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2015 Volume 34 Issue 11
2015, 34(11): 1633-1640
doi: 10.14102/j.cnki.0254-5861.2011-0705
Abstract:
The geometries, relative stabilities, energy gaps, binding energies, frequencies, electronic structures and magnetic properties of the AunM- clusters (1≤n≤8; M=In, Tl) are systematically investigated by the first-principles method at the PW91PW91 level with the basis set of CEP-121G. The results show that doping with a single In/Tl atom can dramatically affect the ground-state geometries of gold clusters. The energy calculations show that the M-doped can enhance the stability of Aun+1- clusters and change their chemical activities. NPA results show charge transfers occur among the atoms and valence electrons within one atom. The calculated energy gap shows the same odd-even alternation tendency with cluster size. Furthermore, both the total and local magnetic moments display an obvious even-odd alternation phenomenon with the increase of gold atoms.
The geometries, relative stabilities, energy gaps, binding energies, frequencies, electronic structures and magnetic properties of the AunM- clusters (1≤n≤8; M=In, Tl) are systematically investigated by the first-principles method at the PW91PW91 level with the basis set of CEP-121G. The results show that doping with a single In/Tl atom can dramatically affect the ground-state geometries of gold clusters. The energy calculations show that the M-doped can enhance the stability of Aun+1- clusters and change their chemical activities. NPA results show charge transfers occur among the atoms and valence electrons within one atom. The calculated energy gap shows the same odd-even alternation tendency with cluster size. Furthermore, both the total and local magnetic moments display an obvious even-odd alternation phenomenon with the increase of gold atoms.
2015, 34(11): 1641-1651
doi: 10.14102/j.cnki.0254-5861.2011-0664
Abstract:
From the bioassay tests, 14 neuraminidase inhibitors (NIs) flavones and dihydro-flavones derivatives from natural plants displayed different degree of inhibitory activities. Further-more, compounds No. 8 and 14 showed good inhibitory activity against influenza A virus with IC50=835.4 and 860.6 μg/mL. Then, to investigate interactions between NIs and neuraminidase (NA), molecular docking was performed. Docking results indicated that Arg118, Asp151, Arg292 and Arg371 were the key residues in the active pocket of 2ht8. Main influencing factors of interactions between NIs and NA were hydrogen bond and electrostatic, then hydrophobic factor. Moreover, experimental activities of NIs were consistent with total scores of the docking. In order to understand the chemical-biological interactions governing their activities toward NA, QSAR models of 14 NIs were developed. The obtained HQSAR (hologram quantitative structure activity relationship), PLS (partial least squares) and SRA (stepwise regression analysis) models were robust and had good exterior predictive capabilities. Moreover, squared multiple correlation coefficients (R2) and squared cross-validated correlation coefficients (Q2) of HQSAR and PLS models based on descriptors by Gaussian and Sarchitect were 0.832 and 0.721, 0.925 and 0.688, 0.892 and 0.692, respectively. R2 and SE (standard error) of SRA model based on descriptors by Gaussian were 0.922 and 0.072. Therefore, these models may be further used to design and evaluate the bioactivity of new compounds.
From the bioassay tests, 14 neuraminidase inhibitors (NIs) flavones and dihydro-flavones derivatives from natural plants displayed different degree of inhibitory activities. Further-more, compounds No. 8 and 14 showed good inhibitory activity against influenza A virus with IC50=835.4 and 860.6 μg/mL. Then, to investigate interactions between NIs and neuraminidase (NA), molecular docking was performed. Docking results indicated that Arg118, Asp151, Arg292 and Arg371 were the key residues in the active pocket of 2ht8. Main influencing factors of interactions between NIs and NA were hydrogen bond and electrostatic, then hydrophobic factor. Moreover, experimental activities of NIs were consistent with total scores of the docking. In order to understand the chemical-biological interactions governing their activities toward NA, QSAR models of 14 NIs were developed. The obtained HQSAR (hologram quantitative structure activity relationship), PLS (partial least squares) and SRA (stepwise regression analysis) models were robust and had good exterior predictive capabilities. Moreover, squared multiple correlation coefficients (R2) and squared cross-validated correlation coefficients (Q2) of HQSAR and PLS models based on descriptors by Gaussian and Sarchitect were 0.832 and 0.721, 0.925 and 0.688, 0.892 and 0.692, respectively. R2 and SE (standard error) of SRA model based on descriptors by Gaussian were 0.922 and 0.072. Therefore, these models may be further used to design and evaluate the bioactivity of new compounds.
2015, 34(11): 1652-1658
doi: 10.14102/j.cnki.0254-5861.2011-0779
Abstract:
Bis(tricyclohexyltin) pimelicarboxylate, [(CH2)5(CO2SnCy3)2] (1), has been synthesized by the reaction of tricyclohexyltin hydroxide with pimelic acid and characterized by means of IR, 1H and 13C NMR, elemental analysis and X-ray diffraction. Complex 1 crystallizes in triclinic space group P1 with a=11.569(3), b=12.0419(2), c=17.3988(4) Å, α=81.4310(10), β=79.8270(10), γ=69.7060(10)°, V=2227.60(9) Å3, Z=2, C43H76O4Sn2, Mr=894.42, Dc=1.333 g·cm-3, μ=1.157 mm-1, F(000)=932, GOOF=1.339, the final R=0.0452 and wR=0.1333 for 6709 observed reflections (I>2σ(I)). Complex 1 shows discrete dimeric structures and the tin atoms have a distorted tetrahedral geometry. The 1D chain structure of complex 1 is formed by intermolecular Sn…O interactions. Complex 1 displays good thermal stability under 553 K and has selective antibacterial property. Complex 1 is strong in vitro anti-tumor activity against five human tumor cell lines, Colo205, HepG2, MCF-7, Hela and NCI-H460, and is significantly higher than that in the clinical use of carboplatin.
Bis(tricyclohexyltin) pimelicarboxylate, [(CH2)5(CO2SnCy3)2] (1), has been synthesized by the reaction of tricyclohexyltin hydroxide with pimelic acid and characterized by means of IR, 1H and 13C NMR, elemental analysis and X-ray diffraction. Complex 1 crystallizes in triclinic space group P1 with a=11.569(3), b=12.0419(2), c=17.3988(4) Å, α=81.4310(10), β=79.8270(10), γ=69.7060(10)°, V=2227.60(9) Å3, Z=2, C43H76O4Sn2, Mr=894.42, Dc=1.333 g·cm-3, μ=1.157 mm-1, F(000)=932, GOOF=1.339, the final R=0.0452 and wR=0.1333 for 6709 observed reflections (I>2σ(I)). Complex 1 shows discrete dimeric structures and the tin atoms have a distorted tetrahedral geometry. The 1D chain structure of complex 1 is formed by intermolecular Sn…O interactions. Complex 1 displays good thermal stability under 553 K and has selective antibacterial property. Complex 1 is strong in vitro anti-tumor activity against five human tumor cell lines, Colo205, HepG2, MCF-7, Hela and NCI-H460, and is significantly higher than that in the clinical use of carboplatin.
2015, 34(11): 1659-1664
doi: 10.14102/j.cnki.0254-5861.2011-0734
Abstract:
The title compound 1-(2-fluorobenzyl)-3-methoxy-4-methyl-1H-1,2,4-triazol-5(4H)-one (C11H12FN3O2) was synthesized, and its structure was confirmed by 1H NMR, IR, MS, elemental analysis and X-ray diffraction. It crystallizes in the monoclinic system, space group P1 with a=6.919(3), b=8.525(4), c=9.811(4) Å, α=84.22(2), β=71.028(19), γ=86.10(2)°, Dc=1.448 g/cm3, Z=2, V=544.2(4) Å3, F(000)=248, the final R=0.0379 and wR=0.0913 for 1709 observed reflections with I>2σ(I). The preliminary biological test shows that the title compound shows weak inhibitory activities against Phytophthora infestans, Botrytis cinerea, Corynespora cassiicola, Rhizoctonia solani and Pythium ultimum.
The title compound 1-(2-fluorobenzyl)-3-methoxy-4-methyl-1H-1,2,4-triazol-5(4H)-one (C11H12FN3O2) was synthesized, and its structure was confirmed by 1H NMR, IR, MS, elemental analysis and X-ray diffraction. It crystallizes in the monoclinic system, space group P1 with a=6.919(3), b=8.525(4), c=9.811(4) Å, α=84.22(2), β=71.028(19), γ=86.10(2)°, Dc=1.448 g/cm3, Z=2, V=544.2(4) Å3, F(000)=248, the final R=0.0379 and wR=0.0913 for 1709 observed reflections with I>2σ(I). The preliminary biological test shows that the title compound shows weak inhibitory activities against Phytophthora infestans, Botrytis cinerea, Corynespora cassiicola, Rhizoctonia solani and Pythium ultimum.
2015, 34(11): 1665-1674
doi: 10.14102/j.cnki.0254-5861.2011-0879
Abstract:
A three-dimensional (3D) Keggin-type heteropolytungstate{Zn(phen)3}3[ZnW12O40]·9H2O 1 (phen=1,10-phenanthroline) has been synthesized through a conventional hydrothermal synthesis and was characterized by X-ray single-crystal diffraction analysis, X-ray powder diffraction (XRD), IR, UV-DRS, thermogravimetric analysis (TGA), thermal-dependent 2D-IR correlation spectroscopy (2D-COS IR) and Raman spectrum. Crystal data for compound 1: trigonal system, space group R3 with a=b=25.268(4), c=17.462(5) Å, γ=120°, V=9655(4) Å3 and Z=3. Compound 1 is allomorphic to {Co(phen)3}3[CoW12O40]·9H2O 2, which has been reported by Feng Chai et al. In compound 2, its prominent feature is that the decisive role of water molecules (O-H…O) builds a 3D supramolecular structure. However, in the structure of compound 1, the interlayer space is filled by Zn(phen)3]2+ cations which linked the layers via C-H…O hydrogen bonding interactions to construct a three-dimensional framework. Two compounds are different in weak interactions, so we identify them by Thermal-dependent 2D-COS IR. Moreover, the fluorescence of compound 1 was also described.
A three-dimensional (3D) Keggin-type heteropolytungstate{Zn(phen)3}3[ZnW12O40]·9H2O 1 (phen=1,10-phenanthroline) has been synthesized through a conventional hydrothermal synthesis and was characterized by X-ray single-crystal diffraction analysis, X-ray powder diffraction (XRD), IR, UV-DRS, thermogravimetric analysis (TGA), thermal-dependent 2D-IR correlation spectroscopy (2D-COS IR) and Raman spectrum. Crystal data for compound 1: trigonal system, space group R3 with a=b=25.268(4), c=17.462(5) Å, γ=120°, V=9655(4) Å3 and Z=3. Compound 1 is allomorphic to {Co(phen)3}3[CoW12O40]·9H2O 2, which has been reported by Feng Chai et al. In compound 2, its prominent feature is that the decisive role of water molecules (O-H…O) builds a 3D supramolecular structure. However, in the structure of compound 1, the interlayer space is filled by Zn(phen)3]2+ cations which linked the layers via C-H…O hydrogen bonding interactions to construct a three-dimensional framework. Two compounds are different in weak interactions, so we identify them by Thermal-dependent 2D-COS IR. Moreover, the fluorescence of compound 1 was also described.
2015, 34(11): 1675-1681
doi: 10.14102/j.cnki.0254-5861.2011-0737
Abstract:
A new photochromic diarylethene, [1-(2-methyl-5-(4-chlorophenyl)-3-thienyl-2-(2-methoxylphenyl)]perfluorocyclopentene (1o, C23H15ClF6OS) was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the triclinic system, space group P1 with a=9.421(1), b=10.4664(1), c=11.2988(2), α=88.014(1), β=76.976(1), γ=82.319(1)°, Z=2, V=1075.7(2) Å3, Dc=1.509 mg/m3, μ=0.339 mm-1, F(000)=496, the final R=0.0353 and wR=0.0922 for 3303 observed reflections (I>2σ(I)). Further study demonstrated this compound underwent reversible photochromism with high contrast color-switching between colorless and blue in hexane. Upon UV/Vis irradiation, the fluorescence quenching efficiency can be attached to ca. 98% and recover to the initial state which exhibits high contrast fluorescent-switching between "on" and "off" states.
A new photochromic diarylethene, [1-(2-methyl-5-(4-chlorophenyl)-3-thienyl-2-(2-methoxylphenyl)]perfluorocyclopentene (1o, C23H15ClF6OS) was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the triclinic system, space group P1 with a=9.421(1), b=10.4664(1), c=11.2988(2), α=88.014(1), β=76.976(1), γ=82.319(1)°, Z=2, V=1075.7(2) Å3, Dc=1.509 mg/m3, μ=0.339 mm-1, F(000)=496, the final R=0.0353 and wR=0.0922 for 3303 observed reflections (I>2σ(I)). Further study demonstrated this compound underwent reversible photochromism with high contrast color-switching between colorless and blue in hexane. Upon UV/Vis irradiation, the fluorescence quenching efficiency can be attached to ca. 98% and recover to the initial state which exhibits high contrast fluorescent-switching between "on" and "off" states.
2015, 34(11): 1682-1688
doi: 10.14102/j.cnki.0254-5861.2011-0723
Abstract:
A new coordination compound, Ni(C6H12N4)2SO4·4H2O(NSH-HMTA) (HMTA, hexamethylenetetramine, C6H12N4), has been synthesized and its single crystals were obtained. NSH-HMTA belongs to the triclinic system, space group P1 with a=9.2534(6), b=13.3131(2), c=16.0373(2) Å, α=65.981(6), β=89.792(3), γ=89.677(4)°, Mr=880.2, Z=2, V=1804.6(3) Å3, μ=1.254 mm-1, F(000)=932, R=0.0555 (I>2σ(I)) and wR=0.1908 for 19343 observed reflections. HMTA substitutes for water molecules are located at the para-positions, forming a stretching octahedral nickel ion unit. Thermo-gravimetric analysis shows that the dehydration temperature of NSH-HMTA is about 92℃. The characteristic UV peaks are approximately 10 nm red-shifted by the absorption of octahedral HMTA complex ion units.
A new coordination compound, Ni(C6H12N4)2SO4·4H2O(NSH-HMTA) (HMTA, hexamethylenetetramine, C6H12N4), has been synthesized and its single crystals were obtained. NSH-HMTA belongs to the triclinic system, space group P1 with a=9.2534(6), b=13.3131(2), c=16.0373(2) Å, α=65.981(6), β=89.792(3), γ=89.677(4)°, Mr=880.2, Z=2, V=1804.6(3) Å3, μ=1.254 mm-1, F(000)=932, R=0.0555 (I>2σ(I)) and wR=0.1908 for 19343 observed reflections. HMTA substitutes for water molecules are located at the para-positions, forming a stretching octahedral nickel ion unit. Thermo-gravimetric analysis shows that the dehydration temperature of NSH-HMTA is about 92℃. The characteristic UV peaks are approximately 10 nm red-shifted by the absorption of octahedral HMTA complex ion units.
2015, 34(11): 1689-1696
doi: 10.14102/j.cnki.0254-5861.2011-0725
Abstract:
The macrocyclic ligand ⊂-H2pyN2-O3ane (2) was readily prepared in a diluted condition in THF. The mixture of 2 and Ni(OTf)2 in DMF using Et4NOH as the base source gave a mononuclear square planar complex (Et4N)[Ni(OH)(⊂-pyN2-O3ane)] (3). Addition of Fe(OTf)2 into the solution of 3 in DMF instantly generated a hexagonal molecular nickel-wheel 4 in 72% yield. Both 3 and 4 were characterized by X-ray crystallography on a MoKα radiation diffractometer (λ=0.71073 Å): the crystal of 3 was grown in space group P212121 with a=12.079(5), b=15.099(6), c=17.299(8) Å, V=3160(2) Å3, Z=4, Dc=1.369 g/cm3, F(000)=1384, C33H44N4NiO6, Mr=651.43, μ=0.665 cm-1, R=0.0353, wR=0.0668 for 4548 observed reflections with I>2σ(I); 4 is in space group P21/n with a=17.7416(17), b=17.5490(17), c=29.036(3) Å, β=106.195(2)°, V=8681.5(14) Å3, Z=2, Dc=1.352 g/cm3, F(000)=3704, C170H190N22Ni6O40, Mr=3533.70, μ=719 cm-1, R=0.0841 and wR=0.2339 for 9371 observed reflections with I>2σ(I).
The macrocyclic ligand ⊂-H2pyN2-O3ane (2) was readily prepared in a diluted condition in THF. The mixture of 2 and Ni(OTf)2 in DMF using Et4NOH as the base source gave a mononuclear square planar complex (Et4N)[Ni(OH)(⊂-pyN2-O3ane)] (3). Addition of Fe(OTf)2 into the solution of 3 in DMF instantly generated a hexagonal molecular nickel-wheel 4 in 72% yield. Both 3 and 4 were characterized by X-ray crystallography on a MoKα radiation diffractometer (λ=0.71073 Å): the crystal of 3 was grown in space group P212121 with a=12.079(5), b=15.099(6), c=17.299(8) Å, V=3160(2) Å3, Z=4, Dc=1.369 g/cm3, F(000)=1384, C33H44N4NiO6, Mr=651.43, μ=0.665 cm-1, R=0.0353, wR=0.0668 for 4548 observed reflections with I>2σ(I); 4 is in space group P21/n with a=17.7416(17), b=17.5490(17), c=29.036(3) Å, β=106.195(2)°, V=8681.5(14) Å3, Z=2, Dc=1.352 g/cm3, F(000)=3704, C170H190N22Ni6O40, Mr=3533.70, μ=719 cm-1, R=0.0841 and wR=0.2339 for 9371 observed reflections with I>2σ(I).
2015, 34(11): 1697-1702
doi: 10.14102/j.cnki.0254-5861.2011-0726
Abstract:
A new metal-organic coordination polymer, [Ag(L)(NO3)]n (1, L=β-amino-β-(pyrid-2-yl)acrylonitrile), has been synthesized by solvent method at ambient temperature and characterized through single-crystal diffraction, Fourier transformed infrared spectrum (FTIR), elemental analysis, thermogravimetry analysis (TGA) and fluorescent measurements. 1 crystallizes in the triclinic system, space group P1 with a=7.3600(3), b=8.5095(17), c=9.2936(14) Å, α=66.65(6), β=70.56(7), γ=71.59(6)°, V=492.4(4) Å3, μ=2.043 mm-1, Dc=2.104 Mg/m3, Z=2, Mr=312.01, F(000)=302, the final R=0.0347 and wR=0.0987 for 3924 observed reflections with I>2σ(I).
A new metal-organic coordination polymer, [Ag(L)(NO3)]n (1, L=β-amino-β-(pyrid-2-yl)acrylonitrile), has been synthesized by solvent method at ambient temperature and characterized through single-crystal diffraction, Fourier transformed infrared spectrum (FTIR), elemental analysis, thermogravimetry analysis (TGA) and fluorescent measurements. 1 crystallizes in the triclinic system, space group P1 with a=7.3600(3), b=8.5095(17), c=9.2936(14) Å, α=66.65(6), β=70.56(7), γ=71.59(6)°, V=492.4(4) Å3, μ=2.043 mm-1, Dc=2.104 Mg/m3, Z=2, Mr=312.01, F(000)=302, the final R=0.0347 and wR=0.0987 for 3924 observed reflections with I>2σ(I).
2015, 34(11): 1703-1708
doi: 10.14102/j.cnki.0254-5861.2011-0729
Abstract:
A heterometallic metal-organic framework, AgIn(nicotinate)4·1.5DMF, was obtain-ed from the reaction of nicotinic acid, AgNO3 and In(NO3)3 in DMF. The complex was characterized by elemental analysis, infrared spectrum, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Crystal data are: C28.5H26.5N5.5O9.5AgIn, orthorhombic space group I222, a=10.775(15), b=11.939(18), c=13.93(2) Å, V=1792(5) Å3, Z=2, Dc=1.521 mg/m3, μ=1.244 mm-1, F(000)=816, the final R=0.0672 and wR=0.1812 for 1912 observed reflections with I>2σ(I). Single-crystal X-ray structure analysis reveals that nicotinate bridges In(Ⅲ) and Ag(I) through carboxylate chelating with In(Ⅲ) and pyridyl nitrogen atom coordinating to Ag(I), generating a new 2D network consisting of tetrahedral building units of [AgN4]+ and [In(COO)4]-.
A heterometallic metal-organic framework, AgIn(nicotinate)4·1.5DMF, was obtain-ed from the reaction of nicotinic acid, AgNO3 and In(NO3)3 in DMF. The complex was characterized by elemental analysis, infrared spectrum, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Crystal data are: C28.5H26.5N5.5O9.5AgIn, orthorhombic space group I222, a=10.775(15), b=11.939(18), c=13.93(2) Å, V=1792(5) Å3, Z=2, Dc=1.521 mg/m3, μ=1.244 mm-1, F(000)=816, the final R=0.0672 and wR=0.1812 for 1912 observed reflections with I>2σ(I). Single-crystal X-ray structure analysis reveals that nicotinate bridges In(Ⅲ) and Ag(I) through carboxylate chelating with In(Ⅲ) and pyridyl nitrogen atom coordinating to Ag(I), generating a new 2D network consisting of tetrahedral building units of [AgN4]+ and [In(COO)4]-.
2015, 34(11): 1709-1716
doi: 10.14102/j.cnki.0254-5861.2011-0730
Abstract:
Two novel coordination compounds, [Cd2(HBTC)2(DPPZ)2(H2O)3]·2H2O (1) and [Cu2(HBTC)2(DPPZ)2(H2O)]n (2) based on 1,3,5-benzenetricarboxylic acid (H3BTC) and dipyrido[3,2-a:2',3'-c]phenazine (DPPZ) ligands, have been constructed under hydrothermal conditions. Two complexes are characterized by elemental analysis, IR and single-crystal X-ray diffraction. Structural analyses show that both complexes 1 and 2 present the three-dimensional supramolecular structures. In addition, two complexes exhibit luminescence property.
Two novel coordination compounds, [Cd2(HBTC)2(DPPZ)2(H2O)3]·2H2O (1) and [Cu2(HBTC)2(DPPZ)2(H2O)]n (2) based on 1,3,5-benzenetricarboxylic acid (H3BTC) and dipyrido[3,2-a:2',3'-c]phenazine (DPPZ) ligands, have been constructed under hydrothermal conditions. Two complexes are characterized by elemental analysis, IR and single-crystal X-ray diffraction. Structural analyses show that both complexes 1 and 2 present the three-dimensional supramolecular structures. In addition, two complexes exhibit luminescence property.
2015, 34(11): 1717-1722
doi: 10.14102/j.cnki.0254-5861.2011-0740
Abstract:
Two novel interpenetrating diamond frameworks, namely [Cd(mal)(bix)]n (1) and {[Zn(sub)(bib)]n·H2O}n (2) (H2mal=maleic acid, H2sub=suberic acid, bix=1,4-bis(imidazol-1-ylmethyl)-benzene, bib=1,4-bis(N-imidazolyl)butane) were hydrothermally synthesized and characterized by elemental analysis, infrared spectra (IR), and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the orthorhombic system with space group Pnma and features a 3-fold interpenetrating diamond framework. Compound 2 exhibits a 4-fold interpenetrating diamond network. The luminescent properties of these two compounds have also been investigated in detail.
Two novel interpenetrating diamond frameworks, namely [Cd(mal)(bix)]n (1) and {[Zn(sub)(bib)]n·H2O}n (2) (H2mal=maleic acid, H2sub=suberic acid, bix=1,4-bis(imidazol-1-ylmethyl)-benzene, bib=1,4-bis(N-imidazolyl)butane) were hydrothermally synthesized and characterized by elemental analysis, infrared spectra (IR), and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the orthorhombic system with space group Pnma and features a 3-fold interpenetrating diamond framework. Compound 2 exhibits a 4-fold interpenetrating diamond network. The luminescent properties of these two compounds have also been investigated in detail.
2015, 34(11): 1723-1728
doi: 10.14102/j.cnki.0254-5861.2011-0743
Abstract:
Three lanthanide coordination polymers [Ln(bcpb)0.5(NO3)(DEF)2] (Ln=Y (1), Tb (2), Eu (3), H4bcpb=2,5-bis(2,4-dicarboxyphenyl) pyridine and DEF=N,N-diethylformamide)) have been solvothermally synthesized under hydrothermal conditions with a novel H4bcpb ligand and trivalent lanthanide nitrates. Single-crystal X-ray diffraction analysis reveals that compounds 1~3 are isostructural and crystallize in the monoclinic system, space group P21/n. Crystal data for 1: C20H26N4O9Y, Mr=555.36, a=13.022(9), b=17.778(12), c=10.861(8) Å, β=100.208(3)°, V=2475(3) Å3, Z=4; Crystal data for 2: C20H26N4O9Tb, Mr=625.37, a=13.0476(4), b=17.8037(7), c=10.9398(3) Å, β=100.008(4)°, V=2496.4(12) Å3, Z=4; Crystal data for 3: C20H26N4O9Eu, Mr=618.41, a=13.055(4), b=17.833(5), c=10.893(3) Å, β=100.133(4)°, V=2496.4(12) Å3, Z=4. The compounds were characterized by thermogravimetric analysis (TGA), IR spectroscopy, and X-ray single-crystal diffraction. Compounds 1~3 all feature 2D networks with -ABAB-fashions. The luminescent properties of compounds 1~3 and free H4bcpb ligand were investigated at room temperature. The results show that the H4bcpb ligand can efficiently transfer energy to the Tb(Ⅲ) ions, while the energy is not fully transferred from the H4bcpb ligand to the Eu(Ⅲ) ions.
Three lanthanide coordination polymers [Ln(bcpb)0.5(NO3)(DEF)2] (Ln=Y (1), Tb (2), Eu (3), H4bcpb=2,5-bis(2,4-dicarboxyphenyl) pyridine and DEF=N,N-diethylformamide)) have been solvothermally synthesized under hydrothermal conditions with a novel H4bcpb ligand and trivalent lanthanide nitrates. Single-crystal X-ray diffraction analysis reveals that compounds 1~3 are isostructural and crystallize in the monoclinic system, space group P21/n. Crystal data for 1: C20H26N4O9Y, Mr=555.36, a=13.022(9), b=17.778(12), c=10.861(8) Å, β=100.208(3)°, V=2475(3) Å3, Z=4; Crystal data for 2: C20H26N4O9Tb, Mr=625.37, a=13.0476(4), b=17.8037(7), c=10.9398(3) Å, β=100.008(4)°, V=2496.4(12) Å3, Z=4; Crystal data for 3: C20H26N4O9Eu, Mr=618.41, a=13.055(4), b=17.833(5), c=10.893(3) Å, β=100.133(4)°, V=2496.4(12) Å3, Z=4. The compounds were characterized by thermogravimetric analysis (TGA), IR spectroscopy, and X-ray single-crystal diffraction. Compounds 1~3 all feature 2D networks with -ABAB-fashions. The luminescent properties of compounds 1~3 and free H4bcpb ligand were investigated at room temperature. The results show that the H4bcpb ligand can efficiently transfer energy to the Tb(Ⅲ) ions, while the energy is not fully transferred from the H4bcpb ligand to the Eu(Ⅲ) ions.
2015, 34(11): 1729-1734
doi: 10.14102/j.cnki.0254-5861.2011-0754
Abstract:
Two novel Ag coordination polymers based on tetrazole-yl acylamide, Ag(NTAA) (1, H-NTAA=N-(1H-tetrazol-5-yl)acetamide) and Ag(NTPA) (2, H-NTPA=N-(1H-tetrazol-5-yl)propionamide) have been synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction. Compound 1 features a 3-connected 4·82-fes network and com-pound 2 displays a ladder-like chain. The different structures between 1 and 2 are mainly related with the substituent groups of tetrazole-yl acylamide.
Two novel Ag coordination polymers based on tetrazole-yl acylamide, Ag(NTAA) (1, H-NTAA=N-(1H-tetrazol-5-yl)acetamide) and Ag(NTPA) (2, H-NTPA=N-(1H-tetrazol-5-yl)propionamide) have been synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction. Compound 1 features a 3-connected 4·82-fes network and com-pound 2 displays a ladder-like chain. The different structures between 1 and 2 are mainly related with the substituent groups of tetrazole-yl acylamide.
2015, 34(11): 1735-1741
doi: 10.14102/j.cnki.0254-5861.2011-0739
Abstract:
The C-Cl bond of N-(2-chlorophenyl)acetamide (1) was successfully activated by tetrakis(trimethylphosphine)nickel(0). The four-coordinate nickel(Ⅱ) chloride complex trans-[(C6H4NHC(=O)Me)Ni(PMe3)2Cl] (2) as a C-Cl bond activation product was obtained without coordination of the amide group. Phosphonium salt Cl-[Me3P+-ortho-C6H4NHC(=O)Me] (3) was isolated by reacting complex 2 as a starting material under 1 bar of CO at room temperature. The molecular and crystal structures of 2 were determined by single-crystal X-ray diffraction.
The C-Cl bond of N-(2-chlorophenyl)acetamide (1) was successfully activated by tetrakis(trimethylphosphine)nickel(0). The four-coordinate nickel(Ⅱ) chloride complex trans-[(C6H4NHC(=O)Me)Ni(PMe3)2Cl] (2) as a C-Cl bond activation product was obtained without coordination of the amide group. Phosphonium salt Cl-[Me3P+-ortho-C6H4NHC(=O)Me] (3) was isolated by reacting complex 2 as a starting material under 1 bar of CO at room temperature. The molecular and crystal structures of 2 were determined by single-crystal X-ray diffraction.
2015, 34(11): 1742-1748
doi: 10.14102/j.cnki.0254-5861.2011-0747
Abstract:
Three complexes, (PBT)W(CO)5 (1), (3,5-Me2PBT)W(CO)5 (2) and (3,5-Pri2PBT)W(CO)5 (3) (PBT=1H-(pyrazol-1-ylmethyl)-1,2,3-benzotriazole), were synthesized, and two of them were structurally characterized by X-ray crystallography. Complex 1 crystallizes in monoclinic with space group P21/c, a=1.0828(2), b=2.1655(4), c=0.6982(1) nm, β=93.39(3)°, V=1.6343(6) nm3, Z=4, Dc=2.126 g/cm3, F(000)=992, μ=7.107 mm-1, S=0.990, the final R=0.0301 and wR=0.0685. Complex 2 crystallizes in triclinic with space group P1, a=0.95021(8), b=0.98391(6), c=1.1433(1) nm, α=68.792(7), β=77.860(8), γ=75.533(6)°, V=0.9563(1) nm3, Z=2, Dc=1.914 g/cm3, F(000)=528, μ=6.078 mm-1, S=1.042, the final R=0.0253 and wR=0.0549. 1H-(Pyrazol-1-ylmethyl)-1,2,3-benzotriazoles acted as monodentate ligands through the 3-position nitrogen of the triazolyl group, and the pyrazolyl nitrogen did not participate in coordinating to the metal centers in these complexes. Their UV and fluorescence properties have been studied.
Three complexes, (PBT)W(CO)5 (1), (3,5-Me2PBT)W(CO)5 (2) and (3,5-Pri2PBT)W(CO)5 (3) (PBT=1H-(pyrazol-1-ylmethyl)-1,2,3-benzotriazole), were synthesized, and two of them were structurally characterized by X-ray crystallography. Complex 1 crystallizes in monoclinic with space group P21/c, a=1.0828(2), b=2.1655(4), c=0.6982(1) nm, β=93.39(3)°, V=1.6343(6) nm3, Z=4, Dc=2.126 g/cm3, F(000)=992, μ=7.107 mm-1, S=0.990, the final R=0.0301 and wR=0.0685. Complex 2 crystallizes in triclinic with space group P1, a=0.95021(8), b=0.98391(6), c=1.1433(1) nm, α=68.792(7), β=77.860(8), γ=75.533(6)°, V=0.9563(1) nm3, Z=2, Dc=1.914 g/cm3, F(000)=528, μ=6.078 mm-1, S=1.042, the final R=0.0253 and wR=0.0549. 1H-(Pyrazol-1-ylmethyl)-1,2,3-benzotriazoles acted as monodentate ligands through the 3-position nitrogen of the triazolyl group, and the pyrazolyl nitrogen did not participate in coordinating to the metal centers in these complexes. Their UV and fluorescence properties have been studied.
2015, 34(11): 1749-1755
doi: 10.14102/j.cnki.0254-5861.2011-0784
Abstract:
We successfully synthesized a new cobalt(Ⅱ) coordination polymer under hydro-thermal conditions, [Co(L)0.5(chdc)(H2O)]n (L=1,4-bis(thiabendazole)butane, H2chdc=1,4-cyclo-hexanedicarboxylic acid), which were then characterized by elemental analyses, TG, IR spectro-scopy and single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c with a=10.2855(12), b=9.3606(11), c=20.436(3) Å, β=91.573°, V=1966.8(4) Å3, Z=4, C20H22CoN3O5S, Mr=475.40, Dc=1.605 g/cm3, μ=1.018 mm-1 and F(000)=984. The complex possesses a uninodal three-connected hcb Shubnikov hexagonal plane structure with {63} topology. These planes are further linked into a 3D supramolecular network via O-H…O hydrogen bonds involving coordinated water molecules and oxygen atoms of chdc2- ligands. The fluorescence and catalytic activities of the complex for degradation of Congo red in a Fenton-like process were investigated.
We successfully synthesized a new cobalt(Ⅱ) coordination polymer under hydro-thermal conditions, [Co(L)0.5(chdc)(H2O)]n (L=1,4-bis(thiabendazole)butane, H2chdc=1,4-cyclo-hexanedicarboxylic acid), which were then characterized by elemental analyses, TG, IR spectro-scopy and single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c with a=10.2855(12), b=9.3606(11), c=20.436(3) Å, β=91.573°, V=1966.8(4) Å3, Z=4, C20H22CoN3O5S, Mr=475.40, Dc=1.605 g/cm3, μ=1.018 mm-1 and F(000)=984. The complex possesses a uninodal three-connected hcb Shubnikov hexagonal plane structure with {63} topology. These planes are further linked into a 3D supramolecular network via O-H…O hydrogen bonds involving coordinated water molecules and oxygen atoms of chdc2- ligands. The fluorescence and catalytic activities of the complex for degradation of Congo red in a Fenton-like process were investigated.
2015, 34(11): 1756-1760
doi: 10.14102/j.cnki.0254-5861.2011-0757
Abstract:
A new Pb(Ⅱ)-based coordination polymer, [Pb(L)]n (1), was hydrothermally synthesized and its structure was determined by single-crystal X-ray diffraction (H2L=octane-1,8-dicarboxylic acid). Compound 1 crystallizes in orthorhombic, space group Pnma with a=32.061(4), b=7.2597(8), c=4.8084(5) Å, V=1119.2(2) Å3, Z=4, C10H16O4Pb, Mr=407.42, Dc=2.418 g/cm3, F(000)=760, μ(MoKa)=15.066 mm-1, R=0.0270 and wR=0.0666. In 1, each Pb(Ⅱ) cation is coordinated by six carboxylate oxygen atoms from four L2- anions. Each L2- anion bridges three Pb(Ⅱ) atoms in a μ3:η2:η1:η1 mode to form a 3D framework. The structure of 1 was characterized by IR spectrum and thermogravimetric analysis. Moreover, solid state luminescent property of 1 was also investigated.
A new Pb(Ⅱ)-based coordination polymer, [Pb(L)]n (1), was hydrothermally synthesized and its structure was determined by single-crystal X-ray diffraction (H2L=octane-1,8-dicarboxylic acid). Compound 1 crystallizes in orthorhombic, space group Pnma with a=32.061(4), b=7.2597(8), c=4.8084(5) Å, V=1119.2(2) Å3, Z=4, C10H16O4Pb, Mr=407.42, Dc=2.418 g/cm3, F(000)=760, μ(MoKa)=15.066 mm-1, R=0.0270 and wR=0.0666. In 1, each Pb(Ⅱ) cation is coordinated by six carboxylate oxygen atoms from four L2- anions. Each L2- anion bridges three Pb(Ⅱ) atoms in a μ3:η2:η1:η1 mode to form a 3D framework. The structure of 1 was characterized by IR spectrum and thermogravimetric analysis. Moreover, solid state luminescent property of 1 was also investigated.
2015, 34(11): 1761-1767
doi: 10.14102/j.cnki.0254-5861.2011-0763
Abstract:
A cuprous dimer [Cu(POP)]2(pz4B)BF4·(CH3CN)3 (1, POP=bis(2-(diphenylphos-phanyl)phenyl)ether, pz4B-=tetrakis(pyrazol-i-yl)borate anion) was synthesized from the reaction of Cu(CH3CN)4BF4, POP and Kpz4B in CH3CN at room temperature. The compound was characterized by elemental analysis and X-ray single-Crystal structure analysis. It crystallizes in monoclinic, space group P21/c with a=12.3491(2), b=20.8845(3), c=33.0657(4) Å, β=94.251(1)°, V=8504.3(2) Å3, Z=4, Mr=1693.21, Dc=1.322 g/cm3, F(000)=3496, μ=1.843 mm-1, GOOF=1.031, the final R=0.0442 and wR=0.1235 for 14397 observed reflections with I>2σ(I). 1 is an ionic compound. It is composed of a BF4-anion and a {[Cu(POP)]2(pz4B)}+ cation. The cation contains two [Cu(POP)]+ cationic moieties and a pz4B- anionic linker. The Cu(I) ions show a distorted tetrahedral coordination geometry defined by two nitrogen atoms from a pz4B- bridging ligand and two phosphorous atoms from a POP terminal chelating ligand. The complex emits blue luminescence with the maximum peak at 457 nm with 3% quantum yield in solid state at room temperature. The Cu(I) centers are essentially electronically separated because both HOMO and LUMO contain very little contribution from the bridging ligand. The unexpected low emission is ascribed to the intramolecular interaction of the emissive centers.
A cuprous dimer [Cu(POP)]2(pz4B)BF4·(CH3CN)3 (1, POP=bis(2-(diphenylphos-phanyl)phenyl)ether, pz4B-=tetrakis(pyrazol-i-yl)borate anion) was synthesized from the reaction of Cu(CH3CN)4BF4, POP and Kpz4B in CH3CN at room temperature. The compound was characterized by elemental analysis and X-ray single-Crystal structure analysis. It crystallizes in monoclinic, space group P21/c with a=12.3491(2), b=20.8845(3), c=33.0657(4) Å, β=94.251(1)°, V=8504.3(2) Å3, Z=4, Mr=1693.21, Dc=1.322 g/cm3, F(000)=3496, μ=1.843 mm-1, GOOF=1.031, the final R=0.0442 and wR=0.1235 for 14397 observed reflections with I>2σ(I). 1 is an ionic compound. It is composed of a BF4-anion and a {[Cu(POP)]2(pz4B)}+ cation. The cation contains two [Cu(POP)]+ cationic moieties and a pz4B- anionic linker. The Cu(I) ions show a distorted tetrahedral coordination geometry defined by two nitrogen atoms from a pz4B- bridging ligand and two phosphorous atoms from a POP terminal chelating ligand. The complex emits blue luminescence with the maximum peak at 457 nm with 3% quantum yield in solid state at room temperature. The Cu(I) centers are essentially electronically separated because both HOMO and LUMO contain very little contribution from the bridging ligand. The unexpected low emission is ascribed to the intramolecular interaction of the emissive centers.
2015, 34(11): 1768-1778
doi: 10.14102/j.cnki.0254-5861.2011-0756
Abstract:
In this paper, a new solvent-free crystal phase transformation approach for fabrication of nano β-form oxytitanium phthalocyanine (TiOPc) with high crystallinity and excellent photoconductive properties is reported. The amorphous TiOPc powder is transformed to nano-β-TiOPc by the thermal-induction under a certain temperature in a simple way. According to the research of a series of conditions related to the thermal process, we get nice nano-β-TiOPc whose crystallinity is higher than 97% at 300℃ for annealing 2 hours. The morphology of nano-β-TiOPc is studied by SEM and TEM. Laser organic photoconductors doped β-TiOPc as the charge generation material are prepared to detect their photoelectric performance, and the results show decent photoconductive properties.
In this paper, a new solvent-free crystal phase transformation approach for fabrication of nano β-form oxytitanium phthalocyanine (TiOPc) with high crystallinity and excellent photoconductive properties is reported. The amorphous TiOPc powder is transformed to nano-β-TiOPc by the thermal-induction under a certain temperature in a simple way. According to the research of a series of conditions related to the thermal process, we get nice nano-β-TiOPc whose crystallinity is higher than 97% at 300℃ for annealing 2 hours. The morphology of nano-β-TiOPc is studied by SEM and TEM. Laser organic photoconductors doped β-TiOPc as the charge generation material are prepared to detect their photoelectric performance, and the results show decent photoconductive properties.
2015, 34(11): 1779-1785
doi: 10.14102/j.cnki.0254-5861.2011-0987
Abstract:
α- and β-Ga2O3 were prepared via a precipitation method. The as-prepared α- and β-Ga2O3 were characterized by X-ray diffraction (XRD), N2-sorption BET surface area, UV-vis diffuse reflectance spectra (DRS), photoluminescence spectroscopy (PL) and electron spin resonancespectroscopy (ESR). The photocatalytic activities of Ga2O3 were evaluated by the photocatalytic degradation of tetracycline sydrochloride solution. The results showed that the photocatalytic activity of β-Ga2O3 was higher than that of α-Ga2O3 and β-Ga2O3 obtained at the calcination temperature of 900℃, which showed the best photocatalytic activity. The reasons for the differences in photocatalytic activity of Ga2O3 are discussed in terms of crystallinity, surface area, crystals and electronic structures.
α- and β-Ga2O3 were prepared via a precipitation method. The as-prepared α- and β-Ga2O3 were characterized by X-ray diffraction (XRD), N2-sorption BET surface area, UV-vis diffuse reflectance spectra (DRS), photoluminescence spectroscopy (PL) and electron spin resonancespectroscopy (ESR). The photocatalytic activities of Ga2O3 were evaluated by the photocatalytic degradation of tetracycline sydrochloride solution. The results showed that the photocatalytic activity of β-Ga2O3 was higher than that of α-Ga2O3 and β-Ga2O3 obtained at the calcination temperature of 900℃, which showed the best photocatalytic activity. The reasons for the differences in photocatalytic activity of Ga2O3 are discussed in terms of crystallinity, surface area, crystals and electronic structures.
