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2015 Volume 34 Issue 7
2015, 34(7): 985-994
doi: 10.14102/j.cnki.0254-5861.2011-0690
Abstract:
In this paper, the reaction mechanism of HOCO with its radical has been investigated deeply by density functional theory (DFT), while the geometries and harmonic vibration frequencies of the reactants, intermediates, transition states and products have been calculated at the B3LYP/6-311++G** level. The CCSD(T)/cc-pVQZ method was used to further calculate the single-point energy of each stationary point along the reaction channel. The result shows that channels (b) and (d) via carbon-carbon intermediates are competing with the ones (e), (f), (i) and (l) through carbon-oxygen intermediates, and the six channels are dominant for the title reaction to produce HCOOH and CO2. The result also indicates that the hydrogen abstraction from the HOCO radical can be performed quickly by the self-interaction of HOCO in the absence of other radicals or atoms, which indirectly proves for the first time that the ground-state cis-HOCO radical is not decomposed by the tunneling effect. In addition, the charges of natural population analysis (NPA) and the variation of chemical bonds have been analyzed by the Natural Bond Orbital (NBO) method along with the important reaction path.
In this paper, the reaction mechanism of HOCO with its radical has been investigated deeply by density functional theory (DFT), while the geometries and harmonic vibration frequencies of the reactants, intermediates, transition states and products have been calculated at the B3LYP/6-311++G** level. The CCSD(T)/cc-pVQZ method was used to further calculate the single-point energy of each stationary point along the reaction channel. The result shows that channels (b) and (d) via carbon-carbon intermediates are competing with the ones (e), (f), (i) and (l) through carbon-oxygen intermediates, and the six channels are dominant for the title reaction to produce HCOOH and CO2. The result also indicates that the hydrogen abstraction from the HOCO radical can be performed quickly by the self-interaction of HOCO in the absence of other radicals or atoms, which indirectly proves for the first time that the ground-state cis-HOCO radical is not decomposed by the tunneling effect. In addition, the charges of natural population analysis (NPA) and the variation of chemical bonds have been analyzed by the Natural Bond Orbital (NBO) method along with the important reaction path.
2015, 34(7): 995-1003
doi: 10.14102/j.cnki.0254-5861.2011-0626
Abstract:
Based on the relationship between the quantitative structure and property (QSPR) of organic compounds, the surface electrostatic potential parameters of 29 polychlorinated diphenyl sulfides (PCDPSs) with experimental values were calculated and extracted, and Multiple Linear Regression (MLR) was used to model the linear relationship between the physicochemical properties (octanol/water partition coefficient, high performance liquid chromatography capacity factor) and molecular structure parameters of PCDPSs. The result shows that the main factors that affect the n-octanol/water partition coefficient and high performance liquid chromatography capacity factor are respectively the number of chlorin atoms substituted on the benzene ring (NCl) and the lowest unoccupied molecular orbital energy (ELUMO). Secondly, there are also molecular surface electrostatic potentials. This indicates that the molecular surface electrostatic potentials can effectively express the quantitative relationship between the physicochemical properties of PCDPSs and their molecule descriptions. The QSPR models established have strong stability and predictive ability. This also has proved the applicability of molecular surface electrostatic potential parameters in QSPR of PCDPSs.
Based on the relationship between the quantitative structure and property (QSPR) of organic compounds, the surface electrostatic potential parameters of 29 polychlorinated diphenyl sulfides (PCDPSs) with experimental values were calculated and extracted, and Multiple Linear Regression (MLR) was used to model the linear relationship between the physicochemical properties (octanol/water partition coefficient, high performance liquid chromatography capacity factor) and molecular structure parameters of PCDPSs. The result shows that the main factors that affect the n-octanol/water partition coefficient and high performance liquid chromatography capacity factor are respectively the number of chlorin atoms substituted on the benzene ring (NCl) and the lowest unoccupied molecular orbital energy (ELUMO). Secondly, there are also molecular surface electrostatic potentials. This indicates that the molecular surface electrostatic potentials can effectively express the quantitative relationship between the physicochemical properties of PCDPSs and their molecule descriptions. The QSPR models established have strong stability and predictive ability. This also has proved the applicability of molecular surface electrostatic potential parameters in QSPR of PCDPSs.
2015, 34(7): 1004-1012
doi: 10.14102/j.cnki.0254-5861.2011-0636
Abstract:
Theoretical investigations on the insertion reaction mechanisms of three-membered-ring silylenoid H2SiLiF with GeH3R (R=F, OH, NH2) have been systematically carried out by combined density functional theory (DFT) and ab initio quantum chemical calculations. The geometries of all stationary points for these reactions were optimized using the B3LYP method and then the QCISD method was used to calculate the single-point energies. The calculated results indicate that, there are one precursor complex (Q), one transition state (TS), and one intermediate (IM) which connect the reactants and the products along the potential energy surface. The insertion reactions of three-membered-ring silylenoid with GeH3R proceed in a concerted manner, forming H2RSi-GeH3 and LiF. The calculated potential energy barriers of the three reactions are 29.17, 30.90, and 54.07 kJ/mol, and the reaction energies for the three reactions are -127.05, -116.91, and -103.31 kJ/mol, respectively. The insertion reactions in solvents are similar to those in vacuum. Under the same situation, the insertion reactions should occur easily in the following order: GeH3-F> GeH3-OH> GeH3-NH2. The elucidations of the mechanism of these insertion reactions provided a new mode of silicon-germanium bond formation.
Theoretical investigations on the insertion reaction mechanisms of three-membered-ring silylenoid H2SiLiF with GeH3R (R=F, OH, NH2) have been systematically carried out by combined density functional theory (DFT) and ab initio quantum chemical calculations. The geometries of all stationary points for these reactions were optimized using the B3LYP method and then the QCISD method was used to calculate the single-point energies. The calculated results indicate that, there are one precursor complex (Q), one transition state (TS), and one intermediate (IM) which connect the reactants and the products along the potential energy surface. The insertion reactions of three-membered-ring silylenoid with GeH3R proceed in a concerted manner, forming H2RSi-GeH3 and LiF. The calculated potential energy barriers of the three reactions are 29.17, 30.90, and 54.07 kJ/mol, and the reaction energies for the three reactions are -127.05, -116.91, and -103.31 kJ/mol, respectively. The insertion reactions in solvents are similar to those in vacuum. Under the same situation, the insertion reactions should occur easily in the following order: GeH3-F> GeH3-OH> GeH3-NH2. The elucidations of the mechanism of these insertion reactions provided a new mode of silicon-germanium bond formation.
2015, 34(7): 1013-1018
doi: 10.14102/j.cnki.0254-5861.2011-0674
Abstract:
A new compound 3-(2-(3,5-diphenyl-4,5-dihydropyrazol-1-yl)thiazol-4-yl)-2H-chromen-2-one was synthesized by cyclocondensation of 3,5-diphenyl-4,5-dihydropyrazole-1-carbothioamide with 3-(2-bromoacetyl)-2H-chromen-2-one in ethanol at reflux for 2 hrs. The compound was characterized by IR, 1H-NMR, 13C-NMR and single-crystal X-ray diffraction analysis. The newly synthesized compound (C27H19N3O2S) crystallizes in the triclinic system, space group P1 with a=5.2476(6), b=18.289(2), c=23.115(3)Å, α=93.546(7), β=94.715(6), γ=92.347(7)°, V=2204.3(4)Å3, Z=4, Mr=449.51, crystal size=0.38mm×0.22mm×0.16mm, (I>2σ(I))=35317, 9736, 3785,Rint=0.081, (Δρ)max=0.19 and (Δρ)min=-0.24 e·Å-3. DNA interaction studies revealed that the target compound strongly interacts with DNA through an intercalation binding mode and the binding constant of the compound is 7.45×104M-1.
A new compound 3-(2-(3,5-diphenyl-4,5-dihydropyrazol-1-yl)thiazol-4-yl)-2H-chromen-2-one was synthesized by cyclocondensation of 3,5-diphenyl-4,5-dihydropyrazole-1-carbothioamide with 3-(2-bromoacetyl)-2H-chromen-2-one in ethanol at reflux for 2 hrs. The compound was characterized by IR, 1H-NMR, 13C-NMR and single-crystal X-ray diffraction analysis. The newly synthesized compound (C27H19N3O2S) crystallizes in the triclinic system, space group P1 with a=5.2476(6), b=18.289(2), c=23.115(3)Å, α=93.546(7), β=94.715(6), γ=92.347(7)°, V=2204.3(4)Å3, Z=4, Mr=449.51, crystal size=0.38mm×0.22mm×0.16mm, (I>2σ(I))=35317, 9736, 3785,Rint=0.081, (Δρ)max=0.19 and (Δρ)min=-0.24 e·Å-3. DNA interaction studies revealed that the target compound strongly interacts with DNA through an intercalation binding mode and the binding constant of the compound is 7.45×104M-1.
2015, 34(7): 1019-1027
doi: 10.14102/j.cnki.0254-5861.2011-0648
Abstract:
[Zn(L)(CH3OH)3] (H2L=N-(1-phenyl-3-methyl-4-propenylidene-5-pyrazolone)-salicylidene hydrazide) has been synthesized by the reaction of zinc nitrate and ligand H2L. The complex crystallizes in orthorhombic system, space group Pbca with a=5.888(15), b=14.564(14), c=22.20(2)Å, V=5137(8)Å3, Z=8 and F(000)=2184. The ligand serves as a negative bivalent tridentate chelating agent to coordinate with the central zinc(Ⅱ) atom. DNA-binding was studied by UV-Vis spectral analysis and ethidium bromide (EB) displacement experiments. The results showed that the DNA-binding constant of the complex is 5.1×104M-1. Antitumor activity of [Zn(L)(CH3OH)3] and the ligand have been investigated by MTT assay, which indicated that the complex has better cytotoxicity to Eca-109 and HeLa than free ligand.
[Zn(L)(CH3OH)3] (H2L=N-(1-phenyl-3-methyl-4-propenylidene-5-pyrazolone)-salicylidene hydrazide) has been synthesized by the reaction of zinc nitrate and ligand H2L. The complex crystallizes in orthorhombic system, space group Pbca with a=5.888(15), b=14.564(14), c=22.20(2)Å, V=5137(8)Å3, Z=8 and F(000)=2184. The ligand serves as a negative bivalent tridentate chelating agent to coordinate with the central zinc(Ⅱ) atom. DNA-binding was studied by UV-Vis spectral analysis and ethidium bromide (EB) displacement experiments. The results showed that the DNA-binding constant of the complex is 5.1×104M-1. Antitumor activity of [Zn(L)(CH3OH)3] and the ligand have been investigated by MTT assay, which indicated that the complex has better cytotoxicity to Eca-109 and HeLa than free ligand.
2015, 34(7): 1028-1034
doi: 10.14102/j.cnki.0254-5861.2011-0586
Abstract:
Two novel complexes, [Bi(Ⅲ)(S2CNBnEt)3] 1 and [Bi(Ⅲ)(S2CNPPPy-2)3] 2, were synthesized and characterized by elemental analysis, IR, 1H NMR, 13C NMR, TG-DTG and X-ray single-crystal diffraction. The structure reveals that complex 1 belongs to the monoclinic system, space group P21/c with a=11.457(5), b=17.437(8), c=33.439(14)Å, β=98.499(8)°, Z=4, V=6607(5)Å3, Dc=1.689 g·cm-3, F(000)=3328, μ=5.742 mm-1, the final R=0.0906, wR=0.1678 and S=1.032. The structure indicates that complex 2 belongs to the triclinic system, space group P1 with a=12.608(9), b=12.622(8), c=12.49(6)Å, α=102.652(15), β=103.013(14), γ=109.698(10)°, Z=1, V=1762.3(19)Å3, Dc=1.741 g·cm-3, F(000)=916, μ=5.395 mm-1, the final R=0.0482, wR=0.1206 and S=1.046. In the two complexes, each six-coordinated Bi(Ⅲ) atom adopts a pentagonal pyramidal configuration with six sulfur atoms from three ligands, and the dimmer structures are formed by weak interactions of Bi…S between two molecules. The anticancer activities of the two complexes were studied by evaluating their cytotoxicities against several human cancer cell lines using the MTT assay. Results indicated complex 2 showed moderate cytotoxic effects on the selected cancer cells.
Two novel complexes, [Bi(Ⅲ)(S2CNBnEt)3] 1 and [Bi(Ⅲ)(S2CNPPPy-2)3] 2, were synthesized and characterized by elemental analysis, IR, 1H NMR, 13C NMR, TG-DTG and X-ray single-crystal diffraction. The structure reveals that complex 1 belongs to the monoclinic system, space group P21/c with a=11.457(5), b=17.437(8), c=33.439(14)Å, β=98.499(8)°, Z=4, V=6607(5)Å3, Dc=1.689 g·cm-3, F(000)=3328, μ=5.742 mm-1, the final R=0.0906, wR=0.1678 and S=1.032. The structure indicates that complex 2 belongs to the triclinic system, space group P1 with a=12.608(9), b=12.622(8), c=12.49(6)Å, α=102.652(15), β=103.013(14), γ=109.698(10)°, Z=1, V=1762.3(19)Å3, Dc=1.741 g·cm-3, F(000)=916, μ=5.395 mm-1, the final R=0.0482, wR=0.1206 and S=1.046. In the two complexes, each six-coordinated Bi(Ⅲ) atom adopts a pentagonal pyramidal configuration with six sulfur atoms from three ligands, and the dimmer structures are formed by weak interactions of Bi…S between two molecules. The anticancer activities of the two complexes were studied by evaluating their cytotoxicities against several human cancer cell lines using the MTT assay. Results indicated complex 2 showed moderate cytotoxic effects on the selected cancer cells.
2015, 34(7): 1035-1040
doi: 10.14102/j.cnki.0254-5861.2011-0622
Abstract:
2-Benzyl-7-butoxyl-9-isobutyl-1-methyl-β-carboline bromide (H-2-65) was synthesized by the reaction of Harmine with 1-iodobutane via N9-alkylation, demethyl and N2-quaternarization to obtain the new compound. The results demonstrate that H-2-65 has more remarkable anticancer activities in vitro. The results of 1H NMR, 13C NMR, DEPT, gCOSY, gHSQC, gHMBC, MS, single-crystal X-ray diffraction and elemental analysis showed that the title compound crystallizes in the triclinic system, space group P1 with a=9.545(5), b=11.724(5), c=11.839(6)Å, α=77.530(6), β=87.169(6), γ=72.823(5)°, Z=2, V=1235.8(10)Å3, Dc=1.294 g·cm-3, F(000)=504, the final R=0.0453, wR=0.1262 and S=1.044.
2-Benzyl-7-butoxyl-9-isobutyl-1-methyl-β-carboline bromide (H-2-65) was synthesized by the reaction of Harmine with 1-iodobutane via N9-alkylation, demethyl and N2-quaternarization to obtain the new compound. The results demonstrate that H-2-65 has more remarkable anticancer activities in vitro. The results of 1H NMR, 13C NMR, DEPT, gCOSY, gHSQC, gHMBC, MS, single-crystal X-ray diffraction and elemental analysis showed that the title compound crystallizes in the triclinic system, space group P1 with a=9.545(5), b=11.724(5), c=11.839(6)Å, α=77.530(6), β=87.169(6), γ=72.823(5)°, Z=2, V=1235.8(10)Å3, Dc=1.294 g·cm-3, F(000)=504, the final R=0.0453, wR=0.1262 and S=1.044.
2015, 34(7): 1041-1055
doi: 10.14102/j.cnki.0254-5861.2011-0584
Abstract:
The geometries, stability, electronic and magnetic properties of Mn4TM (TM=3d, 4d) clusters have been systematically studied by means of a density functional theory with generalized gradient approximation. Except Mn4Tc, the most stable structures for Mn4TM clusters are all the distorted triangular bi-pyramid structures with the transition-metal atom at the vertex or at the middle plane. The systemic study on average binding energy and HOMO-LUMO energy gap demonstrates that TM-doping could stabilize the host cluster. For entire Mn4TM clusters, the total magnetic moments are increased in various degrees compared with pure Mn5 cluster, except the Mn4Tc. Mn4Ni and Mn4Pd cluster possess a larger ferromagnetic alignment moment (20 μB), which suggests their potential applications as an ideal construct primitive of the high-density holographic storage material. The different doping atoms resulting in various magnetic properties are also elucidated in this paper.
The geometries, stability, electronic and magnetic properties of Mn4TM (TM=3d, 4d) clusters have been systematically studied by means of a density functional theory with generalized gradient approximation. Except Mn4Tc, the most stable structures for Mn4TM clusters are all the distorted triangular bi-pyramid structures with the transition-metal atom at the vertex or at the middle plane. The systemic study on average binding energy and HOMO-LUMO energy gap demonstrates that TM-doping could stabilize the host cluster. For entire Mn4TM clusters, the total magnetic moments are increased in various degrees compared with pure Mn5 cluster, except the Mn4Tc. Mn4Ni and Mn4Pd cluster possess a larger ferromagnetic alignment moment (20 μB), which suggests their potential applications as an ideal construct primitive of the high-density holographic storage material. The different doping atoms resulting in various magnetic properties are also elucidated in this paper.
2015, 34(7): 1056-1062
doi: 10.14102/j.cnki.0254-5861.2011-0659
Abstract:
The subsolidus phase relations of the ternary system ZnO-MoO3-Bi2O3 have been investigated by X-ray diffraction (XRD) analyses. The phase diagrams have been constructed. There are eight binary compounds and no ternary compound in the ZnO-MoO3-Bi2O3 system. This system can be divided into nine three-phase regions. From the phase relations of ZnO-MoO3-Bi2O3 system, the possible component regions for ZnO single crystal flux growth are ZnO-Zn3Mo2O9-Bi2MoO6, ZnO-Bi2MoO6-Bi26Mo10O69, ZnO-Bi26Mo10O69-Bi14MoO24, and ZnO-Bi14MoO24-Bi38ZnO58.
The subsolidus phase relations of the ternary system ZnO-MoO3-Bi2O3 have been investigated by X-ray diffraction (XRD) analyses. The phase diagrams have been constructed. There are eight binary compounds and no ternary compound in the ZnO-MoO3-Bi2O3 system. This system can be divided into nine three-phase regions. From the phase relations of ZnO-MoO3-Bi2O3 system, the possible component regions for ZnO single crystal flux growth are ZnO-Zn3Mo2O9-Bi2MoO6, ZnO-Bi2MoO6-Bi26Mo10O69, ZnO-Bi26Mo10O69-Bi14MoO24, and ZnO-Bi14MoO24-Bi38ZnO58.
2015, 34(7): 1063-1068
doi: 10.14102/j.cnki.0254-5861.2011-0302
Abstract:
A new metal-organic coordination polymer [Zn2(trz)2(mpda)(H2O)]n (1, trz=1,2,4-triazole, H2mpda=2,6-dimethylpyridine-3,5-dicarboxylic acid) was synthesized and characterized by single-crystal X-ray analyses. The crystal is of monoclinic system, space group P21/c, a=9.619(3), b=8.920(3), c=22.159(6)Å, β=96.897(4)°, V=1887.3(9)Å3, Z=4, Mr=478.04, Dc=1.682 Mg/m3, F(000)=960, the final R=0.0264 and wR=0.0870 (I>2σ(I)). Compound 1 consists of {[Zn4(trz)4]4+}n layers, which are further connected by mpda2- to complete a three-dimensional structure. The title compound exhibits luminescence at λmax=415 nm upon excitation at 364 nm.
A new metal-organic coordination polymer [Zn2(trz)2(mpda)(H2O)]n (1, trz=1,2,4-triazole, H2mpda=2,6-dimethylpyridine-3,5-dicarboxylic acid) was synthesized and characterized by single-crystal X-ray analyses. The crystal is of monoclinic system, space group P21/c, a=9.619(3), b=8.920(3), c=22.159(6)Å, β=96.897(4)°, V=1887.3(9)Å3, Z=4, Mr=478.04, Dc=1.682 Mg/m3, F(000)=960, the final R=0.0264 and wR=0.0870 (I>2σ(I)). Compound 1 consists of {[Zn4(trz)4]4+}n layers, which are further connected by mpda2- to complete a three-dimensional structure. The title compound exhibits luminescence at λmax=415 nm upon excitation at 364 nm.
2015, 34(7): 1069-1079
doi: 10.14102/j.cnki.0254-5861.2011-0526
Abstract:
Two new metal-organic complexes [Cd2(1,4-BDC)(4-pytyp)(H2O)4]·(1,4-BDC) (1) and [Cu2(1,4-BDC)(4-pytyp)2(H2O)2]·(1,4-BDC)·8H2O (2) (4-pytyp=4'-(4"-pyridyl)-2,2':6',2"-terpyridine, 1,4-H2BDC=1,4-benzenedicarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.
Two new metal-organic complexes [Cd2(1,4-BDC)(4-pytyp)(H2O)4]·(1,4-BDC) (1) and [Cu2(1,4-BDC)(4-pytyp)2(H2O)2]·(1,4-BDC)·8H2O (2) (4-pytyp=4'-(4"-pyridyl)-2,2':6',2"-terpyridine, 1,4-H2BDC=1,4-benzenedicarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.
2015, 34(7): 1080-1086
doi: 10.14102/j.cnki.0254-5861.2011-0562
Abstract:
A complex [Cd2Na2(BOABA)2(H2O)8]·H2O (1) was synthesized by using 2,4-bisoxyacetate-benzoic acid (H3BOABA) and Cd(OH)2. It was characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a two-dimensional 3-connected rigid plane. The interactions between the ligand and its complex with DNA were studied by EtBr fluorescence probe. Photoluminescent studies indicate that the complex may be excellent candidates for potential photoactive materials.
A complex [Cd2Na2(BOABA)2(H2O)8]·H2O (1) was synthesized by using 2,4-bisoxyacetate-benzoic acid (H3BOABA) and Cd(OH)2. It was characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a two-dimensional 3-connected rigid plane. The interactions between the ligand and its complex with DNA were studied by EtBr fluorescence probe. Photoluminescent studies indicate that the complex may be excellent candidates for potential photoactive materials.
2015, 34(7): 1087-1091
doi: 10.14102/j.cnki.0254-5861.2011-0587
Abstract:
A new polymeric znic(Ⅱ) coordination polymer, [Zn2(bptc)·(H2O)4]n·nCH3OH 1, was synthesized by the hydrothermal reaction of Zn(NO3)2·6H2O with 1,1'-biphenyl-2,2',6,6'-tetracarboxylic acid (H4bptc) and structurally characterized by single-crystal diffraction, IR and elemental analysis. The polymer crystallizes in the orthorhombic system, space group Pnna with a=13.411(1), b=16.418(2), c=9.178(7)Å, V=2025.2(3)Å3, Z=4, C17H14O13Zn2, Mr=557.06, Dc=1.827 g/cm3, F(000)=1120, μ(MoKα)=2.439 mm-1. The final R and wR are 0.0548 and 0.1691 for 1279 observed reflections with I>2σ(I). In this compound, the bptc4- anion adopts monodentate bridging coordination modes connecting the zinc(Ⅱ) ions to form a 1D chain structure, which furnishes a 2D supramolecular architecture through hydrogen bonding interactions formed by carboxylic oxygen atoms of bpdc, oxygen atoms of crystalline methanol and water molecules. Complex 1 displays an emissive maximum at 435 nm in the solid state at room temperature.
A new polymeric znic(Ⅱ) coordination polymer, [Zn2(bptc)·(H2O)4]n·nCH3OH 1, was synthesized by the hydrothermal reaction of Zn(NO3)2·6H2O with 1,1'-biphenyl-2,2',6,6'-tetracarboxylic acid (H4bptc) and structurally characterized by single-crystal diffraction, IR and elemental analysis. The polymer crystallizes in the orthorhombic system, space group Pnna with a=13.411(1), b=16.418(2), c=9.178(7)Å, V=2025.2(3)Å3, Z=4, C17H14O13Zn2, Mr=557.06, Dc=1.827 g/cm3, F(000)=1120, μ(MoKα)=2.439 mm-1. The final R and wR are 0.0548 and 0.1691 for 1279 observed reflections with I>2σ(I). In this compound, the bptc4- anion adopts monodentate bridging coordination modes connecting the zinc(Ⅱ) ions to form a 1D chain structure, which furnishes a 2D supramolecular architecture through hydrogen bonding interactions formed by carboxylic oxygen atoms of bpdc, oxygen atoms of crystalline methanol and water molecules. Complex 1 displays an emissive maximum at 435 nm in the solid state at room temperature.
2015, 34(7): 1092-1098
doi: 10.14102/j.cnki.0254-5861.2011-0596
Abstract:
Complexes Cl-RuⅡ(dppe)2(FeCl4)·2CH2Cl2 (2) and Br-RuⅡ(dppe)2(FeBr4)·2CH2Cl2 (3) were prepared by the reaction of trans-RuⅡ(dppe)2Cl2 (1) with FeX3 (X=Cl, Br). More interestingly, the central Ru atoms of RuⅡ(dppe)-based complexes (2 and 3) define a tetragonal pyramid with five-coordination. The temperature dependence magnetic susceptibilities indicate that the χMT values of complexes 2 and 3 are almost constant at 50~300 K, and the χMT values sharply decrease with further decreasing the temperature at low temperature due to the zero-field splitting (ZFS) of high spin Fe(Ⅲ) ions.
Complexes Cl-RuⅡ(dppe)2(FeCl4)·2CH2Cl2 (2) and Br-RuⅡ(dppe)2(FeBr4)·2CH2Cl2 (3) were prepared by the reaction of trans-RuⅡ(dppe)2Cl2 (1) with FeX3 (X=Cl, Br). More interestingly, the central Ru atoms of RuⅡ(dppe)-based complexes (2 and 3) define a tetragonal pyramid with five-coordination. The temperature dependence magnetic susceptibilities indicate that the χMT values of complexes 2 and 3 are almost constant at 50~300 K, and the χMT values sharply decrease with further decreasing the temperature at low temperature due to the zero-field splitting (ZFS) of high spin Fe(Ⅲ) ions.
2015, 34(7): 1099-1106
doi: 10.14102/j.cnki.0254-5861.2011-0597
Abstract:
The zinc complex with neutral organochalcogen ligand Mbit, [(Mbit)2Zn](ClO4)2 (1, Mbit=1,1'-methylenebis(3-methyl-imidazole-2-thione)), has been synthesized and characterized. The complex has been characterized by elemental analysis, NMR and IR spectra. The molecular structure of 1 has been determined by X-ray crystallography. For the complex, C18H24Cl2N8O8S4Zn, Mr=744.96, triclinic, space group P1, a=11.2923(18), b=11.9353(19), c=13.837(3)Å, α=114.763(2), β=92.132(2), γ=116.039(2)°, V=1464.6(5)Å3, Z=2, Dc=1.689 g/cm3, λ=1.54184Å, μ=1.363 mm-1, F(000)=760, S=1.098, the final R=0.0554 and wR=0.0.1579. Complex 1 exhibits photocatalytic activity for methyl orange (MO) degradation under UV light and shows good stability toward photocatalysis.
The zinc complex with neutral organochalcogen ligand Mbit, [(Mbit)2Zn](ClO4)2 (1, Mbit=1,1'-methylenebis(3-methyl-imidazole-2-thione)), has been synthesized and characterized. The complex has been characterized by elemental analysis, NMR and IR spectra. The molecular structure of 1 has been determined by X-ray crystallography. For the complex, C18H24Cl2N8O8S4Zn, Mr=744.96, triclinic, space group P1, a=11.2923(18), b=11.9353(19), c=13.837(3)Å, α=114.763(2), β=92.132(2), γ=116.039(2)°, V=1464.6(5)Å3, Z=2, Dc=1.689 g/cm3, λ=1.54184Å, μ=1.363 mm-1, F(000)=760, S=1.098, the final R=0.0554 and wR=0.0.1579. Complex 1 exhibits photocatalytic activity for methyl orange (MO) degradation under UV light and shows good stability toward photocatalysis.
2015, 34(7): 1107-1112
doi: 10.14102/j.cnki.0254-5861.2011-0613
Abstract:
A new complex [Rh(COD)(2,2'-bipy)]·[Rh(COD)Cl2] (COD=1,5-cyclooctadiene, 2,2'-bipy=2,2'-bipyridine) has been synthesized and characterized by elemental analyses, NMR and single-crystal X-ray diffraction. The complex crystallizes in triclinic system, space group P1 with a=7.4782(14), b=10.1400(11), c=16.6982(14)Å, α=103.494(11), β=91.996(13), γ=103.829(12)°, C26H32Cl2N2Rh2, Mr=649.26, V=1190.0(3)Å3, Dc=1.812 g/cm3, Z=2, F(000)=652, μ(MoKα)=1.629 mm-1, R=0.0286 and wR=0.0463 for 3718 observed reflections (I>2σ(I)). The complex was linked to form 1D chains by hydrogen bonding interaction (C-H…Cl), and further to construct a 2D layer structure by π…π stacking interactions between the pyridine rings of 2,2'-bipy ligands. The hydroformylation catalyzed by the title complex was also studied.
A new complex [Rh(COD)(2,2'-bipy)]·[Rh(COD)Cl2] (COD=1,5-cyclooctadiene, 2,2'-bipy=2,2'-bipyridine) has been synthesized and characterized by elemental analyses, NMR and single-crystal X-ray diffraction. The complex crystallizes in triclinic system, space group P1 with a=7.4782(14), b=10.1400(11), c=16.6982(14)Å, α=103.494(11), β=91.996(13), γ=103.829(12)°, C26H32Cl2N2Rh2, Mr=649.26, V=1190.0(3)Å3, Dc=1.812 g/cm3, Z=2, F(000)=652, μ(MoKα)=1.629 mm-1, R=0.0286 and wR=0.0463 for 3718 observed reflections (I>2σ(I)). The complex was linked to form 1D chains by hydrogen bonding interaction (C-H…Cl), and further to construct a 2D layer structure by π…π stacking interactions between the pyridine rings of 2,2'-bipy ligands. The hydroformylation catalyzed by the title complex was also studied.
2015, 34(7): 1113-1120
doi: 10.14102/j.cnki.0254-5861.2011-0618
Abstract:
By using solvothermal method, two new metal coordination polymers based on 2,5-furandicarboxylic acid (H2FDA) ligand and 4,4'-bipyridine (bipy), [Cu(FDA)(4,4'-bipy)(DMF)]n·solvent (1) and {[Zn(4,4'-bipy)(FDA)(DMF)]·DMF}n (2), were produced and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR and powder X-ray diffraction. Compound 1 crystallizes in monoclinic space group P21/c with a=11.104(2), b=10.396(2), c=18.772(4)Å, β=96.20(3)°, V=2154.2(7)Å3, Dc=1.378 g/cm3, C19H17CuN3O6, Mr=446.90, F(000)=916, μ(MoKα)=1.05 mm-1, Z=4, R=0.0691 and wR=0.1341 for 3537 observed reflections (I>2σ(I)), and R=0.1062 and wR=0.1482 for all data. Compound 2 crystallizes in monoclinic space group C2/c with a=29.779(6), b=9.6417(19), c=17.292(3)Å, β=105.69(3)°, V=4779.9(16)Å3, Dc=1.445 g/cm3, C22H22N4O7Zn, Mr=519.81, F(000)=2144, μ(MoKα)=1.08 mm-1, Z=8, R=0.0641 and wR=0.1007 for 2985 observed reflections (I>2σ(I)), and R=0.1028 and wR=0.1112 for all data. Different coordination geometry of metal ions, square pyramid of Cu2+ and trigonal bipyramid of Zn2+, bring about different orientations of FDA2- ligands as well as 4,4'-bipyridine ligands, and furthermore distinct assembly structures for 1 and 2. The thermal stabilities of 1 and 2 are also investigated.
By using solvothermal method, two new metal coordination polymers based on 2,5-furandicarboxylic acid (H2FDA) ligand and 4,4'-bipyridine (bipy), [Cu(FDA)(4,4'-bipy)(DMF)]n·solvent (1) and {[Zn(4,4'-bipy)(FDA)(DMF)]·DMF}n (2), were produced and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR and powder X-ray diffraction. Compound 1 crystallizes in monoclinic space group P21/c with a=11.104(2), b=10.396(2), c=18.772(4)Å, β=96.20(3)°, V=2154.2(7)Å3, Dc=1.378 g/cm3, C19H17CuN3O6, Mr=446.90, F(000)=916, μ(MoKα)=1.05 mm-1, Z=4, R=0.0691 and wR=0.1341 for 3537 observed reflections (I>2σ(I)), and R=0.1062 and wR=0.1482 for all data. Compound 2 crystallizes in monoclinic space group C2/c with a=29.779(6), b=9.6417(19), c=17.292(3)Å, β=105.69(3)°, V=4779.9(16)Å3, Dc=1.445 g/cm3, C22H22N4O7Zn, Mr=519.81, F(000)=2144, μ(MoKα)=1.08 mm-1, Z=8, R=0.0641 and wR=0.1007 for 2985 observed reflections (I>2σ(I)), and R=0.1028 and wR=0.1112 for all data. Different coordination geometry of metal ions, square pyramid of Cu2+ and trigonal bipyramid of Zn2+, bring about different orientations of FDA2- ligands as well as 4,4'-bipyridine ligands, and furthermore distinct assembly structures for 1 and 2. The thermal stabilities of 1 and 2 are also investigated.
2015, 34(7): 1121-1127
doi: 10.14102/j.cnki.0254-5861.2011-0623
Abstract:
Two novel titanium compounds [(E)-N'-(2,6-diisopropylphenyl)-N-(2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenyl)benzimidamido]titanium trichloride (1) and [N-(2-(4,4-dimethyl-4,5-dihydrooxaz-ol-2-yl)phenyl)-6-(2,4,6-triisopropyl-phenyl) pyridin-2-amido]titanium trichloride (2) were synthesized by reacting the corresponding ligand with diethylaminetitaniumtrichloride in equal molar ratios. The compounds were characterized with 1H, 13C NMR, elemental analysis and single-crystal X-ray diffraction analysis. The geometry of both compounds is distorted octahedron. The three nitrogen and one chlorine atoms are in the equatorial plane. Compound 1 crystallizes in orthorhombic system, space group P212121 with a=10.3520(4), b=16.5750(7), c=17.1530(7)Å, Z=4 and V=2943.2(2)Å3. Compound 2 crystalizes in the monoclinic system, space group P21/c with a=15.6400(11), b=10.12.60(7), c=22.9120(14)Å, Z=4 and V=3558.5(4)Å3. The synthesized compounds were employed for ethylene polymerization catalysis. Both complexes showed moderate activity when activated with dry methylaluminoxane (dMAO) and complex 1 produced very high molecular weight polyethylene.
Two novel titanium compounds [(E)-N'-(2,6-diisopropylphenyl)-N-(2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenyl)benzimidamido]titanium trichloride (1) and [N-(2-(4,4-dimethyl-4,5-dihydrooxaz-ol-2-yl)phenyl)-6-(2,4,6-triisopropyl-phenyl) pyridin-2-amido]titanium trichloride (2) were synthesized by reacting the corresponding ligand with diethylaminetitaniumtrichloride in equal molar ratios. The compounds were characterized with 1H, 13C NMR, elemental analysis and single-crystal X-ray diffraction analysis. The geometry of both compounds is distorted octahedron. The three nitrogen and one chlorine atoms are in the equatorial plane. Compound 1 crystallizes in orthorhombic system, space group P212121 with a=10.3520(4), b=16.5750(7), c=17.1530(7)Å, Z=4 and V=2943.2(2)Å3. Compound 2 crystalizes in the monoclinic system, space group P21/c with a=15.6400(11), b=10.12.60(7), c=22.9120(14)Å, Z=4 and V=3558.5(4)Å3. The synthesized compounds were employed for ethylene polymerization catalysis. Both complexes showed moderate activity when activated with dry methylaluminoxane (dMAO) and complex 1 produced very high molecular weight polyethylene.
2015, 34(7): 1128-1134
doi: 10.14102/j.cnki.0254-5861.2011-0627
Abstract:
Hydrothermal reaction of Cd(OAc)2, 4-amino-3,5-bis(2-pyridyl)-1,2,4-triazole (2-bpt) and tetrabromoterephthalic acid (H2tbta) yields a novel layered network {[Cd(2-bpt)(tbta)](H2O)3}n (1), which has been structurally determined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P1 with a=9.384(3), b=10.652(3), c=14.096(4)Å, α=78.616(4), β=87.101(5), γ=86.555(5)°, V=1377.7(6)Å3, Z=2, Mr=884.43, Dc=2.132 g/cm3, F(000)=844, μ=6.644 mm-1, R=0.0461 and wR=0.1173. The adjacent CdⅡ centers are connected via two 2-bpt molecules to form a 6-membered bimetallic ring, and such rings are further bridged via tbta2- ligands to afford an infinite 2D coordination framework. Besides, these adjacent layers are extended to the resultant 3D supramolecular network via H-bonding interactions. In addition, the thermal stability and fluorescent properties of complex 1 have also been investigated.
Hydrothermal reaction of Cd(OAc)2, 4-amino-3,5-bis(2-pyridyl)-1,2,4-triazole (2-bpt) and tetrabromoterephthalic acid (H2tbta) yields a novel layered network {[Cd(2-bpt)(tbta)](H2O)3}n (1), which has been structurally determined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P1 with a=9.384(3), b=10.652(3), c=14.096(4)Å, α=78.616(4), β=87.101(5), γ=86.555(5)°, V=1377.7(6)Å3, Z=2, Mr=884.43, Dc=2.132 g/cm3, F(000)=844, μ=6.644 mm-1, R=0.0461 and wR=0.1173. The adjacent CdⅡ centers are connected via two 2-bpt molecules to form a 6-membered bimetallic ring, and such rings are further bridged via tbta2- ligands to afford an infinite 2D coordination framework. Besides, these adjacent layers are extended to the resultant 3D supramolecular network via H-bonding interactions. In addition, the thermal stability and fluorescent properties of complex 1 have also been investigated.
2015, 34(7): 1135-1144
doi: 10.14102/j.cnki.0254-5861.2011-0662
Abstract:
Two new cadmium(Ⅱ)-thiocyanato coordination polymers with 4,4'-dimethyl-2,2'-bipyridine (4,4'-dm-2,2'-bpy) and 4,4'-dimethoxy-2,2'-bipyridine (4,4'-dmo-2,2'-bpy) as chelating ligands were synthesized and characterized by elemental analysis, IR and 1H NMR spectroscopy and X-ray crystallography. Thermal properties were also studied as well. These complexes have formed as [Cd(4,4'-dm-2,2'-bpy)(NCS)2]n (1) and [Cd(4,4'-dmo-2,2'-bpy)(NCS)2]n (2). The coordination numbers of CdⅡ in 1 and 2 are six (CdN4S2). Direction of bridging of thiocyanato anions in 1 and 2 created one- and two-dimensional coordination polymers, respectively. The supramolecular features in these complexes were guided and controlled by weak directional intermolecular interactions.
Two new cadmium(Ⅱ)-thiocyanato coordination polymers with 4,4'-dimethyl-2,2'-bipyridine (4,4'-dm-2,2'-bpy) and 4,4'-dimethoxy-2,2'-bipyridine (4,4'-dmo-2,2'-bpy) as chelating ligands were synthesized and characterized by elemental analysis, IR and 1H NMR spectroscopy and X-ray crystallography. Thermal properties were also studied as well. These complexes have formed as [Cd(4,4'-dm-2,2'-bpy)(NCS)2]n (1) and [Cd(4,4'-dmo-2,2'-bpy)(NCS)2]n (2). The coordination numbers of CdⅡ in 1 and 2 are six (CdN4S2). Direction of bridging of thiocyanato anions in 1 and 2 created one- and two-dimensional coordination polymers, respectively. The supramolecular features in these complexes were guided and controlled by weak directional intermolecular interactions.
