Login In
2016 Volume 35 Issue 11
2016, 35(11): 1637-1644
doi: 10.14102/j.cnki.0254-5861.2011-1199
Abstract:
Two iodoargentate hybrids templated by viologen or viologen-like cations, i.e.[MV(Ag2I4)]n (1) and [MBYP(AgI2)]n (2), (MV2+=methyl viologen, MBYP+=1-methyl-2,2'-bipyridine) have been synthesized in polar organic solvents. (Ag2I4)n2- and (AgI2)n2-chains in both compounds were constructed from edge-sharing of normal and distorted AgI4 tetrahedra, and a 2-D supramolecular layer based on C-H…I hydrogen bond was observed in 1. The band gaps of 1.54 and 2.67 eV indicated their semiconductor nature. Their band gap difference was led by different hydrogen bond donors in MV2+ and MBYP+, which result in more diffused p-π* antibonding orbitals in MV2+.
Two iodoargentate hybrids templated by viologen or viologen-like cations, i.e.[MV(Ag2I4)]n (1) and [MBYP(AgI2)]n (2), (MV2+=methyl viologen, MBYP+=1-methyl-2,2'-bipyridine) have been synthesized in polar organic solvents. (Ag2I4)n2- and (AgI2)n2-chains in both compounds were constructed from edge-sharing of normal and distorted AgI4 tetrahedra, and a 2-D supramolecular layer based on C-H…I hydrogen bond was observed in 1. The band gaps of 1.54 and 2.67 eV indicated their semiconductor nature. Their band gap difference was led by different hydrogen bond donors in MV2+ and MBYP+, which result in more diffused p-π* antibonding orbitals in MV2+.
2016, 35(11): 1645-1654
doi: 10.14102/j.cnki.0254-5861.2011-1220
Abstract:
Three new vortioxexine (VOT) salts with salicylic acid (SA), 5-fluorouracil (FU) and (p-nitrophenyl)-acetic acid (PA) have been synthesized and characterized in detail. In VOT-SA(1:1), the protonated VOT and deprotonated salicylic anion form a tetrameric unit with the R44 (12) synthon via N(1)-H(1)…O(1)a (a:x-1, y, z) and N(1)-H(2)…O(2)b (b:-x, -y, -z+1) hydrogen bonds. However, in VOT-FU(1:2), the protonated VOT and deprotonated 5-fluorouracil anion feature an R44 (16) ring motif via N(1)-H(1)…O(2)c (c:-x+1, -y+1, -z+1) and N(1)-H(2)…O(1)d (d:x, y-1, z) hydrogen bonds. The neutral FU extends the R44 (16) ring to form a two-dimensional structure through R22(8) N-H…O and N(6)-H(4)…N(4)e (e:-x+1, y-1/2, -z+1/2) hydrogen bonds. In VOT-PA(1:1), PA molecules are linked through N(1)-H(1)…O(1)f (f:-x+1, y+1/2, -z+1) and N(1)-H(2)…O(2), which forms a right-handed helical structure. Furthermore, components of the crystalline phase have also been investigated in terms of their corresponding Hirshfeld surface, and the salification improves the equilibrium solubilities and dissolution rates of VOT in three salts at 25℃ in water.
Three new vortioxexine (VOT) salts with salicylic acid (SA), 5-fluorouracil (FU) and (p-nitrophenyl)-acetic acid (PA) have been synthesized and characterized in detail. In VOT-SA(1:1), the protonated VOT and deprotonated salicylic anion form a tetrameric unit with the R44 (12) synthon via N(1)-H(1)…O(1)a (a:x-1, y, z) and N(1)-H(2)…O(2)b (b:-x, -y, -z+1) hydrogen bonds. However, in VOT-FU(1:2), the protonated VOT and deprotonated 5-fluorouracil anion feature an R44 (16) ring motif via N(1)-H(1)…O(2)c (c:-x+1, -y+1, -z+1) and N(1)-H(2)…O(1)d (d:x, y-1, z) hydrogen bonds. The neutral FU extends the R44 (16) ring to form a two-dimensional structure through R22(8) N-H…O and N(6)-H(4)…N(4)e (e:-x+1, y-1/2, -z+1/2) hydrogen bonds. In VOT-PA(1:1), PA molecules are linked through N(1)-H(1)…O(1)f (f:-x+1, y+1/2, -z+1) and N(1)-H(2)…O(2), which forms a right-handed helical structure. Furthermore, components of the crystalline phase have also been investigated in terms of their corresponding Hirshfeld surface, and the salification improves the equilibrium solubilities and dissolution rates of VOT in three salts at 25℃ in water.
2016, 35(11): 1655-1665
doi: 10.14102/j.cnki.0254-5861.2011-1082
Abstract:
A new strategy for the synthesis of polyoxometalate-based (POM-based) metalorganic materials was developed. The approach takes the advantage of the ability of phenanthroline derivative base to build strong noncovalent interactions. Three POM-based metal-organic compounds,[Mn(MOPIP)2(OH)2][Mn(MOPIP)2(OH)(SiW12O40)]·6H2O (1),[Cu2(MOPIP)2(OH)2(H2O)]2-(SiW12O40)·5H2O (2) and [Co(Mo2O7)(MOPIP)]n (3) (MOPIP=2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline), were synthesized under hydrothermal conditions. Single-crystal X-ray analysis reveals that compound 1 displays a mononuclear cluster. These clusters are interconnected by a framework of π…π stacking interactions to from a chain and layer structure. Compound 2 shows a multinuclear cluster with Keggin-type polyoxoanions[SiW12O40]4- as building blocks. Strong hydrogen bonding interactions extend these multinuclear clusters into a two-dimensional layer. Compound 3 is a coordination polymer, in which [Mo2O7]2- polyoxoanions connect the Co(Ⅱ) ions running along the direction of one of the crystallographic axes to from a linear chain. Adjacent chains are further assembled into a two-dimensional network by strong hydrogen bonding interactions. The main structural traits in all of the compounds are that polyoxometalate acts as inorganic building blocks and connect metal ions to form cluster structure and coordination polymer. In addition, the photocatalytic activities and mechanism of compounds 1~3 on the degradation of Rhodamine B (RhB) under UV irradiation have been investigated in detail.
A new strategy for the synthesis of polyoxometalate-based (POM-based) metalorganic materials was developed. The approach takes the advantage of the ability of phenanthroline derivative base to build strong noncovalent interactions. Three POM-based metal-organic compounds,[Mn(MOPIP)2(OH)2][Mn(MOPIP)2(OH)(SiW12O40)]·6H2O (1),[Cu2(MOPIP)2(OH)2(H2O)]2-(SiW12O40)·5H2O (2) and [Co(Mo2O7)(MOPIP)]n (3) (MOPIP=2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline), were synthesized under hydrothermal conditions. Single-crystal X-ray analysis reveals that compound 1 displays a mononuclear cluster. These clusters are interconnected by a framework of π…π stacking interactions to from a chain and layer structure. Compound 2 shows a multinuclear cluster with Keggin-type polyoxoanions[SiW12O40]4- as building blocks. Strong hydrogen bonding interactions extend these multinuclear clusters into a two-dimensional layer. Compound 3 is a coordination polymer, in which [Mo2O7]2- polyoxoanions connect the Co(Ⅱ) ions running along the direction of one of the crystallographic axes to from a linear chain. Adjacent chains are further assembled into a two-dimensional network by strong hydrogen bonding interactions. The main structural traits in all of the compounds are that polyoxometalate acts as inorganic building blocks and connect metal ions to form cluster structure and coordination polymer. In addition, the photocatalytic activities and mechanism of compounds 1~3 on the degradation of Rhodamine B (RhB) under UV irradiation have been investigated in detail.
2016, 35(11): 1666-1672
doi: 10.14102/j.cnki.0254-5861.2011-1188
Abstract:
A novel zero-dimensional heteronuclear cluster based on N-(phosphonomethyl)imino-diacetic acid (H4PMIDA) and Phen (1,10-phenanthroline),[Zn6Co9(PMIDA)6(Phen)6(NO3)4(H2O)6]·2NO3·16H2O, has been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectrum, thermal analysis, and single-crystal X-ray diffraction. The isolated 15-nuclearity cluster[Zn6Co9(PMIDA)6(Phen)6(NO3)4(H2O)6]2+ was constructed by four kinds of ligands, and its charges are balanced by NO3-. Each isolated cluster is further extended into a 3D supramolecular network through π…π interaction and C-H…O hydrogen bonds. Moreover, the solid-state fluorescent property of this complex has also been investigated at room temperature.
A novel zero-dimensional heteronuclear cluster based on N-(phosphonomethyl)imino-diacetic acid (H4PMIDA) and Phen (1,10-phenanthroline),[Zn6Co9(PMIDA)6(Phen)6(NO3)4(H2O)6]·2NO3·16H2O, has been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectrum, thermal analysis, and single-crystal X-ray diffraction. The isolated 15-nuclearity cluster[Zn6Co9(PMIDA)6(Phen)6(NO3)4(H2O)6]2+ was constructed by four kinds of ligands, and its charges are balanced by NO3-. Each isolated cluster is further extended into a 3D supramolecular network through π…π interaction and C-H…O hydrogen bonds. Moreover, the solid-state fluorescent property of this complex has also been investigated at room temperature.
2016, 35(11): 1673-1678
doi: 10.14102/j.cnki.0254-5861.2011-1200
Abstract:
Single crystals of Nd:La3Ga5SiO14 (NLGS) and Nd:La3Ga5.5Ta0.5O14 (NLGT) were grown by Czochralski method. Both crystals exhibit a langasite structure (space group D32 (P321) with Z=1), whose general formula is A3BC2D3O14, where A, B, C and D represent the dodecahedral, octahedral and tetrahedral positions, respectively. The adding of low content of Nd does not change the crystal structure. Although they are isostructural, the distribution of atoms among the symmetric sites is different. While NLGT exhibits a perfect orderly structure, NLGS exhibits an intrinsically disordered structure due to the random distribution of Ga and Si atoms at the C3(2) symmetry sites. To understand what changes occur in the phonon distribution when Ta replaces Si, we recorded and analyzed room temperature polarized Raman spectra. We observe 8A1+18E modes for NLGS and 10A1+13E for NLGT crystals. When Si is substituted by Ta, we observe that the wavenumber of some modes related to vibrations involving Ga and O atoms decreases. This agrees with the fact that the Ga-O bonds are shorter in NLGS than in NLGT.
Single crystals of Nd:La3Ga5SiO14 (NLGS) and Nd:La3Ga5.5Ta0.5O14 (NLGT) were grown by Czochralski method. Both crystals exhibit a langasite structure (space group D32 (P321) with Z=1), whose general formula is A3BC2D3O14, where A, B, C and D represent the dodecahedral, octahedral and tetrahedral positions, respectively. The adding of low content of Nd does not change the crystal structure. Although they are isostructural, the distribution of atoms among the symmetric sites is different. While NLGT exhibits a perfect orderly structure, NLGS exhibits an intrinsically disordered structure due to the random distribution of Ga and Si atoms at the C3(2) symmetry sites. To understand what changes occur in the phonon distribution when Ta replaces Si, we recorded and analyzed room temperature polarized Raman spectra. We observe 8A1+18E modes for NLGS and 10A1+13E for NLGT crystals. When Si is substituted by Ta, we observe that the wavenumber of some modes related to vibrations involving Ga and O atoms decreases. This agrees with the fact that the Ga-O bonds are shorter in NLGS than in NLGT.
2016, 35(11): 1679-1685
doi: 10.14102/j.cnki.0254-5861.2011-1189
Abstract:
Cd-rich portion of the pseudo-binary system Cd3B2O6-Zn3B2O6 was investigated. A new cadmium zinc borate, Cd2.42Zn0.58B2O6, was synthesized successfully by a traditional solid-state reaction method. The compound crystallizes in the monoclinic space group C2/c with a=17.3048, b=8.4356, c=10.2962 Å, β=93.157°, V=1500.7(2) Å3, Dc=5.683 g/cm3, F(000)=2301, Z=24, R=0.0351 and wR=0.0741. In its structure, BO3 triangle, CdO6 and CdO5 (or ZnO5) polyhedra are joined together by sharing bridging O atoms to form an intricate three-dimensional framework. A comparison of the structures of Cd2.42Zn0.58B2O6, α-Cd3B2O6 and β-Cd3B2O6 is presented. The IR spectrum confirms the presence of BO3 unit. The UV cut-off wavelength of Cd2.42Zn0.58B2O6 is 313 nm. The differential thermal analysis (DTA) suggests that Cd2.42Zn0.58B2O6 is an incongruent melting compound.
Cd-rich portion of the pseudo-binary system Cd3B2O6-Zn3B2O6 was investigated. A new cadmium zinc borate, Cd2.42Zn0.58B2O6, was synthesized successfully by a traditional solid-state reaction method. The compound crystallizes in the monoclinic space group C2/c with a=17.3048, b=8.4356, c=10.2962 Å, β=93.157°, V=1500.7(2) Å3, Dc=5.683 g/cm3, F(000)=2301, Z=24, R=0.0351 and wR=0.0741. In its structure, BO3 triangle, CdO6 and CdO5 (or ZnO5) polyhedra are joined together by sharing bridging O atoms to form an intricate three-dimensional framework. A comparison of the structures of Cd2.42Zn0.58B2O6, α-Cd3B2O6 and β-Cd3B2O6 is presented. The IR spectrum confirms the presence of BO3 unit. The UV cut-off wavelength of Cd2.42Zn0.58B2O6 is 313 nm. The differential thermal analysis (DTA) suggests that Cd2.42Zn0.58B2O6 is an incongruent melting compound.
2016, 35(11): 1686-1693
doi: 10.14102/j.cnki.0254-5861.2011-1213
Abstract:
A novel copper(Ⅱ) complex with the reduced Schiff base,[Cu(L)2]·H2O (I, HL=N-(4-hydroxybenzyl)-L-serine), was prepared in aqueous solution and characterized by elemental analysis, FT-IR, electrospray ionization mass spectrometry and single-crystal X-ray diffraction. Complex I crystallizes in the orthorhombic system, space group P212121, with a=8.9040(18), b=9.1530(18), c=24.891(5) Å, V=2028.6(7) Å3, Z=4, C20H26CuN2O9, Mr=501.97, Dc=1.644g·cm3, μ=1.135 mm-1, F(000)=1044, GOOF=1.194, the final R=0.0484 and wR=0.1420 for 6186 observed reflections (I>2σ(I)). In I, two L- anions are coordinated to the copper ion in tridentate and bidentate chelating modes, respectively, resulting in the coordinated geometry of copper ion to be a distorted square pyramid. The intermolecular hydrogen bonds between the complexes, complexes and lattice water molecules lead to a 2D supramolecular network. The bioactivity of the complex as a potential PTPs inhibitory agent in vitro was investigated, displaying potent inhibition against PTP1B (IC50, 0.27 μM) and TCPTP (IC50, 0.57 μM) with a moderate selectivity.
A novel copper(Ⅱ) complex with the reduced Schiff base,[Cu(L)2]·H2O (I, HL=N-(4-hydroxybenzyl)-L-serine), was prepared in aqueous solution and characterized by elemental analysis, FT-IR, electrospray ionization mass spectrometry and single-crystal X-ray diffraction. Complex I crystallizes in the orthorhombic system, space group P212121, with a=8.9040(18), b=9.1530(18), c=24.891(5) Å, V=2028.6(7) Å3, Z=4, C20H26CuN2O9, Mr=501.97, Dc=1.644g·cm3, μ=1.135 mm-1, F(000)=1044, GOOF=1.194, the final R=0.0484 and wR=0.1420 for 6186 observed reflections (I>2σ(I)). In I, two L- anions are coordinated to the copper ion in tridentate and bidentate chelating modes, respectively, resulting in the coordinated geometry of copper ion to be a distorted square pyramid. The intermolecular hydrogen bonds between the complexes, complexes and lattice water molecules lead to a 2D supramolecular network. The bioactivity of the complex as a potential PTPs inhibitory agent in vitro was investigated, displaying potent inhibition against PTP1B (IC50, 0.27 μM) and TCPTP (IC50, 0.57 μM) with a moderate selectivity.
2016, 35(11): 1694-1699
doi: 10.14102/j.cnki.0254-5861.2011-1218
Abstract:
The new title compound, chiral 2-(3-methyl-2,3-dihydrobenzo[b][1,4]oxazin-4-yl)-2-oxoethyl acetate, has been synthesized via reduction, cyclization and acylation reaction. The structure of the product has been confirmed by IR, 1H NMR, 13C NMR, LC-MS (ESI) and single-crystal X-ray diffraction. (R)-2-(3-methyl-2,3-dihydrobenzo[b][1,4]oxazin-4-yl)-2-oxoethyl acetate crystallizes in monoclinic, space group P21/c with a=11.867(2), b=8.4087(2), c=14.325(6) Å, β=117.59(2)°, Z=4, V=1266.9(6) Å3, Dc=1.307 g/cm3, F(000)=528, μ(MoKα)=0.097 mm-1, R=0.0453 and wR=0.1237; (S)-2-(3-methyl-2,3-dihydrobenzo[b][1,4]oxazin-4-yl)-2-oxoethyl acetate belongs to the triclinic system, space group P1 with a=8.2647(17), b=8.7034(17), c=9.5479(19) Å, α=105.33(3), β=100.95(3), γ=105.14(3)°, Z=2, V=614.1(2) Å3, Dc=1.348 g/cm3, F(000)=264, μ(MoKα)=0.10 mm-1, R=0.0613 and wR=0.1037. Both of the molecules prefer to form crystal packing through C-H…O hydrogen bonds.
The new title compound, chiral 2-(3-methyl-2,3-dihydrobenzo[b][1,4]oxazin-4-yl)-2-oxoethyl acetate, has been synthesized via reduction, cyclization and acylation reaction. The structure of the product has been confirmed by IR, 1H NMR, 13C NMR, LC-MS (ESI) and single-crystal X-ray diffraction. (R)-2-(3-methyl-2,3-dihydrobenzo[b][1,4]oxazin-4-yl)-2-oxoethyl acetate crystallizes in monoclinic, space group P21/c with a=11.867(2), b=8.4087(2), c=14.325(6) Å, β=117.59(2)°, Z=4, V=1266.9(6) Å3, Dc=1.307 g/cm3, F(000)=528, μ(MoKα)=0.097 mm-1, R=0.0453 and wR=0.1237; (S)-2-(3-methyl-2,3-dihydrobenzo[b][1,4]oxazin-4-yl)-2-oxoethyl acetate belongs to the triclinic system, space group P1 with a=8.2647(17), b=8.7034(17), c=9.5479(19) Å, α=105.33(3), β=100.95(3), γ=105.14(3)°, Z=2, V=614.1(2) Å3, Dc=1.348 g/cm3, F(000)=264, μ(MoKα)=0.10 mm-1, R=0.0613 and wR=0.1037. Both of the molecules prefer to form crystal packing through C-H…O hydrogen bonds.
2016, 35(11): 1700-1707
doi: 10.14102/j.cnki.0254-5861.2011-1197
Abstract:
A new cadmium borophosphate, KCdBP2O7(OH)2, was synthesized by using boric acid flux method. The crystal structure was determined by single-crystal X-ray diffraction analysis (monoclinic, space group P21/c, a=12.103(2), b=8.8737(18), c=7.1266(14) Å, β=101.69(3)°, V=749.5(3) Å3 and Z=4). The framework of KCdBP2O7(OH)2 is constructed from the connection of infinite [CdO6] octahedral chains and open-branched chains[(BP2Φ9)2]n (Φ=O, OH), giving rise to a 2D layered structure viewed along the [100] direction. The K+ ionic conductivity measured for KCdBP2O7(OH)2 was 3.47×1--8 S·cm-1 at 583 K.
A new cadmium borophosphate, KCdBP2O7(OH)2, was synthesized by using boric acid flux method. The crystal structure was determined by single-crystal X-ray diffraction analysis (monoclinic, space group P21/c, a=12.103(2), b=8.8737(18), c=7.1266(14) Å, β=101.69(3)°, V=749.5(3) Å3 and Z=4). The framework of KCdBP2O7(OH)2 is constructed from the connection of infinite [CdO6] octahedral chains and open-branched chains[(BP2Φ9)2]n (Φ=O, OH), giving rise to a 2D layered structure viewed along the [100] direction. The K+ ionic conductivity measured for KCdBP2O7(OH)2 was 3.47×1--8 S·cm-1 at 583 K.
2016, 35(11): 1708-1713
doi: 10.14102/j.cnki.0254-5861.2011-1278
Abstract:
Aspergillus flavus causes serious disease on important agriculture crops, and its secondary metabolic products-aflatoxins are most potent toxin and carcinogen for animal and human. Structural and functional studies of A. flavus proteins may provide insights into the identification of potential therapeutic targets and prevention of damage caused by A. flavus. Here, we report the expression, purification, crystallization and preliminary crystallographic analysis of NDK protein from A. flavus. The NDK protein was expressed in E. coli and purified by using a series of chromatographic methods to >98% purity. The recombinant protein was crystallized and the crystals diffracted to 2.4 Å resolution. The crystal of NDK is in space group of C121 with a=190.84, b=169.47, c=146.94 Å. Preliminary data analysis indicated that the NDK molecule assembles into a multimer in the asymmetric unit.
Aspergillus flavus causes serious disease on important agriculture crops, and its secondary metabolic products-aflatoxins are most potent toxin and carcinogen for animal and human. Structural and functional studies of A. flavus proteins may provide insights into the identification of potential therapeutic targets and prevention of damage caused by A. flavus. Here, we report the expression, purification, crystallization and preliminary crystallographic analysis of NDK protein from A. flavus. The NDK protein was expressed in E. coli and purified by using a series of chromatographic methods to >98% purity. The recombinant protein was crystallized and the crystals diffracted to 2.4 Å resolution. The crystal of NDK is in space group of C121 with a=190.84, b=169.47, c=146.94 Å. Preliminary data analysis indicated that the NDK molecule assembles into a multimer in the asymmetric unit.
2016, 35(11): 1714-1722
doi: 10.14102/j.cnki.0254-5861.2011-1150
Abstract:
Three indium metal-organic frameworks (In-MOFs),[In(BTB)(2,2'-bipy)]·NMP (1),[In(BTB)(2,2'-bipy)]·NMP·2H2O (2), and [In(BTB)(NMP)]·0.5NMP (3), have been constructed by the solvothermal reaction of In(NO3)3(OH)2·5H2O and 1,3,5-benzenetribenzoic acid (H3BTB) in similar reaction conditions, and characterized by single-crystal X-ray crystallography, power X-ray diffraction (PXRD), infrared spectroscopy (IR), elemental analysis (EA) and thermogravimetry analysis (TGA). Complex 1 bears a two-dimensional (2D) layered structure of 6,3-connected hcb net topology, and complexes 2 and 3 have 2-fold interpenetrating structures based on 6,3-connected layer, which display the same net topologies with the C33-symmetric H3BTB ligands as 3-connected linkers and the In(Ⅲ) ions as 6-connected nodes. Moreover, the fluorescent properties of 1~3 have also been studied.
Three indium metal-organic frameworks (In-MOFs),[In(BTB)(2,2'-bipy)]·NMP (1),[In(BTB)(2,2'-bipy)]·NMP·2H2O (2), and [In(BTB)(NMP)]·0.5NMP (3), have been constructed by the solvothermal reaction of In(NO3)3(OH)2·5H2O and 1,3,5-benzenetribenzoic acid (H3BTB) in similar reaction conditions, and characterized by single-crystal X-ray crystallography, power X-ray diffraction (PXRD), infrared spectroscopy (IR), elemental analysis (EA) and thermogravimetry analysis (TGA). Complex 1 bears a two-dimensional (2D) layered structure of 6,3-connected hcb net topology, and complexes 2 and 3 have 2-fold interpenetrating structures based on 6,3-connected layer, which display the same net topologies with the C33-symmetric H3BTB ligands as 3-connected linkers and the In(Ⅲ) ions as 6-connected nodes. Moreover, the fluorescent properties of 1~3 have also been studied.
2016, 35(11): 1723-1727
doi: 10.14102/j.cnki.0254-5861.2011-1153
Abstract:
A new coordination complex[In(pda)1.5(bpy)]n (1, H2pda=1,4-phenylenediacetic acid, bpy=2,2'-bipyridine) has been synthesized under hydrothermal conditions and characterized by IR spectrum, elemental analysis, PXRD and single-crystal X-ray diffraction analysis. Crystal data for the title complex are as follows:monoclinic system, space group P21/n with a=11.8015(7), b=15.9551(10), c=11.8858(8) Å, β=94.844(6)°, V=2230.0(2) Å3, Mr=559.25, Z=4, F(000)=1124, Dc=1.666 g/cm3, μ(MoKα)=1.106 mm-1, R=0.0269 and wR=0.0569 for 4534 observed reflections with I>2σ(I). Complex 1 displays a 3D supermolecular structure based on the 1D zizag chains. Fluorescence spectrum measurement indicates that complex 1 shows strong fluorescence emission with a maximum peak at 447 nm in the solid state at room temperature.
A new coordination complex[In(pda)1.5(bpy)]n (1, H2pda=1,4-phenylenediacetic acid, bpy=2,2'-bipyridine) has been synthesized under hydrothermal conditions and characterized by IR spectrum, elemental analysis, PXRD and single-crystal X-ray diffraction analysis. Crystal data for the title complex are as follows:monoclinic system, space group P21/n with a=11.8015(7), b=15.9551(10), c=11.8858(8) Å, β=94.844(6)°, V=2230.0(2) Å3, Mr=559.25, Z=4, F(000)=1124, Dc=1.666 g/cm3, μ(MoKα)=1.106 mm-1, R=0.0269 and wR=0.0569 for 4534 observed reflections with I>2σ(I). Complex 1 displays a 3D supermolecular structure based on the 1D zizag chains. Fluorescence spectrum measurement indicates that complex 1 shows strong fluorescence emission with a maximum peak at 447 nm in the solid state at room temperature.
2016, 35(11): 1728-1735
doi: 10.14102/j.cnki.0254-5861.2011-1151
Abstract:
Two 1D chain metal-organic framework complexes, {Co[(C10H5N3O5)-(H2O)2·H2O]}n (1) and {Cd[(C10H5N3O5)(H2O)2]}n (2), based on a T-shaped tripodal ligand 4-(4,5-dicarboxy-1H-imidazol-2-yl) pyridine 1-oxide (H3DCImPyO) have been reacted under hydrothermal conditions, and were characterized by single-crystal X-ray structure analysis, fluorescent analysis and thermal gravimetric analysis. According to single-crystal X-ray determination, complex 1 crystallizes in the monoclinic system, space group P21/n with a=9.4930(13), b=13.2024(18), c=10.5203(14) Å, β=98.402(2)°, Z=4, V=1304.4(3) Å3; and complex 2 crystallizes in the monoclinic system, space group C2/c with a=13.557(3), b=13.568(3), c=6.7804(13) Å, β=105.095(2)°, Z=4 and V=1204.2(4) Å3. Fluorescent analysis of complex 2 showed an intense emission band at 466 nm when the exciting radiation was set at 360 nm. Dielectric constants of complexes 1 and 2 were measured at different frequencies with temperature variation.
Two 1D chain metal-organic framework complexes, {Co[(C10H5N3O5)-(H2O)2·H2O]}n (1) and {Cd[(C10H5N3O5)(H2O)2]}n (2), based on a T-shaped tripodal ligand 4-(4,5-dicarboxy-1H-imidazol-2-yl) pyridine 1-oxide (H3DCImPyO) have been reacted under hydrothermal conditions, and were characterized by single-crystal X-ray structure analysis, fluorescent analysis and thermal gravimetric analysis. According to single-crystal X-ray determination, complex 1 crystallizes in the monoclinic system, space group P21/n with a=9.4930(13), b=13.2024(18), c=10.5203(14) Å, β=98.402(2)°, Z=4, V=1304.4(3) Å3; and complex 2 crystallizes in the monoclinic system, space group C2/c with a=13.557(3), b=13.568(3), c=6.7804(13) Å, β=105.095(2)°, Z=4 and V=1204.2(4) Å3. Fluorescent analysis of complex 2 showed an intense emission band at 466 nm when the exciting radiation was set at 360 nm. Dielectric constants of complexes 1 and 2 were measured at different frequencies with temperature variation.
2016, 35(11): 1736-1744
doi: 10.14102/j.cnki.0254-5861.2011-1154
Abstract:
A chiral lanthanide metal-organic framework based on enantiopure camphoric acid (D-H2cam),[Nd3(D-cam)8(H2O)4Cl]n (1), has been synthesized and characterized by single-crystal X-ray structural analysis, elemental analysis, IR, thermal gravimetric, and X-ray powder diffraction. Crystal data for the title compound are as follows:orthorhombic system, space group P212121 with a=13.8287(7), b=14.0715(7), c=25.7403(12) Å, V=5008.8(4) Å3, Mr=1333.08, Z=4, F(000)=2644, Dc=1.768 g/cm3, μ(MoKα)=3.189 mm-1, the final R=0.0351 and wR=0.0814 (I>2σ(I)). Compound 1 displays an 8-connected bcu topology 3D framework and hydrogen-bonding interactions stabilize the solid-state structure. The vibrational circular dichroism (VCD) spectrum and second-order nonlinear optical effect of compound 1 have been studied in the solid state.
A chiral lanthanide metal-organic framework based on enantiopure camphoric acid (D-H2cam),[Nd3(D-cam)8(H2O)4Cl]n (1), has been synthesized and characterized by single-crystal X-ray structural analysis, elemental analysis, IR, thermal gravimetric, and X-ray powder diffraction. Crystal data for the title compound are as follows:orthorhombic system, space group P212121 with a=13.8287(7), b=14.0715(7), c=25.7403(12) Å, V=5008.8(4) Å3, Mr=1333.08, Z=4, F(000)=2644, Dc=1.768 g/cm3, μ(MoKα)=3.189 mm-1, the final R=0.0351 and wR=0.0814 (I>2σ(I)). Compound 1 displays an 8-connected bcu topology 3D framework and hydrogen-bonding interactions stabilize the solid-state structure. The vibrational circular dichroism (VCD) spectrum and second-order nonlinear optical effect of compound 1 have been studied in the solid state.
2016, 35(11): 1745-1753
doi: 10.14102/j.cnki.0254-5861.2011-1160
Abstract:
Two zinc(Ⅱ) complexes, namely,[Zn(L1)Cl2]2 (1) and {[Zn(L2)(tbta)]·3H2O}n (2) (L1=1,3-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2tbta=tetrabromoterephthalic acid, L2=1,3-bis(2-methylbenzimidazol-1-yl)-2-propanol), have been successfully obtained under hydrothermal conditions. Complex 1 displays a binuclear structure which is further extended into a 1D supramolecular chain through π-π stacking. Complex 2 features a 2D (4,4) network based on a L2/tbta2- double linker. The thermal stability, fluorescence properties and catalytic activities of two complexes for the degradation of methyl orange in a Fenton-like process were discussed.
Two zinc(Ⅱ) complexes, namely,[Zn(L1)Cl2]2 (1) and {[Zn(L2)(tbta)]·3H2O}n (2) (L1=1,3-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2tbta=tetrabromoterephthalic acid, L2=1,3-bis(2-methylbenzimidazol-1-yl)-2-propanol), have been successfully obtained under hydrothermal conditions. Complex 1 displays a binuclear structure which is further extended into a 1D supramolecular chain through π-π stacking. Complex 2 features a 2D (4,4) network based on a L2/tbta2- double linker. The thermal stability, fluorescence properties and catalytic activities of two complexes for the degradation of methyl orange in a Fenton-like process were discussed.
2016, 35(11): 1754-1763
doi: 10.14102/j.cnki.0254-5861.2011-1156
Abstract:
Three new cobalt triarylcorroles with sterically hindered haloginated phenyl rings were synthesized and characterized by UV-vis, 1H NMR spectroscopy, mass spectrometry and electrochemistry. The compounds are represented as (Ar)3CorCo(PPh3), where Cor is a trianion of the corrole macrocycle and Ar is a 2-ClPh (1), 2,6-diClPh (2) or 2,6-diFPh (3) group on each of the three meso-positions. The structures of 1 and 3 were characterized in the solid state by single-crystal X-ray analysis. Rotating-disk electrode was utilized to examine the electrocatalytic activity of the corroles for reduction of O2 in 1.0 M HClO4. Effect of the sterically hindered meso-substituents on UV-vis spectra and redox potentials as well as the electrocatalytic activity for reduction of dioxygen was discussed.
Three new cobalt triarylcorroles with sterically hindered haloginated phenyl rings were synthesized and characterized by UV-vis, 1H NMR spectroscopy, mass spectrometry and electrochemistry. The compounds are represented as (Ar)3CorCo(PPh3), where Cor is a trianion of the corrole macrocycle and Ar is a 2-ClPh (1), 2,6-diClPh (2) or 2,6-diFPh (3) group on each of the three meso-positions. The structures of 1 and 3 were characterized in the solid state by single-crystal X-ray analysis. Rotating-disk electrode was utilized to examine the electrocatalytic activity of the corroles for reduction of O2 in 1.0 M HClO4. Effect of the sterically hindered meso-substituents on UV-vis spectra and redox potentials as well as the electrocatalytic activity for reduction of dioxygen was discussed.
2016, 35(11): 1764-1769
doi: 10.14102/j.cnki.0254-5861.2011-1159
Abstract:
Two new isostructure nickel(Ⅱ) coordination polymers,[Ni2(5-Me-ip)(1,2-Bie)(H2O)2]n (1) and [Ni2(5-Br-ip)(1,2-Bie)(H2O)2]n (2) (5-Me-H2ip=5-methylisophthalic acid, 5-Br-H2ip=5-mromoisophthalic acid, 1,2-Bie=1,2-bis(imidazole)ethane), have been synthesized and structurally characterized by single-crystal X-ray diffraction. The result shows that complexes 1 and 2 crystallize in orthorhombic system, space group Pna21 with a=16.3602(13), b=10.1465(8), c=21.8803(17) Å, V=3632.1(5) Å3, Z=4, Dc=1.525 g/cm3, F(000)=1728, R=0.0292 and wR=0.0668 for 6646 observed reflections (I>2σ(I)) for complex 1 and a=16.409(3), b=10.1625(17), c=21.918(4) Å, V=3654.9(11) Å3, Z=4, Dc=1.752 g/cm3, F(000)=1936, R=0.0309 and wR=0.0600 for 6809 observed reflections (I>2σ(I)) for complex 2. They both feature zigzag 2D layer structures, which are further staked along the a-axis through π…π and hydrogen interactions to form 3D supramolecular structures.
Two new isostructure nickel(Ⅱ) coordination polymers,[Ni2(5-Me-ip)(1,2-Bie)(H2O)2]n (1) and [Ni2(5-Br-ip)(1,2-Bie)(H2O)2]n (2) (5-Me-H2ip=5-methylisophthalic acid, 5-Br-H2ip=5-mromoisophthalic acid, 1,2-Bie=1,2-bis(imidazole)ethane), have been synthesized and structurally characterized by single-crystal X-ray diffraction. The result shows that complexes 1 and 2 crystallize in orthorhombic system, space group Pna21 with a=16.3602(13), b=10.1465(8), c=21.8803(17) Å, V=3632.1(5) Å3, Z=4, Dc=1.525 g/cm3, F(000)=1728, R=0.0292 and wR=0.0668 for 6646 observed reflections (I>2σ(I)) for complex 1 and a=16.409(3), b=10.1625(17), c=21.918(4) Å, V=3654.9(11) Å3, Z=4, Dc=1.752 g/cm3, F(000)=1936, R=0.0309 and wR=0.0600 for 6809 observed reflections (I>2σ(I)) for complex 2. They both feature zigzag 2D layer structures, which are further staked along the a-axis through π…π and hydrogen interactions to form 3D supramolecular structures.
2016, 35(11): 1770-1776
doi: 10.14102/j.cnki.0254-5861.2011-1163
Abstract:
The coordination polymer [Mn2(cipt)2(aic)2]n (cipt=2-(3-chlorophenyl)-1Himidazo[4,5-f][1,10]phenanthroline, aic=5-amino-isophthalic acid) has been obtained from hydrothermal reaction and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. The title compound crystallizes in the triclinic system, space group P1, with a=11.523(3), b=12.162(3), c=18.706(5) Å, β=81.789(5)°, V=2455.2(1) Å3, C54H32Cl2Mn2N10O8, Mr=1129.68, Z=2, Dc=1.528 g/cm3, μ=0.692 mm-1, F(000)=1148, R=0.064 and wR=0.145 for 9571 observed reflections (I>2σ(I)). In this polymer, the Mn(Ⅱ) atoms adopt different coordination modes. The Mn(1) atom is five-coordinated, forming a distorted tetragonal pyramidal geometry. Mn(2) atom is six-coordinated to get a distorted octahedral geometry, which is different from the Mn(1) atom. Each Mn(Ⅱ) atom is linked by aic ligands with neighboring Mn(Ⅱ) atoms, forming an infinite one-dimensional (1D) double-chain structure. The existence of N-H…O hydrogen bonding interactions leads the 1D chains to generate a 2D structure. Luminescent properties for the ligand cipt and compound 1 have also been discussed in detail.
The coordination polymer [Mn2(cipt)2(aic)2]n (cipt=2-(3-chlorophenyl)-1Himidazo[4,5-f][1,10]phenanthroline, aic=5-amino-isophthalic acid) has been obtained from hydrothermal reaction and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. The title compound crystallizes in the triclinic system, space group P1, with a=11.523(3), b=12.162(3), c=18.706(5) Å, β=81.789(5)°, V=2455.2(1) Å3, C54H32Cl2Mn2N10O8, Mr=1129.68, Z=2, Dc=1.528 g/cm3, μ=0.692 mm-1, F(000)=1148, R=0.064 and wR=0.145 for 9571 observed reflections (I>2σ(I)). In this polymer, the Mn(Ⅱ) atoms adopt different coordination modes. The Mn(1) atom is five-coordinated, forming a distorted tetragonal pyramidal geometry. Mn(2) atom is six-coordinated to get a distorted octahedral geometry, which is different from the Mn(1) atom. Each Mn(Ⅱ) atom is linked by aic ligands with neighboring Mn(Ⅱ) atoms, forming an infinite one-dimensional (1D) double-chain structure. The existence of N-H…O hydrogen bonding interactions leads the 1D chains to generate a 2D structure. Luminescent properties for the ligand cipt and compound 1 have also been discussed in detail.
2016, 35(11): 1777-1786
doi: 10.14102/j.cnki.0254-5861.2011-0943
Abstract:
Two new tetrazole 1-acetato complexes,[Ag(1-tza)(phen)]∞ (1) and [Cd(1-tza)2(2,2'-bipy)]∞ (2) (1-Htza=tetrazole 1-acetato, phen=1,10-phenanthroline, 2,2'-bipy=2,2'-bipyridine), have been synthesized by solvothermal synthesis and structurally characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. Complex 1 shows a 1-D chained structure, while the structure of 2 contains two 1-D chains, which is the first 1-tza-based complex containing three different coordination modes of the 1-tza ligand. The aromatic stacking effects play an important role in the formation of supramolecular frameworks of these two complexes. Photoluminescent studies show that the two complexes exhibit efficient luminescence. In addition, optical diffuse reflectance spectra and thermogravimetric analyses of 1 and 2 have also been investigated.
Two new tetrazole 1-acetato complexes,[Ag(1-tza)(phen)]∞ (1) and [Cd(1-tza)2(2,2'-bipy)]∞ (2) (1-Htza=tetrazole 1-acetato, phen=1,10-phenanthroline, 2,2'-bipy=2,2'-bipyridine), have been synthesized by solvothermal synthesis and structurally characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. Complex 1 shows a 1-D chained structure, while the structure of 2 contains two 1-D chains, which is the first 1-tza-based complex containing three different coordination modes of the 1-tza ligand. The aromatic stacking effects play an important role in the formation of supramolecular frameworks of these two complexes. Photoluminescent studies show that the two complexes exhibit efficient luminescence. In addition, optical diffuse reflectance spectra and thermogravimetric analyses of 1 and 2 have also been investigated.
2016, 35(11): 1787-1796
doi: 10.14102/j.cnki.0254-5861.2011-1071
Abstract:
Syntheses, structures and magnetic properties of two nitrophenyl substituted nitronyl nitroxide radical-lanthanide complexes[Ln(hfac)3(NITmNO2)2] (Ln=Sm(Ⅲ) (1), Tb(Ⅲ) (2), hfac=hexafluoroacetylacetonate, NITmNO2=2-(3-nitrophenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) have been described in this paper. X-ray analysis shows that the two complexes have similar mononuclear trispin radical-Ln(Ⅲ)-radical structures, in which the central Ln(Ⅲ) ions are all eight coordinated in D2d dodecahedral (DD) geometry formed by six oxygen atoms from three hfac and two oxygen atoms from nitronyl nitroxide. The magnetic study indicates the antiferromagnetic interaction between Sm(Ⅲ) ion and NITmNO2 in complex 1, while weak ferromagnetic interaction between Tb(Ⅲ) ion and NITmNO2 in complex 2.
Syntheses, structures and magnetic properties of two nitrophenyl substituted nitronyl nitroxide radical-lanthanide complexes[Ln(hfac)3(NITmNO2)2] (Ln=Sm(Ⅲ) (1), Tb(Ⅲ) (2), hfac=hexafluoroacetylacetonate, NITmNO2=2-(3-nitrophenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) have been described in this paper. X-ray analysis shows that the two complexes have similar mononuclear trispin radical-Ln(Ⅲ)-radical structures, in which the central Ln(Ⅲ) ions are all eight coordinated in D2d dodecahedral (DD) geometry formed by six oxygen atoms from three hfac and two oxygen atoms from nitronyl nitroxide. The magnetic study indicates the antiferromagnetic interaction between Sm(Ⅲ) ion and NITmNO2 in complex 1, while weak ferromagnetic interaction between Tb(Ⅲ) ion and NITmNO2 in complex 2.
2016, 35(11): 1797-1804
doi: 10.14102/j.cnki.0254-5861.2011-1243
Abstract:
Two new Cd(Ⅱ) coordination polymers,[Cd(PT)(1,4-BDC)0.5]n (1) and [Cd(PT) (1,3-BDC)0.5]n (2) (HPT=3-(pyridin-2-yl)-1,2,4-triazole, 1,4-H2BDC=1,4-benzenedicarboxylic acid, 1,3-H2BDC=1,3-benzenedicarboxylic acid), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. Complexes 1 and 2 are both three-dimensional coordination polymers with two-dimensional sheet structures bridged by the deprotonated carboxylate ligands. In 1, 1,4-BDC2- bridges the layered network to generate a quadrangular framework, and 2 owns a sexangular framework, which was caused by the different steric hindrance between 1,4-BDC2- and 1,3-BDC2-. Their thermal stabilities and photoluminescent properties have been also investigated.
Two new Cd(Ⅱ) coordination polymers,[Cd(PT)(1,4-BDC)0.5]n (1) and [Cd(PT) (1,3-BDC)0.5]n (2) (HPT=3-(pyridin-2-yl)-1,2,4-triazole, 1,4-H2BDC=1,4-benzenedicarboxylic acid, 1,3-H2BDC=1,3-benzenedicarboxylic acid), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. Complexes 1 and 2 are both three-dimensional coordination polymers with two-dimensional sheet structures bridged by the deprotonated carboxylate ligands. In 1, 1,4-BDC2- bridges the layered network to generate a quadrangular framework, and 2 owns a sexangular framework, which was caused by the different steric hindrance between 1,4-BDC2- and 1,3-BDC2-. Their thermal stabilities and photoluminescent properties have been also investigated.
