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2013 Volume 29 Issue 7
2013, 29(7): 1333-1338
doi: 10.3969/j.issn.1001-4861.2013.00.277
Abstract:
A mild and highly efficient hydrothermal synthesis method for uniform magnesium silicate nanotubes was developed from normal Mg(OH)2 and SiO2 powders with the assistance of potassium hydroxide and sodium hydroxide. The samples were characterized by XRD, TEM, IR, and nitrogen adsorption-desorption. The synthetic process was studied by XRD, TEM, etc. The results indicate that the eutectic solution of potassium hydroxide and sodium hydroxide offers higher dissolvability for the reactants and benefits the reaction between the reactants. This composite-hydroxide-assisted approach is a mild and highly efficient procedure for the synthesis of high quality magnesium silicate nanotubes at 250 ℃ in a short duration of 36 hours, while it needs over 7 days at 250 ℃ for traditional hydrothermal method.
A mild and highly efficient hydrothermal synthesis method for uniform magnesium silicate nanotubes was developed from normal Mg(OH)2 and SiO2 powders with the assistance of potassium hydroxide and sodium hydroxide. The samples were characterized by XRD, TEM, IR, and nitrogen adsorption-desorption. The synthetic process was studied by XRD, TEM, etc. The results indicate that the eutectic solution of potassium hydroxide and sodium hydroxide offers higher dissolvability for the reactants and benefits the reaction between the reactants. This composite-hydroxide-assisted approach is a mild and highly efficient procedure for the synthesis of high quality magnesium silicate nanotubes at 250 ℃ in a short duration of 36 hours, while it needs over 7 days at 250 ℃ for traditional hydrothermal method.
2013, 29(7): 1339-1344
doi: 10.3969/j.issn.1001-4861.2013.00.233
Abstract:
Silica antireflective coatings modified by hexamethyldisilazane (HMDS) were deposited on clean substrates by sol-gel process. The effects of HMDS on the contamination resistant capability and laser-induced damage threshold (LIDT) of coatings were investigated. With the modified sol the resultant coatings were hydrophobic and the contact angle for water increased with the increasing amount of HMDS in the reaction mixture. The antireflective properties were retained after HMDS-treatment and the transmission maximum values were above 99%. The introduction of HMDS into silica sols had also increased the LIDT of coatings from 24.3 J·cm-2 to 37 J·cm-2 when the molar ratio of HMDS to TEOS was 0.05:1. After some of the hydroxyl groups on the surface of the SiO2 particle were replaced by methyl groups, from which the SiO2 particle gained a water-repellent surface, the stability of coatings in vacuum were increased. The peak transmittance of modified sample decreased only 0.25% after conserved in vacuum circumstance for 168 hours, in contrast to 2% reduction for the unmodified sample. At the same time, the LIDT of modified coating retained a high LIDT of 30.8 J·cm-2.
Silica antireflective coatings modified by hexamethyldisilazane (HMDS) were deposited on clean substrates by sol-gel process. The effects of HMDS on the contamination resistant capability and laser-induced damage threshold (LIDT) of coatings were investigated. With the modified sol the resultant coatings were hydrophobic and the contact angle for water increased with the increasing amount of HMDS in the reaction mixture. The antireflective properties were retained after HMDS-treatment and the transmission maximum values were above 99%. The introduction of HMDS into silica sols had also increased the LIDT of coatings from 24.3 J·cm-2 to 37 J·cm-2 when the molar ratio of HMDS to TEOS was 0.05:1. After some of the hydroxyl groups on the surface of the SiO2 particle were replaced by methyl groups, from which the SiO2 particle gained a water-repellent surface, the stability of coatings in vacuum were increased. The peak transmittance of modified sample decreased only 0.25% after conserved in vacuum circumstance for 168 hours, in contrast to 2% reduction for the unmodified sample. At the same time, the LIDT of modified coating retained a high LIDT of 30.8 J·cm-2.
2013, 29(7): 1345-1354
doi: 10.3969/j.issn.1001-4861.2013.00.226
Abstract:
In this paper, the precursor hydrazine titanium succinic acid was first prepared by pH value controlled precipitation method, after that, the titanium black pigment, namely, black titanium suboxides with large surface area were prepared by thermal decomposing the precursor. The black titanium suboxides were characterized by Brunauer-Emmett-Teller (BET) surface area, Energy dispersive x-ray spectrometry (EDS), X-ray Photoelectron Spectroscopy(XPS),X-ray diffraction patterns (XRD), high resolution scanning electron microscopy (HRSEM), nitrogen sorption analysis, laser particle size analyzer, and color i5 colorimeter spectrophotometer. The composition of black titanium suboxides was determined as 2TiO2·Ti2O3, and its surface area is 53.854 4 m2·g-1. The influences of acid source, the amount of hydrazine hydrate, acid/TiCl3 ratio, reaction time, pH, NaOH concentration, the calcination temperature and various reaction parameters on the particle size, the distribution uniformity and blackness of black titanium suboxides were discussed. The composition of the precursor with its molecular formula as [Ti(C4H4O4)2]0.85·2Ti2O3·6N2H4·3H2O was analyzed by Elemental analyzer and plasma spectrometer. From these data, the formation mechanism of the black titanium suboxides was deduced. These provide an important basis for the preparation of novel mixed-valence material black titanium suboxides.
In this paper, the precursor hydrazine titanium succinic acid was first prepared by pH value controlled precipitation method, after that, the titanium black pigment, namely, black titanium suboxides with large surface area were prepared by thermal decomposing the precursor. The black titanium suboxides were characterized by Brunauer-Emmett-Teller (BET) surface area, Energy dispersive x-ray spectrometry (EDS), X-ray Photoelectron Spectroscopy(XPS),X-ray diffraction patterns (XRD), high resolution scanning electron microscopy (HRSEM), nitrogen sorption analysis, laser particle size analyzer, and color i5 colorimeter spectrophotometer. The composition of black titanium suboxides was determined as 2TiO2·Ti2O3, and its surface area is 53.854 4 m2·g-1. The influences of acid source, the amount of hydrazine hydrate, acid/TiCl3 ratio, reaction time, pH, NaOH concentration, the calcination temperature and various reaction parameters on the particle size, the distribution uniformity and blackness of black titanium suboxides were discussed. The composition of the precursor with its molecular formula as [Ti(C4H4O4)2]0.85·2Ti2O3·6N2H4·3H2O was analyzed by Elemental analyzer and plasma spectrometer. From these data, the formation mechanism of the black titanium suboxides was deduced. These provide an important basis for the preparation of novel mixed-valence material black titanium suboxides.
2013, 29(7): 1355-1360
doi: 10.3969/j.issn.1001-4861.2013.00.218
Abstract:
To solve the main problems encountered in the lithium-sulfur battery research and practical application, a simple and effective hydrothermal reduction of graphene oxide was employed to encapsulate commercial carbon nanotube-sulfur (CNT-S) nanocomposite in this study, then an effective type of graphene coated CNT-S nanostructure was formed. The polysulphide anions diffusion phenomenon was effectively restrained by the graphene coating structure. The nanocomposites were characterized by X-ray diffraction and scanning electron microscope. The results indicated that elemental sulfur was uniformly distributed across the CNT, and a layer of graphene coated on the surface of CNT-S nanocomposite. The electrochemical test results showed that the graphene coating nanostructure obviously improved the lithium-sulfur battery performance of the CNT-S nanocomposite.
To solve the main problems encountered in the lithium-sulfur battery research and practical application, a simple and effective hydrothermal reduction of graphene oxide was employed to encapsulate commercial carbon nanotube-sulfur (CNT-S) nanocomposite in this study, then an effective type of graphene coated CNT-S nanostructure was formed. The polysulphide anions diffusion phenomenon was effectively restrained by the graphene coating structure. The nanocomposites were characterized by X-ray diffraction and scanning electron microscope. The results indicated that elemental sulfur was uniformly distributed across the CNT, and a layer of graphene coated on the surface of CNT-S nanocomposite. The electrochemical test results showed that the graphene coating nanostructure obviously improved the lithium-sulfur battery performance of the CNT-S nanocomposite.
2013, 29(7): 1361-1368
doi: 10.3969/j.issn.1001-4861.2013.00.204
Abstract:
High-quality oil-soluble CuInS2/ZnS core/shell quantum dots (QDs) have been synthesized successfully using a non-hot-injection method. The as-prepared QDs exhibits tunable photoluminescence (PL) emission (PL peak, 550~800 nm) with a maximum PL quantum yield (QY) up to 80%. Furthermore, in this study, we explored further the water transfer of oil-soluble CuInS2/ZnS QDs by using temperature-sensitive poly(N-isopropylacryla-mide-co-Acrylamide-co-Octadecylacrylate) (P(NIPA-co-AAm-co-ODA)) micelle. The QDs-loaded micelle not only shows favorable PL properties, but also maintains the initial sensitive thermal responsibility. These results confirm the promising potential of cadmium-free CuInS2/ZnS QDs as a fluorescent probe for the biological imaging of micelle.
High-quality oil-soluble CuInS2/ZnS core/shell quantum dots (QDs) have been synthesized successfully using a non-hot-injection method. The as-prepared QDs exhibits tunable photoluminescence (PL) emission (PL peak, 550~800 nm) with a maximum PL quantum yield (QY) up to 80%. Furthermore, in this study, we explored further the water transfer of oil-soluble CuInS2/ZnS QDs by using temperature-sensitive poly(N-isopropylacryla-mide-co-Acrylamide-co-Octadecylacrylate) (P(NIPA-co-AAm-co-ODA)) micelle. The QDs-loaded micelle not only shows favorable PL properties, but also maintains the initial sensitive thermal responsibility. These results confirm the promising potential of cadmium-free CuInS2/ZnS QDs as a fluorescent probe for the biological imaging of micelle.
2013, 29(7): 1369-1374
doi: 10.3969/j.issn.1001-4861.2013.00.205
Abstract:
A new complex [Cd(BIMB)0.5(glu)]n based on rigid ligand BIMB (BIMB=1,4-bis(imidazol-1-yl)benzene) and flexible ligand H2glu (H2glu=glutaric acid) has been synthesized by hydrothermal method and characterized by IR and elemental analysis. The complex crystallizes in the monoclinic system P21/c space group, a=0.822 06(5) nm,b=0.774 38(5) nm, c=1.877 93(10) nm, β=107.966°, V=1.137 nm3, Z=4, F(000)=684. In complex, the adjacent Cd(Ⅱ) atoms are connected by two glu2-ligands to result in 1D chains, which are further linked by another glu2-ligand to generate a 2D layers, and the adjacent 2D layers are linked by BIMB ligand to result in a 3D framework. The TGA analysis shows the complex has good thermal stability. The fluorescence analysis reveals the complex has good fluorescence property. CCDC: 891527.
A new complex [Cd(BIMB)0.5(glu)]n based on rigid ligand BIMB (BIMB=1,4-bis(imidazol-1-yl)benzene) and flexible ligand H2glu (H2glu=glutaric acid) has been synthesized by hydrothermal method and characterized by IR and elemental analysis. The complex crystallizes in the monoclinic system P21/c space group, a=0.822 06(5) nm,b=0.774 38(5) nm, c=1.877 93(10) nm, β=107.966°, V=1.137 nm3, Z=4, F(000)=684. In complex, the adjacent Cd(Ⅱ) atoms are connected by two glu2-ligands to result in 1D chains, which are further linked by another glu2-ligand to generate a 2D layers, and the adjacent 2D layers are linked by BIMB ligand to result in a 3D framework. The TGA analysis shows the complex has good thermal stability. The fluorescence analysis reveals the complex has good fluorescence property. CCDC: 891527.
2013, 29(7): 1375-1384
doi: 10.3969/j.issn.1001-4861.2013.00.239
Abstract:
Two ion-pair compounds with the formula of (BMIB)[(Ni(mnt)2]2 (1) and (BMIO)[(Ni(mnt)2]2 (2) (mnt=maleonitrile dithiolate, BMIB=1,4-bis(1-methylimidazolium)butane, BMIO=1,8-bis(1-methylimidazolium)octane) were synthesized and characterized structurally. In 1, the [Ni(mnt)2]-form a trimer anions and a mixed column, respectively. The packing structures of 2 are different from 1, the cations and the anions form the irregular alignments. Compound 1 and 2 show remarkable near-IR absorption behavior in the region of 861 and 857 nm respectively. The electrochemical behaviors in the solid state depend on the hydrocarbon chain length in the countercation moiety. Investigations of variable-temperature magnetic susceptibility indicated that 1 shows weak paramagnetic feature from 2 to 400 K; the magnetic susceptibility data were fit to the Curie-Weiss equation. 2 is a spin gap system but its magnetic behavior does not follow the Blaney-Bowers spin dimer model. CCDC: 908109, 1; 908110, 2.
Two ion-pair compounds with the formula of (BMIB)[(Ni(mnt)2]2 (1) and (BMIO)[(Ni(mnt)2]2 (2) (mnt=maleonitrile dithiolate, BMIB=1,4-bis(1-methylimidazolium)butane, BMIO=1,8-bis(1-methylimidazolium)octane) were synthesized and characterized structurally. In 1, the [Ni(mnt)2]-form a trimer anions and a mixed column, respectively. The packing structures of 2 are different from 1, the cations and the anions form the irregular alignments. Compound 1 and 2 show remarkable near-IR absorption behavior in the region of 861 and 857 nm respectively. The electrochemical behaviors in the solid state depend on the hydrocarbon chain length in the countercation moiety. Investigations of variable-temperature magnetic susceptibility indicated that 1 shows weak paramagnetic feature from 2 to 400 K; the magnetic susceptibility data were fit to the Curie-Weiss equation. 2 is a spin gap system but its magnetic behavior does not follow the Blaney-Bowers spin dimer model. CCDC: 908109, 1; 908110, 2.
2013, 29(7): 1385-1390
doi: 10.3969/j.issn.1001-4861.2013.00.213
Abstract:
Two isostructural heteronuclear complexes [Fe(phen)3]2[FeLn(H2O)(tiron)3]·6H2O (Ln=Ho (1) and Yb (2)), Na2H2tiron=disodium 4,5-dihydro-xybenzene-1,3-disulfonate) were self-assembly synthesized via hydrothermal reaction. The complexes crystallized in the cubic system, space group P213. In [FeLn(H2O)(tiron)3]6-unit was revealed that the Fe3+ ion is in a FeO6 distorted trigonal anti-prism coordination polyhedron completed by six phenolate O atoms from three tiron4-ligands, and Ln3+ in a LnO7 distorted monocapped trigonal anti-prism coordination polyhedron completed by three phenolate μ2-O atoms and three O atoms from sulfonate groups of three ligands and one O atom from coordinated water. The [Fe(phen)3]3+ cations and [FeCe(tiron)3]6-anions via π-π interaction between phen ligands and electric attraction between cations and anions was assembled into multi-dimensional supramolecule. The magnetic properties of the complexes were been determined in the temperature range 2~300 K, indicating that the antiferromagnetic interaction between the central Ln(Ⅲ)-Fe(Ⅲ) ions. CCDC: 866880, 1; 867589, 2.
Two isostructural heteronuclear complexes [Fe(phen)3]2[FeLn(H2O)(tiron)3]·6H2O (Ln=Ho (1) and Yb (2)), Na2H2tiron=disodium 4,5-dihydro-xybenzene-1,3-disulfonate) were self-assembly synthesized via hydrothermal reaction. The complexes crystallized in the cubic system, space group P213. In [FeLn(H2O)(tiron)3]6-unit was revealed that the Fe3+ ion is in a FeO6 distorted trigonal anti-prism coordination polyhedron completed by six phenolate O atoms from three tiron4-ligands, and Ln3+ in a LnO7 distorted monocapped trigonal anti-prism coordination polyhedron completed by three phenolate μ2-O atoms and three O atoms from sulfonate groups of three ligands and one O atom from coordinated water. The [Fe(phen)3]3+ cations and [FeCe(tiron)3]6-anions via π-π interaction between phen ligands and electric attraction between cations and anions was assembled into multi-dimensional supramolecule. The magnetic properties of the complexes were been determined in the temperature range 2~300 K, indicating that the antiferromagnetic interaction between the central Ln(Ⅲ)-Fe(Ⅲ) ions. CCDC: 866880, 1; 867589, 2.
2013, 29(7): 1391-1399
doi: 10.3969/j.issn.1001-4861.2013.00.244
Abstract:
Sulfur-doped carbon microspheres (SCMSs) with mean size of about 4 μm were prepared successfully by a simple one-step sulfur-assisted hydrothermal carbonization (ASHTC) method. Soluble starch was used as carbon precursor and sublime sulfur as sulfur source. The as-prepared SCMSs were characterized systematically by means of SEM, TEM, XRD, N2 absorption-desorption isotherms, FTIR, XPS, and solid NMR. The existing forms of sulfur in SCMSs were also discussed. It was found that monodispersed SCMSs with high output could be obtained under high starch concentration (1.0 g·mL-1) and sulfur atoms could be introduced into carbon networks easily, indicating that the ASHTC is a powerful method for SCMS synthesis. For comparison, carbon microspheres (CMSs) were synthesized by conventional hydrothermal carbonization of starch in the absence of sulfur under the same hydrothermal conditions. Experimental results show that the as-synthesized SCMSs exhibit much higher specific surface area than that of CMSs. The reason of the increase of surface area of SCMSs may be due to the structural and chemical defects resulted from the sulfur doping. The chemical defects come from the-S-S-,-S-,-SO2-and-SO-groups, while the structural defects result from the substitution of graphite hexatomic-rings by thiophene five-membered rings in SCMSs.
Sulfur-doped carbon microspheres (SCMSs) with mean size of about 4 μm were prepared successfully by a simple one-step sulfur-assisted hydrothermal carbonization (ASHTC) method. Soluble starch was used as carbon precursor and sublime sulfur as sulfur source. The as-prepared SCMSs were characterized systematically by means of SEM, TEM, XRD, N2 absorption-desorption isotherms, FTIR, XPS, and solid NMR. The existing forms of sulfur in SCMSs were also discussed. It was found that monodispersed SCMSs with high output could be obtained under high starch concentration (1.0 g·mL-1) and sulfur atoms could be introduced into carbon networks easily, indicating that the ASHTC is a powerful method for SCMS synthesis. For comparison, carbon microspheres (CMSs) were synthesized by conventional hydrothermal carbonization of starch in the absence of sulfur under the same hydrothermal conditions. Experimental results show that the as-synthesized SCMSs exhibit much higher specific surface area than that of CMSs. The reason of the increase of surface area of SCMSs may be due to the structural and chemical defects resulted from the sulfur doping. The chemical defects come from the-S-S-,-S-,-SO2-and-SO-groups, while the structural defects result from the substitution of graphite hexatomic-rings by thiophene five-membered rings in SCMSs.
2013, 29(7): 1400-1406
doi: 10.3969/j.issn.1001-4861.2013.00.197
Abstract:
Ba0.98Bi0.02(Ti0.9Zr0.1)1-xCuxO3(x=0, 0.01, 0.02, 0.03) were prepared by conventional solid-state reaction methods. The effect of Bi3+ as donor doping in A-site and Cu2+ as acceptor doping in B-site on structure and dielectric properties were investigated by XRD, LCR and other techniques. The results revealed that when x=0.03, the second phase occurred. The order of the defect dipoles stability from low to high is [2BiBa·+VBa"]、[2BiBa·+CuTi/Zr"], [CuTi/Zr"+Vo··] by GULP. Combined with the experiments, the analysis shown that the relaxation degree were closely related to the variety of defect dipoles, when x=0.01, the defect dipoles [2BiBa·+CuTi/Zr"] were dominant. With increasing Cu2+ content, the dielectric constants increased, and the dielectric constants were inversely proportional to the bond valance sum of B-site and proportional to the varieties of octahedral BO6 volume.
Ba0.98Bi0.02(Ti0.9Zr0.1)1-xCuxO3(x=0, 0.01, 0.02, 0.03) were prepared by conventional solid-state reaction methods. The effect of Bi3+ as donor doping in A-site and Cu2+ as acceptor doping in B-site on structure and dielectric properties were investigated by XRD, LCR and other techniques. The results revealed that when x=0.03, the second phase occurred. The order of the defect dipoles stability from low to high is [2BiBa·+VBa"]、[2BiBa·+CuTi/Zr"], [CuTi/Zr"+Vo··] by GULP. Combined with the experiments, the analysis shown that the relaxation degree were closely related to the variety of defect dipoles, when x=0.01, the defect dipoles [2BiBa·+CuTi/Zr"] were dominant. With increasing Cu2+ content, the dielectric constants increased, and the dielectric constants were inversely proportional to the bond valance sum of B-site and proportional to the varieties of octahedral BO6 volume.
2013, 29(7): 1407-1413
doi: 10.3969/j.issn.1001-4861.2013.00.196
Abstract:
The influence of NaBF4 on graphite anode for Li-ion battery was studied by adding it into the process of slurry preparation with the methods of galvanostatic charge-discharge, CV, EIS, SEM and EDS. The results showed that: when the amount of NaBF4 was 2%, not only the reversible capacity at the initial cycle was improved, but also the efficiency. The performances of self-discharge and the cycle stability were all both improved. And its self-discharge rate calculated by capacity was 0.87%·d-1, reduced15% than it without NaBF4. The results of CV, EDS and SEM tests both suggested that, NaBF4 involved in the process of SEI formation, changing its components and morphology.
The influence of NaBF4 on graphite anode for Li-ion battery was studied by adding it into the process of slurry preparation with the methods of galvanostatic charge-discharge, CV, EIS, SEM and EDS. The results showed that: when the amount of NaBF4 was 2%, not only the reversible capacity at the initial cycle was improved, but also the efficiency. The performances of self-discharge and the cycle stability were all both improved. And its self-discharge rate calculated by capacity was 0.87%·d-1, reduced15% than it without NaBF4. The results of CV, EDS and SEM tests both suggested that, NaBF4 involved in the process of SEI formation, changing its components and morphology.
2013, 29(7): 1414-1418
doi: 10.3969/j.issn.1001-4861.2013.00.212
Abstract:
A new complex, Na3[Na5(dhns)2]·(phen)4·2H2O, was obtained from the self-assembly of disodium 2,7-dihydroxy-naphthalene-3,6-disulfonate (Na2H2dhns) and 1,10-phenanthroline (Phen) in a water-ethanol solution. The compound was characterized by elemental analysis, IR, TGA, and X-ray diffraction single crystal structure analyses. The compound crystallizes in the orthorhombic system, space group Pna21, a=2.829 85(12) nm, b=1.038 99(14) nm, c=2.259 23(13) nm, V=6.642 6(10) nm3, Z=4, Dc=1.573 g·cm-3, R1=0.050 6, wR2=0.124 0, S=1.05. CCDC: 881794.
A new complex, Na3[Na5(dhns)2]·(phen)4·2H2O, was obtained from the self-assembly of disodium 2,7-dihydroxy-naphthalene-3,6-disulfonate (Na2H2dhns) and 1,10-phenanthroline (Phen) in a water-ethanol solution. The compound was characterized by elemental analysis, IR, TGA, and X-ray diffraction single crystal structure analyses. The compound crystallizes in the orthorhombic system, space group Pna21, a=2.829 85(12) nm, b=1.038 99(14) nm, c=2.259 23(13) nm, V=6.642 6(10) nm3, Z=4, Dc=1.573 g·cm-3, R1=0.050 6, wR2=0.124 0, S=1.05. CCDC: 881794.
2013, 29(7): 1419-1427
doi: 10.3969/j.issn.1001-4861.2013.00.172
Abstract:
In order to further promote the photocatalytic activity of polyhedral titanium dioxide with special exposed facets, the core-shell and hollow structured polyhedral titanium dioxide were controllably prepared by a facile hydrothermal method. The structure, morphology and photocatalytic property of core-shell and hollow structured TiO2 were characterized by means of powder X-ray diffraction (XRD), field emission scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV-Vis absorption spectra measurement, respectively. SEM and TEM observations showed that as-resulting two kinds of TiO2 have a tunnel-like hollow, polyhedral shell-layer structure with opened (001)/(001) surface planes. The formation of the two kinds of novel structures might be due to the effect of both complexing and weak acid etching. The photodegradation to Methylene Blue of the as-resulting TiO2 were tested in the presence of peroxide. The results showed that the photocatalytic activity of the resulting two kinds of TiO2 structures could be promoted even higher with the additive of preoxide, which can be ascribed to their large specific surfaces, and the fact that the·OH provided by peroxide can efficiently separate e-/h+ pairs on the surface of titanium dioxide.
In order to further promote the photocatalytic activity of polyhedral titanium dioxide with special exposed facets, the core-shell and hollow structured polyhedral titanium dioxide were controllably prepared by a facile hydrothermal method. The structure, morphology and photocatalytic property of core-shell and hollow structured TiO2 were characterized by means of powder X-ray diffraction (XRD), field emission scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV-Vis absorption spectra measurement, respectively. SEM and TEM observations showed that as-resulting two kinds of TiO2 have a tunnel-like hollow, polyhedral shell-layer structure with opened (001)/(001) surface planes. The formation of the two kinds of novel structures might be due to the effect of both complexing and weak acid etching. The photodegradation to Methylene Blue of the as-resulting TiO2 were tested in the presence of peroxide. The results showed that the photocatalytic activity of the resulting two kinds of TiO2 structures could be promoted even higher with the additive of preoxide, which can be ascribed to their large specific surfaces, and the fact that the·OH provided by peroxide can efficiently separate e-/h+ pairs on the surface of titanium dioxide.
2013, 29(7): 1428-1432
doi: 10.3969/j.issn.1001-4861.2013.00.243
Abstract:
A new nickel(Ⅱ) complex: [Ni(tribentacn)](ClO4)2, (tribentacn=1,4,7-tris-(benzimidazole-2-yl-methyl)-1,4,7-triazacyclononane), has been synthesized and characterized by elemental analysis and IR spectra. The crystal structure of this complex was determined by X-ray diffraction analysis, crystallized in the triclinic system, space group P1, Z=2, a=1.208 01(8) nm, b=1.217 66(8) nm, c=1.281 42(8) nm, α=78.809(3)°, β=77.094(2)°, γ=66.460(3)°, R1=0.078 0. The nickel(Ⅱ) atom is octahedrally coordinated by six nitrogen atoms of three benzimidazoles and 1,4,7-triazacyclononane (tacn). The electrochemical property and interactions with pBR322 DNA of the complex were studied. CCDC: 841482.
A new nickel(Ⅱ) complex: [Ni(tribentacn)](ClO4)2, (tribentacn=1,4,7-tris-(benzimidazole-2-yl-methyl)-1,4,7-triazacyclononane), has been synthesized and characterized by elemental analysis and IR spectra. The crystal structure of this complex was determined by X-ray diffraction analysis, crystallized in the triclinic system, space group P1, Z=2, a=1.208 01(8) nm, b=1.217 66(8) nm, c=1.281 42(8) nm, α=78.809(3)°, β=77.094(2)°, γ=66.460(3)°, R1=0.078 0. The nickel(Ⅱ) atom is octahedrally coordinated by six nitrogen atoms of three benzimidazoles and 1,4,7-triazacyclononane (tacn). The electrochemical property and interactions with pBR322 DNA of the complex were studied. CCDC: 841482.
2013, 29(7): 1433-1441
doi: 10.3969/j.issn.1001-4861.2013.00.234
Abstract:
Reactions of 5-amino-tetrazole (HATz) and 4-pyridinecarboxylic acid (HPyc) with ZnSO4·7H2O or Zn(NO3)2·6H2O under N,N'-dimethylformamide (DMF) solvothermal condition, yielded two new Zn(Ⅱ) coordination polymers of {[(CH3)2NH2]·[Zn(ATz)(SO4)]}n (1) and {[Zn(ATz)(Pyc)]·0.5DMF}n (2), respectively, which have been structurally characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. The results of structural analysis reveal that complex 1 possesses an 2D undulated layer structure, in which 2D anion (4,4) layer of [Zn(ATz)(SO4)]nn-and [(CH3)2NH2]+ cations are assembled together via strong hydrogen bonding interactions. A remarkable feature of complex 2 is a two-fold interpenetrating 3D microporous metal-organic framework with 4-connected diamondoid topology, in which free DMF molecules locate in the channels. Luminescent properties studies indicate that complexes 1 and 2 exhibit intense fluorescent emissions at λmax=445 nm and 458 nm when excited at 350 nm, respectively, in the solid state at room temperature. CCDC: 921342, 1; 921343, 2.
Reactions of 5-amino-tetrazole (HATz) and 4-pyridinecarboxylic acid (HPyc) with ZnSO4·7H2O or Zn(NO3)2·6H2O under N,N'-dimethylformamide (DMF) solvothermal condition, yielded two new Zn(Ⅱ) coordination polymers of {[(CH3)2NH2]·[Zn(ATz)(SO4)]}n (1) and {[Zn(ATz)(Pyc)]·0.5DMF}n (2), respectively, which have been structurally characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. The results of structural analysis reveal that complex 1 possesses an 2D undulated layer structure, in which 2D anion (4,4) layer of [Zn(ATz)(SO4)]nn-and [(CH3)2NH2]+ cations are assembled together via strong hydrogen bonding interactions. A remarkable feature of complex 2 is a two-fold interpenetrating 3D microporous metal-organic framework with 4-connected diamondoid topology, in which free DMF molecules locate in the channels. Luminescent properties studies indicate that complexes 1 and 2 exhibit intense fluorescent emissions at λmax=445 nm and 458 nm when excited at 350 nm, respectively, in the solid state at room temperature. CCDC: 921342, 1; 921343, 2.
2013, 29(7): 1442-1446
doi: 10.3969/j.issn.1001-4861.2013.00.206
Abstract:
Dibenzyl tin complex with salicylidene-2-aminophenol was synthesised by the reaction of dibenzyl tin dichloride with salicylidene-2-aminophenol Schiff Bases. The crystal structures have been determined by X-ray diffraction. It belongs to monoclinic system, space group P21/n with a=1.110 03(3) nm, b=1.719 87(5) nm, c=1.176 09(3) nm, β=100.564 0(10)°, V=2.207 23(10) nm3, Z=4, Dc=1.541 g·cm-3, μ(Mo Kα)=11.81 cm-1,F(000)= 1 023, R1=0.026 8, wR2=0.061 9. The tin atom is rendered five-coordination in a distorted tigonal bipyram idal-structure. The study on the title complex has been performed with quantum chemistry calculation. The stabilities, the orbital energies and composition characteristics of some frontier molecular orbitals of the complex have been investigated. The photoluminescent property of complexes was investigated. CCDC: 934721.
Dibenzyl tin complex with salicylidene-2-aminophenol was synthesised by the reaction of dibenzyl tin dichloride with salicylidene-2-aminophenol Schiff Bases. The crystal structures have been determined by X-ray diffraction. It belongs to monoclinic system, space group P21/n with a=1.110 03(3) nm, b=1.719 87(5) nm, c=1.176 09(3) nm, β=100.564 0(10)°, V=2.207 23(10) nm3, Z=4, Dc=1.541 g·cm-3, μ(Mo Kα)=11.81 cm-1,F(000)= 1 023, R1=0.026 8, wR2=0.061 9. The tin atom is rendered five-coordination in a distorted tigonal bipyram idal-structure. The study on the title complex has been performed with quantum chemistry calculation. The stabilities, the orbital energies and composition characteristics of some frontier molecular orbitals of the complex have been investigated. The photoluminescent property of complexes was investigated. CCDC: 934721.
2013, 29(7): 1447-1453
doi: 10.3969/j.issn.1001-4861.2013.00.240
Abstract:
Two Schiff Bases (L1 and L2) and their palladium complexes (1 and 2) were prepared by the condensation of 2,6-diisopropylaniline with benzaldehyde and 2,4-dichlorobenzaldehyde, respectively, and characterized by elemental analysis, IR-spectroscopy and single crystal X-ray diffraction. Compared with known structures of Schiff base (L1) and its palladium complex (1), we discovered that the introduction of electro-withdrawing groups of L2 and complex 2 have effects on antimicrobial and catalytic activities. The antimicrobial activities results indicated that the ligands and their complexes perform good activities, and the complexes have better effect than the ligands, and the electro-withdrawing groups will effectively improve the activities. The Heck reactions of bromobenzene with acrylic acid catalyzed by complex 1 and 2 have also been studied. We have investigated the effect of different factors (bases, temperature and solvent) on reaction and finally determined the optimum reaction condition. The catalytic activities results shown that the electro-withdrawing groups of ligands will increase the steric effect of 1 and 2, and reducing their activities. CCDC: 882286,L1; 882287, 2; 222403, 1; 882289, 2.
Two Schiff Bases (L1 and L2) and their palladium complexes (1 and 2) were prepared by the condensation of 2,6-diisopropylaniline with benzaldehyde and 2,4-dichlorobenzaldehyde, respectively, and characterized by elemental analysis, IR-spectroscopy and single crystal X-ray diffraction. Compared with known structures of Schiff base (L1) and its palladium complex (1), we discovered that the introduction of electro-withdrawing groups of L2 and complex 2 have effects on antimicrobial and catalytic activities. The antimicrobial activities results indicated that the ligands and their complexes perform good activities, and the complexes have better effect than the ligands, and the electro-withdrawing groups will effectively improve the activities. The Heck reactions of bromobenzene with acrylic acid catalyzed by complex 1 and 2 have also been studied. We have investigated the effect of different factors (bases, temperature and solvent) on reaction and finally determined the optimum reaction condition. The catalytic activities results shown that the electro-withdrawing groups of ligands will increase the steric effect of 1 and 2, and reducing their activities. CCDC: 882286,L1; 882287, 2; 222403, 1; 882289, 2.
2013, 29(7): 1454-1458
doi: 10.3969/j.issn.1001-4861.2013.00.203
Abstract:
A 1D ribbon-like structure coordination polymer of [Co(DMPhTPY)V2O6]n (DMPhTPY=6,6"-dimethyl-4'-phenyl-2,2':6',2"-terpyridine)was synthesized under the hydrothermal condition. The structure was characterized by elemental analysis, IR and X-ray single crystal diffraction. The crystal structure of the complex belongs to triclinic system, space group P1. Thermal stability, photoluminescence property and magnetic susceptibility of the complex have been investigated. The results show that the title complex has high thermal stability and antiferromagnetic exchange interaction between the Co(Ⅱ) ions. CCDC: 880007.
A 1D ribbon-like structure coordination polymer of [Co(DMPhTPY)V2O6]n (DMPhTPY=6,6"-dimethyl-4'-phenyl-2,2':6',2"-terpyridine)was synthesized under the hydrothermal condition. The structure was characterized by elemental analysis, IR and X-ray single crystal diffraction. The crystal structure of the complex belongs to triclinic system, space group P1. Thermal stability, photoluminescence property and magnetic susceptibility of the complex have been investigated. The results show that the title complex has high thermal stability and antiferromagnetic exchange interaction between the Co(Ⅱ) ions. CCDC: 880007.
2013, 29(7): 1459-1464
doi: 10.3969/j.issn.1001-4861.2013.00.255
Abstract:
In this paper, a novel Mn-Ce mixed-metal complex [Mn3Ce2(O)5(O2CPh)9(CH3OH)3]·2CH3CN (1·2CH3CN, HO2CPh is benzoic acid) has been synthesized using the synthetic method of oxidation Mn2+ ions by (NH4)2Ce(NO3)6. The obtained complex were fully characterized by X-ray single crystal structural diffraction, IR, elemental analysis, and magnetic investigation. The structure analysis indicates that the complex crystallizes in triclinic system, P1 space group. In the complex, two Mn4+ ions, two Ce4+ ions and four bridging μ3-O atoms comprise an irregular cubane which is further linked to the other Mn3+ ion by another μ3-O atom. There are no hydrogen bonds but slightly strong π-π stacking interactions between clusters in the crystal cell. Magnetic investigation shows that weak ferromagnetic interactions between Mn ions are present within the cluster, and the values of the spin ground state S and magnetic anisotropy are 5 and-0.31 cm-1, respectively. The complex do not possess frequency-dependent on alternating-current magnetic susceptibilities. CCDC: 912993.
In this paper, a novel Mn-Ce mixed-metal complex [Mn3Ce2(O)5(O2CPh)9(CH3OH)3]·2CH3CN (1·2CH3CN, HO2CPh is benzoic acid) has been synthesized using the synthetic method of oxidation Mn2+ ions by (NH4)2Ce(NO3)6. The obtained complex were fully characterized by X-ray single crystal structural diffraction, IR, elemental analysis, and magnetic investigation. The structure analysis indicates that the complex crystallizes in triclinic system, P1 space group. In the complex, two Mn4+ ions, two Ce4+ ions and four bridging μ3-O atoms comprise an irregular cubane which is further linked to the other Mn3+ ion by another μ3-O atom. There are no hydrogen bonds but slightly strong π-π stacking interactions between clusters in the crystal cell. Magnetic investigation shows that weak ferromagnetic interactions between Mn ions are present within the cluster, and the values of the spin ground state S and magnetic anisotropy are 5 and-0.31 cm-1, respectively. The complex do not possess frequency-dependent on alternating-current magnetic susceptibilities. CCDC: 912993.
2013, 29(7): 1465-1470
doi: 10.3969/j.issn.1001-4861.2013.00.232
Abstract:
Li4Ti5O12/graphene nanocomposite was synthesized using thermally exfoliated graphene with a three-dimensional continuous nanoporous structure as the matrix. The precursors were introduced into the interior nanopores of thermally exfoliated graphene by the ethanol evaporation method. After heat treatment, Li4Ti5O12 nanoparticles were formed in situ in the nanopores of thermally exfoliated graphene. As an anode material for lithium-ion batteries, the three-dimensional continuous structure of thermally exfoliated graphene ensures sufficient contact between Li4Ti5O12 and graphene during the long cycling. Consequently, the nanocomposite shows superior cyclic stability. The capacity retention is still as high as 94% after 5 000 cycles at 5C.
Li4Ti5O12/graphene nanocomposite was synthesized using thermally exfoliated graphene with a three-dimensional continuous nanoporous structure as the matrix. The precursors were introduced into the interior nanopores of thermally exfoliated graphene by the ethanol evaporation method. After heat treatment, Li4Ti5O12 nanoparticles were formed in situ in the nanopores of thermally exfoliated graphene. As an anode material for lithium-ion batteries, the three-dimensional continuous structure of thermally exfoliated graphene ensures sufficient contact between Li4Ti5O12 and graphene during the long cycling. Consequently, the nanocomposite shows superior cyclic stability. The capacity retention is still as high as 94% after 5 000 cycles at 5C.
2013, 29(7): 1471-1479
doi: 10.3969/j.issn.1001-4861.2013.00.200
Abstract:
The synthesis, crystal structure, and sorption properties of [Cu2(EBTC)(H2O)2]·8H2O·DMF·DMSO (abbreviated as 1, EBTC=1,1'-ethynebenzene-3,3',5,5'-tetracarboxylate; DMF=N,N-dimethyl formamide; DMSO=dimethyl sulfoxide) are reported. 1 features two kinds of cavities with a diameter of 0.85 nm and 0.85×2.15 nm, which are enclosed respectively by six and twelve tetracarboxylate-bridged [Cu2(CO2)4] paddle-wheels and extended by the EBTC linkers into a three-dimensional (3D) supramolecular structure with 1D channels accommodating the solvent molecules. It adopts the (3,4)-c net of fof (sqc 1575) topology, possesses very large solvent accessible pore volume which reaches 72.8% of the unit cell volume. After removal of the solvent molecules, the desolvated 1a exhibits permanent porosity verified by an N2 sorption isotherm with a Langmuir surface area of 2844 m2·g-1 and Brunauer-Emmett-Teller (BET) surface area of 1 852 m2·g-1. It displays significant uptake of gases (H2, CO2, CH4, C2H2) and relatively high adsorption enthalpies. Especially, it is notable that 1a exhibits the highest acetylene storage of 252 cm3·g-1 at 273 K under 1.0×105 Pa with higher adsorption enthalpy (34.5 kJ·mol-1 at the coverage of 1 mmol·g-1) among all porous metal-organic materials reported to date. CCDC: 744108.
The synthesis, crystal structure, and sorption properties of [Cu2(EBTC)(H2O)2]·8H2O·DMF·DMSO (abbreviated as 1, EBTC=1,1'-ethynebenzene-3,3',5,5'-tetracarboxylate; DMF=N,N-dimethyl formamide; DMSO=dimethyl sulfoxide) are reported. 1 features two kinds of cavities with a diameter of 0.85 nm and 0.85×2.15 nm, which are enclosed respectively by six and twelve tetracarboxylate-bridged [Cu2(CO2)4] paddle-wheels and extended by the EBTC linkers into a three-dimensional (3D) supramolecular structure with 1D channels accommodating the solvent molecules. It adopts the (3,4)-c net of fof (sqc 1575) topology, possesses very large solvent accessible pore volume which reaches 72.8% of the unit cell volume. After removal of the solvent molecules, the desolvated 1a exhibits permanent porosity verified by an N2 sorption isotherm with a Langmuir surface area of 2844 m2·g-1 and Brunauer-Emmett-Teller (BET) surface area of 1 852 m2·g-1. It displays significant uptake of gases (H2, CO2, CH4, C2H2) and relatively high adsorption enthalpies. Especially, it is notable that 1a exhibits the highest acetylene storage of 252 cm3·g-1 at 273 K under 1.0×105 Pa with higher adsorption enthalpy (34.5 kJ·mol-1 at the coverage of 1 mmol·g-1) among all porous metal-organic materials reported to date. CCDC: 744108.
2013, 29(7): 1480-1484
doi: 10.3969/j.issn.1001-4861.2013.00.223
Abstract:
Under hydrothermal conditions, NdCl3·6H2O reacts with 3-H2CPOA (3-H2CPOA=3-carboxyphenoxyace-tatic acid) and phen (phen=1,10-phenanthroline), producing a novel coordination polymer [Nd(3-CPOA)1.5(phen)]n (1). Complex 1 crystallizes in monoclinic space group P21/c, with a=0.982 7(8),b=1.140 6(10), c=2.115 8(19) nm, β=90.574(9)°, V=2.371(4) nm3, and Z=4. X-ray diffraction studies show that complex 1 possesses a three-dimensional framework structure based on a binuclear unit. Magnetic studies for complex 1 indicate the presence of stronger antiferromagnetic coupling between the adjacent Nd(Ⅲ) ions. CCDC: 888765.
Under hydrothermal conditions, NdCl3·6H2O reacts with 3-H2CPOA (3-H2CPOA=3-carboxyphenoxyace-tatic acid) and phen (phen=1,10-phenanthroline), producing a novel coordination polymer [Nd(3-CPOA)1.5(phen)]n (1). Complex 1 crystallizes in monoclinic space group P21/c, with a=0.982 7(8),b=1.140 6(10), c=2.115 8(19) nm, β=90.574(9)°, V=2.371(4) nm3, and Z=4. X-ray diffraction studies show that complex 1 possesses a three-dimensional framework structure based on a binuclear unit. Magnetic studies for complex 1 indicate the presence of stronger antiferromagnetic coupling between the adjacent Nd(Ⅲ) ions. CCDC: 888765.
2013, 29(7): 1485-1489
doi: 10.3969/j.issn.1001-4861.2013.00.217
Abstract:
A tetracyanonickelate-nickel complex {[Ni(i-Pr3TACN)][Ni(CN)4]}2·2H2O (1) has been synthesized by self-assembly using K2[Ni(CN)4] and [NiPr3TACN]Cl2, (i-Pr3TACN=1,4, 7-Triisopropyl-1,4,7-Triazacyclononane). The X-ray character shows there is a discrete tetramer water clusters in 1. Within the cluster, the four water molecules are fully coplanar and each water monomer acts as both single hydrogen bond donor and acceptor. The magnetic susceptibility shows an antiferromagnetic interaction between the Ni(Ⅱ) ions and the J values is -1.09 cm-1. CCDC: 727702.
A tetracyanonickelate-nickel complex {[Ni(i-Pr3TACN)][Ni(CN)4]}2·2H2O (1) has been synthesized by self-assembly using K2[Ni(CN)4] and [NiPr3TACN]Cl2, (i-Pr3TACN=1,4, 7-Triisopropyl-1,4,7-Triazacyclononane). The X-ray character shows there is a discrete tetramer water clusters in 1. Within the cluster, the four water molecules are fully coplanar and each water monomer acts as both single hydrogen bond donor and acceptor. The magnetic susceptibility shows an antiferromagnetic interaction between the Ni(Ⅱ) ions and the J values is -1.09 cm-1. CCDC: 727702.
2013, 29(7): 1490-1496
doi: 10.3969/j.issn.1001-4861.2013.00.236
Abstract:
fac-Tris(2-(4-trifluoromethylphenyl)pyridine)iridium (Ir(tfmppy)3) was prepared by conventional method and its crystal structure was determined. Excitation at either π→π* or MLCT absorption band of Ir(tfmppy)3 in CH2Cl2 solution leads to the same MLCT emission maxima at 525 nm with Commission Internationale de L'Eclairage (CIE) coordinates of (0.31, 0.62) and the emission quantum yield is 4.59% in CH2Cl2 (by reference to an aerated aqueous solution of [Ru(bpy)3]Cl2 as the standard solution). Organic light-emitting diodes (OLEDs) based on the green electrophosphorescent complex in ITO/TAPC (1,1-bis [4-[N,N-di(p-tolyl)amino]phenyl]cyclohexane, 60 nm)/Ir(tfmppy)3 (x%):mCP (1,3-bis (carbazol-9-yl)benzene, 30 nm)/TPBi (2,2',2"-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole, 60 nm)/LiF (1 nm)/Al (100 nm) were investigated. The device with 4% dopant concentration shows a maximum current efficiency of 33.95 cd·A-1 at 4 197 cd·m-2, a maximum brightness of 43 612 cd·m-2 at 12.7 V, and CIE coordinates of (0.31, 0.61). The device with 6% dopant concentration exhibits a maximum power efficiency of 27.29 cd·A-1 at 1 981 cd·m-2, a maximum brightness of 33 071 cd·m-2 at 9.6 V. The electron mobility of Ir(tfmppy)3 is 4.24×10-6 cm2·(V·s)-1 under electric field of 1 300 (V·cm-1)1/2 via transient electroluminescence (TEL) method, which is close to that of Alq3 (tri(8-hydroxyquinoline)aluminum) emitter. CCDC: 887658.
fac-Tris(2-(4-trifluoromethylphenyl)pyridine)iridium (Ir(tfmppy)3) was prepared by conventional method and its crystal structure was determined. Excitation at either π→π* or MLCT absorption band of Ir(tfmppy)3 in CH2Cl2 solution leads to the same MLCT emission maxima at 525 nm with Commission Internationale de L'Eclairage (CIE) coordinates of (0.31, 0.62) and the emission quantum yield is 4.59% in CH2Cl2 (by reference to an aerated aqueous solution of [Ru(bpy)3]Cl2 as the standard solution). Organic light-emitting diodes (OLEDs) based on the green electrophosphorescent complex in ITO/TAPC (1,1-bis [4-[N,N-di(p-tolyl)amino]phenyl]cyclohexane, 60 nm)/Ir(tfmppy)3 (x%):mCP (1,3-bis (carbazol-9-yl)benzene, 30 nm)/TPBi (2,2',2"-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole, 60 nm)/LiF (1 nm)/Al (100 nm) were investigated. The device with 4% dopant concentration shows a maximum current efficiency of 33.95 cd·A-1 at 4 197 cd·m-2, a maximum brightness of 43 612 cd·m-2 at 12.7 V, and CIE coordinates of (0.31, 0.61). The device with 6% dopant concentration exhibits a maximum power efficiency of 27.29 cd·A-1 at 1 981 cd·m-2, a maximum brightness of 33 071 cd·m-2 at 9.6 V. The electron mobility of Ir(tfmppy)3 is 4.24×10-6 cm2·(V·s)-1 under electric field of 1 300 (V·cm-1)1/2 via transient electroluminescence (TEL) method, which is close to that of Alq3 (tri(8-hydroxyquinoline)aluminum) emitter. CCDC: 887658.
Synthesis, Structure and Properties of Sm(Ⅲ) and Dy(Ⅲ) Complexes with Pyridine-2,5-dicarboxylic Acid
2013, 29(7): 1497-1503
doi: 10.3969/j.issn.1001-4861.2013.00.214
Abstract:
Two new Lanthanide complexes [Ln(pydc)2(H2O)5]·4H2O (Ln=Sm (1), Dy (2)) were obtained by the hydrothennal reactions of Ln(NO3)3·6H2O, pyridine-2,5-dicarboxylic acid (H2pydc) with 1:1 mole ratio. Single-crystal X-ray diffraction analysis reveals that both the crystals belong to monoclinic,space group C2/c. The structure and property of complexes have been characterized by elemental analysis, thermal analyses, IR spectra and Fluorescence. The single crystal structures show that the two complexes are isomorphic and have zero-dimensional structures and hydrogen bonds result in three-dimensional supramolecular structures. the coordination number of central ion Ln(Ⅲ) is nine. The complex 1 and 2 exhibit intense luminescence in the liquid state at room temperature. CCDC: 869044, 1; 874032, 2.
Two new Lanthanide complexes [Ln(pydc)2(H2O)5]·4H2O (Ln=Sm (1), Dy (2)) were obtained by the hydrothennal reactions of Ln(NO3)3·6H2O, pyridine-2,5-dicarboxylic acid (H2pydc) with 1:1 mole ratio. Single-crystal X-ray diffraction analysis reveals that both the crystals belong to monoclinic,space group C2/c. The structure and property of complexes have been characterized by elemental analysis, thermal analyses, IR spectra and Fluorescence. The single crystal structures show that the two complexes are isomorphic and have zero-dimensional structures and hydrogen bonds result in three-dimensional supramolecular structures. the coordination number of central ion Ln(Ⅲ) is nine. The complex 1 and 2 exhibit intense luminescence in the liquid state at room temperature. CCDC: 869044, 1; 874032, 2.
2013, 29(7): 1504-1512
doi: 10.3969/j.issn.1001-4861.2013.00.215
Abstract:
The new monomeric complexes of [M(MPA)2(H2O)2] (1: M=Co; 2: M=Ni) (HMPA=5-methyl-1H-pyrazole-3-carboxylic acid) were synthesized by the reaction of 5-methyl-1H-pyrazole-3-carboxylic acid with CoCl2·6H2O and Ni(NO3)2·6H2O, respectively. The compounds were characterized by elemental analysis, IR spectra, single crystal X-ray diffraction. The structural parameters of 1 and 2 were analyzed as follows: 1, Hexagonal, R3c, a=1.48394(4) nm, b=1.483 94(4) nm, c=3.207 66(6) nm, V=6.1172(3) nm3, Z=18; 2, Hexagonal, R3c, a=1.466 53(14) nm, b= 1.466 53(14) nm, c=3.243 0(6) nm, V=6.040 3(14) nm3, Z=18. Metal ions have all octahedral geometry coordinated by two nitrogen atoms and two oxygen atoms from two MPA-ligands, two oxygen atoms from two H2O molecules. In both complexes, the independent components [M(MPA)2(H2O)2] are connected by intermolecular hydrogen bonds to form a three-dimensional architecture with hexagonal channels. Thermogravimetric analyses show that 1 and 2 have higher thermal stability. In addition, the luminescent properties and electrochemical properties of complexes 1 and 2 have also been investigated. CCDC: 900677, 1; 900678, 2.
The new monomeric complexes of [M(MPA)2(H2O)2] (1: M=Co; 2: M=Ni) (HMPA=5-methyl-1H-pyrazole-3-carboxylic acid) were synthesized by the reaction of 5-methyl-1H-pyrazole-3-carboxylic acid with CoCl2·6H2O and Ni(NO3)2·6H2O, respectively. The compounds were characterized by elemental analysis, IR spectra, single crystal X-ray diffraction. The structural parameters of 1 and 2 were analyzed as follows: 1, Hexagonal, R3c, a=1.48394(4) nm, b=1.483 94(4) nm, c=3.207 66(6) nm, V=6.1172(3) nm3, Z=18; 2, Hexagonal, R3c, a=1.466 53(14) nm, b= 1.466 53(14) nm, c=3.243 0(6) nm, V=6.040 3(14) nm3, Z=18. Metal ions have all octahedral geometry coordinated by two nitrogen atoms and two oxygen atoms from two MPA-ligands, two oxygen atoms from two H2O molecules. In both complexes, the independent components [M(MPA)2(H2O)2] are connected by intermolecular hydrogen bonds to form a three-dimensional architecture with hexagonal channels. Thermogravimetric analyses show that 1 and 2 have higher thermal stability. In addition, the luminescent properties and electrochemical properties of complexes 1 and 2 have also been investigated. CCDC: 900677, 1; 900678, 2.
2013, 29(7): 1513-1520
doi: 10.3969/j.issn.1001-4861.2013.00.192
Abstract:
The complexation of α,α',δ,δ'-tetramethylcucurbit[6]uril (TMeQ[6]) complexes with transition-metal ions was studied by differential pulse voltammetry (DPV). The results reveal that this water-soluble cage-type compound shows very high selectivity for Pb2+ and Cd2+, while it is a masking compound for other transition-metal ions, particularly for Fe3+, Co2+, Zn2+, and Cr3+, due to a sharp decrease in the DPV peak current of these metal ions in the presence of TMeQ[6]. Binding constants were determined from voltammetric data. The Pb2+ and Cd2+ cations display a high binding affinity for TMeQ[6] (KPb2+=2.12×109 L2·mol-2, KCd2+=2.10×109 L2·mol-2) and form 2:1 nM2+/nTMeQ[6] complexes. The crystal structure of TMeQ[6]-Pb2+ indicates a 2:1 (nM2+/nTMeQ[6]) complex in the solid state, which is consistent with the results in solution. CCDC: 723280.
The complexation of α,α',δ,δ'-tetramethylcucurbit[6]uril (TMeQ[6]) complexes with transition-metal ions was studied by differential pulse voltammetry (DPV). The results reveal that this water-soluble cage-type compound shows very high selectivity for Pb2+ and Cd2+, while it is a masking compound for other transition-metal ions, particularly for Fe3+, Co2+, Zn2+, and Cr3+, due to a sharp decrease in the DPV peak current of these metal ions in the presence of TMeQ[6]. Binding constants were determined from voltammetric data. The Pb2+ and Cd2+ cations display a high binding affinity for TMeQ[6] (KPb2+=2.12×109 L2·mol-2, KCd2+=2.10×109 L2·mol-2) and form 2:1 nM2+/nTMeQ[6] complexes. The crystal structure of TMeQ[6]-Pb2+ indicates a 2:1 (nM2+/nTMeQ[6]) complex in the solid state, which is consistent with the results in solution. CCDC: 723280.
2013, 29(7): 1521-1526
doi: 10.3969/j.issn.1001-4861.2013.00.235
Abstract:
Two new V(V) complexes, [VOL1(C2H5O)]2(1) (H2L1=2-hydroxyacetophenone salicyloylhydrazone) and [VOL2(i-C3H7O)](2) (H2L2=salicylaldehyde salicyloylhydrazone) have been synthesized and characterized by elemental analysis, IR, UV and X-Ray diffraction. Complex 1 reveals a centrosymmetric dimer, in which the two vanadium centers are bridged by phenolic oxygen atoms. Each vanadium(V) in 1 exhibits a slightly distorted octahedral geometry. While complex 2 is a mononuclear structure, in which vanadium(V) has a distorted square-pyramidal geometry. Complex 2 forms an infinite 1D chain-like supramolecular structure by intermolecular hydrogen bonds. The electrochemical property for complex 2 was studied with an electrochemical analyzer. CCDC: 889674, 1; 889675, 2.
Two new V(V) complexes, [VOL1(C2H5O)]2(1) (H2L1=2-hydroxyacetophenone salicyloylhydrazone) and [VOL2(i-C3H7O)](2) (H2L2=salicylaldehyde salicyloylhydrazone) have been synthesized and characterized by elemental analysis, IR, UV and X-Ray diffraction. Complex 1 reveals a centrosymmetric dimer, in which the two vanadium centers are bridged by phenolic oxygen atoms. Each vanadium(V) in 1 exhibits a slightly distorted octahedral geometry. While complex 2 is a mononuclear structure, in which vanadium(V) has a distorted square-pyramidal geometry. Complex 2 forms an infinite 1D chain-like supramolecular structure by intermolecular hydrogen bonds. The electrochemical property for complex 2 was studied with an electrochemical analyzer. CCDC: 889674, 1; 889675, 2.
2013, 29(7): 1527-1532
doi: 10.3969/j.issn.1001-4861.2013.00.209
Abstract:
The self-assembly of 4-(1H-Imidazol-1-yl)benzoic acid and CdCl2 under hydrothermal condition gave a new 1D cadmium coordination polymer, [Cd(imbz)(Cl)(H2O)]n (1) (imbz=4-(1H-Imidazol-1-yl)benzoate), which has been characterized by elemental analysis, IR, TGA and single-crystal X-ray diffraction. The imbz ligands link the Cd(Ⅱ) ions to form an infinite 1D zigzag chain, which the neighboring zigzag chains are further connected into a ladder chain through μ2-Cl ligands. The photoluminescence and lifetime of complex 1 in the solid state at room temperature have been studied. CCDC: 890931.
The self-assembly of 4-(1H-Imidazol-1-yl)benzoic acid and CdCl2 under hydrothermal condition gave a new 1D cadmium coordination polymer, [Cd(imbz)(Cl)(H2O)]n (1) (imbz=4-(1H-Imidazol-1-yl)benzoate), which has been characterized by elemental analysis, IR, TGA and single-crystal X-ray diffraction. The imbz ligands link the Cd(Ⅱ) ions to form an infinite 1D zigzag chain, which the neighboring zigzag chains are further connected into a ladder chain through μ2-Cl ligands. The photoluminescence and lifetime of complex 1 in the solid state at room temperature have been studied. CCDC: 890931.
2013, 29(7): 1533-1538
doi: 10.3969/j.issn.1001-4861.2013.00.207
Abstract:
Two complexes constructed with 2,4'-biphenyldicarboxylic acid (2,4'-H2bpdc), 1,10-phenanthroline derivative ligands and metallic salts, namely, {[Co(2,4'-bpdc)(L)(H2O)]·H2O}n (1), [Mn(2,4'-bpdc)(L)(H2O)]n (2) (L=imidazo[4,5-f][1,10]phenanthroline) were synthesized under hydrothermal reaction. The complexes are characterized by elemental analysis, single crystal X-ray diffraction and thermogravimetric analysis. Complex 1 has a 1D chain structure. Complex 2 forms a one-dimensional double-chain structure. They both further linked into a three-dimensional net structure via the intermolecular hydrogen bonds and aromatic π-π interactions. CCDC: 934719, 1; 934720,2.
Two complexes constructed with 2,4'-biphenyldicarboxylic acid (2,4'-H2bpdc), 1,10-phenanthroline derivative ligands and metallic salts, namely, {[Co(2,4'-bpdc)(L)(H2O)]·H2O}n (1), [Mn(2,4'-bpdc)(L)(H2O)]n (2) (L=imidazo[4,5-f][1,10]phenanthroline) were synthesized under hydrothermal reaction. The complexes are characterized by elemental analysis, single crystal X-ray diffraction and thermogravimetric analysis. Complex 1 has a 1D chain structure. Complex 2 forms a one-dimensional double-chain structure. They both further linked into a three-dimensional net structure via the intermolecular hydrogen bonds and aromatic π-π interactions. CCDC: 934719, 1; 934720,2.
2013, 29(7): 1539-1544
doi: 10.3969/j.issn.1001-4861.2013.00.257
Abstract:
A novel homochiral metal-organic framework is successfully constructed by an achiral ligand and 1D helical CuCN chains: [Cu4(CN)4(L)2]n (L=tetrakis(3-pyridyloxymethylene)methane) (1); the helixes assembled by copper(Ⅰ) and CN groups in situ generated are left-handed and transform the framework to chiral. This is the first example of chiral MOFs induced by flexible conformation of semigrid tetrahedral ligand. In addition, the chiral property of bulk products is confirmed by VCD spectra, the thermal stability and dielectric properties are also investigated. CCDC: 921046.
A novel homochiral metal-organic framework is successfully constructed by an achiral ligand and 1D helical CuCN chains: [Cu4(CN)4(L)2]n (L=tetrakis(3-pyridyloxymethylene)methane) (1); the helixes assembled by copper(Ⅰ) and CN groups in situ generated are left-handed and transform the framework to chiral. This is the first example of chiral MOFs induced by flexible conformation of semigrid tetrahedral ligand. In addition, the chiral property of bulk products is confirmed by VCD spectra, the thermal stability and dielectric properties are also investigated. CCDC: 921046.
2013, 29(7): 1545-1550
doi: 10.3969/j.issn.1001-4861.2013.00.253
Abstract:
Bi2Ti2O7 thin films were prepared on the functionalized octadecyl-trichloro-silane (OTS)-covered fluorine-doped SnO2 (FTO) substrates by self-assembled monolayer (SAM) technique using Bi(NO3)3·5H2O and Ti(OC4H9)4 as raw materials. The test of the hydrophilicity of the substrate surface indicates that UV irradiation turns the surface of OTS-SAM film from hydrophobicity to hydrophilicity and realizes the functionalization. The composition, microstructure and microtopography of Bi2Ti2O7 thin films were characterized by X-ray Diffraction (XRD), Energy Dispersive X-ray Spectrometry (EDS), Scanning Electron Microscopy (SEM) and Atomic Force Microscope (AFM). The results indicate that the as-prepared Bi2Ti2O7 thin films are homogeneous and dense when the concentration of the deposited solution is 0.02 mol·L-1. The dielectric constant is 153 at 100 kHz and the dielectric loss is 0.089 for a 0.4 μm-thick film annealed at 560 ℃ for 1 h.
Bi2Ti2O7 thin films were prepared on the functionalized octadecyl-trichloro-silane (OTS)-covered fluorine-doped SnO2 (FTO) substrates by self-assembled monolayer (SAM) technique using Bi(NO3)3·5H2O and Ti(OC4H9)4 as raw materials. The test of the hydrophilicity of the substrate surface indicates that UV irradiation turns the surface of OTS-SAM film from hydrophobicity to hydrophilicity and realizes the functionalization. The composition, microstructure and microtopography of Bi2Ti2O7 thin films were characterized by X-ray Diffraction (XRD), Energy Dispersive X-ray Spectrometry (EDS), Scanning Electron Microscopy (SEM) and Atomic Force Microscope (AFM). The results indicate that the as-prepared Bi2Ti2O7 thin films are homogeneous and dense when the concentration of the deposited solution is 0.02 mol·L-1. The dielectric constant is 153 at 100 kHz and the dielectric loss is 0.089 for a 0.4 μm-thick film annealed at 560 ℃ for 1 h.
2013, 29(7): 1551-1556
doi: 10.3969/j.issn.1001-4861.2013.00.216
Abstract:
A binuclear Pb(Ⅱ) complex [Pb2(CA)4(Medpq)2] (HCA=cinnamic acid, Medpq=2-methyldipyrido[3,2-f:2,3'-h]quinoxaline) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, UV-Vis spectrum, TG, fluorescent emission, single-crystal X-ray diffraction and theoretical calculations. Title compound crystallizes in triclinic, space group P1 with a=0.854 35(17) nm, b=1.250 9(3) nm, c=1.436 6(3) nm, α=107.45(3)°, β=105.63(3)°, γ=97.04(3)°. In the crystal structure, the lead atom is seven-coordinated with two nitrogen atoms from Medpq ligand and five oxygen atoms from three cinnamic acid ligands. Natural bond orbital (NBO) analysis was performed by using the NBO method built in Gaussian 03 Program. The calculation results shown an covalent interaction between the coordinated atoms and Pb(Ⅱ) ion. CCDC: 859036.
A binuclear Pb(Ⅱ) complex [Pb2(CA)4(Medpq)2] (HCA=cinnamic acid, Medpq=2-methyldipyrido[3,2-f:2,3'-h]quinoxaline) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, UV-Vis spectrum, TG, fluorescent emission, single-crystal X-ray diffraction and theoretical calculations. Title compound crystallizes in triclinic, space group P1 with a=0.854 35(17) nm, b=1.250 9(3) nm, c=1.436 6(3) nm, α=107.45(3)°, β=105.63(3)°, γ=97.04(3)°. In the crystal structure, the lead atom is seven-coordinated with two nitrogen atoms from Medpq ligand and five oxygen atoms from three cinnamic acid ligands. Natural bond orbital (NBO) analysis was performed by using the NBO method built in Gaussian 03 Program. The calculation results shown an covalent interaction between the coordinated atoms and Pb(Ⅱ) ion. CCDC: 859036.
2013, 29(7): 1557-1562
doi: 10.3969/j.issn.1001-4861.2013.00.211
Abstract:
Two cerium(Ⅳ) complexes [Ce(dipic)3]·(H2bipy)·4H2O (1) and [Ce(dipic)3]·(H2bpa)·3.5H2O (2) (2,6-H2dipic=2,6-pyridinedicarboxylic acid, bipy=4,4'-bipyridine, bpa=Bis(4-pyridyl)amine) have been hydrothermally synthesized and structurally characterized via elemental analysis, IR spectra, TG and single-crystal X-ray diffraction. Both complexes crystallize in triclinic, space group P1 with a=1.014 32(11) nm, b=1.253 64(13) nm, c=1.448 89(14) nm, V=1.662 77(6) nm3, Z=2, R1=0.064 1, wR2=0.149 4 for 1, and a=1.039 30(5) nm, b=1.604 02(8) nm, c=2.021 65(10) nm, V=3.304 5(3) nm3, Z=2, R1=0.039 8 and wR2=0.104 9 for 2. The central metal Ce(Ⅳ) ions of both complexes are surrounded by three wholly unprotonated dipicolinate groups in the usual tridentate mode. Thermogravimetric analysis shows that the two complexes are stable up to 64 and 50℃, respectively. CCDC: 856834, 1; 856608, 2.
Two cerium(Ⅳ) complexes [Ce(dipic)3]·(H2bipy)·4H2O (1) and [Ce(dipic)3]·(H2bpa)·3.5H2O (2) (2,6-H2dipic=2,6-pyridinedicarboxylic acid, bipy=4,4'-bipyridine, bpa=Bis(4-pyridyl)amine) have been hydrothermally synthesized and structurally characterized via elemental analysis, IR spectra, TG and single-crystal X-ray diffraction. Both complexes crystallize in triclinic, space group P1 with a=1.014 32(11) nm, b=1.253 64(13) nm, c=1.448 89(14) nm, V=1.662 77(6) nm3, Z=2, R1=0.064 1, wR2=0.149 4 for 1, and a=1.039 30(5) nm, b=1.604 02(8) nm, c=2.021 65(10) nm, V=3.304 5(3) nm3, Z=2, R1=0.039 8 and wR2=0.104 9 for 2. The central metal Ce(Ⅳ) ions of both complexes are surrounded by three wholly unprotonated dipicolinate groups in the usual tridentate mode. Thermogravimetric analysis shows that the two complexes are stable up to 64 and 50℃, respectively. CCDC: 856834, 1; 856608, 2.
