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2016 Volume 35 Issue 3
2016, 35(3): 341-347
doi: 10.14102/j.cnki.0254-5861.2011-0978
Abstract:
Two new quaternary rare-earth chalcogenides, Al0.42Sm3(Si0.74Al0.26)S7 (1) and Al0.38Gd3(Si0.86Al0.14)S7 (2), have been synthesized by a facile solid-state route with boron as the reducing reagent. They crystallize in the noncentrosymmetric hexagonal space group P63, belonging to the Ce6Al3.33S14 structure-type. Their 3-D structures feature 3-D frameworks constructed by RES8 bicapped trigonal prisms, and Al and Si occupy the octahedral and tetrahedral voids, respectively. Al(2) and Si(1) co-occupying the 2b site and Al(1) partially occupying the 2a site have to be considered for the stability of the structures and charge balances. The Ce6Al3.33S14 structure-type compounds with their rich compositions and traits are discussed. The diffuse reflectance spectrum measurement of 2 indicates that it has an energy gap of 2.13 eV.
Two new quaternary rare-earth chalcogenides, Al0.42Sm3(Si0.74Al0.26)S7 (1) and Al0.38Gd3(Si0.86Al0.14)S7 (2), have been synthesized by a facile solid-state route with boron as the reducing reagent. They crystallize in the noncentrosymmetric hexagonal space group P63, belonging to the Ce6Al3.33S14 structure-type. Their 3-D structures feature 3-D frameworks constructed by RES8 bicapped trigonal prisms, and Al and Si occupy the octahedral and tetrahedral voids, respectively. Al(2) and Si(1) co-occupying the 2b site and Al(1) partially occupying the 2a site have to be considered for the stability of the structures and charge balances. The Ce6Al3.33S14 structure-type compounds with their rich compositions and traits are discussed. The diffuse reflectance spectrum measurement of 2 indicates that it has an energy gap of 2.13 eV.
2016, 35(3): 348-354
doi: 10.14102/j.cnki.0254-5861.2011-0893
Abstract:
A novel mononuclear copper(II) complex [Cu(bbmc)Cl2]·DMF, where bbmc is 1, 1-bis(1H-benzoimidazol-2-ylmethyl)cyclohexane, was synthesized and characterized by X-ray single-crystal structure analysis. The complex crystallizes in triclinic, space group P1 with a = 9.1088(5), b = 11.0075(4), c = 14.2326(6) Å, α = 97.188(3), β = 96.394(4), γ = 111.430(4)°, V = 1298.73(10) Å3, Z = 2, Dc = 1.409 g/cm3, μ(MoKα) = 1.074 mm-1, F(000) = 572, S = 1.078, R = 0.0381 and wR = 0.0876 for 5593 observed reflections with I > 2σ(I). The central Cu(II) ion adopts a distorted tetrahedral geometry coordinated by two nitrogen atoms of the ligand and two chloride ions. The complex showed its thermal decomposition temperature up to 226 ℃ and exhibited an irreversible one-electron transfer process involving CuII/CuI couple.
A novel mononuclear copper(II) complex [Cu(bbmc)Cl2]·DMF, where bbmc is 1, 1-bis(1H-benzoimidazol-2-ylmethyl)cyclohexane, was synthesized and characterized by X-ray single-crystal structure analysis. The complex crystallizes in triclinic, space group P1 with a = 9.1088(5), b = 11.0075(4), c = 14.2326(6) Å, α = 97.188(3), β = 96.394(4), γ = 111.430(4)°, V = 1298.73(10) Å3, Z = 2, Dc = 1.409 g/cm3, μ(MoKα) = 1.074 mm-1, F(000) = 572, S = 1.078, R = 0.0381 and wR = 0.0876 for 5593 observed reflections with I > 2σ(I). The central Cu(II) ion adopts a distorted tetrahedral geometry coordinated by two nitrogen atoms of the ligand and two chloride ions. The complex showed its thermal decomposition temperature up to 226 ℃ and exhibited an irreversible one-electron transfer process involving CuII/CuI couple.
2016, 35(3): 355-360
doi: 10.14102/j.cnki.0254-5861.2011-0868
Abstract:
A 2D plane coordination compound [Ag2(Dpya)2.(NO3)2]n was synthesized and characterized by FT-IR, elemental analysis and TG analysis. The red crystal was obtained via solvent diffusion method at room temperature and is slightly soluble in organic solvents. Its structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P1 with a = 10.7995(13), b = 7.4748(8), c = 18.364(2) Å, β = 98.916(4)°, V = 1464.5(3) Å3, Z = 2, C26H28Ag2N10O6, Mr = 792.32, Dc = 1.302 Mg/m3, F(000) = 792, µ(MoKa) = 1.356 mm-1, R = 0.0575 and wR = 0.0826. The compound [Ag2(Dpya)2.(NO3)2]n is a two-dimensional structure and there are two kinds of coordination configurations about the Ag atoms in the compound. The Ag(1) center is tetrahedrally coordinated with two O atoms of NO3- and two N atoms from the ligand Dpya. Meanwhile, the Ag(2) is five-coordinated by five O atoms from three NO3-anions. The Ag centers (Ag(1) and Ag(2)) connect to themselves as well as with each other by the bridging NO3-anions. And the coordination compound shows photoluminescence with an emission peak at 530 nm (λex = 450 nm) as the ligand Dpya.
A 2D plane coordination compound [Ag2(Dpya)2.(NO3)2]n was synthesized and characterized by FT-IR, elemental analysis and TG analysis. The red crystal was obtained via solvent diffusion method at room temperature and is slightly soluble in organic solvents. Its structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P1 with a = 10.7995(13), b = 7.4748(8), c = 18.364(2) Å, β = 98.916(4)°, V = 1464.5(3) Å3, Z = 2, C26H28Ag2N10O6, Mr = 792.32, Dc = 1.302 Mg/m3, F(000) = 792, µ(MoKa) = 1.356 mm-1, R = 0.0575 and wR = 0.0826. The compound [Ag2(Dpya)2.(NO3)2]n is a two-dimensional structure and there are two kinds of coordination configurations about the Ag atoms in the compound. The Ag(1) center is tetrahedrally coordinated with two O atoms of NO3- and two N atoms from the ligand Dpya. Meanwhile, the Ag(2) is five-coordinated by five O atoms from three NO3-anions. The Ag centers (Ag(1) and Ag(2)) connect to themselves as well as with each other by the bridging NO3-anions. And the coordination compound shows photoluminescence with an emission peak at 530 nm (λex = 450 nm) as the ligand Dpya.
2016, 35(3): 361-370
doi: 10.14102/j.cnki.0254-5861.2011-0885
Abstract:
Two new lanthanide complexes with ethoxybenzene-substituted nitronyl nitroxide radical (NIT-C8H9O) and hexafluoroacetylacetonate (hfac) ligand, [Gd(NIT-C8H9O)2(hfac)3]·C7H16 (1) and [Tb(NIT-C8H9O)2(hfac)3]·C7H16 (2), have been successfully synthesized and characterized by IR spectroscopy, elemental analyses, thermogravimetry analyses, and single-crystal X-ray diffraction. Both 1 and 2 exhibit a mononuclear structure in which the nitronyl nitroxide radical and hfac ligand act as monodentate and bidentate chelating modes, respectively. Magnetic studies show that ferromagnetic interactions (between intramolecular Gd and radical) and antiferromagnetic interactions (between the intramolecular radicals) coexist in complex 1. No obvious frequency dependent out-of-phase signals were observed in complex 2.
Two new lanthanide complexes with ethoxybenzene-substituted nitronyl nitroxide radical (NIT-C8H9O) and hexafluoroacetylacetonate (hfac) ligand, [Gd(NIT-C8H9O)2(hfac)3]·C7H16 (1) and [Tb(NIT-C8H9O)2(hfac)3]·C7H16 (2), have been successfully synthesized and characterized by IR spectroscopy, elemental analyses, thermogravimetry analyses, and single-crystal X-ray diffraction. Both 1 and 2 exhibit a mononuclear structure in which the nitronyl nitroxide radical and hfac ligand act as monodentate and bidentate chelating modes, respectively. Magnetic studies show that ferromagnetic interactions (between intramolecular Gd and radical) and antiferromagnetic interactions (between the intramolecular radicals) coexist in complex 1. No obvious frequency dependent out-of-phase signals were observed in complex 2.
2016, 35(3): 371-374
doi: 10.14102/j.cnki.0254-5861.2011-0881
Abstract:
Two novel naphthol derivatives (1 and 2) were synthesized and characterized via IR, 1H NMR, and HRMS. The structure of compound 2 was verified by single-crystal X-ray crystallography. It crystallizes in monoclinic, space group C2/c with a = 21.6725(9), b = 6.0127(3), c = 25.5405(14) Å, β = 94.716(5)°, V = 3316.9(3) Å3, Z = 8, F(000) = 1384, Dc = 1.511 Mg/m3, Mr = 377.22 and μ = 2.487 mm-1. In addition, their cholinesterase inhibitory activities in vitro toward Electrophorus electricus acetylcholinesterase (eelAChE) and horse serum butyrylcholinesterase (eqBChE) were further determined. The results showed that compound 1 as a new acetylcholinesterase (AChE) inhibitor displayed higher AChE inhibitory activity (IC50 = 1.4 μM), which could be considered for Alzheimer’s disease therapeutics.
Two novel naphthol derivatives (1 and 2) were synthesized and characterized via IR, 1H NMR, and HRMS. The structure of compound 2 was verified by single-crystal X-ray crystallography. It crystallizes in monoclinic, space group C2/c with a = 21.6725(9), b = 6.0127(3), c = 25.5405(14) Å, β = 94.716(5)°, V = 3316.9(3) Å3, Z = 8, F(000) = 1384, Dc = 1.511 Mg/m3, Mr = 377.22 and μ = 2.487 mm-1. In addition, their cholinesterase inhibitory activities in vitro toward Electrophorus electricus acetylcholinesterase (eelAChE) and horse serum butyrylcholinesterase (eqBChE) were further determined. The results showed that compound 1 as a new acetylcholinesterase (AChE) inhibitor displayed higher AChE inhibitory activity (IC50 = 1.4 μM), which could be considered for Alzheimer’s disease therapeutics.
2016, 35(3): 375-382
doi: 10.14102/j.cnki.0254-5861.2011-0876
Abstract:
Two lanthanide-oxo-cluster polymers were synthesized by hydrothermal reaction using Ln2O3 as initial lanthanide materials: [Ln4(SO4)4(OH)4(H2O)7]·4H2O (Ln = Er 1, Ho 2), and characterized by PXRD, IR spectra, X-ray single-crystal diffraction, 2D IR correlation spectra and UV-visible absorption spectra. Single-crystal X-ray analyses reveal that compounds 1 and 2 are isostructural, and they are both crystallized in the orthorhombic system Pccn space group. Compound 1 is a 3D lanthanide cluster polymer based on tetranuclear cubane-like [Er4(μ3-OH)4]8+ cations and SO42- anions. The overall structure of 1 can be assigned to 6-connected pcu-type topology with the point symbol of (412.63).
Two lanthanide-oxo-cluster polymers were synthesized by hydrothermal reaction using Ln2O3 as initial lanthanide materials: [Ln4(SO4)4(OH)4(H2O)7]·4H2O (Ln = Er 1, Ho 2), and characterized by PXRD, IR spectra, X-ray single-crystal diffraction, 2D IR correlation spectra and UV-visible absorption spectra. Single-crystal X-ray analyses reveal that compounds 1 and 2 are isostructural, and they are both crystallized in the orthorhombic system Pccn space group. Compound 1 is a 3D lanthanide cluster polymer based on tetranuclear cubane-like [Er4(μ3-OH)4]8+ cations and SO42- anions. The overall structure of 1 can be assigned to 6-connected pcu-type topology with the point symbol of (412.63).
2016, 35(3): 383-391
doi: 10.14102/j.cnki.0254-5861.2011-0859
Abstract:
Hydrothermal reactions of 3-cyanopyridine and NaN3 with ZnCl2 or CdCl2·5/2H2O in the presence of 1, 4-benzenedicarboxylic acid (H2bdc) yielded two new coordination polymers, {[Zn(3-ptz)(bdc)0.5(H2O)2]n·2H2O}n (1) and [Cd2(3-ptz)2Cl2]n (2), based on in situ synthesized 5-(3-pyridyl)tetrazolate (3-ptz-) organic ligand. They have been structurally characterized by elemental analysis (EA), infrared spectroscopy (IR) and single-crystal/powder X-ray diffraction (PXRD). In 1, two Zn(II) ions are linked together through two µ2-(3-ptz-) ligands to form a dimeric unit of [Zn(µ2-3-ptz)(H2O)2]22+, which is further connected with other equivalent units by µ2-bdc2- spacers, resulting in an infinite 1D polymeric chain of [Zn2(3-ptz)2(H2O)2(bdc)]n, and then strong hydrogen bonding interactions extend these 1D chains into a 3D supramolecular structure. In 2, the Cd(II) ions are connected through µ4-(3-ptz-) ligands and Cl- anions, leading to infinite 2D layers of [Cd2(3-ptz)Cl2]nn+, which are further linked by another µ4-(3-ptz-) pillared ligand to form a 3D layered-pillared framework architecture of [Cd2(3-ptz)2Cl2]n. Furthermore, thermal stability of these compounds was measured by thermogravimetric analysis (TGA) and their photoluminescent properties were also investigated in the solid state at room temperature.
Hydrothermal reactions of 3-cyanopyridine and NaN3 with ZnCl2 or CdCl2·5/2H2O in the presence of 1, 4-benzenedicarboxylic acid (H2bdc) yielded two new coordination polymers, {[Zn(3-ptz)(bdc)0.5(H2O)2]n·2H2O}n (1) and [Cd2(3-ptz)2Cl2]n (2), based on in situ synthesized 5-(3-pyridyl)tetrazolate (3-ptz-) organic ligand. They have been structurally characterized by elemental analysis (EA), infrared spectroscopy (IR) and single-crystal/powder X-ray diffraction (PXRD). In 1, two Zn(II) ions are linked together through two µ2-(3-ptz-) ligands to form a dimeric unit of [Zn(µ2-3-ptz)(H2O)2]22+, which is further connected with other equivalent units by µ2-bdc2- spacers, resulting in an infinite 1D polymeric chain of [Zn2(3-ptz)2(H2O)2(bdc)]n, and then strong hydrogen bonding interactions extend these 1D chains into a 3D supramolecular structure. In 2, the Cd(II) ions are connected through µ4-(3-ptz-) ligands and Cl- anions, leading to infinite 2D layers of [Cd2(3-ptz)Cl2]nn+, which are further linked by another µ4-(3-ptz-) pillared ligand to form a 3D layered-pillared framework architecture of [Cd2(3-ptz)2Cl2]n. Furthermore, thermal stability of these compounds was measured by thermogravimetric analysis (TGA) and their photoluminescent properties were also investigated in the solid state at room temperature.
2016, 35(3): 392-396
doi: 10.14102/j.cnki.0254-5861.2011-0849
Abstract:
A new dimeric Mn(II) complex, namely, [Mn(L)(PIP)]2·H2O (1), was synthesized under hydrothermal condition (H2L = 3-carboxy-1-carboxymethyl-2-oxidopyridinium and PIP = 2-(pyridin-3-yl)-1H-imidazo[4, 5-f][1, 10]phenanthroline). It crystallizes in triclinic, space group P1 with a = 9.2037(13), b = 9.6794(13), c = 14.649(3) Å, α = 94.858(3), β = 94.928(3), γ = 114.468(2)°, V = 1172.9(3) Å3, Z = 1, C52H34Mn2N12O11, Mr = 1112.79, Dc = 1.575 g/cm3, F(000) = 568, μ(MoKa) = 0.618 mm-1, R = 0.0432 and wR = 0.1151. In 1, two L anions bridge two Mn(II) atoms to give a dimeric [Mn(L)(PIP)] unit with the Mn…Mn distance of 3.009(2) Å. The two PIP ligands are located on both sides of the dimer, which provides suitable π-π stacking interactions between PIP ligands. By these π-π stacking interactions, adjacent dimers are extended into a two-dimensional supramolecular layer. Further, the strong N-H…O hydrogen bond stabilizes the supramolecular layer structure of 1. Moreover, the thermal behavior and luminescent property of 1 have been studied.
A new dimeric Mn(II) complex, namely, [Mn(L)(PIP)]2·H2O (1), was synthesized under hydrothermal condition (H2L = 3-carboxy-1-carboxymethyl-2-oxidopyridinium and PIP = 2-(pyridin-3-yl)-1H-imidazo[4, 5-f][1, 10]phenanthroline). It crystallizes in triclinic, space group P1 with a = 9.2037(13), b = 9.6794(13), c = 14.649(3) Å, α = 94.858(3), β = 94.928(3), γ = 114.468(2)°, V = 1172.9(3) Å3, Z = 1, C52H34Mn2N12O11, Mr = 1112.79, Dc = 1.575 g/cm3, F(000) = 568, μ(MoKa) = 0.618 mm-1, R = 0.0432 and wR = 0.1151. In 1, two L anions bridge two Mn(II) atoms to give a dimeric [Mn(L)(PIP)] unit with the Mn…Mn distance of 3.009(2) Å. The two PIP ligands are located on both sides of the dimer, which provides suitable π-π stacking interactions between PIP ligands. By these π-π stacking interactions, adjacent dimers are extended into a two-dimensional supramolecular layer. Further, the strong N-H…O hydrogen bond stabilizes the supramolecular layer structure of 1. Moreover, the thermal behavior and luminescent property of 1 have been studied.
2016, 35(3): 397-403
doi: 10.14102/j.cnki.0254-5861.2011-0853
Abstract:
Compound [Cd1.5(ppt)Br2(H2O)]2n (1), where Hppt = 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1, 2, 4-triazole, has been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectra, powder XRD, and X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P1 with a = 7.4402(6), b = 8.0570(7), c = 12.8674(11) Å, a = 89.7300(10), b = 89.8570(10), g = 68.3910(10)°, V = 717.13(10) Å3, Z = 1, Dc = 2.638 g/cm3, μ = 7.824 mm-1, F(000) = 534, the final R = 0.0324 and wR = 0.1084 for 2324 observed reflections with I > 2s(I). X-ray diffraction analyses revealed that complex 1 is a 2D layered coordination polymer constructed from the linkage of [Cd3(μ-Br)4] trinuclear units with ppt- spacers, and a 3D supramolecular architecture is further assembled in 1 via hydrogen-bonding contacts. Fluorescence measurements show that 1 has medium fluorescent emission at 450 nm.
Compound [Cd1.5(ppt)Br2(H2O)]2n (1), where Hppt = 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1, 2, 4-triazole, has been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectra, powder XRD, and X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P1 with a = 7.4402(6), b = 8.0570(7), c = 12.8674(11) Å, a = 89.7300(10), b = 89.8570(10), g = 68.3910(10)°, V = 717.13(10) Å3, Z = 1, Dc = 2.638 g/cm3, μ = 7.824 mm-1, F(000) = 534, the final R = 0.0324 and wR = 0.1084 for 2324 observed reflections with I > 2s(I). X-ray diffraction analyses revealed that complex 1 is a 2D layered coordination polymer constructed from the linkage of [Cd3(μ-Br)4] trinuclear units with ppt- spacers, and a 3D supramolecular architecture is further assembled in 1 via hydrogen-bonding contacts. Fluorescence measurements show that 1 has medium fluorescent emission at 450 nm.
2016, 35(3): 404-412
doi: 10.14102/j.cnki.0254-5861.2011-0866
Abstract:
Two new Co(II) coordination polymers, {[Co3(Hchda)2(chda)2(bpp)2(H2O)2]}n 1 and {[Co(chda)(bpe)(H2O)]·3H2O}n 2 (H2chda = 1, 1-cyclohexanediacetic acid, bpp = 1, 3-bis(4-pyridinyl)propane and bpe = 1, 2-bis(4-pyridinyl)ethylene), were hydrothermally synthe-sized and then characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. Complex 1 possesses an infinite metal-organic layer based on triply bridged linear trinuclear subunits and complex 2 exhibits a square (4, 4) grid layer with dangling lateral arms resulting from eight-membered rings above and below the layer. In addition, magnetic properties of complexes 1 and 2 are also given.
Two new Co(II) coordination polymers, {[Co3(Hchda)2(chda)2(bpp)2(H2O)2]}n 1 and {[Co(chda)(bpe)(H2O)]·3H2O}n 2 (H2chda = 1, 1-cyclohexanediacetic acid, bpp = 1, 3-bis(4-pyridinyl)propane and bpe = 1, 2-bis(4-pyridinyl)ethylene), were hydrothermally synthe-sized and then characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. Complex 1 possesses an infinite metal-organic layer based on triply bridged linear trinuclear subunits and complex 2 exhibits a square (4, 4) grid layer with dangling lateral arms resulting from eight-membered rings above and below the layer. In addition, magnetic properties of complexes 1 and 2 are also given.
2016, 35(3): 413-420
doi: 10.14102/j.cnki.0254-5861.2011-0856
Abstract:
The photochromic title compound, C26H18F6N2OS2, contains a 2, 5-dimethylthio-phene ring and a N-formyl aminoquinolinyl thiophene ring on the C=C double bond of the cyclopentene ring. The dihedral angles between the cyclopentene and attached N-formyl aminoquinolinyl thiophene ring and 2, 5-dimethylthiophene ring are 63.0° and 137.1°, respectively. The dihedral angle between the thiophene ring and the adjacent aminoquinoline ring is 5.7°. The molecule adopts an antiparallel conformation, with a distance between the two photoreactive C atoms of 3.763 Å. In addition, the absorption and fluorescence spectral changes were measured in acetonitile and solid at room temperature, and the result showed that the title compound could undergo photochromic reaction in both states.
The photochromic title compound, C26H18F6N2OS2, contains a 2, 5-dimethylthio-phene ring and a N-formyl aminoquinolinyl thiophene ring on the C=C double bond of the cyclopentene ring. The dihedral angles between the cyclopentene and attached N-formyl aminoquinolinyl thiophene ring and 2, 5-dimethylthiophene ring are 63.0° and 137.1°, respectively. The dihedral angle between the thiophene ring and the adjacent aminoquinoline ring is 5.7°. The molecule adopts an antiparallel conformation, with a distance between the two photoreactive C atoms of 3.763 Å. In addition, the absorption and fluorescence spectral changes were measured in acetonitile and solid at room temperature, and the result showed that the title compound could undergo photochromic reaction in both states.
2016, 35(3): 421-427
doi: 10.14102/j.cnki.0254-5861.2011-0878
Abstract:
A novel 3D metal-organic coordination polymer with helical chains based on a flexible 5-(imidazol-1-ylmethyl)isophthalic acid (H2L) as a main ligand and 1, 2-bis(4-pyridyl)ethane(bpa) as a N-containing ancillary ligand, [CdL(bpa)0.5]n (1), has been obtained under hydrothermal conditions and characterized by elemental analysis, powder X-ray diffraction (PXRD), IR, thermal gravimetric analyses (TGA) and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 10.984(2), b = 10.1829(12), c = 17.782(3) Å, β = 123.156(11)°, V = 1665.1(5) Å3, Z = 4, Mr = 448.72, Dc = 1.790 g/cm3, Rint = 0.0871, F(000) = 892, the final R = 0.0687 and wR = 0.1294 for 2920 observed reflections (I > 2σ(I)). In complex 1, the L2- anions connect Cd(II) ions to form two-dimensional metal-organic layers (Cd2L2)n, in which the 1D helical chains (Cd-L)n are alternately arranged in a right-and left-handed sequence. These layers are further linked to build a 3D network by the bpa ligand. In addtion, photo-luminescent properties for 1 are also investigated.
A novel 3D metal-organic coordination polymer with helical chains based on a flexible 5-(imidazol-1-ylmethyl)isophthalic acid (H2L) as a main ligand and 1, 2-bis(4-pyridyl)ethane(bpa) as a N-containing ancillary ligand, [CdL(bpa)0.5]n (1), has been obtained under hydrothermal conditions and characterized by elemental analysis, powder X-ray diffraction (PXRD), IR, thermal gravimetric analyses (TGA) and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 10.984(2), b = 10.1829(12), c = 17.782(3) Å, β = 123.156(11)°, V = 1665.1(5) Å3, Z = 4, Mr = 448.72, Dc = 1.790 g/cm3, Rint = 0.0871, F(000) = 892, the final R = 0.0687 and wR = 0.1294 for 2920 observed reflections (I > 2σ(I)). In complex 1, the L2- anions connect Cd(II) ions to form two-dimensional metal-organic layers (Cd2L2)n, in which the 1D helical chains (Cd-L)n are alternately arranged in a right-and left-handed sequence. These layers are further linked to build a 3D network by the bpa ligand. In addtion, photo-luminescent properties for 1 are also investigated.
2016, 35(3): 428-436
doi: 10.14102/j.cnki.0254-5861.2011-0880
Abstract:
Solvent dependent assembly obtained two novel Ni coordination polymers with H2tbtpa and flexible 1, 2-bix ligand (H2tbtpa = tetrabromoterephthalic acid and 1, 2-bix = 1, 2-bis(imidazol-1-ylmethyl)benzene), formulated as [Ni0.5(tbtpa)0.5(1, 2-bix)·(H2O)]n (1) and [Ni(tbtpa)(1, 2-bix)(H2O)2]n (2). They have been structurally characterized by single-crystal and powder X-ray diffraction, elemental analysis, FT-IR spectra and TGA. Compound 1 crystalizes in triclinic, space group P1 with a = 9.0276(4), b = 10.0012(6), c = 11.4955(5) Å, α = 69.121(5), β = 76.398(4), γ = 89.668(4)°, C36H32Br4NiN8O6, Mr = 1051.04, V = 939.05(8) Å3, Z = 1, Dc = 1.859 g·cm-3, μ = 6.222 mm-1, F(000) = 520, 8.502≤2θ≤134.16°, λ(CuKα) = 1.54184 Å, T = 294(6) K, the final R = 0.0750, wR = 0.1988 and S = 1.033. Compound 2 crystalizes in triclinic, space group P1 with a = 11.1257(7), b = 11.5062(6), c = 12.3529(4) Å, α = 88.861(3), β = 84.572(4), γ = 64.235(6)°, C22H18Br4NiN4O6, Mr = 812.75, V = 1417.36(1) Å3, Z = 2, Dc = 1.904 g·cm-3, μ = 7.968 mm-1, F(000) = 788, 7.2≤2θ≤134.1°, λ(CuKα) = 1.54184 Å, T = 294(6) K, the final R = 0.0414, wR = 0.0865 and S = 1.025. 1 shows a two-dimensional (4, 4)-sql topology and 2 manifests a three-dimensional 658 CdSO4 topology coordination polymer network.
Solvent dependent assembly obtained two novel Ni coordination polymers with H2tbtpa and flexible 1, 2-bix ligand (H2tbtpa = tetrabromoterephthalic acid and 1, 2-bix = 1, 2-bis(imidazol-1-ylmethyl)benzene), formulated as [Ni0.5(tbtpa)0.5(1, 2-bix)·(H2O)]n (1) and [Ni(tbtpa)(1, 2-bix)(H2O)2]n (2). They have been structurally characterized by single-crystal and powder X-ray diffraction, elemental analysis, FT-IR spectra and TGA. Compound 1 crystalizes in triclinic, space group P1 with a = 9.0276(4), b = 10.0012(6), c = 11.4955(5) Å, α = 69.121(5), β = 76.398(4), γ = 89.668(4)°, C36H32Br4NiN8O6, Mr = 1051.04, V = 939.05(8) Å3, Z = 1, Dc = 1.859 g·cm-3, μ = 6.222 mm-1, F(000) = 520, 8.502≤2θ≤134.16°, λ(CuKα) = 1.54184 Å, T = 294(6) K, the final R = 0.0750, wR = 0.1988 and S = 1.033. Compound 2 crystalizes in triclinic, space group P1 with a = 11.1257(7), b = 11.5062(6), c = 12.3529(4) Å, α = 88.861(3), β = 84.572(4), γ = 64.235(6)°, C22H18Br4NiN4O6, Mr = 812.75, V = 1417.36(1) Å3, Z = 2, Dc = 1.904 g·cm-3, μ = 7.968 mm-1, F(000) = 788, 7.2≤2θ≤134.1°, λ(CuKα) = 1.54184 Å, T = 294(6) K, the final R = 0.0414, wR = 0.0865 and S = 1.025. 1 shows a two-dimensional (4, 4)-sql topology and 2 manifests a three-dimensional 658 CdSO4 topology coordination polymer network.
2016, 35(3): 437-441
doi: 10.14102/j.cnki.0254-5861.2011-0846
Abstract:
Hydrothermal reaction of naphthalene-1, 8-dicarboxylate with PbCl2 leads to a new coordination polymer compound, Pb(C12H6O4). Single-crystal X-ray diffraction analysis reveals that it crystallizes in monoclinic, space group P21/c with a = 13.1648(18), b = 5.3881(8), c = 14.599(2) Å, β = 95.759(2)°, V = 1030.3(3) Å3, Z = 4, Mr = 384.32, Dc = 2.7167 g/cm3, F(000) = 768, μ(MoKα) = 16.37 mm-1, R = 0.043 and wR = 0.097. The structure of Pb(C12H6O4) was refined by two components non-merohedral twinning model with the twin law of (-1000-100.22401) and twinning ratio of 0.736:0.264. In this structure, the Pb atoms are surrounded by five O atoms from ligands into PbO5 polyhedra, which are further interconnected to form a 2D layer structure parallel to the bc-plane.
Hydrothermal reaction of naphthalene-1, 8-dicarboxylate with PbCl2 leads to a new coordination polymer compound, Pb(C12H6O4). Single-crystal X-ray diffraction analysis reveals that it crystallizes in monoclinic, space group P21/c with a = 13.1648(18), b = 5.3881(8), c = 14.599(2) Å, β = 95.759(2)°, V = 1030.3(3) Å3, Z = 4, Mr = 384.32, Dc = 2.7167 g/cm3, F(000) = 768, μ(MoKα) = 16.37 mm-1, R = 0.043 and wR = 0.097. The structure of Pb(C12H6O4) was refined by two components non-merohedral twinning model with the twin law of (-1000-100.22401) and twinning ratio of 0.736:0.264. In this structure, the Pb atoms are surrounded by five O atoms from ligands into PbO5 polyhedra, which are further interconnected to form a 2D layer structure parallel to the bc-plane.
2016, 35(3): 442-448
doi: 10.14102/j.cnki.0254-5861.2011-0915
Abstract:
A series of 10-substituted 9-aryl-3, 4, 6, 7, 9, 10-hexahydroacridine-1, 8(2H, 5H)-dione derivatives 2 were synthesized by a two-step reaction. All the compounds were characterized by IR, MS, and 1H NMR. Crystals of 1a and 2c were obtained and determined by X-ray single-crystal diffraction. Crystal data of 1a: C20H22O5, orthorhombic system, space group Pbcn, a = 15.8888(19), b = 18.228(2), c = 11.6926(13) Å, V = 3386.4(7) Å3, Z = 8, F(000) = 1456, Dc = 1.343 g/cm3, R = 0.0456 and wR = 0.1600. Crystal data of 2c: C26H24ClNO3, monoclinic system, space group P21/n, a = 8.628(2), b = 10.912(3), c = 22.425(7) Å, β = 90.786(4)°, V = 2111.1(10) Å3, Z = 4, F(000) = 912, Dc = 1.365 g/cm3, R = 0.0613, and wR = 0.1196. The results of biological experiments show that compounds 2b and 2c could inhibit the proliferation of HepG2 cells.
A series of 10-substituted 9-aryl-3, 4, 6, 7, 9, 10-hexahydroacridine-1, 8(2H, 5H)-dione derivatives 2 were synthesized by a two-step reaction. All the compounds were characterized by IR, MS, and 1H NMR. Crystals of 1a and 2c were obtained and determined by X-ray single-crystal diffraction. Crystal data of 1a: C20H22O5, orthorhombic system, space group Pbcn, a = 15.8888(19), b = 18.228(2), c = 11.6926(13) Å, V = 3386.4(7) Å3, Z = 8, F(000) = 1456, Dc = 1.343 g/cm3, R = 0.0456 and wR = 0.1600. Crystal data of 2c: C26H24ClNO3, monoclinic system, space group P21/n, a = 8.628(2), b = 10.912(3), c = 22.425(7) Å, β = 90.786(4)°, V = 2111.1(10) Å3, Z = 4, F(000) = 912, Dc = 1.365 g/cm3, R = 0.0613, and wR = 0.1196. The results of biological experiments show that compounds 2b and 2c could inhibit the proliferation of HepG2 cells.
2016, 35(3): 449-456
doi: 10.14102/j.cnki.0254-5861.2011-0904
Abstract:
The three-dimensional holographic vector of atomic interaction field (3D-HoVAIF) is used to characterize the molecular structures of 45 nitroaromatic compounds. Two quantitative structure-toxicity relationship (QSAR) models are built up by stepwise regression (SMR), multiple linear regression (MLR) and partial least-squares regression (PLS). The correlation coefficients (R) of the models are 0.960 and 0.961, respectively. Then the models are evaluated by performing the cross-validation with the leave-one-out (LOO) procedure and the correlation coefficients (RCV) are 0.949 and 0.941, respectively. The results show that the descriptors can successfully describe the structures of organic compounds. The stability and predictability of the model are satisfactory.
The three-dimensional holographic vector of atomic interaction field (3D-HoVAIF) is used to characterize the molecular structures of 45 nitroaromatic compounds. Two quantitative structure-toxicity relationship (QSAR) models are built up by stepwise regression (SMR), multiple linear regression (MLR) and partial least-squares regression (PLS). The correlation coefficients (R) of the models are 0.960 and 0.961, respectively. Then the models are evaluated by performing the cross-validation with the leave-one-out (LOO) procedure and the correlation coefficients (RCV) are 0.949 and 0.941, respectively. The results show that the descriptors can successfully describe the structures of organic compounds. The stability and predictability of the model are satisfactory.
2016, 35(3): 457-464
doi: 10.14102/j.cnki.0254-5861.2011-0913
Abstract:
The novel Schiff base (E)-8-chloro-N'-(4-(dimethylamino)benzylidene)-[1, 2, 4]tria-zolo[4, 3-a]pyridine-3-carbohydrazide was synthesized and characterized by 1H NMR, MS, elemental analysis and X-ray diffraction. The compound crystallizes in the monoclinic space group P21/c with a = 7.091(2), b = 10.750(3), c = 21.380(6) Å, β = 96.299(6)°, V = 1619.7(8) Å3, Z = 4 and R = 0.0351. Theoretical calculation of the title compound was carried out with the B3LYP/6-31G basis set. The frontier orbital energy and atomic net charges were discussed. It is found that the experimental data show good agreement with the calculated values. And the compound exhibits good antifungal activity against Stemphylium lycopersici (Enjoji) Yamamoto.
The novel Schiff base (E)-8-chloro-N'-(4-(dimethylamino)benzylidene)-[1, 2, 4]tria-zolo[4, 3-a]pyridine-3-carbohydrazide was synthesized and characterized by 1H NMR, MS, elemental analysis and X-ray diffraction. The compound crystallizes in the monoclinic space group P21/c with a = 7.091(2), b = 10.750(3), c = 21.380(6) Å, β = 96.299(6)°, V = 1619.7(8) Å3, Z = 4 and R = 0.0351. Theoretical calculation of the title compound was carried out with the B3LYP/6-31G basis set. The frontier orbital energy and atomic net charges were discussed. It is found that the experimental data show good agreement with the calculated values. And the compound exhibits good antifungal activity against Stemphylium lycopersici (Enjoji) Yamamoto.
2016, 35(3): 465-471
doi: 10.14102/j.cnki.0254-5861.2011-0989
Abstract:
A novel copper(II) complex based on chiral amino-alcohol derived Schiff base ligand, [Cu4(R-L)4(H2O)2]·(CH3COOH)2·(H2O) (1, (R)-H2L = (R)-3-phenyl-2-(2-hydroxy-3-methoxybenzylideneamino) propane-1-ol), was synthesized and characterized by EA, IR, UV-Vis, ESI-MS, circular dichroism spectra and single-crystal X-ray diffraction. Complex 1 crystallizes in orthorhombic, space group R21212 with a = 15.7660(14), b = 49.526(3), c = 10.4213(9) Å, V = 8137.2(12) Å3, Z = 4, C72H81Cu4N4O19, Mr = 1560.57, m = 1.096 mm-1, F(000) = 3244, Flack = 0.06(3), the final R = 0.0924 and wR = 0.2451 (I > 2s(I)) for 41108 observed reflections. The interactions of the complex with calf thymus DNA (CT-DNA) were investigated by some spectroscopic technique methods. The results show the complex exhibits strong binding with CT-DNA. In addition, in vitro cytotoxicity test of 1 towards four kinds of human cancerous cell lines (HeLa, HL-60, Caco-2 and A549) showed substantial cytotoxic activity. The experimental investigations indicated that the chirality of complex 1 play an important role in cytotoxicity and interactions with DNA.
A novel copper(II) complex based on chiral amino-alcohol derived Schiff base ligand, [Cu4(R-L)4(H2O)2]·(CH3COOH)2·(H2O) (1, (R)-H2L = (R)-3-phenyl-2-(2-hydroxy-3-methoxybenzylideneamino) propane-1-ol), was synthesized and characterized by EA, IR, UV-Vis, ESI-MS, circular dichroism spectra and single-crystal X-ray diffraction. Complex 1 crystallizes in orthorhombic, space group R21212 with a = 15.7660(14), b = 49.526(3), c = 10.4213(9) Å, V = 8137.2(12) Å3, Z = 4, C72H81Cu4N4O19, Mr = 1560.57, m = 1.096 mm-1, F(000) = 3244, Flack = 0.06(3), the final R = 0.0924 and wR = 0.2451 (I > 2s(I)) for 41108 observed reflections. The interactions of the complex with calf thymus DNA (CT-DNA) were investigated by some spectroscopic technique methods. The results show the complex exhibits strong binding with CT-DNA. In addition, in vitro cytotoxicity test of 1 towards four kinds of human cancerous cell lines (HeLa, HL-60, Caco-2 and A549) showed substantial cytotoxic activity. The experimental investigations indicated that the chirality of complex 1 play an important role in cytotoxicity and interactions with DNA.
2016, 35(3): 472-480
doi: 10.14102/j.cnki.0254-5861.2011-1041
Abstract:
CuFe2O4-TiO2/graphene nanocomposites have been prepared via a one-step hy-drothermal method, and the as-prepared CuFe2O4-TiO2/graphene was characterized by X-ray powder diffraction, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy. The transmission electron microscopy demonstrated that CuFe2O4-TiO2 nanoparticles were successfully dispersed on the graphene sheets. Photocatalytic activity of nanocomposites was evaluated in terms of degradation of methylene blue (MB) dye solution under visible light radiation. Results showed that the photocatalytic efficiency of CuFe2O4-TiO2/graphene nanocomposites was higher than its individual pure oxides (CuFe2O4 or TiO2) and TiO2/graphene. The enhancing photocatalytic activity performance of the CuFe2O4-TiO2/graphene nanocomposites may attributed to the mutual effect between the CuFe2O4, TiO2 nanoparticles and the graphene sheets. Moreover, CuFe2O4 nanoparticles have excellent magnetic property, which makes the CuFe2O4-TiO2/graphene heteroarchitecture magnetically recyclable in a suspension system.
CuFe2O4-TiO2/graphene nanocomposites have been prepared via a one-step hy-drothermal method, and the as-prepared CuFe2O4-TiO2/graphene was characterized by X-ray powder diffraction, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy. The transmission electron microscopy demonstrated that CuFe2O4-TiO2 nanoparticles were successfully dispersed on the graphene sheets. Photocatalytic activity of nanocomposites was evaluated in terms of degradation of methylene blue (MB) dye solution under visible light radiation. Results showed that the photocatalytic efficiency of CuFe2O4-TiO2/graphene nanocomposites was higher than its individual pure oxides (CuFe2O4 or TiO2) and TiO2/graphene. The enhancing photocatalytic activity performance of the CuFe2O4-TiO2/graphene nanocomposites may attributed to the mutual effect between the CuFe2O4, TiO2 nanoparticles and the graphene sheets. Moreover, CuFe2O4 nanoparticles have excellent magnetic property, which makes the CuFe2O4-TiO2/graphene heteroarchitecture magnetically recyclable in a suspension system.
2016, 35(3): 481-486
doi: 10.14102/j.cnki.0254-5861.2011-0921
Abstract:
The potassium tantalate niobate KTa0.63Nb0.37O3 single crystal with large size and good quality was synthesized by Czochralski method. The crystal composition and structure were determined by electric probe microanalysis (EPMA) and X-ray diffraction (XRD) technique, respectively. The sequence of phase transitions of the as-grown crystal was investigated by Raman scattering technique. What features in the phonon spectrum corresponding to each phase transition, namely cubic to tetragonal (C-T), tetragonal to orthorhombic (T-R) and orthorhombic to rhom-bohedral (O-R), is discussed. Following the features the C-T phase transition point measured is in the vicinity of -40 ℃, and the difference from theoretical value was discussed; T-O phase transition point is at around -130 ℃, while the O-R phase transition point was not obtained due to the band overlapping and experiment limit.
The potassium tantalate niobate KTa0.63Nb0.37O3 single crystal with large size and good quality was synthesized by Czochralski method. The crystal composition and structure were determined by electric probe microanalysis (EPMA) and X-ray diffraction (XRD) technique, respectively. The sequence of phase transitions of the as-grown crystal was investigated by Raman scattering technique. What features in the phonon spectrum corresponding to each phase transition, namely cubic to tetragonal (C-T), tetragonal to orthorhombic (T-R) and orthorhombic to rhom-bohedral (O-R), is discussed. Following the features the C-T phase transition point measured is in the vicinity of -40 ℃, and the difference from theoretical value was discussed; T-O phase transition point is at around -130 ℃, while the O-R phase transition point was not obtained due to the band overlapping and experiment limit.
2016, 35(3): 487-497
doi: 10.14102/j.cnki.0254-5861.2011-1098
Abstract:
Aerogel materials possess a wide variety of excellent functions, hence a striking number of applications have developed for them. In this paper, we present a historic review of the aerogel materials, showing the main concepts, research methods, important scientific problems, formation mechanism, structure characteristics and essence of aerogel. More applications are evolving as the scientific and engineering community, which becomes familiar with the unusual and exceptional physical properties of aerogels. In addition, we also discuss the huge development potential and prospect of polysaccharide aerogels as the research trend in the future.
Aerogel materials possess a wide variety of excellent functions, hence a striking number of applications have developed for them. In this paper, we present a historic review of the aerogel materials, showing the main concepts, research methods, important scientific problems, formation mechanism, structure characteristics and essence of aerogel. More applications are evolving as the scientific and engineering community, which becomes familiar with the unusual and exceptional physical properties of aerogels. In addition, we also discuss the huge development potential and prospect of polysaccharide aerogels as the research trend in the future.
