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2015 Volume 34 Issue 6
2015, 34(6): 813-821
doi: 10.14102/j.cnki.0254-5861.2011-0590
Abstract:
The electron transport properties of various molecular junctions based on the thiol-ended oligosilane are investigated through density functional theory combined with non-equilibrium Green's function formalism. Our calculations show that oligosilanes doped by the phenyl and-C10H6 groups demonstrate better rectifying effect and their rectification ratios are up to 15.41 and 65.13 for their molecular junctions. The current-voltage (I-V) curves of all the Au/ modified oligosilane/Au systems in this work are illustrated by frontier molecular orbitals, transmission spectra and density of states under zero bias. And their rectifying behaviors are analyzed through transmission spectra.
The electron transport properties of various molecular junctions based on the thiol-ended oligosilane are investigated through density functional theory combined with non-equilibrium Green's function formalism. Our calculations show that oligosilanes doped by the phenyl and-C10H6 groups demonstrate better rectifying effect and their rectification ratios are up to 15.41 and 65.13 for their molecular junctions. The current-voltage (I-V) curves of all the Au/ modified oligosilane/Au systems in this work are illustrated by frontier molecular orbitals, transmission spectra and density of states under zero bias. And their rectifying behaviors are analyzed through transmission spectra.
2015, 34(6): 822-836
doi: 10.14102/j.cnki.0254-5861.2011-0610
Abstract:
We have investigated the reaction mechanism for N2O decomposition on Cu13 via density functional theory. It is found that N2O decomposition on the cluster is more prone to be along the Eley-Rideal (ER) pathway in comparison with the Langmuir-Hinshelwood (LH) channel. There exists structural relaxation for Cu13 cluster in the reaction, which may influence the catalytic activity of cluster for the subsequent N2O decomposition. The core atom in the Cu13 cluster is substituted with the Fe, Co, or Ni to enhance structural stability and prevent from the obvious configuration relaxation in the reaction. Note that these bimetallic clusters are of icosahedra as the Cu13. They have activities for N2O dissociation along ER pathway and the heteroatom in the cluster can prevent configuration from relaxation. Finally, the Ni@Cu12 cluster can be as a superior catalyst in a complete catalytic cycle via comparison in this study.
We have investigated the reaction mechanism for N2O decomposition on Cu13 via density functional theory. It is found that N2O decomposition on the cluster is more prone to be along the Eley-Rideal (ER) pathway in comparison with the Langmuir-Hinshelwood (LH) channel. There exists structural relaxation for Cu13 cluster in the reaction, which may influence the catalytic activity of cluster for the subsequent N2O decomposition. The core atom in the Cu13 cluster is substituted with the Fe, Co, or Ni to enhance structural stability and prevent from the obvious configuration relaxation in the reaction. Note that these bimetallic clusters are of icosahedra as the Cu13. They have activities for N2O dissociation along ER pathway and the heteroatom in the cluster can prevent configuration from relaxation. Finally, the Ni@Cu12 cluster can be as a superior catalyst in a complete catalytic cycle via comparison in this study.
2015, 34(6): 837-852
doi: 10.14102/j.cnki.0254-5861.2011-0620
Abstract:
The adsorptions of a series of alkali metal (AM) atoms, Li, Na, K, Rb and Cs, on a Si(001)-2×2 surface at 0.25 monolayer coverage have been investigated systematically by means of density functional theory calculations. The effects of the size of AM atoms on the Si(001) surface are focused in the present work by examining the most stable adsorption site, diffusion path, band structure, charge transfer, and the change of work function for different adsorbates. Our results suggest that, when the interactions among AM atoms are neglectable, these AM atoms can be divided into three classes. For Li and Na atoms, they show unique site preferences, and correspond to the strongest and weakest AM-Si interactions, respectively. In particular, the band structure calculation indicates that the nature of Li-Si interaction differs significantly from others. For the adsorptions of other AM atoms with larger size (namely, K, Rb and Cs), the similarities in the atomic and electronic structures are observed, implying that the atom size has little influence on the adsorption behavior for these large AM atoms on the Si(001) surface.
The adsorptions of a series of alkali metal (AM) atoms, Li, Na, K, Rb and Cs, on a Si(001)-2×2 surface at 0.25 monolayer coverage have been investigated systematically by means of density functional theory calculations. The effects of the size of AM atoms on the Si(001) surface are focused in the present work by examining the most stable adsorption site, diffusion path, band structure, charge transfer, and the change of work function for different adsorbates. Our results suggest that, when the interactions among AM atoms are neglectable, these AM atoms can be divided into three classes. For Li and Na atoms, they show unique site preferences, and correspond to the strongest and weakest AM-Si interactions, respectively. In particular, the band structure calculation indicates that the nature of Li-Si interaction differs significantly from others. For the adsorptions of other AM atoms with larger size (namely, K, Rb and Cs), the similarities in the atomic and electronic structures are observed, implying that the atom size has little influence on the adsorption behavior for these large AM atoms on the Si(001) surface.
2015, 34(6): 853-857
doi: 10.14102/j.cnki.0254-5861.2010-1479
Abstract:
The synthesis of the title molecule was achieved by the reaction of 2,4-dichlorobenzoyl chloride with potassium thiocyanate in 1:1 molar ratio in dry acetonitrile to afford the corresponding isothiocyante in situ followed by the treatment with 2-aminobiphenyl. The structure of the target compound was established by elemental analysis, FTIR, 1H, 13C NMR and mass spectroscopy and unequivocally confirmed by the crystallographic data. The title compound crystallizes in the monoclinic space group P21/n with a=13.356(2), b=7.0761(11), c=20.539(3) Å, β=105.723(4)°, V=1868.5(5) Å3 and Z=4.
The synthesis of the title molecule was achieved by the reaction of 2,4-dichlorobenzoyl chloride with potassium thiocyanate in 1:1 molar ratio in dry acetonitrile to afford the corresponding isothiocyante in situ followed by the treatment with 2-aminobiphenyl. The structure of the target compound was established by elemental analysis, FTIR, 1H, 13C NMR and mass spectroscopy and unequivocally confirmed by the crystallographic data. The title compound crystallizes in the monoclinic space group P21/n with a=13.356(2), b=7.0761(11), c=20.539(3) Å, β=105.723(4)°, V=1868.5(5) Å3 and Z=4.
2015, 34(6): 858-870
doi: 10.14102/j.cnki.0254-5861.2010-1491
Abstract:
The title compound was synthesized by the base catalyzed reaction of 5-((quinolin-8-yloxy)methyl)-1,3,4-oxadiazole-2(3H)-thione with methyl chloroacetate. The structure was supported by the spectroscopic data and unambiguously confirmed by single-crystal X-ray diffraction studies. It crystallizes from a methanol solution in the triclinic space group P1 with unit cell dimensions a=7.4509(9), b=10.2389(12), c=12.2299(15) Å, α=74.771(2), β=77.956(2), γ=69.263(2)°, V=834.98(17) Å3 and Z=2. In order to gain some valuable insights into the molecular structure, the quantum mechanical calculations were performed using both HF and time-dependent density functional theory at the B3LYP/6-31G(d,p) level. The molecular geometry from X-ray determination of the title compound in the ground state has been compared using the Hartree-Fock (HF) and density functional theory (DFT) with the 6-31G(d) basis set. The calculated results show that the DFT and HF can well reproduce the structure of the title compound. The energetic behavior of the title compound was examined using the B3LYP method with the 6-31G(d) basis set. The harmonic vibrational frequencies calculated have been compared with the experimental FTIR and FT-Raman spectra. The restricted Hartree-Fock and density functional theory-based nuclear magnetic resonance (NMR) calculation procedure was also performed, and it was used for assigning the 13C and 1H NMR chemical shifts of the title compound. Moreover, molecular electrostatic potential and thermodynamic parameters of the title compound were investigated by theoretical calculations.
The title compound was synthesized by the base catalyzed reaction of 5-((quinolin-8-yloxy)methyl)-1,3,4-oxadiazole-2(3H)-thione with methyl chloroacetate. The structure was supported by the spectroscopic data and unambiguously confirmed by single-crystal X-ray diffraction studies. It crystallizes from a methanol solution in the triclinic space group P1 with unit cell dimensions a=7.4509(9), b=10.2389(12), c=12.2299(15) Å, α=74.771(2), β=77.956(2), γ=69.263(2)°, V=834.98(17) Å3 and Z=2. In order to gain some valuable insights into the molecular structure, the quantum mechanical calculations were performed using both HF and time-dependent density functional theory at the B3LYP/6-31G(d,p) level. The molecular geometry from X-ray determination of the title compound in the ground state has been compared using the Hartree-Fock (HF) and density functional theory (DFT) with the 6-31G(d) basis set. The calculated results show that the DFT and HF can well reproduce the structure of the title compound. The energetic behavior of the title compound was examined using the B3LYP method with the 6-31G(d) basis set. The harmonic vibrational frequencies calculated have been compared with the experimental FTIR and FT-Raman spectra. The restricted Hartree-Fock and density functional theory-based nuclear magnetic resonance (NMR) calculation procedure was also performed, and it was used for assigning the 13C and 1H NMR chemical shifts of the title compound. Moreover, molecular electrostatic potential and thermodynamic parameters of the title compound were investigated by theoretical calculations.
2015, 34(6): 871-878
doi: 10.14102/j.cnki.0254-5861.2011-0598
Abstract:
The title compound diethyl 2-(3,4-dichloroisothiazol-5-yl)-4-(trifluoromethyl)-4,5-dihydrothiazol-4-yl-3-methylbenzoate (C15H9Cl2F3N2O2S2, Mr=441.26) was prepared from methyl 3,4-dichloroisothiazole-5-carboxylate as the starting material by four steps of reaction. Its structure was characterized by IR, 1H-NMR, 13C-NMR, EA and single-crystal X-ray diffraction. The crystal of the title compound belongs to the monoclinic system, space group P21/c with a=8.8437(18), b=16.128(3), c=12.305(3) Å, β=91.68(3)°, V=1754.4(6) Å3, Z=4, Dc=1.671 g/cm3, μ(MoKa)=0.71073 mm-1, F(000)=888, R=0.0384 and wR=0.0778. Weak π-π interactions occur between the isothiazole rings and phenyl rings of adjacent molecules to form a one-dimensional chain and stabilize the crystal structure. Bioassay indicates that the title compound has good activity against the fungi and TMV tested.
The title compound diethyl 2-(3,4-dichloroisothiazol-5-yl)-4-(trifluoromethyl)-4,5-dihydrothiazol-4-yl-3-methylbenzoate (C15H9Cl2F3N2O2S2, Mr=441.26) was prepared from methyl 3,4-dichloroisothiazole-5-carboxylate as the starting material by four steps of reaction. Its structure was characterized by IR, 1H-NMR, 13C-NMR, EA and single-crystal X-ray diffraction. The crystal of the title compound belongs to the monoclinic system, space group P21/c with a=8.8437(18), b=16.128(3), c=12.305(3) Å, β=91.68(3)°, V=1754.4(6) Å3, Z=4, Dc=1.671 g/cm3, μ(MoKa)=0.71073 mm-1, F(000)=888, R=0.0384 and wR=0.0778. Weak π-π interactions occur between the isothiazole rings and phenyl rings of adjacent molecules to form a one-dimensional chain and stabilize the crystal structure. Bioassay indicates that the title compound has good activity against the fungi and TMV tested.
2015, 34(6): 879-884
doi: 10.14102/j.cnki.0254-5861.2011-0630
Abstract:
Two new α-aminophosphonate derivatives containing thieno[2,3-d]pyrimidine, diethyl(((6-ethyl-2-methyl-4-oxothieno[2,3-d]pyrimidin-3(4H)-yl)amino)(4-methoxyphenyl)methyl) phosphonate (1 and diethyl((4-bromophenyl)((6-ethyl-2-methyl-4-oxothieno[2,3-d]pyrimidin-3 (4H)-yl)amino)methyl)phosphonate (2), have been synthesized by a facial phosphorylated reaction, and their structures were characterized by NMR, IR, HRMS and X-ray single-crystal diffraction. Compound 1 (C21H28N3O5PS, Mr=465.49) belongs to the orthorhombic system, space group P212121, with a=10.83653(16), b=12.04906(19), c=18.0061(3) Å, V=2351.06(6) Å3, Z=4, Dc=1.315 g/cm3, μ=2.177 mm-1, F(000)=984.0, the final R=0.0389 and wR=0.0985 for all data. Compound 2 (C20H25BrN3O4PS, Mr=514.37) belongs to the orthorhombic system, space group P212121, with a=10.9187(5), b=11.9522(4), c=17.7667(7) Å, V=2318.60(16) Å3, Z=4, Dc=1.474 g/cm3, μ=4.175 mm-1, F(000)=1056.0, the final R=0.0367 and wR=0.0946 for all data.
Two new α-aminophosphonate derivatives containing thieno[2,3-d]pyrimidine, diethyl(((6-ethyl-2-methyl-4-oxothieno[2,3-d]pyrimidin-3(4H)-yl)amino)(4-methoxyphenyl)methyl) phosphonate (1 and diethyl((4-bromophenyl)((6-ethyl-2-methyl-4-oxothieno[2,3-d]pyrimidin-3 (4H)-yl)amino)methyl)phosphonate (2), have been synthesized by a facial phosphorylated reaction, and their structures were characterized by NMR, IR, HRMS and X-ray single-crystal diffraction. Compound 1 (C21H28N3O5PS, Mr=465.49) belongs to the orthorhombic system, space group P212121, with a=10.83653(16), b=12.04906(19), c=18.0061(3) Å, V=2351.06(6) Å3, Z=4, Dc=1.315 g/cm3, μ=2.177 mm-1, F(000)=984.0, the final R=0.0389 and wR=0.0985 for all data. Compound 2 (C20H25BrN3O4PS, Mr=514.37) belongs to the orthorhombic system, space group P212121, with a=10.9187(5), b=11.9522(4), c=17.7667(7) Å, V=2318.60(16) Å3, Z=4, Dc=1.474 g/cm3, μ=4.175 mm-1, F(000)=1056.0, the final R=0.0367 and wR=0.0946 for all data.
2015, 34(6): 885-893
doi: 10.14102/j.cnki.0254-5861.2011-0593
Abstract:
Two hydrazone ligands (E)-N'-(2-hydroxy-5-methoxybenzylidene)-2-hydroxybenzohydrazide (HLa) and (E)-N'-(3,5-dichloro-2-hydroxybenzylidene)-4-methoxybenzohydrazide (HLb) were prepared and characterized by IR, UV-Vis and 1H NMR spectra. Based on the hydrazone ligands, two new structurally similar vanadium(V) complexes, [VOLaL]·CH3OH (1) and [VOLbL] (2), where L is the monoanionic form of benzohydroxamic acid (HL), were prepared and characterized by IR and UV-Vis spectra, and single-crystal X-ray diffraction. Complex 1 crystallizes as the monoclinic space group P21/n, with a=7.5208(10), b=15.490(2), c=20.8929(18) Å, β=96.373(2)°, V=2418.9(5) Å3, Z=4, R=0.0831, wR=0.2607 and GOOF=1.061. Complex 2 crystallizes as the monoclinic space group P21/c, with a=11.8577(18), b=16.468(2), c=12.2288(18) Å, β=106.064(2)°, V=2294.7(6) Å3, Z=4, R=0.0741, wR=0.1745 and GOOF=1.014. X-ray analysis indicates that the complexes are mononuclear vanadium (V) species, with the V atoms located in the octahedral coordination. The hydrazone ligands and the complexes were evaluated for their antibacterial (Bacillus subtilis, Staphylococcus aureus, Escherichia coli, and Pseudomonas fluorescence) and antifungal (Candida albicans and Aspergillus niger) activities by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide) method.
Two hydrazone ligands (E)-N'-(2-hydroxy-5-methoxybenzylidene)-2-hydroxybenzohydrazide (HLa) and (E)-N'-(3,5-dichloro-2-hydroxybenzylidene)-4-methoxybenzohydrazide (HLb) were prepared and characterized by IR, UV-Vis and 1H NMR spectra. Based on the hydrazone ligands, two new structurally similar vanadium(V) complexes, [VOLaL]·CH3OH (1) and [VOLbL] (2), where L is the monoanionic form of benzohydroxamic acid (HL), were prepared and characterized by IR and UV-Vis spectra, and single-crystal X-ray diffraction. Complex 1 crystallizes as the monoclinic space group P21/n, with a=7.5208(10), b=15.490(2), c=20.8929(18) Å, β=96.373(2)°, V=2418.9(5) Å3, Z=4, R=0.0831, wR=0.2607 and GOOF=1.061. Complex 2 crystallizes as the monoclinic space group P21/c, with a=11.8577(18), b=16.468(2), c=12.2288(18) Å, β=106.064(2)°, V=2294.7(6) Å3, Z=4, R=0.0741, wR=0.1745 and GOOF=1.014. X-ray analysis indicates that the complexes are mononuclear vanadium (V) species, with the V atoms located in the octahedral coordination. The hydrazone ligands and the complexes were evaluated for their antibacterial (Bacillus subtilis, Staphylococcus aureus, Escherichia coli, and Pseudomonas fluorescence) and antifungal (Candida albicans and Aspergillus niger) activities by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide) method.
2015, 34(6): 894-898
doi: 10.14102/j.cnki.0254-5861.2011-0572
Abstract:
A new compound, [H2N(CH3)2]2[Zn(btec)].H2O (1, H4btec=1,2,4,5-benzenetetracarboxylic acid) has been solvothermally synthesized and structurally characterized by singlecrystal X-ray diffraction. The crystal structure is of monoclinic, space group P21/c with a=9.5741(3), b=14.5044(4), c=13.7329(5) Å, β=100.582(4)°, V=1874.61(10) Å3, C14H20N2O9Zn, Mr=425.7, Z=4, Dc=1.387 g/cm3, μ=1.349 mm-1, F(000)=776, R=0.0560 and wR=0.1684 for 2834 observed reflections (I>2σ(I)). Compound 1 based on μ4-btec and tetrahedral building unit features a three-dimensional (3D) anionic framework with mixed connected nou topology. The luminescent property and thermogravimetric analysis of compound 1 are investigated.
A new compound, [H2N(CH3)2]2[Zn(btec)].H2O (1, H4btec=1,2,4,5-benzenetetracarboxylic acid) has been solvothermally synthesized and structurally characterized by singlecrystal X-ray diffraction. The crystal structure is of monoclinic, space group P21/c with a=9.5741(3), b=14.5044(4), c=13.7329(5) Å, β=100.582(4)°, V=1874.61(10) Å3, C14H20N2O9Zn, Mr=425.7, Z=4, Dc=1.387 g/cm3, μ=1.349 mm-1, F(000)=776, R=0.0560 and wR=0.1684 for 2834 observed reflections (I>2σ(I)). Compound 1 based on μ4-btec and tetrahedral building unit features a three-dimensional (3D) anionic framework with mixed connected nou topology. The luminescent property and thermogravimetric analysis of compound 1 are investigated.
2015, 34(6): 899-905
doi: 10.14102/j.cnki.0254-5861.2011-0575
Abstract:
A new coordination polymer [Cd2(5-IPA)(HL)2(H2O)2]·4H2O (1) was prepared under hydrothermal conditions based on 5-hydroxy-isophthalic acid (5-H2IPA) with multi-N-donor ligand 1-(1H-imidazol-4-yl)-3-(4H-tetrazol-5-yl)benzene (H2L). The complex was characterized by IR spectroscopy, TGA, X-ray powder and single-crystal diffraction. It crystallizes in the monoclinic system, space group C2/c with a=23.6291(18), b=9.9847(8), c=17.7244(14) Å, β=124.6180(10)°, V=3441.4(5) Å3, Z=4, C28H30N12O11Cd2, Mr=935.44, Dc=1.805 g/cm3, μ=1.313 mm-1, S=1.055, F(000)=1864, the final R=0.049 and wR=0.1315 for 2985 observed reflections (I>2σ(I)). The central metal Cd(II) atoms with octahedral coordination geometry are six-coordinated by three oxygen and three nitrogen atoms. The HL- ligands from the deprotonated H2L connect Cd(II) atoms to form two-dimensional (2D) double-layer fes networks which are further pillared by 5-IPA2− ligands into a rare binodal (3, 4)-connected three-dimensional (3D) architecture with a (4·6·8)(4·62·83) fsc-3,4-C2/c topology. Solid state luminescent property and sorption property of 1 have been investigated.
A new coordination polymer [Cd2(5-IPA)(HL)2(H2O)2]·4H2O (1) was prepared under hydrothermal conditions based on 5-hydroxy-isophthalic acid (5-H2IPA) with multi-N-donor ligand 1-(1H-imidazol-4-yl)-3-(4H-tetrazol-5-yl)benzene (H2L). The complex was characterized by IR spectroscopy, TGA, X-ray powder and single-crystal diffraction. It crystallizes in the monoclinic system, space group C2/c with a=23.6291(18), b=9.9847(8), c=17.7244(14) Å, β=124.6180(10)°, V=3441.4(5) Å3, Z=4, C28H30N12O11Cd2, Mr=935.44, Dc=1.805 g/cm3, μ=1.313 mm-1, S=1.055, F(000)=1864, the final R=0.049 and wR=0.1315 for 2985 observed reflections (I>2σ(I)). The central metal Cd(II) atoms with octahedral coordination geometry are six-coordinated by three oxygen and three nitrogen atoms. The HL- ligands from the deprotonated H2L connect Cd(II) atoms to form two-dimensional (2D) double-layer fes networks which are further pillared by 5-IPA2− ligands into a rare binodal (3, 4)-connected three-dimensional (3D) architecture with a (4·6·8)(4·62·83) fsc-3,4-C2/c topology. Solid state luminescent property and sorption property of 1 have been investigated.
2015, 34(6): 906-910
doi: 10.14102/j.cnki.0254-5861.2011-0614
Abstract:
Under solvothermal conditions, a new trinuclear Zn(II) complex, [Zn3(bpdc)3(DPNDI)]· 3NMF (1, H2bpdc=biphenyl-4,4'-dicarboxylate, N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide (DPNDI) and NMF=N-methylformamide), has been synthesized with mixed organic ligands. Complex 1 is of monoclinic, space group P21/n with a=11.167(5), b=14.806(5), c=19.494(5) Å, V=3154.6(19) Å3, Z=2, Mr=1455.24, Dc=1.532 g/cm3, F(000)=1484 and µ=1.212 mm−1. The final refinement gave R=0.0343 and wR=0.0419 for 6209 reflections with I>2σ(I). Single-crystal X-ray analysis reveals that complex 1 features a 3D structure based on the trinuclear Zn(II) units. Complex 1 shows three-fold interpenetrating hex topology. Furthermore, the luminescent property 1 is investigated.
Under solvothermal conditions, a new trinuclear Zn(II) complex, [Zn3(bpdc)3(DPNDI)]· 3NMF (1, H2bpdc=biphenyl-4,4'-dicarboxylate, N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide (DPNDI) and NMF=N-methylformamide), has been synthesized with mixed organic ligands. Complex 1 is of monoclinic, space group P21/n with a=11.167(5), b=14.806(5), c=19.494(5) Å, V=3154.6(19) Å3, Z=2, Mr=1455.24, Dc=1.532 g/cm3, F(000)=1484 and µ=1.212 mm−1. The final refinement gave R=0.0343 and wR=0.0419 for 6209 reflections with I>2σ(I). Single-crystal X-ray analysis reveals that complex 1 features a 3D structure based on the trinuclear Zn(II) units. Complex 1 shows three-fold interpenetrating hex topology. Furthermore, the luminescent property 1 is investigated.
2015, 34(6): 911-916
doi: 10.14102/j.cnki.0254-5861.2011-0625
Abstract:
A new one-dimensional polymer, [Zn(SC6H4S)(1,3-DPA)]n (1, SC6H4S=1,4-benzenedithiolate and 1,3-DPA=1,3-diaminepropane), has been synthesized and characterized by elemental analysis, PXRD, IR spectra, and single-crystal X-ray diffraction. The complex crystallizes in triclinic system, space group P1, with a=6.7119(1), b=9.0230(2), c=10.4943(2) Å, α=69.288(1), β=75.848(1), γ=81.513(1)°, V=575.123(19) Å3, Dc=1.615 g/cm3, Z=2, F(000)=288; the final S=1.070, R=0.0234, and wR=0.0551. The compound consists of an infinite zigzag chain formed by [Zn(1,3-DPA)]2+ units joined by SC6H4S ligands. Each chain interacts with neighboring chains via weak N-H···S hydrogen bonds to form an extended three-dimensional (3D) supramolecular network. The thermal and photoluminescent properties of 1 have also been investigated.
A new one-dimensional polymer, [Zn(SC6H4S)(1,3-DPA)]n (1, SC6H4S=1,4-benzenedithiolate and 1,3-DPA=1,3-diaminepropane), has been synthesized and characterized by elemental analysis, PXRD, IR spectra, and single-crystal X-ray diffraction. The complex crystallizes in triclinic system, space group P1, with a=6.7119(1), b=9.0230(2), c=10.4943(2) Å, α=69.288(1), β=75.848(1), γ=81.513(1)°, V=575.123(19) Å3, Dc=1.615 g/cm3, Z=2, F(000)=288; the final S=1.070, R=0.0234, and wR=0.0551. The compound consists of an infinite zigzag chain formed by [Zn(1,3-DPA)]2+ units joined by SC6H4S ligands. Each chain interacts with neighboring chains via weak N-H···S hydrogen bonds to form an extended three-dimensional (3D) supramolecular network. The thermal and photoluminescent properties of 1 have also been investigated.
2015, 34(6): 917-924
doi: 10.14102/j.cnki.0254-5861.2011-0634
Abstract:
The novel dinuclear copper complex [Cu2(H2O)2(DMF)2(L)2] (1, H2L=5-phenyl-2H-1,2,3-triazole-4-carboxylic acid, DMF=N,N-dimethyl-formamide) has been synthesized and characterized by X-ray single-crystal diffraction. The compound crystallizes in triclinic system, space group P1 with a=9.591, b=10.508, c=15.515 Å, β=75.11°, V=1446.2 Å3, Z=2, Mr=683.62, Dc=1.570 g/cm3, μ=1.531 mm-1, F(000)=700, the final R=0.0404 and wR=0.1130 for 5327 observed reflections with I>2σ(I). In each unit of the complex, two Cu2+ ions coordinated with two triazole ligands to form a dimeric [5,6,5] tricyclic structure. The central Cu atom is five-coordinated, and each copper atom shows a square pyramidal geometry. The crystal structure is stabilized by the inversion-related O-H···O hydrogen bond and C-H···O hydrogen bonding interactions to form a layer structure. Fluorescent spectra show an obvious quenching of fluorescence compared with free 1,2,3-triazole ligand. The results of agarose gel electrophoresis indicate that this complex can cleave the plasmid supercoiled DNA within shorter time in the 50-folds excess of ascorbate under physiological conditions, providing a new example in the research for artificial metal nucleic acid enzyme.
The novel dinuclear copper complex [Cu2(H2O)2(DMF)2(L)2] (1, H2L=5-phenyl-2H-1,2,3-triazole-4-carboxylic acid, DMF=N,N-dimethyl-formamide) has been synthesized and characterized by X-ray single-crystal diffraction. The compound crystallizes in triclinic system, space group P1 with a=9.591, b=10.508, c=15.515 Å, β=75.11°, V=1446.2 Å3, Z=2, Mr=683.62, Dc=1.570 g/cm3, μ=1.531 mm-1, F(000)=700, the final R=0.0404 and wR=0.1130 for 5327 observed reflections with I>2σ(I). In each unit of the complex, two Cu2+ ions coordinated with two triazole ligands to form a dimeric [5,6,5] tricyclic structure. The central Cu atom is five-coordinated, and each copper atom shows a square pyramidal geometry. The crystal structure is stabilized by the inversion-related O-H···O hydrogen bond and C-H···O hydrogen bonding interactions to form a layer structure. Fluorescent spectra show an obvious quenching of fluorescence compared with free 1,2,3-triazole ligand. The results of agarose gel electrophoresis indicate that this complex can cleave the plasmid supercoiled DNA within shorter time in the 50-folds excess of ascorbate under physiological conditions, providing a new example in the research for artificial metal nucleic acid enzyme.
2015, 34(6): 925-930
doi: 10.14102/j.cnki.0254-5861.2011-0638
Abstract:
A new coordination complex [Cd2(ip)2(bpp)]n (1, H2ip=isophthalic acid, bpp=1,3-bis-(4-pyridyl) propane) has been synthesized and structurally characterized. Crystal data for the title complex are as follows: triclinic system, space group P1 with a=9.6724(6), b=10.2243(6), c=14.8205(9) Å, α=88.927(5), β=71.664(6), γ=75.767(5)°, V=1345.79(14) Å3, Mr=751.29, Z=2, F(000)=740, Dc=1.854 g/cm3, μ(MoKα)=1.636 mm-1, R=0.0259 and wR=0.0623 for 4754 observed reflections with I>2σ(I). X-ray structure analysis reveals that complex 1 holds a 3D architecture based on α-Po primitive cubic units with the [Cd4(COO)8] units treated as 6-connected nodes. Solid-state properties for 1, such as infrared spectroscopy, elemental analyses, thermal stability and luminescent property, have also been investigated.
A new coordination complex [Cd2(ip)2(bpp)]n (1, H2ip=isophthalic acid, bpp=1,3-bis-(4-pyridyl) propane) has been synthesized and structurally characterized. Crystal data for the title complex are as follows: triclinic system, space group P1 with a=9.6724(6), b=10.2243(6), c=14.8205(9) Å, α=88.927(5), β=71.664(6), γ=75.767(5)°, V=1345.79(14) Å3, Mr=751.29, Z=2, F(000)=740, Dc=1.854 g/cm3, μ(MoKα)=1.636 mm-1, R=0.0259 and wR=0.0623 for 4754 observed reflections with I>2σ(I). X-ray structure analysis reveals that complex 1 holds a 3D architecture based on α-Po primitive cubic units with the [Cd4(COO)8] units treated as 6-connected nodes. Solid-state properties for 1, such as infrared spectroscopy, elemental analyses, thermal stability and luminescent property, have also been investigated.
2015, 34(6): 931-937
doi: 10.14102/j.cnki.0254-5861.2011-0639
Abstract:
Thermal treatment of the pyridyl side chain functionalized tetramethyl cyclopentadiene C5Me4CH2(C5H4N) with Fe(CO)5, Ru3(CO)12 and Mo(CO)6 in refluxing xylene respectively gave the corresponding dinuclear metal carbonyl complexes 1~3. These complexes have been characterized by elemental analysis, IR and 1H NMR spectra. The molecular structures of 1~3 were determined by X-ray diffraction analysis.
Thermal treatment of the pyridyl side chain functionalized tetramethyl cyclopentadiene C5Me4CH2(C5H4N) with Fe(CO)5, Ru3(CO)12 and Mo(CO)6 in refluxing xylene respectively gave the corresponding dinuclear metal carbonyl complexes 1~3. These complexes have been characterized by elemental analysis, IR and 1H NMR spectra. The molecular structures of 1~3 were determined by X-ray diffraction analysis.
2015, 34(6): 938-944
doi: 10.14102/j.cnki.0254-5861.2011-0624
Abstract:
Hydrothermal reaction of benzene-1,2,4,5-tetracarboxylic (Btec) dianhydride with La2O3 lead to a new organometallic compound, [La2(betc)(Hbtec)(H2O)3][HCONH(CH3)2] (I). Single-crystal X-ray diffraction analysis reveals that it crystallizes in monoclinic space group P21/n that mimics orthorhombic space group Pnma (viz. pseudo-merohedral twinning structure) with a=7.6002(16), b=18.954(4), c=18.213(4) Å, β=90.121(3)°, V=2623.5(9) Å3, Z=4, Mr=907.21, D c=2.297 g/cm3, F(000)=1752, μ(MoKα)=3.32 mm-1, R=0.0575 and wR=0.0956. The structure of I features a 3-D framework constructed by La(III) cations, btec4- ligands, Hbtec3- ligands and coordinated water molecule. All of the La(III) cations are 10-coordinated by O atoms into 1-D infinite chains, which are further interconnected by C atoms of btec ligands to form a 3-D framework.
Hydrothermal reaction of benzene-1,2,4,5-tetracarboxylic (Btec) dianhydride with La2O3 lead to a new organometallic compound, [La2(betc)(Hbtec)(H2O)3][HCONH(CH3)2] (I). Single-crystal X-ray diffraction analysis reveals that it crystallizes in monoclinic space group P21/n that mimics orthorhombic space group Pnma (viz. pseudo-merohedral twinning structure) with a=7.6002(16), b=18.954(4), c=18.213(4) Å, β=90.121(3)°, V=2623.5(9) Å3, Z=4, Mr=907.21, D c=2.297 g/cm3, F(000)=1752, μ(MoKα)=3.32 mm-1, R=0.0575 and wR=0.0956. The structure of I features a 3-D framework constructed by La(III) cations, btec4- ligands, Hbtec3- ligands and coordinated water molecule. All of the La(III) cations are 10-coordinated by O atoms into 1-D infinite chains, which are further interconnected by C atoms of btec ligands to form a 3-D framework.
2015, 34(6): 945-952
doi: 10.14102/j.cnki.0254-5861.2011-0605
Abstract:
Temperature dependent assembly of two novel Cd coordination polymers with the phen and H2MIP ligands (phen=1,10-phenanthrolion and H2MIP=5-methyl-isophthalic acid), formulated as Cd2(MIP)2(phen)2 (1) and Cd3(MIP)3(H2MIP)(phen)2 (2). They have been structurally characterized by single-crystal X-ray diffraction, elemental analysis, FT-IR spectra and TGA. 1 crystallizes in the monoclinic space group P2/n, while 2 crystallizes in the triclinic space group P1. 1 shows a 2D (two-dimensional) plane and 2 shows a 1D (one-dimensional) chain. In addition, their solid-state luminescent properties have also been investigated.
Temperature dependent assembly of two novel Cd coordination polymers with the phen and H2MIP ligands (phen=1,10-phenanthrolion and H2MIP=5-methyl-isophthalic acid), formulated as Cd2(MIP)2(phen)2 (1) and Cd3(MIP)3(H2MIP)(phen)2 (2). They have been structurally characterized by single-crystal X-ray diffraction, elemental analysis, FT-IR spectra and TGA. 1 crystallizes in the monoclinic space group P2/n, while 2 crystallizes in the triclinic space group P1. 1 shows a 2D (two-dimensional) plane and 2 shows a 1D (one-dimensional) chain. In addition, their solid-state luminescent properties have also been investigated.
2015, 34(6): 953-959
doi: 10.14102/j.cnki.0254-5861.2011-0640
Abstract:
One novel binuclear Co(Ⅱ) coordination polymer ∞1[Co2(4,4'-bpy)2(L)4] (1, bpy=bipyridine, HL=2-fluorbenzoic acid) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complex 1 crystallizes in the monoclinic system, space group P21/c with a=11.163(2), b=21.943(4), c=9.6381(19) Å, β=113.92(3)°, V=2158.2(7) Å3, Z=4, Dc=1.518 g/cm3, Mr=493.31, F(000)=1004, R=0.0303 and wR=0.0808 for 3614 observed reflections (I>2σ(I)). Complex 1 exhibits a 3D Schlafli symbol (4.62)(4.66.83) topological framework, and the magnetic characterization shows weak antiferromagnetic coupling exchange between two Co ions.
One novel binuclear Co(Ⅱ) coordination polymer ∞1[Co2(4,4'-bpy)2(L)4] (1, bpy=bipyridine, HL=2-fluorbenzoic acid) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complex 1 crystallizes in the monoclinic system, space group P21/c with a=11.163(2), b=21.943(4), c=9.6381(19) Å, β=113.92(3)°, V=2158.2(7) Å3, Z=4, Dc=1.518 g/cm3, Mr=493.31, F(000)=1004, R=0.0303 and wR=0.0808 for 3614 observed reflections (I>2σ(I)). Complex 1 exhibits a 3D Schlafli symbol (4.62)(4.66.83) topological framework, and the magnetic characterization shows weak antiferromagnetic coupling exchange between two Co ions.
2015, 34(6): 960-964
doi: 10.14102/j.cnki.0254-5861.2011-0682
Abstract:
A new Zn(II) complex, [Zn(L)(IPP)(H2O)]·2H2O (1, H2L=3-carboxy-1-carboxymethyl-2-oxidopyridinium and IPP=2-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol), was synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a=8.5023(17), b=9.945(2), c=15.573(3) Å, α=95.87(3), β=102.56(3), γ=100.73(3)o, V=1248.7(4) Å3, Z=2, C27H22N5O9Zn, Mr=625.87, Dc=1.665 g/cm3, F(000)=642, μ(MoKa)=1.053 mm-1, R=0.0474 and wR=0.1352. In 1, one L2-, one IPP and one water molecule coordinate to the same Zn(II) atom to give a discrete complex with two lattice water molecules. Adjacent [Zn(L)(IPP)(H2O)]·2H2O molecules interact through π-π stacking between two IPP ligands to form a supramolecular chain. The N-H···O and O-H···N hydrogen bonds further stabilize the supramolecular chain structure of 1. The solid state luminescent property of 1 was also studied.
A new Zn(II) complex, [Zn(L)(IPP)(H2O)]·2H2O (1, H2L=3-carboxy-1-carboxymethyl-2-oxidopyridinium and IPP=2-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol), was synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a=8.5023(17), b=9.945(2), c=15.573(3) Å, α=95.87(3), β=102.56(3), γ=100.73(3)o, V=1248.7(4) Å3, Z=2, C27H22N5O9Zn, Mr=625.87, Dc=1.665 g/cm3, F(000)=642, μ(MoKa)=1.053 mm-1, R=0.0474 and wR=0.1352. In 1, one L2-, one IPP and one water molecule coordinate to the same Zn(II) atom to give a discrete complex with two lattice water molecules. Adjacent [Zn(L)(IPP)(H2O)]·2H2O molecules interact through π-π stacking between two IPP ligands to form a supramolecular chain. The N-H···O and O-H···N hydrogen bonds further stabilize the supramolecular chain structure of 1. The solid state luminescent property of 1 was also studied.
2015, 34(6): 965-972
doi: 10.14102/j.cnki.0254-5861.2011-0704
Abstract:
Three complexes [AMP][Ni(mnt)2]·CH3CN (1, AMP=1-(9-anthrylmethyl)pyridinium), [DPI]2[Ni(mnt)2]I (2, DPI=diphenyliodonium) and [DD][Ni(mnt)2]2·2H2O (3, DD=dimethylenediamine) have been prepared and characterized by elemental analyses and IR spectroscopy. X-ray diffraction studies show that three complexes crystallize in the same triclinic space group P1, and anionic accumulations are formed in a column shape. The results show that different counter-cations could induce versatile anionic stacks. The structures of three complexes exhibit rich hydrogen bonding interactions. In addition, UV-VIS properties of them are also investigated.
Three complexes [AMP][Ni(mnt)2]·CH3CN (1, AMP=1-(9-anthrylmethyl)pyridinium), [DPI]2[Ni(mnt)2]I (2, DPI=diphenyliodonium) and [DD][Ni(mnt)2]2·2H2O (3, DD=dimethylenediamine) have been prepared and characterized by elemental analyses and IR spectroscopy. X-ray diffraction studies show that three complexes crystallize in the same triclinic space group P1, and anionic accumulations are formed in a column shape. The results show that different counter-cations could induce versatile anionic stacks. The structures of three complexes exhibit rich hydrogen bonding interactions. In addition, UV-VIS properties of them are also investigated.
2015, 34(6): 973-978
doi: 10.14102/j.cnki.0254-5861.2011-0776
Abstract:
A new dinuclear manganese complex [Mn2(L)2(2,2'-bipy)2(H2O)5]2·3H2O has been synthesized with MnSO4·H2O, 2,2'-bibenzoic acid (H2L) and 2,2'-bipyridine(2,2'-bipy) in the mixed solvent ethanol and water. It crystallizes in monoclinic, space group P1 with a=9.9944(10), b=21.939(2), c=25.628(3) Å, α=108.429(3), β=100.613(4), γ=102.821(3)°, V=4997.9(9) Å3, D c=1.355 g/cm3, Z=2, F(000)=2108, GOOF=1.074, the R=0.0626 and wR=0.1531. The structure of the complex contains two [Mn2(L)2(2,2'-bipy)2] units, ten coordinated H2O molecules and three uncoordinated H2O molecules. The fluorescence, thermal stability and magnetic properties of the complex were investigated.
A new dinuclear manganese complex [Mn2(L)2(2,2'-bipy)2(H2O)5]2·3H2O has been synthesized with MnSO4·H2O, 2,2'-bibenzoic acid (H2L) and 2,2'-bipyridine(2,2'-bipy) in the mixed solvent ethanol and water. It crystallizes in monoclinic, space group P1 with a=9.9944(10), b=21.939(2), c=25.628(3) Å, α=108.429(3), β=100.613(4), γ=102.821(3)°, V=4997.9(9) Å3, D c=1.355 g/cm3, Z=2, F(000)=2108, GOOF=1.074, the R=0.0626 and wR=0.1531. The structure of the complex contains two [Mn2(L)2(2,2'-bipy)2] units, ten coordinated H2O molecules and three uncoordinated H2O molecules. The fluorescence, thermal stability and magnetic properties of the complex were investigated.
