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2014 Volume 33 Issue 10
2014, 33(10): 1421-1430
Abstract:
Recently, the investigation of novel molecularly imprinted polymers (MIPs) has attracted a lot of interest and becomes a fascinating field. The phenobarbital (PHN) was taken as an imprinted molecule and the 2-vinyl-4,6-diamino-1,3,5-triazine (VDAT) was considered as a functional monomer in this study. The geometry optimization, natural bond orbital (NBO) charge, and molecular electrostatic potential (MEP) of PHN and VDAT were studied at the M062X level belonging to one of the hybrid density functional theories. Furthermore, we discussed the bonding conditions of PHN molecular imprinted polymers (PHN-MIPs) via the hydrogen bond length and atoms in molecules (AIM) theory. The rebinding property of PHN-MIPs was also researched. The results of MEP and NBO charge analysis were coincident. The stability property was excellent when the ratio of PHN and VDAT was 1:4. Except the classic hydrogen bonds, non-classical hydrogen bonds also existed in the imprinted polymers. By simulating the rebinding energies between the pentobarbital (PNT), barbital (BAR), and PHN-MIPs after the elution of PHN, the rebinding property of PHN-MIPs to PHN was excellent when PNT and BAR existed all at once. This research can provide theoretical reference for the synthesis and characterization of novel PHN-MIPs.
Recently, the investigation of novel molecularly imprinted polymers (MIPs) has attracted a lot of interest and becomes a fascinating field. The phenobarbital (PHN) was taken as an imprinted molecule and the 2-vinyl-4,6-diamino-1,3,5-triazine (VDAT) was considered as a functional monomer in this study. The geometry optimization, natural bond orbital (NBO) charge, and molecular electrostatic potential (MEP) of PHN and VDAT were studied at the M062X level belonging to one of the hybrid density functional theories. Furthermore, we discussed the bonding conditions of PHN molecular imprinted polymers (PHN-MIPs) via the hydrogen bond length and atoms in molecules (AIM) theory. The rebinding property of PHN-MIPs was also researched. The results of MEP and NBO charge analysis were coincident. The stability property was excellent when the ratio of PHN and VDAT was 1:4. Except the classic hydrogen bonds, non-classical hydrogen bonds also existed in the imprinted polymers. By simulating the rebinding energies between the pentobarbital (PNT), barbital (BAR), and PHN-MIPs after the elution of PHN, the rebinding property of PHN-MIPs to PHN was excellent when PNT and BAR existed all at once. This research can provide theoretical reference for the synthesis and characterization of novel PHN-MIPs.
2014, 33(10): 1431-1435
Abstract:
The thermoelectric properties of CuGaTe2 crystal are investigated by using the first-principles method and semi-classical Boltzmann theory. We find that the electronic structure of CuGaTe2 is favorable for p-type doping. The transport coefficients can be tuned by doping and changing the work temperature to yield an optimized thermoelectric performance. The optimal doping concentration is 2×1020 cm-3, in which the maximum ZT value can reach 1.65 at 900 K. The results suggest CuGaTe2 might find promising applications as good thermoelectric materials, particularly at high temperature.
The thermoelectric properties of CuGaTe2 crystal are investigated by using the first-principles method and semi-classical Boltzmann theory. We find that the electronic structure of CuGaTe2 is favorable for p-type doping. The transport coefficients can be tuned by doping and changing the work temperature to yield an optimized thermoelectric performance. The optimal doping concentration is 2×1020 cm-3, in which the maximum ZT value can reach 1.65 at 900 K. The results suggest CuGaTe2 might find promising applications as good thermoelectric materials, particularly at high temperature.
2014, 33(10): 1436-1442
Abstract:
The first-principles calculations were performed to investigate the stability, band structure, density of states and redox potential of Al-, Ga-, and In-doped monoclinic BiVO4 (mBiVO4). The calculated formation energies show that Al-doped mBiVO4 inducing an O vacancy is energetically favorable with a smaller defect formation value. With the incorporation of Al, Ga, and In, the band gap of the doped systems will be narrowed in the order of Al-doped< Ga-doped< In-doped mBiVO4, which is beneficial for the response to the visible light. And the substitution of an Al or Ga for a V atom will significantly enhance the reducibility of mBiVO4, improving the efficiency of H2 evolution from H2O. Our results show that the photocatalytic activity of mBiVO4 can be modulated by substitutional doping of Al, Ga, and In.
The first-principles calculations were performed to investigate the stability, band structure, density of states and redox potential of Al-, Ga-, and In-doped monoclinic BiVO4 (mBiVO4). The calculated formation energies show that Al-doped mBiVO4 inducing an O vacancy is energetically favorable with a smaller defect formation value. With the incorporation of Al, Ga, and In, the band gap of the doped systems will be narrowed in the order of Al-doped< Ga-doped< In-doped mBiVO4, which is beneficial for the response to the visible light. And the substitution of an Al or Ga for a V atom will significantly enhance the reducibility of mBiVO4, improving the efficiency of H2 evolution from H2O. Our results show that the photocatalytic activity of mBiVO4 can be modulated by substitutional doping of Al, Ga, and In.
2014, 33(10): 1443-1450
Abstract:
A new Schiff base compound ((NSBSH)2bipy·3H2O) based on 5-nitrosalicylal 4-methyl benzene-sulfonohydrazide (abbreviated as NSBSH), formulated as C38H40N8O13S2, has been synthesized by the condensation of 5-nitrosalicylaldehyde and 4-methylbenzenesulfonohydrazide, and structurally characterized by X-ray single-crystal diffraction analysis, elemental analysis and IR spectrum. It crystallizes in monoclinic system, space group P2/c with a=13.7992(16), b=7.1410(8), c=21.403(2) Å, β=95.5660(10)° and V=2099.1(4) Å3. X-ray analysis reveals that there are obvious π-π stacking interactions between two adjacent aromatic ring planes. The intermolecular hydrogen bonding interactions connect the adjacent Schiff base units into a binuclear unit, and further propagate these moieties into a two-dimensional (2D) supramolecular network. The title compound displays strong photoluminescence in the liquid state as well as high thermal stability. The experiment also shows that it has a good antibacterial activity in vitro antibacterial activity against Sarcina.
A new Schiff base compound ((NSBSH)2bipy·3H2O) based on 5-nitrosalicylal 4-methyl benzene-sulfonohydrazide (abbreviated as NSBSH), formulated as C38H40N8O13S2, has been synthesized by the condensation of 5-nitrosalicylaldehyde and 4-methylbenzenesulfonohydrazide, and structurally characterized by X-ray single-crystal diffraction analysis, elemental analysis and IR spectrum. It crystallizes in monoclinic system, space group P2/c with a=13.7992(16), b=7.1410(8), c=21.403(2) Å, β=95.5660(10)° and V=2099.1(4) Å3. X-ray analysis reveals that there are obvious π-π stacking interactions between two adjacent aromatic ring planes. The intermolecular hydrogen bonding interactions connect the adjacent Schiff base units into a binuclear unit, and further propagate these moieties into a two-dimensional (2D) supramolecular network. The title compound displays strong photoluminescence in the liquid state as well as high thermal stability. The experiment also shows that it has a good antibacterial activity in vitro antibacterial activity against Sarcina.
2014, 33(10): 1451-1454
Abstract:
The title compound 2-(4-ethoxybenzoyl)cyclopentane-1,3-dione (C14H14O4) was synthesized, and its crystal structure was studied. It crystallized in the triclinic system, space group P1 with a=8.980(2), b=9.080(2), c=15.482(3) Å, α=93.49(3), β=93.84(3), γ=107.27(3)°, Dc=1.365 g/cm3, Z=4, λ=0.71073 Å, μ(MoKα)=2.769 mm-1, Mr=246.25, V=1198.5(4) Å3, F(000)=520, the final R=0.0559 and wR=0.1278 for 2301 observed reflections with I>2σ(I). In the crystalline state, the molecular skeleton contains one enol grouping, which is intramolecularly hydrogen bonded to a neighboring keto O atom. Preliminary bioassay result showed that this compound provided 93.8% and 87.2% control of B. campestris and A. retroflexus at post-emergence at 375 g/hm2.
The title compound 2-(4-ethoxybenzoyl)cyclopentane-1,3-dione (C14H14O4) was synthesized, and its crystal structure was studied. It crystallized in the triclinic system, space group P1 with a=8.980(2), b=9.080(2), c=15.482(3) Å, α=93.49(3), β=93.84(3), γ=107.27(3)°, Dc=1.365 g/cm3, Z=4, λ=0.71073 Å, μ(MoKα)=2.769 mm-1, Mr=246.25, V=1198.5(4) Å3, F(000)=520, the final R=0.0559 and wR=0.1278 for 2301 observed reflections with I>2σ(I). In the crystalline state, the molecular skeleton contains one enol grouping, which is intramolecularly hydrogen bonded to a neighboring keto O atom. Preliminary bioassay result showed that this compound provided 93.8% and 87.2% control of B. campestris and A. retroflexus at post-emergence at 375 g/hm2.
2014, 33(10): 1455-1459
Abstract:
Two 5-pyrimidinyl-1,2,4-oxadiazoles were synthesized through two different routes and their structures were characterized by single-crystal X-ray diffraction, NMR and MS. Compound 3, 5-(2-chloro-4-methyl-6-phenylpyrimidin-5-yl)-3-phenyl-1,2,4-oxadiazole, crystallizes in orthorhombic, space group Pbca with a=19.1575(11), b=8.2115(5), c=21.2035(12) Å, V=3335.6(3) Å3 and Z=4. Compound 6, 5-(2,6-dichloropyrimidin-4-yl)-3-phenyl-1,2,4-oxadiazole, crystallizes in monoclinic space group Pn with a=8.4275(13), b=5.4088(8), c=13.493(2) Å, β=99.768(3)°, V=4658.6(6) Å3 and Z=8. Preliminary bioassay indicated that the two title compounds had good herbicidal activities.
Two 5-pyrimidinyl-1,2,4-oxadiazoles were synthesized through two different routes and their structures were characterized by single-crystal X-ray diffraction, NMR and MS. Compound 3, 5-(2-chloro-4-methyl-6-phenylpyrimidin-5-yl)-3-phenyl-1,2,4-oxadiazole, crystallizes in orthorhombic, space group Pbca with a=19.1575(11), b=8.2115(5), c=21.2035(12) Å, V=3335.6(3) Å3 and Z=4. Compound 6, 5-(2,6-dichloropyrimidin-4-yl)-3-phenyl-1,2,4-oxadiazole, crystallizes in monoclinic space group Pn with a=8.4275(13), b=5.4088(8), c=13.493(2) Å, β=99.768(3)°, V=4658.6(6) Å3 and Z=8. Preliminary bioassay indicated that the two title compounds had good herbicidal activities.
2014, 33(10): 1460-1466
Abstract:
A new series of quinoxalinophenazine derivatives were synthesized in good yields by the reaction of 2,3-dibromonaphthalene-1,4-dione with different aryl-1,2-diamines in DMF as solvent at 120~130℃ or under reflux conditions. 3,12-dimethylbenzo[a]quinoxalino[2,3-c] phenazine with bidentate character reacts with mercury(Ⅱ) bromide to give suitable crystals. All products were confirmed by IR, 1H and 13C NMR, and the metal complex by single-crystal X-ray method. The crystal (C24H16Br2HgN4, Mr=720.82) belongs to the triclinic system, space group P1 with a=10.186(6), b=10.421(6), c=11.470(7) Å, α=98.670(7), β=95.069(7), γ=109.831(7)°, V=1119.4(12) Å3, Z=2, Dc=2.139 Mg/m3, μ=10.46 mm-1, F(000)=676, R=0.043 and wR=0.115 for 3982 observed reflections with I>2σ(I).
A new series of quinoxalinophenazine derivatives were synthesized in good yields by the reaction of 2,3-dibromonaphthalene-1,4-dione with different aryl-1,2-diamines in DMF as solvent at 120~130℃ or under reflux conditions. 3,12-dimethylbenzo[a]quinoxalino[2,3-c] phenazine with bidentate character reacts with mercury(Ⅱ) bromide to give suitable crystals. All products were confirmed by IR, 1H and 13C NMR, and the metal complex by single-crystal X-ray method. The crystal (C24H16Br2HgN4, Mr=720.82) belongs to the triclinic system, space group P1 with a=10.186(6), b=10.421(6), c=11.470(7) Å, α=98.670(7), β=95.069(7), γ=109.831(7)°, V=1119.4(12) Å3, Z=2, Dc=2.139 Mg/m3, μ=10.46 mm-1, F(000)=676, R=0.043 and wR=0.115 for 3982 observed reflections with I>2σ(I).
2014, 33(10): 1467-1471
Abstract:
The novel crystal of the title compound 2-(((5-(((5,7-dimethyl-[1,2,4]triazolo-[1, 5-a]-pyrimidin-2-yl)thio)methyl)-4-phenyl-4H-1,2,4-triazol-3-yl)thio)methyl)-4H-chromen-4-one methanol solvate (C27H25N7O3S2, Mr=559.66) has been prepared and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monocline system, space group P21/c with a=11.9879(9), b=14.0743(10), c=15.9706(11) Å, β=98.509(2)°, V=2664.9(3) Å3, Z=4, Dc=1.395 g/cm3, F(000)=1168, μ=0.116 mm-1, MoKa radiation (λ=0.71073), R=0.0652, and wR=0.1425 for 5220 observed reflections with I>2σ(I). X-ray diffraction analyses reveal that the molecule adopts a C-shape. The planes of the benzopyrone and triazolopyrimidine were nearly parallel to each other, with a dihedral angle of 1.21(3)°. Intramolecular and intermolecular hydrogen bonds together with π-π interations are found to exist in the structure. The results of MTT assay indicate that the title compound displays excellent antiproliferative activity against two human cancer cell lines.
The novel crystal of the title compound 2-(((5-(((5,7-dimethyl-[1,2,4]triazolo-[1, 5-a]-pyrimidin-2-yl)thio)methyl)-4-phenyl-4H-1,2,4-triazol-3-yl)thio)methyl)-4H-chromen-4-one methanol solvate (C27H25N7O3S2, Mr=559.66) has been prepared and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monocline system, space group P21/c with a=11.9879(9), b=14.0743(10), c=15.9706(11) Å, β=98.509(2)°, V=2664.9(3) Å3, Z=4, Dc=1.395 g/cm3, F(000)=1168, μ=0.116 mm-1, MoKa radiation (λ=0.71073), R=0.0652, and wR=0.1425 for 5220 observed reflections with I>2σ(I). X-ray diffraction analyses reveal that the molecule adopts a C-shape. The planes of the benzopyrone and triazolopyrimidine were nearly parallel to each other, with a dihedral angle of 1.21(3)°. Intramolecular and intermolecular hydrogen bonds together with π-π interations are found to exist in the structure. The results of MTT assay indicate that the title compound displays excellent antiproliferative activity against two human cancer cell lines.
2014, 33(10): 1472-1478
Abstract:
CoO nanostructures with tunable morphology and size have been prepared via a simple one-pot solvothermal synthesis. The as-prepared nanoparticles were fully characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), field-emission scanning electron microscope (FESEM), etc. The morphology and size of the product can be easily controlled by adjusting the raw materials added. Reaction time and the solvent ratio also play important roles in the synthesis of octahedral nanostructures. The magnetic property of the as-prepared samples was also investigated.
CoO nanostructures with tunable morphology and size have been prepared via a simple one-pot solvothermal synthesis. The as-prepared nanoparticles were fully characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), field-emission scanning electron microscope (FESEM), etc. The morphology and size of the product can be easily controlled by adjusting the raw materials added. Reaction time and the solvent ratio also play important roles in the synthesis of octahedral nanostructures. The magnetic property of the as-prepared samples was also investigated.
2014, 33(10): 1479-1487
Abstract:
A new ligand, 2-(2-hydroxyphenyl)-5,6-dichlorobenzimidazole, H2pbmCl2 (1), and a novel MnⅢ complex,[MnⅢ(HpbmCl2)(pbmCl2)(DMF)2] (2), (DMF=N,N-dimethylformamide), have been synthesized and characterized. The crystal of compound 1 (C13H8Cl2N2O, Mr=279.12) belongs to the monoclinic system, space group P21 with a=3.770(5), b=25.20(3), c=5.865(7) Å, β=92.727(17)°, V=556.6(12) Å3, Z=2, Dc=1.665 g/cm3, S=1.137, μ=0.568 mm-1, F(000)=284, the final R=0.0876 and wR=0.2334 for 1848 independent reflections. The molecule is planar due to the presence of a strong intramolecular hydrogen bond between O-H group of phenol and N atom of imidazole. H2pbmCl2 (1) molecules are arranged into a one-dimensional linear chain through intermolecular hydrogen bonds (N-H…O and C-H…Cl). The crystal of complex 2 (C32H27Cl4MnN6O4, Mr=756.34) belongs to the monoclinic system, space group P21/c with a=19.043(10), b=10.808(5), c=18.704(11) Å, β=115.540(6)°, V=3473(3) Å3, Z=4, Dc=1.446 g/cm3, S=1.3, μ=0.733 mm-1, F(000)=1544, the final R=0.1219 and wR=0.2681 for 7811 independent reflections. The Mn ion adopts a distorted octahedral geometry coordinated by two deprotonated H2pbmCl2 ligands and two DMF molecules. The[MnⅢ(HpbmCl2)(pbmCl2)(DMF)2] molecules are arranged into a three-dimensional structure through hydrogen bonds (N-H…N, C-H…N and C-H…Cl) and weak π…π interactions. The activity measurements suggest that complex 2 is able to serve as a catalyst for H2O2 disproportionation reaction to form O2 in neutral water solution.
A new ligand, 2-(2-hydroxyphenyl)-5,6-dichlorobenzimidazole, H2pbmCl2 (1), and a novel MnⅢ complex,[MnⅢ(HpbmCl2)(pbmCl2)(DMF)2] (2), (DMF=N,N-dimethylformamide), have been synthesized and characterized. The crystal of compound 1 (C13H8Cl2N2O, Mr=279.12) belongs to the monoclinic system, space group P21 with a=3.770(5), b=25.20(3), c=5.865(7) Å, β=92.727(17)°, V=556.6(12) Å3, Z=2, Dc=1.665 g/cm3, S=1.137, μ=0.568 mm-1, F(000)=284, the final R=0.0876 and wR=0.2334 for 1848 independent reflections. The molecule is planar due to the presence of a strong intramolecular hydrogen bond between O-H group of phenol and N atom of imidazole. H2pbmCl2 (1) molecules are arranged into a one-dimensional linear chain through intermolecular hydrogen bonds (N-H…O and C-H…Cl). The crystal of complex 2 (C32H27Cl4MnN6O4, Mr=756.34) belongs to the monoclinic system, space group P21/c with a=19.043(10), b=10.808(5), c=18.704(11) Å, β=115.540(6)°, V=3473(3) Å3, Z=4, Dc=1.446 g/cm3, S=1.3, μ=0.733 mm-1, F(000)=1544, the final R=0.1219 and wR=0.2681 for 7811 independent reflections. The Mn ion adopts a distorted octahedral geometry coordinated by two deprotonated H2pbmCl2 ligands and two DMF molecules. The[MnⅢ(HpbmCl2)(pbmCl2)(DMF)2] molecules are arranged into a three-dimensional structure through hydrogen bonds (N-H…N, C-H…N and C-H…Cl) and weak π…π interactions. The activity measurements suggest that complex 2 is able to serve as a catalyst for H2O2 disproportionation reaction to form O2 in neutral water solution.
2014, 33(10): 1488-1494
Abstract:
A novel two-dimensional lead(Ⅱ) coordination polymer 1,[C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand (5-chloro-quinolin-8-yloxy)acetic acid (HL) with PbCl2, and its structure was characterized by IR, elemental analysis, TG-DTA and single-crystal X-ray diffraction analysis. The crystal is of monoclinic system, space group P21/c with a=16.7603(7), b=8.6907(4), c=8.4745(3) Å, β=101.1110(11)°, [C11H7Cl2NO3Pb, Mr=479.27, V=1211.25(9) Å3, Z=4, Dc=2.628 g/cm3, F(000)=880, μ=14.367 mm-1, R=0.0173 and wR=0.0508. The asymmetric unit contains one lead(Ⅱ) cation, one (5-chloro-quinolin-8-yloxy)acetate (L) ligand and a chloride ion. The PbⅡ center is hepta-coordinated in a distorted pentagonal bipyramidal geometry. The coordination sphere of the Pb atom is completed by two oxygen atoms and one nitrogen atom of the same L ligand, two bridging chloride ions and two bridging oxygen atoms of two adjacent L ligands. Two PbⅡ centers are linked by the two L ligands to form a C2-symmetric dimer unit with a planar[Pb2O2] ring. Each dimer unit acts as a secondary building unit (SBU) and links adjacent four dimer units by the chloride atoms and oxygen atoms of carboxylate groups of L, forming a two-dimensional array. Such two-dimensional layers are packed through intermolecular C-H…Cl hydrogen bonds into a three-dimensional supramolecular structure. When the dimer unit is viewed as a 4-connected node, 1 is simplified as a 4-nodal 2-D network with square lattices of the diagonal lengths to be 6.079(1) Å. The fluorescence emission peak of complex 1 appears near 407nm.
A novel two-dimensional lead(Ⅱ) coordination polymer 1,[C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand (5-chloro-quinolin-8-yloxy)acetic acid (HL) with PbCl2, and its structure was characterized by IR, elemental analysis, TG-DTA and single-crystal X-ray diffraction analysis. The crystal is of monoclinic system, space group P21/c with a=16.7603(7), b=8.6907(4), c=8.4745(3) Å, β=101.1110(11)°, [C11H7Cl2NO3Pb, Mr=479.27, V=1211.25(9) Å3, Z=4, Dc=2.628 g/cm3, F(000)=880, μ=14.367 mm-1, R=0.0173 and wR=0.0508. The asymmetric unit contains one lead(Ⅱ) cation, one (5-chloro-quinolin-8-yloxy)acetate (L) ligand and a chloride ion. The PbⅡ center is hepta-coordinated in a distorted pentagonal bipyramidal geometry. The coordination sphere of the Pb atom is completed by two oxygen atoms and one nitrogen atom of the same L ligand, two bridging chloride ions and two bridging oxygen atoms of two adjacent L ligands. Two PbⅡ centers are linked by the two L ligands to form a C2-symmetric dimer unit with a planar[Pb2O2] ring. Each dimer unit acts as a secondary building unit (SBU) and links adjacent four dimer units by the chloride atoms and oxygen atoms of carboxylate groups of L, forming a two-dimensional array. Such two-dimensional layers are packed through intermolecular C-H…Cl hydrogen bonds into a three-dimensional supramolecular structure. When the dimer unit is viewed as a 4-connected node, 1 is simplified as a 4-nodal 2-D network with square lattices of the diagonal lengths to be 6.079(1) Å. The fluorescence emission peak of complex 1 appears near 407nm.
2014, 33(10): 1495-1498
Abstract:
A new dimeric compound,[Zn(bpdc)(L)]2·4H2O (1, L=11-fluoro-dipyrido[3,2-a:2',3'-c]phenazine and bpdc=1,1'-biphenyl-2,2'-dicarboxylate), has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group C2/c with a=23.671(5), b=22.547(5), c=13.741(3) Å, β=123.47(3)°, V=6118(2) Å3, Z=4, C66H44Cl2F2N8O12Zn2, Mr=1380.73, Dc=1.499 g/cm3, F(000)=2816, μ(MoKa)=0.949 mm-1, R=0.0572 and wR=0.1620. In 1, Zn1 and the symmetry formed Zn1 ions are connected by four bridging bidentate carboxylate groups from two independent bpdc anions to yield a binuclear unit with the Zn…Zn separation by bpdc anions of 4.168 Å. Two L ligands are located on both sides of the dimer in chelating bidentate modes. The lateral L ligands from neighboring dimers are paired through strong π-π interactions to result in a fascinating 1D ladder-like supramolecular array. In addition, neighboring supramolecular ladders are packed each other to yield a 3D supramolecular architecture with a 1D channel.
A new dimeric compound,[Zn(bpdc)(L)]2·4H2O (1, L=11-fluoro-dipyrido[3,2-a:2',3'-c]phenazine and bpdc=1,1'-biphenyl-2,2'-dicarboxylate), has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group C2/c with a=23.671(5), b=22.547(5), c=13.741(3) Å, β=123.47(3)°, V=6118(2) Å3, Z=4, C66H44Cl2F2N8O12Zn2, Mr=1380.73, Dc=1.499 g/cm3, F(000)=2816, μ(MoKa)=0.949 mm-1, R=0.0572 and wR=0.1620. In 1, Zn1 and the symmetry formed Zn1 ions are connected by four bridging bidentate carboxylate groups from two independent bpdc anions to yield a binuclear unit with the Zn…Zn separation by bpdc anions of 4.168 Å. Two L ligands are located on both sides of the dimer in chelating bidentate modes. The lateral L ligands from neighboring dimers are paired through strong π-π interactions to result in a fascinating 1D ladder-like supramolecular array. In addition, neighboring supramolecular ladders are packed each other to yield a 3D supramolecular architecture with a 1D channel.
2014, 33(10): 1499-1504
Abstract:
A new complex {[Mn2(IP)2(1,4-bdc)2]·H2O}n(1) (IP=1H-imidazo[4,5-f] [1,10]-phenanthroline, 1,4-H2bdc=1,4-benzendicarboxylic acid), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group Cc with a=20.326(2), b=24.249(2), c=7.621(1) Å, β=108.546(6), V=3561.2(7) Å3, Z=4, Dc=1.672 g/cm3, μ=0.785 mm-1, F(000)=1824, S=1.067, the final R=0.0299 and wR=0.0752. Compound 1 possesses a 2D structural motif, in which two crystallographically independent 1,4-bdc dianions adopt the alternative mode of mixed bis(bidentate) and monodentate-bidentate coordination modes to bridge neighboring Mn(Ⅱ) centers. And the 2D layers are linked up by hydrogen bonding and π…π stacking interactions to form a 3D network. The title compound has good thermal stability and exhibits photoluminescent emission maximum at 518 nm.
A new complex {[Mn2(IP)2(1,4-bdc)2]·H2O}n(1) (IP=1H-imidazo[4,5-f] [1,10]-phenanthroline, 1,4-H2bdc=1,4-benzendicarboxylic acid), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group Cc with a=20.326(2), b=24.249(2), c=7.621(1) Å, β=108.546(6), V=3561.2(7) Å3, Z=4, Dc=1.672 g/cm3, μ=0.785 mm-1, F(000)=1824, S=1.067, the final R=0.0299 and wR=0.0752. Compound 1 possesses a 2D structural motif, in which two crystallographically independent 1,4-bdc dianions adopt the alternative mode of mixed bis(bidentate) and monodentate-bidentate coordination modes to bridge neighboring Mn(Ⅱ) centers. And the 2D layers are linked up by hydrogen bonding and π…π stacking interactions to form a 3D network. The title compound has good thermal stability and exhibits photoluminescent emission maximum at 518 nm.
2014, 33(10): 1505-1515
Abstract:
An unsymmetrical macrocyclic dinuclear Zn(Ⅱ) complex,[Zn2(H0.5L)(OAc)](ClO4)0.5 (1, H2L is the condensation product between 2, 6-diformyl-4-methylphenol and diethylenetriamine), was obtained and characterized by IR spectrum, elemental analysis and X-ray single-crystal diffraction. The complex crystallizes in monoclinic, space group P21/c with a=16.784(2), b=19.474(3), c=10.3364(13) Å, β=92.923(2)°, V=3374.1(7) Å3, Z=4, Dc=1.672 g/cm3, F(000)=1740, μ=1.651 mm-1, the R=0.0609 and wR=0.1696 for 4745 observed reflections (I>2σ(I)). The interactions of the complex with DNA have been measured by electrochemical studies, UV spectroscopy and viscosity experiment. The interactions of the complex with calf thymus DNA were studied by UV-vis spectra and the binding constant is 1.58×104 mol·L-1. The phosphate hydrolysis catalyzed by the complex was investigated using 4-nitrophenyl phosphate (NPP) as the substrate; the observed first order rate constant value is 3.0×10-4 s-1.
An unsymmetrical macrocyclic dinuclear Zn(Ⅱ) complex,[Zn2(H0.5L)(OAc)](ClO4)0.5 (1, H2L is the condensation product between 2, 6-diformyl-4-methylphenol and diethylenetriamine), was obtained and characterized by IR spectrum, elemental analysis and X-ray single-crystal diffraction. The complex crystallizes in monoclinic, space group P21/c with a=16.784(2), b=19.474(3), c=10.3364(13) Å, β=92.923(2)°, V=3374.1(7) Å3, Z=4, Dc=1.672 g/cm3, F(000)=1740, μ=1.651 mm-1, the R=0.0609 and wR=0.1696 for 4745 observed reflections (I>2σ(I)). The interactions of the complex with DNA have been measured by electrochemical studies, UV spectroscopy and viscosity experiment. The interactions of the complex with calf thymus DNA were studied by UV-vis spectra and the binding constant is 1.58×104 mol·L-1. The phosphate hydrolysis catalyzed by the complex was investigated using 4-nitrophenyl phosphate (NPP) as the substrate; the observed first order rate constant value is 3.0×10-4 s-1.
2014, 33(10): 1516-1520
Abstract:
A new coordination polymer,[Cd2(bptc)(L)2(H2O)2]·5H2O (1, L=2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-f] [1,10]phenanthroline and H4bptc=3,3',4,4'-biphenyltetracarboxylic acid), has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a=18.868(4), b=7.2111(14), c=19.464(4) Å, β=95.75(3)°, C54H31Cd2Cl2F2N8O15, Mr=1365.57, V=2635.0(9) Å3, Z=2, Dc=1.721 g/cm3, S=1.034, μ(MoKα)=0.995 mm-1, F(000)=1358, R=0.0501 and wR=0.1076. In 1, each bptc anion bridges four Cd(Ⅱ) atoms to form 2D layer structures, which are further extended by π-π stacking interactions into a 3D supramolecular architecture. The thermal behavior and luminescent properties of the compound have also been studied.
A new coordination polymer,[Cd2(bptc)(L)2(H2O)2]·5H2O (1, L=2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-f] [1,10]phenanthroline and H4bptc=3,3',4,4'-biphenyltetracarboxylic acid), has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a=18.868(4), b=7.2111(14), c=19.464(4) Å, β=95.75(3)°, C54H31Cd2Cl2F2N8O15, Mr=1365.57, V=2635.0(9) Å3, Z=2, Dc=1.721 g/cm3, S=1.034, μ(MoKα)=0.995 mm-1, F(000)=1358, R=0.0501 and wR=0.1076. In 1, each bptc anion bridges four Cd(Ⅱ) atoms to form 2D layer structures, which are further extended by π-π stacking interactions into a 3D supramolecular architecture. The thermal behavior and luminescent properties of the compound have also been studied.
2014, 33(10): 1521-1526
Abstract:
Two dinuclear organotin complexes C8H14(CO2SnCy3)2 (1) (Cy=cyclohexyl group) and C8H14[CO2Sn(CH2CMe2Ph)3]2 (2) were synthesized by the reactions of camphoric acid with tricyclohexyltin hydroxide and bis[tri(2-methyl-2-phenyl)propyltin] oxide under solvothermal conditions, and these complexes were characterized by infrared spectra, elemental analyses, and H NMR spectra. The crystal of 1 belongs to the monoclinic system, space group P21/c with a=1.83478(19), b=1.52707(18), c=1.9849(2) nm, β=122.515(7)°, Z=4, V=4.6896(9) nm3, Dc=1.324 g/cm3, μ(MoKα)=1.103 mm-1, F(000)=1952, R=0.0697 and wR=0.2040. In addition, thermal stability and quantum chemical calculation of 1 were also studied.
Two dinuclear organotin complexes C8H14(CO2SnCy3)2 (1) (Cy=cyclohexyl group) and C8H14[CO2Sn(CH2CMe2Ph)3]2 (2) were synthesized by the reactions of camphoric acid with tricyclohexyltin hydroxide and bis[tri(2-methyl-2-phenyl)propyltin] oxide under solvothermal conditions, and these complexes were characterized by infrared spectra, elemental analyses, and H NMR spectra. The crystal of 1 belongs to the monoclinic system, space group P21/c with a=1.83478(19), b=1.52707(18), c=1.9849(2) nm, β=122.515(7)°, Z=4, V=4.6896(9) nm3, Dc=1.324 g/cm3, μ(MoKα)=1.103 mm-1, F(000)=1952, R=0.0697 and wR=0.2040. In addition, thermal stability and quantum chemical calculation of 1 were also studied.
2014, 33(10): 1527-1532
Abstract:
A new copper complex 2{Cu(C10H8N2)[C8H11O2(COO)](H2O)3}·(H2O)5 with bicycle[2.2.1]hept-2-en-5,6-dicarboxylic acid (H2L)[C7H8(COOH)2], basic copper carbonate and 2,2'-bipyridine has been synthesized in the mixed solvents of methanol and water. It crystallizes in the triclinic system, space group P1, with a=7.4626(5), b=11.9779(8), c=12.9841(8) Å, α=109.7040(10), β=98.7550(10), γ=90.6240(10)°, V=1077.50(12) Å3, Dc=1.538 g/cm3, Z=1, F(000)=520, GOOF=1.065, R=0.0360 and wR=0.0950. The copper ion is coordinated with four oxygen atoms from one H2L molecule and three water molecules together with two nitrogen atoms from the 2,2'-bipyridine molecule, forming a distorted octahedral coordination geometry. The thermal stability and electrochemical properties were also studied.
A new copper complex 2{Cu(C10H8N2)[C8H11O2(COO)](H2O)3}·(H2O)5 with bicycle[2.2.1]hept-2-en-5,6-dicarboxylic acid (H2L)[C7H8(COOH)2], basic copper carbonate and 2,2'-bipyridine has been synthesized in the mixed solvents of methanol and water. It crystallizes in the triclinic system, space group P1, with a=7.4626(5), b=11.9779(8), c=12.9841(8) Å, α=109.7040(10), β=98.7550(10), γ=90.6240(10)°, V=1077.50(12) Å3, Dc=1.538 g/cm3, Z=1, F(000)=520, GOOF=1.065, R=0.0360 and wR=0.0950. The copper ion is coordinated with four oxygen atoms from one H2L molecule and three water molecules together with two nitrogen atoms from the 2,2'-bipyridine molecule, forming a distorted octahedral coordination geometry. The thermal stability and electrochemical properties were also studied.
2014, 33(10): 1533-1538
Abstract:
A two-dimensional (2D) coordination polymer {[Cd2(sdb)2(dpb)2]·3H2O}n (1) was prepared by solvothermal reaction of two types of V-shaped ligands:1,3-dipyridyl benzene (dpb) and deprotonated 4,4'-sulfonyldibenzoic acid (H2sdb). It was characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Complex 1 crystallizes in the monoclinic system, space group Fdd2 with a=46.247(10), b=9.994(2), c=24.267(6) Å, V=11216(4) Å3, C60H46Cd2N4O15S2, Mr=1387.97, Dc=1.559 g/cm3, F(000)=5296.0, μ=0.902 mm-1 and Z=8. Each[Cd(COO)]2 cluster links four sdb2- anions to form infinitely ABAB stacked 2D wave-like sheets, in which each sheet contains the same helical chains, and the helical directions of sheets A and B are reversed. Dpb links the rest coordinated sites of[(COO)Cd]2 cluster to form a 2D network. In addition, the solid fluorescence of 1 and dpb is also studied.
A two-dimensional (2D) coordination polymer {[Cd2(sdb)2(dpb)2]·3H2O}n (1) was prepared by solvothermal reaction of two types of V-shaped ligands:1,3-dipyridyl benzene (dpb) and deprotonated 4,4'-sulfonyldibenzoic acid (H2sdb). It was characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Complex 1 crystallizes in the monoclinic system, space group Fdd2 with a=46.247(10), b=9.994(2), c=24.267(6) Å, V=11216(4) Å3, C60H46Cd2N4O15S2, Mr=1387.97, Dc=1.559 g/cm3, F(000)=5296.0, μ=0.902 mm-1 and Z=8. Each[Cd(COO)]2 cluster links four sdb2- anions to form infinitely ABAB stacked 2D wave-like sheets, in which each sheet contains the same helical chains, and the helical directions of sheets A and B are reversed. Dpb links the rest coordinated sites of[(COO)Cd]2 cluster to form a 2D network. In addition, the solid fluorescence of 1 and dpb is also studied.
2014, 33(10): 1539-1544
Abstract:
A new Eu(Ⅲ) complex, {[Eu(tta)2(C2H5OH)(NO3)]2(bmp)}·bmp (tta=2-thenoyltrifluoro-acetonate, bmp=2,2'-bipyrimidine), has been synthesized and characterized by elemental analysis, IR, luminescence and single-crystal X-ray diffraction analysis. The complex crystallizes in the monoclinic P21/n space group, with a=11.894(6), b=14.235(8), c=19.078(10) Å, β=103.423(9)°, V=3142(3) Å3, Z=2, Mr=1721.10, Dc=1.819 g/cm3, F(000)=1696, the final R=0.0452 and wR=0.1398 for 5375 observed reflections with I>2σ(I). In the complex, each Eu(Ⅲ) ion is coordinated with four oxygen atoms from two tta ligands and two nitrogen atoms from a bmp ligand, three oxygen atoms from one NO3- anion and one ethanol molecule, forming a distorted tricapped trigonal prism geometry. Luminescence measurement indicates that the europium complex is a strong red emitter in the solid state at room temperature.
A new Eu(Ⅲ) complex, {[Eu(tta)2(C2H5OH)(NO3)]2(bmp)}·bmp (tta=2-thenoyltrifluoro-acetonate, bmp=2,2'-bipyrimidine), has been synthesized and characterized by elemental analysis, IR, luminescence and single-crystal X-ray diffraction analysis. The complex crystallizes in the monoclinic P21/n space group, with a=11.894(6), b=14.235(8), c=19.078(10) Å, β=103.423(9)°, V=3142(3) Å3, Z=2, Mr=1721.10, Dc=1.819 g/cm3, F(000)=1696, the final R=0.0452 and wR=0.1398 for 5375 observed reflections with I>2σ(I). In the complex, each Eu(Ⅲ) ion is coordinated with four oxygen atoms from two tta ligands and two nitrogen atoms from a bmp ligand, three oxygen atoms from one NO3- anion and one ethanol molecule, forming a distorted tricapped trigonal prism geometry. Luminescence measurement indicates that the europium complex is a strong red emitter in the solid state at room temperature.
2014, 33(10): 1545-1549
Abstract:
A fluorescent Ni(Ⅱ) complex 1,[Ni(OH-H2Bdc)(Bibimp)]n·nH2O, constructed with 5-hydroxyisophthalic acid (OH-H2Bdc) and 2,6-bis(2-benzimidazolyl)pyridine) (Bibimp) has been synthesized by hydrothermal methods and structurally characterized by elemental analysis, IR spectroscopy, TG/DTG, fluorescence spectrum and single-crystal X-ray diffraction. The title complex crystallizes in triclinic system, space group P1 with a=10.187(2), b=10.273(2), c=13.401(3) Å, α=69.65(3), β=69.66(3), γ=70.61(3)°, V=1196.8(4) Å3, and Z=2. The adjacent chains of complex 1 are stacked offset with respect to each other in an ABAB fashion by van der Waals interactions, and only a weak interlayer nonclassical C-H…O hydrogen bond has been observed. Complex 1 displays strong blue fluorescent emissions at 483 nm in the solid state upon photo-excitation at 365 nm at room temperature.
A fluorescent Ni(Ⅱ) complex 1,[Ni(OH-H2Bdc)(Bibimp)]n·nH2O, constructed with 5-hydroxyisophthalic acid (OH-H2Bdc) and 2,6-bis(2-benzimidazolyl)pyridine) (Bibimp) has been synthesized by hydrothermal methods and structurally characterized by elemental analysis, IR spectroscopy, TG/DTG, fluorescence spectrum and single-crystal X-ray diffraction. The title complex crystallizes in triclinic system, space group P1 with a=10.187(2), b=10.273(2), c=13.401(3) Å, α=69.65(3), β=69.66(3), γ=70.61(3)°, V=1196.8(4) Å3, and Z=2. The adjacent chains of complex 1 are stacked offset with respect to each other in an ABAB fashion by van der Waals interactions, and only a weak interlayer nonclassical C-H…O hydrogen bond has been observed. Complex 1 displays strong blue fluorescent emissions at 483 nm in the solid state upon photo-excitation at 365 nm at room temperature.
2014, 33(10): 1550-1559
Abstract:
Polyoxometalates (POMs) with Cd-coordination complexes acting as supporting units are rarely reported. The linkage of the supporting units with inorganic building block (polyanion) is generally established on terminal O-atoms, but scarcely via bridging O-atoms. By introducing liquid small organic molecule (pyridine, C5NH5) as assistant "structure-directing agent", we obtained a novel organic-inorganic hybrid polytungstate, (Hpy)4[Cd(phen)2(P2W18O62)]·nH2O (1, n≈3, py=pyridine, phen=1,10-phenanthroline), under hydrothermal conditions. The single-crystal X-ray diffraction analysis shows that 1 is the first compound containing an asymmetric heteropolyanion,[Cd(phen)2(P2W18O62)]4-, a Wells-Dawson-type polyanion monosupported by Cd-coordination complex via di-bridging O-atoms.
Polyoxometalates (POMs) with Cd-coordination complexes acting as supporting units are rarely reported. The linkage of the supporting units with inorganic building block (polyanion) is generally established on terminal O-atoms, but scarcely via bridging O-atoms. By introducing liquid small organic molecule (pyridine, C5NH5) as assistant "structure-directing agent", we obtained a novel organic-inorganic hybrid polytungstate, (Hpy)4[Cd(phen)2(P2W18O62)]·nH2O (1, n≈3, py=pyridine, phen=1,10-phenanthroline), under hydrothermal conditions. The single-crystal X-ray diffraction analysis shows that 1 is the first compound containing an asymmetric heteropolyanion,[Cd(phen)2(P2W18O62)]4-, a Wells-Dawson-type polyanion monosupported by Cd-coordination complex via di-bridging O-atoms.
2014, 33(10): 1560-1565
Abstract:
A three-dimensional (3D) barium complex with 1,3,5-benzenetricarboxylic acid (H3BTC), {[Ba1.5(BTC)(H2O)]·(H2O)}n (1), was synthesized in DMF/EtOH/H2O mixed solution under solvothermal conditions, and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric analyses, and photoluminescence measurement. In complex 1, the 2D I2O0 type inorganic layer is constructed by {Ba1O10} and {Ba2O9} polyhedra. Moreover, the solid-state fluorescence measurement reveals a fluorescence emission band at 465 nm under 344 nm excitation, assigned to a charge-transfer transition.
A three-dimensional (3D) barium complex with 1,3,5-benzenetricarboxylic acid (H3BTC), {[Ba1.5(BTC)(H2O)]·(H2O)}n (1), was synthesized in DMF/EtOH/H2O mixed solution under solvothermal conditions, and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric analyses, and photoluminescence measurement. In complex 1, the 2D I2O0 type inorganic layer is constructed by {Ba1O10} and {Ba2O9} polyhedra. Moreover, the solid-state fluorescence measurement reveals a fluorescence emission band at 465 nm under 344 nm excitation, assigned to a charge-transfer transition.
