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2015 Volume 34 Issue 12
2015, 34(12): 1793-1802
doi: 10.14102/j.cnki.0254-5861.2011-0907
Abstract:
To investigate the relationships between structures and toxicities of 13 quaternary ammonium compounds (QACs) to Chlorella pyrenoidosa, 2D- and 3D-QSAR models were built. The 2D-QSAR model included two parameters: averaged polarizability (α) and total connectivity (Tcon). Furthermore, 3D-QSAR models were proposed by using comparative molecular field analysis (CoMFA) and molecular similarity index analysis (CoMSIA). All these models were robust and predictive. To our interest, 3D-QSAR model suggested that the hydrophobicity of substituents was the dominating factor for the toxicities, electrostatic effect was the secondly important, and steric field gave the least contribution. Comparatively, the predictive ability of 3D-QSAR model is slightly more advantageous than that of 2D-QSAR. They can be used complementally in the toxicity description of this kind of compounds.
To investigate the relationships between structures and toxicities of 13 quaternary ammonium compounds (QACs) to Chlorella pyrenoidosa, 2D- and 3D-QSAR models were built. The 2D-QSAR model included two parameters: averaged polarizability (α) and total connectivity (Tcon). Furthermore, 3D-QSAR models were proposed by using comparative molecular field analysis (CoMFA) and molecular similarity index analysis (CoMSIA). All these models were robust and predictive. To our interest, 3D-QSAR model suggested that the hydrophobicity of substituents was the dominating factor for the toxicities, electrostatic effect was the secondly important, and steric field gave the least contribution. Comparatively, the predictive ability of 3D-QSAR model is slightly more advantageous than that of 2D-QSAR. They can be used complementally in the toxicity description of this kind of compounds.
2015, 34(12): 1803-1812
doi: 10.14102/j.cnki.0254-5861.2011-0837
Abstract:
Absorption and emission properties of oxidized graphene quantum dots (GQDs) and amino functionalized GQDs (NG) were explored by B3LYP method combined with 6-31G (d) basis set. The oxygen- and nitrogen-containing groups can tune the intensity as well as the wavelength of absorption and emission. The groups such as hydroxyl, carboxyl, amino, amide, and pyridine-like N can appropriately lengthen the absorption and emission wavelength of GQDs. However, the carbonyl group, graphitic-like N, and pyrrolic-like N obviously decrease the oscillator strength and lengthen the emission wavelength of GQDs out of the visible region. The lowest excited state S1 of NG has the strongest emission in investigated complexes, which indicates that it is an excellent luminous material. The theoretical investigations verify that the oxygen- and nitrogen-related groups can tune the luminescence of GQDs. The fluorescence quenching of GQDs reduced by ammonia mainly depends on the graphitic-like and pyrrolic-like N.
Absorption and emission properties of oxidized graphene quantum dots (GQDs) and amino functionalized GQDs (NG) were explored by B3LYP method combined with 6-31G (d) basis set. The oxygen- and nitrogen-containing groups can tune the intensity as well as the wavelength of absorption and emission. The groups such as hydroxyl, carboxyl, amino, amide, and pyridine-like N can appropriately lengthen the absorption and emission wavelength of GQDs. However, the carbonyl group, graphitic-like N, and pyrrolic-like N obviously decrease the oscillator strength and lengthen the emission wavelength of GQDs out of the visible region. The lowest excited state S1 of NG has the strongest emission in investigated complexes, which indicates that it is an excellent luminous material. The theoretical investigations verify that the oxygen- and nitrogen-related groups can tune the luminescence of GQDs. The fluorescence quenching of GQDs reduced by ammonia mainly depends on the graphitic-like and pyrrolic-like N.
2015, 34(12): 1813-1818
doi: 10.14102/j.cnki.0254-5861.2011-0787
Abstract:
The title compound 1-(3-((benzo[d][1,3]dioxol-5-yloxy)methyl)phenethyl)-4-phenylpiperidin-4-ol (4, C27H29NO4, Mr=431.51) was synthesized by a four-step reaction and characterized by 1H NMR, 13C NMR, elemental analysis and single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a=5.8033(12), b=10.705(2), c=18.393(4) Å, α=83.44(3), β=82.71(3), γ=88.88 (3)°, V=1126.0(4) Å3, Z=1, Dc=1.273 g/cm3, S=1.070, μ=0.681 mm-1, F(000)=460, R=0.0618 and wR=0.1619 for 6452 observed reflections with I>2σ(I). Geometry conformations revealed that the dihedral angle between benzodioxole and aromatic planes contributed to the formation of C-H…π interactions. Hydrogen bonds and van der waals interactions were observed to stabilize the three-dimensional packing structure. The compound showed a moderate inhibitory activity against the prostate cancer cells.
The title compound 1-(3-((benzo[d][1,3]dioxol-5-yloxy)methyl)phenethyl)-4-phenylpiperidin-4-ol (4, C27H29NO4, Mr=431.51) was synthesized by a four-step reaction and characterized by 1H NMR, 13C NMR, elemental analysis and single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a=5.8033(12), b=10.705(2), c=18.393(4) Å, α=83.44(3), β=82.71(3), γ=88.88 (3)°, V=1126.0(4) Å3, Z=1, Dc=1.273 g/cm3, S=1.070, μ=0.681 mm-1, F(000)=460, R=0.0618 and wR=0.1619 for 6452 observed reflections with I>2σ(I). Geometry conformations revealed that the dihedral angle between benzodioxole and aromatic planes contributed to the formation of C-H…π interactions. Hydrogen bonds and van der waals interactions were observed to stabilize the three-dimensional packing structure. The compound showed a moderate inhibitory activity against the prostate cancer cells.
2015, 34(12): 1819-1824
doi: 10.14102/j.cnki.0254-5861.2011-0798
Abstract:
The title compound, (3R,4R)-4,7,7-trimethyl-6-oxabicyclo[3.2.1]octane-3,4-diol (C10H18O3), has been synthesized by using one-step catalytic synthetic method from α-pinene and structurally characterized by means of IR, 1H-NMR, 13C-NMR, HRMS and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/n with a=7.277(4), b=18.177(11), c=7.939(5) Å, β=91.122(8)°, Z=4, V=1049.9(11) Å, Dc=1.178 g/cm3, Mr=186.24, λ(MoKα)=0.71073 Å, μ=0.09 mm-1, F(000)=408, R=0.051 and wR=0.144. The title complex molecules contained two hydroxyls and are connected through hydrogen bonds to generate a two-dimensional network. Especially, the preliminary herbicidal activity results show that the title compound exhibits herbicidal activity against rape (Brassica campestris) and barnyard grass (Echinochloa crusgalli).
The title compound, (3R,4R)-4,7,7-trimethyl-6-oxabicyclo[3.2.1]octane-3,4-diol (C10H18O3), has been synthesized by using one-step catalytic synthetic method from α-pinene and structurally characterized by means of IR, 1H-NMR, 13C-NMR, HRMS and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/n with a=7.277(4), b=18.177(11), c=7.939(5) Å, β=91.122(8)°, Z=4, V=1049.9(11) Å, Dc=1.178 g/cm3, Mr=186.24, λ(MoKα)=0.71073 Å, μ=0.09 mm-1, F(000)=408, R=0.051 and wR=0.144. The title complex molecules contained two hydroxyls and are connected through hydrogen bonds to generate a two-dimensional network. Especially, the preliminary herbicidal activity results show that the title compound exhibits herbicidal activity against rape (Brassica campestris) and barnyard grass (Echinochloa crusgalli).
2015, 34(12): 1825-1829
doi: 10.14102/j.cnki.0254-5861.2011-0825
Abstract:
A new Zn(Ⅱ) complex, [ZnL2Br2] (L=triadimenol) was synthesized by the reaction of ZnBr2 with the commercial fungicide of triadimenol, then characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The crystal structure shows that the complex [ZnL2Br2] crystallizes in orthorhombic, Pnam space group with a=11.263(2), b=8.4478(15), c=36.125(7) Ǻ, V=3437.2(11) Ǻ3, Z=4, C28H36Br2Cl2N6O4Zn, Mr=816.72, Dc=1.578 g/cm3, F(000)=1648, μ=3.236 mm-1, the final R=0.0388 and wR=0.0879 for 2399 observed reflections with I>2σ(I). The central metals adopt square plane coordination geometry. And intermolecular hydrogen bonds connect Zn(Ⅱ) into a one-dimensional chain. In addition, the title complex and triadimenol were screened for antifungal activities against four selected fungi using the mycelial growth rate method. The results indicate that the complex synthesized shows better antifungal activities than the ligand triadimenol.
A new Zn(Ⅱ) complex, [ZnL2Br2] (L=triadimenol) was synthesized by the reaction of ZnBr2 with the commercial fungicide of triadimenol, then characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The crystal structure shows that the complex [ZnL2Br2] crystallizes in orthorhombic, Pnam space group with a=11.263(2), b=8.4478(15), c=36.125(7) Ǻ, V=3437.2(11) Ǻ3, Z=4, C28H36Br2Cl2N6O4Zn, Mr=816.72, Dc=1.578 g/cm3, F(000)=1648, μ=3.236 mm-1, the final R=0.0388 and wR=0.0879 for 2399 observed reflections with I>2σ(I). The central metals adopt square plane coordination geometry. And intermolecular hydrogen bonds connect Zn(Ⅱ) into a one-dimensional chain. In addition, the title complex and triadimenol were screened for antifungal activities against four selected fungi using the mycelial growth rate method. The results indicate that the complex synthesized shows better antifungal activities than the ligand triadimenol.
2015, 34(12): 1830-1840
doi: 10.14102/j.cnki.0254-5861.2011-0864
Abstract:
The title compound, 4-hexyl-1-(4-nitrophenyl)-1-H-1,2,3-triazole (C14H18N4O2), was synthesized using one-pot strategy via click reaction and the structure was characterized mainly by single-crystal X-ray diffraction, NMR, FT-IR and MS. C14H18N4O2 was crystallized from an EtOH/EtOAc solution in triclinic system, space group P1, with a=5.3679(3), b=7.5499(5), c=17.5534(11) Å, α=92.360(4), β=90.359(4), γ=98.864(4)°, V (Å3)=702.24(8), Z=2, crystal size (mm)=0.42×0.26×0.18, Rint=0.096. Packing diagram indicates that there is dimeric interaction between two units via N(3)…H(6). The crystal structure of the title compound (1) is stabilized by intermolecular interactions. In addition, X-ray analysis also reveals C-H…π and π-π interactions in the molecule. Theoretical investigations were performed by using Gaussian 09 software at the B3LYP/6-31G (d,p) level of density finctional theory (DFT) to compare the theoretical results with the experimental and to probe structural properties. The molecular electrostatic potential (MEP) mapped over the entire stabilized geometry of the molecule indicated their chemical reactivities. Furthermore, frontier molecular orbital (electronic properties) was computed at the same level of DFT as used for energy minima structure.
The title compound, 4-hexyl-1-(4-nitrophenyl)-1-H-1,2,3-triazole (C14H18N4O2), was synthesized using one-pot strategy via click reaction and the structure was characterized mainly by single-crystal X-ray diffraction, NMR, FT-IR and MS. C14H18N4O2 was crystallized from an EtOH/EtOAc solution in triclinic system, space group P1, with a=5.3679(3), b=7.5499(5), c=17.5534(11) Å, α=92.360(4), β=90.359(4), γ=98.864(4)°, V (Å3)=702.24(8), Z=2, crystal size (mm)=0.42×0.26×0.18, Rint=0.096. Packing diagram indicates that there is dimeric interaction between two units via N(3)…H(6). The crystal structure of the title compound (1) is stabilized by intermolecular interactions. In addition, X-ray analysis also reveals C-H…π and π-π interactions in the molecule. Theoretical investigations were performed by using Gaussian 09 software at the B3LYP/6-31G (d,p) level of density finctional theory (DFT) to compare the theoretical results with the experimental and to probe structural properties. The molecular electrostatic potential (MEP) mapped over the entire stabilized geometry of the molecule indicated their chemical reactivities. Furthermore, frontier molecular orbital (electronic properties) was computed at the same level of DFT as used for energy minima structure.
2015, 34(12): 1841-1844
doi: 10.14102/j.cnki.0254-5861.2011-0842
Abstract:
7-(Diethylamino)-3-(4-aminophenyl)coumarin has been synthesized in a new one-pot synthesis by a three-step process starting from 4-(diethylamino)salicylaldehyde and 4-nitrophenylacetonitrile. The product was obtained in a good yield with a high degree of purity and characterized by NMR, IR and HR-MS. The orange crystals of the title compound were grown from ethyl acetate solution. The solid state structure was established by X-ray crystallography analysis. The crystal belongs to the orthorombic system, space group Pccn with a=11.1095(5), b=33.0187(15), c=17.2865(7) Å, V=6341.1(5) Å3, C19H20N2O2, Mr=308.37, ρcalc=1.292 g·cm-3, μ=0.085 mm-1, F(000)=2624, the final R=0.0480 and wR=0.1265 (I>2σ(I)).
7-(Diethylamino)-3-(4-aminophenyl)coumarin has been synthesized in a new one-pot synthesis by a three-step process starting from 4-(diethylamino)salicylaldehyde and 4-nitrophenylacetonitrile. The product was obtained in a good yield with a high degree of purity and characterized by NMR, IR and HR-MS. The orange crystals of the title compound were grown from ethyl acetate solution. The solid state structure was established by X-ray crystallography analysis. The crystal belongs to the orthorombic system, space group Pccn with a=11.1095(5), b=33.0187(15), c=17.2865(7) Å, V=6341.1(5) Å3, C19H20N2O2, Mr=308.37, ρcalc=1.292 g·cm-3, μ=0.085 mm-1, F(000)=2624, the final R=0.0480 and wR=0.1265 (I>2σ(I)).
2015, 34(12): 1845-1850
doi: 10.14102/j.cnki.0254-5861.2011-0775
Abstract:
8-Hydroxyquinoline salt of pyrazine-2,3,5,6-tetracarboxylic acid [HQ]2[H2pztc]·2H2O (1) was prepared and characterized by single-crystal X-ray diffraction, NMR, IR, TGA, elemental analysis and fluorescent measurements. Compound 1 crystallizes in orthorhombic, space group Pbcn with a=9.953(3), b=15.966(3), c=16.081(5) Å, V=2555.5(13) Å3, Z=4, μ=0.122 mm-1, Dc=1.514 Mg/m3, T=296(2) K, C26H22N4O12, Mr=582.48, F(000)=1208, S=1.006, R=0.0448 and wR=0.1149. Compound 1 has a three-dimensional (3D) network, in which pyrazine-2,3,5,6-tetracarboxylic acids build up two-dimensional (2D) sheets and 8-hydroxyquinoline cations and water molecules act as pillars to connect the 2D sheets into an extended 3D network through strong intermolecular hydrogen bonding and π…π stacking interactions. Especially, a very short O-H…O hydrogen bond (O…O 2.470(2) Å) between two neighboring [H2pztc] anions was observed.
8-Hydroxyquinoline salt of pyrazine-2,3,5,6-tetracarboxylic acid [HQ]2[H2pztc]·2H2O (1) was prepared and characterized by single-crystal X-ray diffraction, NMR, IR, TGA, elemental analysis and fluorescent measurements. Compound 1 crystallizes in orthorhombic, space group Pbcn with a=9.953(3), b=15.966(3), c=16.081(5) Å, V=2555.5(13) Å3, Z=4, μ=0.122 mm-1, Dc=1.514 Mg/m3, T=296(2) K, C26H22N4O12, Mr=582.48, F(000)=1208, S=1.006, R=0.0448 and wR=0.1149. Compound 1 has a three-dimensional (3D) network, in which pyrazine-2,3,5,6-tetracarboxylic acids build up two-dimensional (2D) sheets and 8-hydroxyquinoline cations and water molecules act as pillars to connect the 2D sheets into an extended 3D network through strong intermolecular hydrogen bonding and π…π stacking interactions. Especially, a very short O-H…O hydrogen bond (O…O 2.470(2) Å) between two neighboring [H2pztc] anions was observed.
2015, 34(12): 1851-1856
doi: 10.14102/j.cnki.0254-5861.2011-0906
Abstract:
The title nickel complex I and cobalt complex Ⅱ were obtained separately from the direct reaction of D-(+)-leucinol with Ni(Ⅱ) chloride and L-(-)-leucinol with Co(Ⅱ) acetate tetrahydrate in anhydrous methanol. The crystal structures of I and Ⅱ were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I: [Ni(C18H45N3O3)]Cl2, orthorhombic, P212121, a=11.2807(9), b=14.7115(11), c=16.3580(13) Å, V=2714.7(4) Å3, Z=4, ρcalcd=1.177 Mg/m3, the final R=0.0407, and 16539 reflections observed with I>2σ(I); For Ⅱ: [Co(C45H108N6O15)], trigonal, R3:H, a=23.981(3), b=23.981(3), c=10.8925(15) Å, γ=120°, V=5425.1(14) Å3, Z=3, ρcalcd=1.002 Mg/m3, the final R=0.0625 for 16556 observed reflections with I>2σ(I). The complexes were then used to catalyze the Henry reaction and obtained good catalytic results. The catalytic activity of the complexes was determined by 1H NMR. And research is going towards the application to other organic reactions such as cyanosilylation reaction.
The title nickel complex I and cobalt complex Ⅱ were obtained separately from the direct reaction of D-(+)-leucinol with Ni(Ⅱ) chloride and L-(-)-leucinol with Co(Ⅱ) acetate tetrahydrate in anhydrous methanol. The crystal structures of I and Ⅱ were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I: [Ni(C18H45N3O3)]Cl2, orthorhombic, P212121, a=11.2807(9), b=14.7115(11), c=16.3580(13) Å, V=2714.7(4) Å3, Z=4, ρcalcd=1.177 Mg/m3, the final R=0.0407, and 16539 reflections observed with I>2σ(I); For Ⅱ: [Co(C45H108N6O15)], trigonal, R3:H, a=23.981(3), b=23.981(3), c=10.8925(15) Å, γ=120°, V=5425.1(14) Å3, Z=3, ρcalcd=1.002 Mg/m3, the final R=0.0625 for 16556 observed reflections with I>2σ(I). The complexes were then used to catalyze the Henry reaction and obtained good catalytic results. The catalytic activity of the complexes was determined by 1H NMR. And research is going towards the application to other organic reactions such as cyanosilylation reaction.
2015, 34(12): 1857-1861
doi: 10.14102/j.cnki.0254-5861.2011-0748
Abstract:
Self-assembly of pyta (pyta=N-(4-pyridylmethyl) triazole) with Ag(I) center by layer-separating diffusion method at ambient temperature gives rise to a new supramolecular [Ag(μ-pyta)ClO4]n which has been characterized by single-crystal X-ray diffraction. The polymer crystallizes in a hexagonal space group R-3 with a=22.456(7), b=22.456(7), c=14.570(1) Å, V=6363(6) Å3, Z=4, C36H36Ag4.5Cl4.5N18O18, Mr=1653.77, Dc=1.726 g/cm3, F(000)=3240, μ(MoKα)=1.625 mm-1, the final R=0.0449 and wR=0.1397 for 2744 observed reflections with I>2σ(I).
Self-assembly of pyta (pyta=N-(4-pyridylmethyl) triazole) with Ag(I) center by layer-separating diffusion method at ambient temperature gives rise to a new supramolecular [Ag(μ-pyta)ClO4]n which has been characterized by single-crystal X-ray diffraction. The polymer crystallizes in a hexagonal space group R-3 with a=22.456(7), b=22.456(7), c=14.570(1) Å, V=6363(6) Å3, Z=4, C36H36Ag4.5Cl4.5N18O18, Mr=1653.77, Dc=1.726 g/cm3, F(000)=3240, μ(MoKα)=1.625 mm-1, the final R=0.0449 and wR=0.1397 for 2744 observed reflections with I>2σ(I).
2015, 34(12): 1862-1868
doi: 10.14102/j.cnki.0254-5861.2011-0707
Abstract:
Two 4,5-dichlorophthalate-based metal complexes, {[Cu(bipy)(dcpa)]·H2O}n (1) and {[Cu2(bipy)2(Hdcpa)3]·H2O·C2H5OH·Hdcpa} (2, H2dcpa=4,5-dichlorophthalic acid and bipy=2,2'-bipyridine), were synthesized and characterized structurally and magnetically. Complex 1 is of orthorhombic system, space group Fdd2 with a=20.5821(8), b=20.9013(12), c=17.0270(7) Å, V=7324.9(6) Å3, Dc=1.707 g/cm3, Mr=470.74, Z=16, F(000)=3792, μ=1.519 mm-1, the final R=0.0223 and wR=0.0549 for 9239 observed reflections with I>2σ(I). Complex 2 crystallizes in triclinic, space group P1 with a=14.1439(12), b=14.2981(12), c=15.1054(14) Å, α=72.121(2), β=77.703(2), γ=81.829(2)°, V=2830.9(4) Å3, Dc=1.689 g/cm3, Mr=1439.55, Z=2, F(000)=1452, μ=1.207 mm-1, the final R=0.0536 and wR=0.0981 for 16422 observed reflections with I>2σ(I). Complex 1 exhibits a diamond-like framework with centrosymmetric binuclear subunits extended by pairs of doubly deprotonated dcpa2- linkers. By contrast, 2 is an asymmetric binuclear entity bridged by carboxylate group of mono deprotonated Hdcpa- ligands. Weak anti- and ferromagnetic interactions are respectively mediated in the carboxylate aggregated binuclear subunits of 1 and 2.
Two 4,5-dichlorophthalate-based metal complexes, {[Cu(bipy)(dcpa)]·H2O}n (1) and {[Cu2(bipy)2(Hdcpa)3]·H2O·C2H5OH·Hdcpa} (2, H2dcpa=4,5-dichlorophthalic acid and bipy=2,2'-bipyridine), were synthesized and characterized structurally and magnetically. Complex 1 is of orthorhombic system, space group Fdd2 with a=20.5821(8), b=20.9013(12), c=17.0270(7) Å, V=7324.9(6) Å3, Dc=1.707 g/cm3, Mr=470.74, Z=16, F(000)=3792, μ=1.519 mm-1, the final R=0.0223 and wR=0.0549 for 9239 observed reflections with I>2σ(I). Complex 2 crystallizes in triclinic, space group P1 with a=14.1439(12), b=14.2981(12), c=15.1054(14) Å, α=72.121(2), β=77.703(2), γ=81.829(2)°, V=2830.9(4) Å3, Dc=1.689 g/cm3, Mr=1439.55, Z=2, F(000)=1452, μ=1.207 mm-1, the final R=0.0536 and wR=0.0981 for 16422 observed reflections with I>2σ(I). Complex 1 exhibits a diamond-like framework with centrosymmetric binuclear subunits extended by pairs of doubly deprotonated dcpa2- linkers. By contrast, 2 is an asymmetric binuclear entity bridged by carboxylate group of mono deprotonated Hdcpa- ligands. Weak anti- and ferromagnetic interactions are respectively mediated in the carboxylate aggregated binuclear subunits of 1 and 2.
2015, 34(12): 1869-1875
doi: 10.14102/j.cnki.0254-5861.2011-0744
Abstract:
Under thermal gradient in solution phase, the reaction of Hg(Ⅱ) and Cd(Ⅱ) salts with 2,3,5,6-tetrakis-(2-pyridyl)pyrazine (tppz) in 1:1 molar ratio afforded dinuclear [{HgI2}2(μ-tppz)] (1) and mononuclear [CdI2(tppz)] (2) complexes. Single-crystal X-ray diffraction structural analysis reveals that the tppz acts as bis-tridentate and tridentate chelating ligands in 1 and 2, respectively. Metal(Ⅱ) ions adopt a distorted square pyramidal geometry and have the same coordination environment in both complexes. Based on the 1H NMR spectroscopy measurements, both complexes decompose in solution and release free tppz.
Under thermal gradient in solution phase, the reaction of Hg(Ⅱ) and Cd(Ⅱ) salts with 2,3,5,6-tetrakis-(2-pyridyl)pyrazine (tppz) in 1:1 molar ratio afforded dinuclear [{HgI2}2(μ-tppz)] (1) and mononuclear [CdI2(tppz)] (2) complexes. Single-crystal X-ray diffraction structural analysis reveals that the tppz acts as bis-tridentate and tridentate chelating ligands in 1 and 2, respectively. Metal(Ⅱ) ions adopt a distorted square pyramidal geometry and have the same coordination environment in both complexes. Based on the 1H NMR spectroscopy measurements, both complexes decompose in solution and release free tppz.
2015, 34(12): 1876-1882
doi: 10.14102/j.cnki.0254-5861.2011-0749
Abstract:
The reactions of 5,5'-bis(2-acylphenyl)diazo-dipyrromethane (H2L) with CuSO4 and NiCl2 resulted in the formation of corresponding mononuclear coordination complexes 2 (CuL) and 3 (NiL). The crystal of complex 2 is of monoclinic system, space group P21 with a=10.040(5), b=11.900(5), c=11.170(5) Å, β=93.057(8)°, V=1332.8(2) Å3, Z=2, C29H28N6O2Cu, Mr=556.11, Dc=1.386 g/cm, F(000)=578 and μ(MoKα)=0.857 mm-1. The crystal of complex 3 belongs to the monoclinic system, space group P21/n with a=12.0445(6), b=17.2101(8), c=16.3304(6) Å, β=128.407(2)°, V=2654.6(2) Å3, Z=4, C29H28N6O2Ni, Mr=551.28, Dc=1.380 g/cm, F(000)=1152 and μ(MoKα)=0.770 mm-1. In both complexes, the metal ions are in square-planar geometry by coordinating to two azo N atoms and two deprotonated pyrrole N atoms. Intramolecular Cu…O=C in complex 2 and intermolecular Ni…O=C in complex 3 were found. The UV-Vis spectra and thermal stability of complexes 2 and 3 were also studied.
The reactions of 5,5'-bis(2-acylphenyl)diazo-dipyrromethane (H2L) with CuSO4 and NiCl2 resulted in the formation of corresponding mononuclear coordination complexes 2 (CuL) and 3 (NiL). The crystal of complex 2 is of monoclinic system, space group P21 with a=10.040(5), b=11.900(5), c=11.170(5) Å, β=93.057(8)°, V=1332.8(2) Å3, Z=2, C29H28N6O2Cu, Mr=556.11, Dc=1.386 g/cm, F(000)=578 and μ(MoKα)=0.857 mm-1. The crystal of complex 3 belongs to the monoclinic system, space group P21/n with a=12.0445(6), b=17.2101(8), c=16.3304(6) Å, β=128.407(2)°, V=2654.6(2) Å3, Z=4, C29H28N6O2Ni, Mr=551.28, Dc=1.380 g/cm, F(000)=1152 and μ(MoKα)=0.770 mm-1. In both complexes, the metal ions are in square-planar geometry by coordinating to two azo N atoms and two deprotonated pyrrole N atoms. Intramolecular Cu…O=C in complex 2 and intermolecular Ni…O=C in complex 3 were found. The UV-Vis spectra and thermal stability of complexes 2 and 3 were also studied.
2015, 34(12): 1883-1888
doi: 10.14102/j.cnki.0254-5861.2011-0767
Abstract:
The title complex, [Co2(bibzim)(H2bibzim)4]·[Co2(H2bibzim)2(Hbibzim)(HL)]2·2H2O (1) (H2bibzim=2,2'-bibenzimidazole, H5L=N,N-bis(phosphonomethyl)aminoacetic acid (HO2CCH2N(CH2PO3H2)2)), was synthesized with hydrothermal reactions. The compound crystallizes in triclinic, space group P1 with a=13.71020(10), b=14.9165(5), c=20.9924(5) Å, α=86.344(9), β=71.214(8), γ=73.757(7)°, C162H124Co6N46O18P4, Mr=3478.52, V=3900.55(16) Å3, Z=2, Dc=1.482 g/cm3, μ(MoKα)=0.747 mm-1, F(000)=1784, the final R=0.0777 and wR=0.2091 for 13598 observed reflections (I>2σ(I)). X-ray diffraction analysis reveals that there are three crystallographically independent Co(Ⅱ) atoms in the complex. The complex consists of binuclear coordination cation, binuclear coordination anion, as well as lattice water molecules, which further aggregate into a 3D framework via hydrogen bonding as well as π-π interactions.
The title complex, [Co2(bibzim)(H2bibzim)4]·[Co2(H2bibzim)2(Hbibzim)(HL)]2·2H2O (1) (H2bibzim=2,2'-bibenzimidazole, H5L=N,N-bis(phosphonomethyl)aminoacetic acid (HO2CCH2N(CH2PO3H2)2)), was synthesized with hydrothermal reactions. The compound crystallizes in triclinic, space group P1 with a=13.71020(10), b=14.9165(5), c=20.9924(5) Å, α=86.344(9), β=71.214(8), γ=73.757(7)°, C162H124Co6N46O18P4, Mr=3478.52, V=3900.55(16) Å3, Z=2, Dc=1.482 g/cm3, μ(MoKα)=0.747 mm-1, F(000)=1784, the final R=0.0777 and wR=0.2091 for 13598 observed reflections (I>2σ(I)). X-ray diffraction analysis reveals that there are three crystallographically independent Co(Ⅱ) atoms in the complex. The complex consists of binuclear coordination cation, binuclear coordination anion, as well as lattice water molecules, which further aggregate into a 3D framework via hydrogen bonding as well as π-π interactions.
2015, 34(12): 1889-1894
doi: 10.14102/j.cnki.0254-5861.2011-0773
Abstract:
A new organic-inorganic hybrid based on tungstophosphate anions and benzotriazole cations, [Na(BTA)2(H2O)2]2[{Cd(BTA)4(H2O)}2(P2W18O62)]·6H2O (1) (BTA=benzotriazole) has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. X-ray analysis showed that both {Na(BTA)2} and {Cd(BTA)4} units are supported on the α-Dawson polyoxoanion [P2W18O62]6- via the surface bridging oxygen atoms. The electrochemical properties of 1 in aqueous solution are studied at room temperature. It was found that 1 presents good electrocatalytic activities for the reduction of NO2-.
A new organic-inorganic hybrid based on tungstophosphate anions and benzotriazole cations, [Na(BTA)2(H2O)2]2[{Cd(BTA)4(H2O)}2(P2W18O62)]·6H2O (1) (BTA=benzotriazole) has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. X-ray analysis showed that both {Na(BTA)2} and {Cd(BTA)4} units are supported on the α-Dawson polyoxoanion [P2W18O62]6- via the surface bridging oxygen atoms. The electrochemical properties of 1 in aqueous solution are studied at room temperature. It was found that 1 presents good electrocatalytic activities for the reduction of NO2-.
2015, 34(12): 1895-1900
doi: 10.14102/j.cnki.0254-5861.2011-0785
Abstract:
A new Cu(Ⅱ) metal-organic coordination polymer, {[Cu2(tbip)2(bie)2]·H2O}n (1, H2tbip=5-tert-butyl isophthalic acid, bie=1,2-bis(imidazol-1'-yl)ethane), was assembled under hydrothermal conditions by the reactions of Cu(Ⅱ) acetate with H2tbip and bie. Complex 1 was characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 crystallizes in triclinic, space group P1, with a=9.9145(10), b=13.2211(13), c=15.4363(15) nm, α=87.0250(10), β=88.3220(10), γ=83.8240(10)°, V=2008.4(3) nm3, Z=2, Dc=1.505 Mg/m3, F(000)=944, μ=1.125 mm-1, S=1.030, the final R=0.0336 and wR=0.0790. The results reveal that complex 1 is a two-dimensional layered structure. In addition, magnetic properties of 1 were also investigated.
A new Cu(Ⅱ) metal-organic coordination polymer, {[Cu2(tbip)2(bie)2]·H2O}n (1, H2tbip=5-tert-butyl isophthalic acid, bie=1,2-bis(imidazol-1'-yl)ethane), was assembled under hydrothermal conditions by the reactions of Cu(Ⅱ) acetate with H2tbip and bie. Complex 1 was characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 crystallizes in triclinic, space group P1, with a=9.9145(10), b=13.2211(13), c=15.4363(15) nm, α=87.0250(10), β=88.3220(10), γ=83.8240(10)°, V=2008.4(3) nm3, Z=2, Dc=1.505 Mg/m3, F(000)=944, μ=1.125 mm-1, S=1.030, the final R=0.0336 and wR=0.0790. The results reveal that complex 1 is a two-dimensional layered structure. In addition, magnetic properties of 1 were also investigated.
2015, 34(12): 1901-1907
doi: 10.14102/j.cnki.0254-5861.2011-0771
Abstract:
A new metal-organic framework based on ethyl 1H-tetrazole-5-acetate (Hetza), [Ag4(etza)4] (1), has been synthesized and characterized by elemental analysis, IR, thermal gravimetric and X-ray structural analysis. Crystal data for the title complex are as follows: triclinic system, space group P1 with a=11.0771(6), b=11.6636(6), c=13.2925(8), α=102.3710(10), β=103.3810(10), γ=90.0890(10)°, V=1629.60(16) Ǻ3, Mr=1052.06, Z=2, F(000)=1024, Dc=2.144 g/cm3, μ(MoKα)=2.438 mm-1, the final R=0.0538 and wR=0.1475 (I>2σ(I)). Complex 1 adopts the (4·82) topological network and the alternately hydrophilic-hydrophilic and hydrophobic- hydrophobic arrangements. The luminescent properties of complex 1 and the free Hetza ligand have been studied in the solid states.
A new metal-organic framework based on ethyl 1H-tetrazole-5-acetate (Hetza), [Ag4(etza)4] (1), has been synthesized and characterized by elemental analysis, IR, thermal gravimetric and X-ray structural analysis. Crystal data for the title complex are as follows: triclinic system, space group P1 with a=11.0771(6), b=11.6636(6), c=13.2925(8), α=102.3710(10), β=103.3810(10), γ=90.0890(10)°, V=1629.60(16) Ǻ3, Mr=1052.06, Z=2, F(000)=1024, Dc=2.144 g/cm3, μ(MoKα)=2.438 mm-1, the final R=0.0538 and wR=0.1475 (I>2σ(I)). Complex 1 adopts the (4·82) topological network and the alternately hydrophilic-hydrophilic and hydrophobic- hydrophobic arrangements. The luminescent properties of complex 1 and the free Hetza ligand have been studied in the solid states.
2015, 34(12): 1908-1914
doi: 10.14102/j.cnki.0254-5861.2011-0759
Abstract:
A new complex, [Ni(H2O)6][Mo2O2S2(edta)]·2H2O (1, edta=ethylenediaminetetraacetate), which was partially-sulfided, was synthesized and characterized by single-crystal X-ray diffraction. Compound 1 belongs to the monoclinic system, C2/c space group with a=7.1844(2), b=12.5626(4), c=27.0201(8) Å, β=93.066(3)°, V=2435.21(14) Å3, C10H28S2Mo2N2NiO18, Mr=779.02, Dc=2.1247 g/cm3, μ(MoKα)=2.035 mm-1, F(000)=1550, Z=4, the final R=0.0366 and wR=0.0656 for 5359 observed reflections (I>2σ(I)). There are one isolated [Ni(H2O)6]2+ cation and one [Mo2O2S2(edta)]2- anion in its asymmetric unit, and they are connected through multiple hydrogen bonds to generate a 3D network. In addition, the thermal behavior of compound 1 and the hydrodesulfurization activity of the catalyst derived from compound 1 were studied.
A new complex, [Ni(H2O)6][Mo2O2S2(edta)]·2H2O (1, edta=ethylenediaminetetraacetate), which was partially-sulfided, was synthesized and characterized by single-crystal X-ray diffraction. Compound 1 belongs to the monoclinic system, C2/c space group with a=7.1844(2), b=12.5626(4), c=27.0201(8) Å, β=93.066(3)°, V=2435.21(14) Å3, C10H28S2Mo2N2NiO18, Mr=779.02, Dc=2.1247 g/cm3, μ(MoKα)=2.035 mm-1, F(000)=1550, Z=4, the final R=0.0366 and wR=0.0656 for 5359 observed reflections (I>2σ(I)). There are one isolated [Ni(H2O)6]2+ cation and one [Mo2O2S2(edta)]2- anion in its asymmetric unit, and they are connected through multiple hydrogen bonds to generate a 3D network. In addition, the thermal behavior of compound 1 and the hydrodesulfurization activity of the catalyst derived from compound 1 were studied.
2015, 34(12): 1915-1921
doi: 10.14102/j.cnki.0254-5861.2011-0753
Abstract:
A new MOF {[Cd3(TCOPM)2bpe]·7(H2O)·2DMF}n based on a C-centered tripodal flexible carboxylate ligand and 1,2-bis(4-pyridyl)ethane ligand (H3TCOPM=tris(p-carboxyphenyl) methane, bpe=1,2-bis(4-pyridyl) ethane) has been synthesized by the hydrothermal reaction in mixed DMF/H2O solution under 95℃. The structure has been determined by single-crystal X-ray diffraction analysis and elemental analysis, IR spectroscopy, and thermogravimetric analysis. Crystal data for the title complex are as follows: triclinic system, space group P1 with a=9.2637(14), b=13.273(2), c=14.160(2) Å, α=9.2637(14), β=13.273(2), γ=105.585(2)°, V=1487.6(4) Å3, Mr=1268.11, Z=1, F(000)=628, Dc=1.416 g/cm3, μ(MoKα)=1.110 mm-1, R=0.0482 and wR=0.1444 for 5207 observed reflections with I>2σ(I). MOF 1 consists of an infinite 3D network using TCOPM3- and bpe as mixed bridge ligands. Fluorescence spectrum measurement indicates that MOF 1 shows strong fluorescence emission at 437 nm (λmax) in the solid state at room temperature and realizes tunable emission spectrum through tuning from single to mixed ligand.
A new MOF {[Cd3(TCOPM)2bpe]·7(H2O)·2DMF}n based on a C-centered tripodal flexible carboxylate ligand and 1,2-bis(4-pyridyl)ethane ligand (H3TCOPM=tris(p-carboxyphenyl) methane, bpe=1,2-bis(4-pyridyl) ethane) has been synthesized by the hydrothermal reaction in mixed DMF/H2O solution under 95℃. The structure has been determined by single-crystal X-ray diffraction analysis and elemental analysis, IR spectroscopy, and thermogravimetric analysis. Crystal data for the title complex are as follows: triclinic system, space group P1 with a=9.2637(14), b=13.273(2), c=14.160(2) Å, α=9.2637(14), β=13.273(2), γ=105.585(2)°, V=1487.6(4) Å3, Mr=1268.11, Z=1, F(000)=628, Dc=1.416 g/cm3, μ(MoKα)=1.110 mm-1, R=0.0482 and wR=0.1444 for 5207 observed reflections with I>2σ(I). MOF 1 consists of an infinite 3D network using TCOPM3- and bpe as mixed bridge ligands. Fluorescence spectrum measurement indicates that MOF 1 shows strong fluorescence emission at 437 nm (λmax) in the solid state at room temperature and realizes tunable emission spectrum through tuning from single to mixed ligand.
2015, 34(12): 1922-1926
doi: 10.14102/j.cnki.0254-5861.2011-0952
Abstract:
A new dinuclear copper(Ⅱ) complex [Cu2(L)2(phen)2]·5H2O (1) with bicycle[2.2.1]hept-2-en-5, 6-dicarboxylic acid (H2L) and 1,10-phenanthroline (phen) as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in the monoclinic space group P21/c, with a=17.925(4), b=19.908(4), c=11.235(2) Å, β=97.65(3)°, V=3973.4(14) Å3, Dc=1.552 g/cm3, Z=8, F(000)=1910, the final GOOF=1.056, R=0.0519 and wR=0.1293. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two copper ions are bridged by two μ2-η1:η0-3-carboxylate groups of L2- anions. The fluorescence and thermal stability properties of 1 were studied. The results show that 1 has an intense fluorescent emission at around 381 nm. The TG analysis shows that 1 is stable below 143℃.
A new dinuclear copper(Ⅱ) complex [Cu2(L)2(phen)2]·5H2O (1) with bicycle[2.2.1]hept-2-en-5, 6-dicarboxylic acid (H2L) and 1,10-phenanthroline (phen) as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in the monoclinic space group P21/c, with a=17.925(4), b=19.908(4), c=11.235(2) Å, β=97.65(3)°, V=3973.4(14) Å3, Dc=1.552 g/cm3, Z=8, F(000)=1910, the final GOOF=1.056, R=0.0519 and wR=0.1293. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two copper ions are bridged by two μ2-η1:η0-3-carboxylate groups of L2- anions. The fluorescence and thermal stability properties of 1 were studied. The results show that 1 has an intense fluorescent emission at around 381 nm. The TG analysis shows that 1 is stable below 143℃.
2015, 34(12): 1927-1934
doi: 10.14102/j.cnki.0254-5861.2011-0928
Abstract:
This paper reported the crystal growth and spectroscopy characters of Cr3+: Li2Mg2(MoO4)3. The refractive index of Cr3+: Li2Mg2(MoO4)3 crystal is 1.87 and the hardness is 270 HV. This crystal shows broadband absorption property with peak wavelength at about 495 and 699 nm. The absorption crosssection is 14.75×10-20 cm2 at 495 nm and 9.63×10-20 cm2 at 699 nm, respectively. The crystal field strength and energy levels of Cr3+ ion were calculated based on the spectroscopic data. The Cr3+: Li2Mg2(MoO4)3 crystal shows broadband emission extending from 750 to 1300 nm even excited at 10 K. The room temperature emission cross section is 72×10-20 cm2 at 926 nm. A discussion of the relation between the spectroscopic properties and crystal field parameters of Cr3+: Li2Mg2(MoO4)3 crystal was presented based on the solid state spectroscopy theory.
This paper reported the crystal growth and spectroscopy characters of Cr3+: Li2Mg2(MoO4)3. The refractive index of Cr3+: Li2Mg2(MoO4)3 crystal is 1.87 and the hardness is 270 HV. This crystal shows broadband absorption property with peak wavelength at about 495 and 699 nm. The absorption crosssection is 14.75×10-20 cm2 at 495 nm and 9.63×10-20 cm2 at 699 nm, respectively. The crystal field strength and energy levels of Cr3+ ion were calculated based on the spectroscopic data. The Cr3+: Li2Mg2(MoO4)3 crystal shows broadband emission extending from 750 to 1300 nm even excited at 10 K. The room temperature emission cross section is 72×10-20 cm2 at 926 nm. A discussion of the relation between the spectroscopic properties and crystal field parameters of Cr3+: Li2Mg2(MoO4)3 crystal was presented based on the solid state spectroscopy theory.
2015, 34(12): 1935-1938
doi: 10.14102/j.cnki.0254-5861.2011-1007
Abstract:
Magnetic α-Fe2O3, γ-Fe2O3 and Fe3O4 were prepared by facile calcination under different temperature from K4[Fe(CN)6] as raw materials, in which the calcined products are α-Fe2O3, Fe3O4 and γ-Fe2O3 at 400 or 700, 500, and 600℃, respectively. The as-prepared compounds were characterized by X-ray powder diffraction and scanning electron microscopy, and their magnetic behavior at room temperature was also studied. This method provided a simple approach to prepare different polymorphic forms of magnetic iron oxides, which may have potential applications in magnetic science, magnetic composite materials, magnetic core, magnetic separation and medical diagnostics.
Magnetic α-Fe2O3, γ-Fe2O3 and Fe3O4 were prepared by facile calcination under different temperature from K4[Fe(CN)6] as raw materials, in which the calcined products are α-Fe2O3, Fe3O4 and γ-Fe2O3 at 400 or 700, 500, and 600℃, respectively. The as-prepared compounds were characterized by X-ray powder diffraction and scanning electron microscopy, and their magnetic behavior at room temperature was also studied. This method provided a simple approach to prepare different polymorphic forms of magnetic iron oxides, which may have potential applications in magnetic science, magnetic composite materials, magnetic core, magnetic separation and medical diagnostics.
2015, 34(12): 1939-1941
doi: 10.14102/j.cnki.0254-5861.2011-1057
Abstract:
Konjac glucomannan nano gel microfibrils were prepared by using electrospinning method. Topology structures were analyzed by Fourier transform infrared spectroscopy (FT-IR) and Field emission scanning electron microscopy (FESEM), while the differential scanning calorimetry (DSC) was carried out to check the thermal stability of the structure. Results reveal that the interaction of KGM intermolecular hydrogen bonds and topological tangle rate are increased by electrospinning, while stable structures of nano gel microfibrils are formed without altering the molecular groups of origin. These structures compose of topological networks of clustered nano fibers with lower porosity and higher density.
Konjac glucomannan nano gel microfibrils were prepared by using electrospinning method. Topology structures were analyzed by Fourier transform infrared spectroscopy (FT-IR) and Field emission scanning electron microscopy (FESEM), while the differential scanning calorimetry (DSC) was carried out to check the thermal stability of the structure. Results reveal that the interaction of KGM intermolecular hydrogen bonds and topological tangle rate are increased by electrospinning, while stable structures of nano gel microfibrils are formed without altering the molecular groups of origin. These structures compose of topological networks of clustered nano fibers with lower porosity and higher density.
