doped ZnO QDs with APTES. The obtained APTES-capped Mg-doped ZnO QDs exhibit excellent water stability and retain visible emissions. The APTES-capped Mg-doped ZnO QDs demonstrate promising applications in MCF-7 cell labeling.
A one-pot method was developed for synthesizing Magnesium-doped ZnO quantum dots (QDs) capped with (3-aminopropyl)triethoxysilane (APTES). The as-prepared quantum dots were characterized by XRD, TEM, UV-Vis, FL (fluorescent spectroscopy) and FTIR. The results show that the Mg-doped quantum dots exhibit greatly enhanced luminescent property and their quantum yield is increased from 11% for un-doped ZnO QDs to 33% for Mg-doped ZnO QDs at Mg-doping content of 30%. In addition, aqueous-stability is achieved by capping the Mg-doped ZnO QDs with APTES. The obtained APTES-capped Mg-doped ZnO QDs exhibit excellent water stability and retain visible emissions. The APTES-capped Mg-doped ZnO QDs demonstrate promising applications in MCF-7 cell labeling.
2015, 31(8): 1651-1660
doi: 10.11862/CJIC.2015.227
Abstract:
Four diverse silver coordination polymers with the same components of silver, 4,4'-bipyridine(4,4'-bipy), and 2-nitro-1,4-benzenedicarboxylic acid (2-H2nbdc) have been synthesized, namely {[Ag(4,4'-bipy)]·2-Hnbdc·2H2O·CH3OH}n (1), {[Ag(4,4'-bipy)(2-Hnbdc)]}n (2), {[Ag2(4,4'-bipy)2(2-nbdc)]·2H2O}n (3), and {[Ag2(4,4'-bipy)2(2-nbdc)(H2O)]·2H2O}n (4), and characterized by IR, elemental analysis, TG, UV, fluorescence spectra, and powder X-ray analysis. The single crystal X-ray analysis showed that complex 1 is a 1D cation-anionic polymer, complex 2 is a 1D double chain without any solvent, and complexes 3 and 4 are 1D chain structures. Diverse structures differ with respect to molecular conformation, coordination modes of 2-Hnbdc, and weak interactions. In these complexes there are weak bonds, π-π aromatic stacking interactions, Ag…Ag interaction, and hydrogen bonding. The diverse structures are related to the thermal stability, UV absorptions, and fluorescence emissions. CCDC: 945166, 1; 945167, 2; 945168, 3; 945169, 4.
Four diverse silver coordination polymers with the same components of silver, 4,4'-bipyridine(4,4'-bipy), and 2-nitro-1,4-benzenedicarboxylic acid (2-H2nbdc) have been synthesized, namely {[Ag(4,4'-bipy)]·2-Hnbdc·2H2O·CH3OH}n (1), {[Ag(4,4'-bipy)(2-Hnbdc)]}n (2), {[Ag2(4,4'-bipy)2(2-nbdc)]·2H2O}n (3), and {[Ag2(4,4'-bipy)2(2-nbdc)(H2O)]·2H2O}n (4), and characterized by IR, elemental analysis, TG, UV, fluorescence spectra, and powder X-ray analysis. The single crystal X-ray analysis showed that complex 1 is a 1D cation-anionic polymer, complex 2 is a 1D double chain without any solvent, and complexes 3 and 4 are 1D chain structures. Diverse structures differ with respect to molecular conformation, coordination modes of 2-Hnbdc, and weak interactions. In these complexes there are weak bonds, π-π aromatic stacking interactions, Ag…Ag interaction, and hydrogen bonding. The diverse structures are related to the thermal stability, UV absorptions, and fluorescence emissions. CCDC: 945166, 1; 945167, 2; 945168, 3; 945169, 4.
2015, 31(8): 1661-1666
doi: 10.11862/CJIC.2015.228
Abstract:
Two complexes [(Cu)(L)(Cl)]·0.5EtOH·1.5H2O and {[Zn(L)(NO3)]·2CH3CN}n (HL is the acylhydrazone ligand derived from 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) and 4-methyl salicylic hydrazide) have been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectroscopy. X-ray diffraction analysis results show that the coordination geometry of the Cu(Ⅱ) ion in 1 is a distorted square planar geometry with nitrogen and two oxygen atoms provided by the enolizated ligand L-1 and one chloride anion. However, in complex 2, the Zn(Ⅱ) ion with a distorted trigonal biyramid coordination geometry is five-coordinated, involving one nitrate anion, one NO2 donor set of an enolizated ligand L- and one pyrazoline nitrogen atom from another adjacent acylhydrazone ligand, thus forming one dimension chain-like framework along b axis. When excited at 310 nm, complex 2 exhibits two strong emissions at 434 and 459 nm, while the ligand shows relatively weak emission at 521 nm. In addition, luminescent decay data show that the mean lifetime τ are 7.352 8 and 7.755 6 μs for HL and complex 2, respectively. CCDC: 1058420, HL·0.5EtOH; 1058421, 1; 1058422, 2.
Two complexes [(Cu)(L)(Cl)]·0.5EtOH·1.5H2O and {[Zn(L)(NO3)]·2CH3CN}n (HL is the acylhydrazone ligand derived from 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) and 4-methyl salicylic hydrazide) have been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectroscopy. X-ray diffraction analysis results show that the coordination geometry of the Cu(Ⅱ) ion in 1 is a distorted square planar geometry with nitrogen and two oxygen atoms provided by the enolizated ligand L-1 and one chloride anion. However, in complex 2, the Zn(Ⅱ) ion with a distorted trigonal biyramid coordination geometry is five-coordinated, involving one nitrate anion, one NO2 donor set of an enolizated ligand L- and one pyrazoline nitrogen atom from another adjacent acylhydrazone ligand, thus forming one dimension chain-like framework along b axis. When excited at 310 nm, complex 2 exhibits two strong emissions at 434 and 459 nm, while the ligand shows relatively weak emission at 521 nm. In addition, luminescent decay data show that the mean lifetime τ are 7.352 8 and 7.755 6 μs for HL and complex 2, respectively. CCDC: 1058420, HL·0.5EtOH; 1058421, 1; 1058422, 2.
