Login In
2016 Volume 35 Issue 8
2016, 35(8): 1157-1166
doi: 10.14102/j.cnki.0254-5861.2011-1340
Abstract:
The connections between the building units of meta-stable lattice were generally considered to be easily disturbed during the doping process, causing serious hindrances blocking the development of functional doped materials. In this work, the synthesis of doped brookite, a typical meta-stable phase of TiO2, has been explored novelly by in-situ adding of cations of VIIIB and IB, IIB elements in the 3rd period (Fe, Co, Ni, Cu, Zn) during the urea-lactate aided low-basicity hydrothermal process. The results showed that only Cu-doped brookite could be successfully synthesized with trace amount of copper intensively internalized into the brookite lattice, while the other dopants lead to the formation of anatase TiO2. Extensive characterizations indicated a two-step doping process, where copper ions were firstly dispersed in an amorphous layer on the lattice surface and then they were internalized into brookite lattice. Cu-doped brookite exhibited significantly enhanced photocatalytic activity in the phenol degradation under visible light compared to bare brookite. The enhancement of catalytic performance was assigned to the impurity band gap and the reduction of charge carriers' recombination introduced by the internalization of Cu ions. The investigation reported herein contributes to the understanding of complex ion-doping effects on the structures of meta-stable materials, and provides hints for obtaining other functional doped materials.
The connections between the building units of meta-stable lattice were generally considered to be easily disturbed during the doping process, causing serious hindrances blocking the development of functional doped materials. In this work, the synthesis of doped brookite, a typical meta-stable phase of TiO2, has been explored novelly by in-situ adding of cations of VIIIB and IB, IIB elements in the 3rd period (Fe, Co, Ni, Cu, Zn) during the urea-lactate aided low-basicity hydrothermal process. The results showed that only Cu-doped brookite could be successfully synthesized with trace amount of copper intensively internalized into the brookite lattice, while the other dopants lead to the formation of anatase TiO2. Extensive characterizations indicated a two-step doping process, where copper ions were firstly dispersed in an amorphous layer on the lattice surface and then they were internalized into brookite lattice. Cu-doped brookite exhibited significantly enhanced photocatalytic activity in the phenol degradation under visible light compared to bare brookite. The enhancement of catalytic performance was assigned to the impurity band gap and the reduction of charge carriers' recombination introduced by the internalization of Cu ions. The investigation reported herein contributes to the understanding of complex ion-doping effects on the structures of meta-stable materials, and provides hints for obtaining other functional doped materials.
2016, 35(8): 1167-1173
doi: 10.14102/j.cnki.0254-5861.2011-1092
Abstract:
The title compound (C37H48BrNO5, 6) was synthesized from ursolic acid and its crystal structure was determined by single-crystal X-ray diffraction analysis. The compound is of orthorhombic system, space group P212121 with a=16.846(3), b=18.844(4), c=11.262(2)Å, Z=4, V=3575.1(13)Å3, Mr=666.67, Dc=1.239 Mg/m3, S=1.002, μ=1.190 mm-1, F(000)=1408, the final R=0.0831 and wR=0.1459 for 2286 observed reflections (I>2σ(I)). The crystal structure is stabilized by two intermolecular hydrogen bonds (N-H(0A)…O(2) and O(1)-H(1A)…O(3)). In the preliminary antitumor assay, the title compound 6 exhibits potent cytotoxic activity against HepG2 and SMMC-7721 cells with IC50 values of 1.64±0.21 and 1.22±0.13 μM, respectively.
The title compound (C37H48BrNO5, 6) was synthesized from ursolic acid and its crystal structure was determined by single-crystal X-ray diffraction analysis. The compound is of orthorhombic system, space group P212121 with a=16.846(3), b=18.844(4), c=11.262(2)Å, Z=4, V=3575.1(13)Å3, Mr=666.67, Dc=1.239 Mg/m3, S=1.002, μ=1.190 mm-1, F(000)=1408, the final R=0.0831 and wR=0.1459 for 2286 observed reflections (I>2σ(I)). The crystal structure is stabilized by two intermolecular hydrogen bonds (N-H(0A)…O(2) and O(1)-H(1A)…O(3)). In the preliminary antitumor assay, the title compound 6 exhibits potent cytotoxic activity against HepG2 and SMMC-7721 cells with IC50 values of 1.64±0.21 and 1.22±0.13 μM, respectively.
2016, 35(8): 1174-1180
doi: 10.14102/j.cnki.0254-5861.2011-1235
Abstract:
The antitumor activities of two alkaloids, evodiamine (EVO) and rutaecarpine (RUT), against MCF-7, SMMC-7721 and SW-1353 cells growth in vitro were investigated by MTT assay. The results showed that the anti-tumor effects of two alkaloids were remarkably different. In order to discover the relationship of antitumor activity and structures of the compounds, the dihedral angle, Natural Electron Configuration, frontier molecular orbital profiles (HOMO, LUMO) and bandgaps of these two compounds have been studied based on density functional theory (DFT) by means of DFT-B3LYP/6-31G (d) in Gaussian 03. The calculation results of dihedral angle showed that EVO, due to the existence of methyl group attached to the N(14) atom, have non-planar and twisted structures, which decrease the stability of EVO and increase the activity of EVO. Furthermore, the bandgaps of RUT are lower than that of EVO, indicating RUT has higher stability than EVO, so the activity of EVO is higher than that of RUT. In addition, the negative charge of N14 atom in EVO is lower than that of in RUT, so the positive charge of N(14) atom in EVO is higher than that of in RUT, which suggests that the nucleophile is easier to aggress the N(14) atom in EVO than that in RUT, so the reason of the different antitumor activities of EVO and RUT may be attacked by nucleophile.
The antitumor activities of two alkaloids, evodiamine (EVO) and rutaecarpine (RUT), against MCF-7, SMMC-7721 and SW-1353 cells growth in vitro were investigated by MTT assay. The results showed that the anti-tumor effects of two alkaloids were remarkably different. In order to discover the relationship of antitumor activity and structures of the compounds, the dihedral angle, Natural Electron Configuration, frontier molecular orbital profiles (HOMO, LUMO) and bandgaps of these two compounds have been studied based on density functional theory (DFT) by means of DFT-B3LYP/6-31G (d) in Gaussian 03. The calculation results of dihedral angle showed that EVO, due to the existence of methyl group attached to the N(14) atom, have non-planar and twisted structures, which decrease the stability of EVO and increase the activity of EVO. Furthermore, the bandgaps of RUT are lower than that of EVO, indicating RUT has higher stability than EVO, so the activity of EVO is higher than that of RUT. In addition, the negative charge of N14 atom in EVO is lower than that of in RUT, so the positive charge of N(14) atom in EVO is higher than that of in RUT, which suggests that the nucleophile is easier to aggress the N(14) atom in EVO than that in RUT, so the reason of the different antitumor activities of EVO and RUT may be attacked by nucleophile.
2016, 35(8): 1181-1185
doi: 10.14102/j.cnki.0254-5861.2011-1127
Abstract:
The title compound 2-(4-chlorophenyl)-1,3-dimethyl-2,3-dihydro-1H-perimidine (C19H17ClN2) was synthesized and characterized by elemental analysis, 1H NMR, HRMS and single-crystal X-ray diffraction. The crystal of the title compound belongs to orthorhombic system, space group Pnma with a=11.385(2), b=12.170(2), c=11.210(2)Å, V=1553.2(5)Å3, Z=4, Dc=1.321 g/cm3, μ(Mo-Kα)=0.244 mm-1, F(000)=648, S=1.309, R=0.0400 and wR (I>2σ(I))=0.1065. X-ray diffraction results showed that the molecular structure is highly symmetric and the new-formed N-heterocyclic ring is non-planar. In addition, the biological experiment showed that the title compound showed inhibitory activities against fungi with varied potencies.
The title compound 2-(4-chlorophenyl)-1,3-dimethyl-2,3-dihydro-1H-perimidine (C19H17ClN2) was synthesized and characterized by elemental analysis, 1H NMR, HRMS and single-crystal X-ray diffraction. The crystal of the title compound belongs to orthorhombic system, space group Pnma with a=11.385(2), b=12.170(2), c=11.210(2)Å, V=1553.2(5)Å3, Z=4, Dc=1.321 g/cm3, μ(Mo-Kα)=0.244 mm-1, F(000)=648, S=1.309, R=0.0400 and wR (I>2σ(I))=0.1065. X-ray diffraction results showed that the molecular structure is highly symmetric and the new-formed N-heterocyclic ring is non-planar. In addition, the biological experiment showed that the title compound showed inhibitory activities against fungi with varied potencies.
2016, 35(8): 1186-1194
doi: 10.14102/j.cnki.0254-5861.2011-1072
Abstract:
Hydrothermal reactions of 5-(tetrazol-5-yl) isophthalic acid with cadmium nitrate/praseodymium nitrate led to two complexes of [Cd3(TZI)2(H2O)11]n (1) and [Pr(TZI)(H2O)5]n (2). Their structures and properties were determined by X-ray diffraction, IR spectroscopy, fluorescence spectrum, thermal gravimetric analyses and elemental analysis. Complex 1 belongs to monoclinic system, I2/c space group, with a=12.8688(3), b=18.0925(3), c=14.5190(3)Å, β=116.054(3)°, V=3036.92(13)Å3, Z=4; complex 2 crystallizes in triclinic, space group P1, with a=7.9690(5), b=9.7665(8), c=10.4353(9)Å, α=116.709(9), β=107.461(6), γ=95.671(6)°, V=665.54(9)Å3 and Z=2. Complex 1 is a 3D planar structure. Complex 2 is a one-dimensional double chain configuration and extends into a 3D network by hydrogen bonds and π-π interactions.
Hydrothermal reactions of 5-(tetrazol-5-yl) isophthalic acid with cadmium nitrate/praseodymium nitrate led to two complexes of [Cd3(TZI)2(H2O)11]n (1) and [Pr(TZI)(H2O)5]n (2). Their structures and properties were determined by X-ray diffraction, IR spectroscopy, fluorescence spectrum, thermal gravimetric analyses and elemental analysis. Complex 1 belongs to monoclinic system, I2/c space group, with a=12.8688(3), b=18.0925(3), c=14.5190(3)Å, β=116.054(3)°, V=3036.92(13)Å3, Z=4; complex 2 crystallizes in triclinic, space group P1, with a=7.9690(5), b=9.7665(8), c=10.4353(9)Å, α=116.709(9), β=107.461(6), γ=95.671(6)°, V=665.54(9)Å3 and Z=2. Complex 1 is a 3D planar structure. Complex 2 is a one-dimensional double chain configuration and extends into a 3D network by hydrogen bonds and π-π interactions.
2016, 35(8): 1195-1203
doi: 10.14102/j.cnki.0254-5861.2011-1031
Abstract:
Two diiron dithiolate complexes[Fe2(CO)6(1,8-S2-2-CH2OOCPhC10H5)] 1 and [Fe2(CO)6(1,8-S2-2-CH2OOCPh-4-NO2C10H5)] 2 were synthesized in high yield. The complexes have been confirmed by single-crystal X-ray diffraction and characterized by IR, UV-Vis, 1H NMR spectroscopy and cyclic voltammetry. They contain a butterfly Fe2S2 core with the Fe1-Fe2 distances of 2.5237(7)Å in 1 and 2.5125(12)Å in 2, falling in the normal range of Fe-Fe bond length (2.49~2.57Å). The cyclic voltammetry has been used to investigate the electrochemical properties and the electrocatalytic proton reduction for 1 and 2. The complexes display reduction peaks at -1.074 V, -1.535 V (1) and -0.869 V, -1.247 V (2) vs. Fc/Fc+, respectively. With using p-TsOH acid of different concentration, the reduction peak of complex 2 grows non-linear; on the contrary, that of complex 1 is linear with the addition of the acid. Cyclic voltammetry revealed the two complexes are good catalysts in the CH3CN/NBu4PF6 solution.
Two diiron dithiolate complexes[Fe2(CO)6(1,8-S2-2-CH2OOCPhC10H5)] 1 and [Fe2(CO)6(1,8-S2-2-CH2OOCPh-4-NO2C10H5)] 2 were synthesized in high yield. The complexes have been confirmed by single-crystal X-ray diffraction and characterized by IR, UV-Vis, 1H NMR spectroscopy and cyclic voltammetry. They contain a butterfly Fe2S2 core with the Fe1-Fe2 distances of 2.5237(7)Å in 1 and 2.5125(12)Å in 2, falling in the normal range of Fe-Fe bond length (2.49~2.57Å). The cyclic voltammetry has been used to investigate the electrochemical properties and the electrocatalytic proton reduction for 1 and 2. The complexes display reduction peaks at -1.074 V, -1.535 V (1) and -0.869 V, -1.247 V (2) vs. Fc/Fc+, respectively. With using p-TsOH acid of different concentration, the reduction peak of complex 2 grows non-linear; on the contrary, that of complex 1 is linear with the addition of the acid. Cyclic voltammetry revealed the two complexes are good catalysts in the CH3CN/NBu4PF6 solution.
2016, 35(8): 1204-1212
doi: 10.14102/j.cnki.0254-5861.2011-1033
Abstract:
The syntheses, crystal structures and magnetic properties of two cyano-bridged heterobimetallic compounds prepared from a paramagnetic RuIII building block, trans-K[RuIII(salchda)(CN)2] (1, salchda=N,N'-bis(salicylidene)-o-cyclohexylenediamine), are described. 1 reacts with hydrated CoCl2 and [MnIII(salchda)(Cl)(H2O)] in MeOH to produce a trinuclear compound {[RuIII(salchda)(CN)]2(μ-CN)2[CoII(MeOH)4]·4MeOH}n (2) and a dinuclear {[RuIII(salchda)(CN)](μ-CN)[MnIII(salchda)(MeOH)]·2MeOH}n (3), respectively. Both compounds exhibit intramolecular ferromagnetic coupling between RuIII and 3-d metal centers via the cyano bridge and intermolecular antiferromagnetic coupling. Moreover, 2 exhibits antiferromagnetic ordering below 3.4 K.
The syntheses, crystal structures and magnetic properties of two cyano-bridged heterobimetallic compounds prepared from a paramagnetic RuIII building block, trans-K[RuIII(salchda)(CN)2] (1, salchda=N,N'-bis(salicylidene)-o-cyclohexylenediamine), are described. 1 reacts with hydrated CoCl2 and [MnIII(salchda)(Cl)(H2O)] in MeOH to produce a trinuclear compound {[RuIII(salchda)(CN)]2(μ-CN)2[CoII(MeOH)4]·4MeOH}n (2) and a dinuclear {[RuIII(salchda)(CN)](μ-CN)[MnIII(salchda)(MeOH)]·2MeOH}n (3), respectively. Both compounds exhibit intramolecular ferromagnetic coupling between RuIII and 3-d metal centers via the cyano bridge and intermolecular antiferromagnetic coupling. Moreover, 2 exhibits antiferromagnetic ordering below 3.4 K.
2016, 35(8): 1213-1221
doi: 10.14102/j.cnki.0254-5861.2011-1029
Abstract:
A novel polymeric zinc(II) complex {[Zn2(TIA)(H2O)3]·(NO3)}n (1, H3TIA=5-(1H-tetrazol-5-yl)isophthalic acid) has been synthesized in mixed solvents under solvothermal conditions and characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 crystallizes in orthorhombic, space group Cmcm with a=10.4210(6), b=23.3526(14), c=6.9214(4)Å, V=1684.37(17)Å3, Z=4, C9H4N5O10Zn2, Mr=472.91, Dc=1.865 g/cm3, F(000)=932, λ(MoKα)=2.909 mm-1, R=0.0423 and wR=0.1287. The complex has good thermal stability and excellent photoluminescent property.
A novel polymeric zinc(II) complex {[Zn2(TIA)(H2O)3]·(NO3)}n (1, H3TIA=5-(1H-tetrazol-5-yl)isophthalic acid) has been synthesized in mixed solvents under solvothermal conditions and characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 crystallizes in orthorhombic, space group Cmcm with a=10.4210(6), b=23.3526(14), c=6.9214(4)Å, V=1684.37(17)Å3, Z=4, C9H4N5O10Zn2, Mr=472.91, Dc=1.865 g/cm3, F(000)=932, λ(MoKα)=2.909 mm-1, R=0.0423 and wR=0.1287. The complex has good thermal stability and excellent photoluminescent property.
2016, 35(8): 1222-1230
doi: 10.14102/j.cnki.0254-5861.2011-1044
Abstract:
One organic-decorated quanternaery[TM(1,2-dap)3]HgSb2Se5(1,2-dap=1,2-dianinopropane, TM=Co (1), Fe (2)) compound has been solvothermally synthesized. The compounds crystallize in triclinic space group P1, with a=11.248(6), b=11.542(7), c=12.180(12)Å, V=1268.7(16)Å3, Z=2, F(000)=1010 for 1 and a=11.311(5), b=11.558(5), c=12.180(9)Å, V=1276.5(12)Å3, Z=2, F(000)=1008 for 2. The crystal structure consists of one-dimensional anionics chains composed of HgSe4 tetrahedra and SbSe3 trigonal pyramids sharing corners and [TM(dap)3]2+ cations. The[HgSb2Se52-]∞ anionic chains run along the [001] direction, and are surrounded by the [TM(dap)3]2+ cations. Meanwhile, 8-ring[Hg2Sb2Se4] and 6-ring[HgSb2Se2] are alternately found. The compounds were structurally characterized by elemental analysis, thermogravimetric analysis, infrared spectroscopy and UV-Vis diffuse reflectance spectroscopy.
One organic-decorated quanternaery[TM(1,2-dap)3]HgSb2Se5(1,2-dap=1,2-dianinopropane, TM=Co (1), Fe (2)) compound has been solvothermally synthesized. The compounds crystallize in triclinic space group P1, with a=11.248(6), b=11.542(7), c=12.180(12)Å, V=1268.7(16)Å3, Z=2, F(000)=1010 for 1 and a=11.311(5), b=11.558(5), c=12.180(9)Å, V=1276.5(12)Å3, Z=2, F(000)=1008 for 2. The crystal structure consists of one-dimensional anionics chains composed of HgSe4 tetrahedra and SbSe3 trigonal pyramids sharing corners and [TM(dap)3]2+ cations. The[HgSb2Se52-]∞ anionic chains run along the [001] direction, and are surrounded by the [TM(dap)3]2+ cations. Meanwhile, 8-ring[Hg2Sb2Se4] and 6-ring[HgSb2Se2] are alternately found. The compounds were structurally characterized by elemental analysis, thermogravimetric analysis, infrared spectroscopy and UV-Vis diffuse reflectance spectroscopy.
2016, 35(8): 1231-1237
doi: 10.14102/j.cnki.0254-5861.2011-1064
Abstract:
A new cobalt(II) compound, {(Me2NH2)4]Co(SIP)2]·2(DMF)·3(H2O)}n (1, H3SIP=5-sulfoisophthalic acid), has been synthesized under solvothermal condition and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal system, space group P421m, with a=14.3080(7), b=14.3080(7), c=12.1837(9)Å, V=2494.2(3)Å3, Z=2, C30H58N6O19S2Co, Mr=929.87, Dc=1.238 g/cm3, μ=0.496 mm-1, F(000)=982, flack parameter of 0.007(9), the final R=0.0767 and wR=0.2110 for 2391 observed reflections with I>2σ(I). The tetrahedral Co(II) ions are linked by carboxylate groups of the 5-sulfoisophthalate ligands to form an anionic two-dimensional (2D) layer displaying a (4,4) square network, which was charge-balanced by the [Me2NH2]+ cations occupying the spaces between the 2D layers. Magnetic properties of 1 have been investigated in detail using direct-current and alternating-current susceptibility measurements.
A new cobalt(II) compound, {(Me2NH2)4]Co(SIP)2]·2(DMF)·3(H2O)}n (1, H3SIP=5-sulfoisophthalic acid), has been synthesized under solvothermal condition and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal system, space group P421m, with a=14.3080(7), b=14.3080(7), c=12.1837(9)Å, V=2494.2(3)Å3, Z=2, C30H58N6O19S2Co, Mr=929.87, Dc=1.238 g/cm3, μ=0.496 mm-1, F(000)=982, flack parameter of 0.007(9), the final R=0.0767 and wR=0.2110 for 2391 observed reflections with I>2σ(I). The tetrahedral Co(II) ions are linked by carboxylate groups of the 5-sulfoisophthalate ligands to form an anionic two-dimensional (2D) layer displaying a (4,4) square network, which was charge-balanced by the [Me2NH2]+ cations occupying the spaces between the 2D layers. Magnetic properties of 1 have been investigated in detail using direct-current and alternating-current susceptibility measurements.
2016, 35(8): 1238-1244
doi: 10.14102/j.cnki.0254-5861.2011-1040
Abstract:
A new 3D Ag(I) coordination polymer {[Ag(AZDB)0.5(bpe)0.5]·H2O}n (1) has been papared by azobenzene-3,3'-dicarboxylicate (H2AZDB), 1,2-bis(4-pyridyl)ethylene (bpe) and silver salts via hydrothermal method. The compound was fully characterized by single-crystal X-ray diffraction, elemental analyses, infrared spectrum (IR), powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The strucrural analysis indicate that compound 1 shows a 3D pillared-layer framework constructed from a unique 1D Ag2O2 ribbon and pyridyl/carboxylicate mixed system, which features a 2-nodal (4, 6)-connected fsc net with a (44·610·8)(44·62) topology. Moreover, the photoluminescent properties have also been discussed.
A new 3D Ag(I) coordination polymer {[Ag(AZDB)0.5(bpe)0.5]·H2O}n (1) has been papared by azobenzene-3,3'-dicarboxylicate (H2AZDB), 1,2-bis(4-pyridyl)ethylene (bpe) and silver salts via hydrothermal method. The compound was fully characterized by single-crystal X-ray diffraction, elemental analyses, infrared spectrum (IR), powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The strucrural analysis indicate that compound 1 shows a 3D pillared-layer framework constructed from a unique 1D Ag2O2 ribbon and pyridyl/carboxylicate mixed system, which features a 2-nodal (4, 6)-connected fsc net with a (44·610·8)(44·62) topology. Moreover, the photoluminescent properties have also been discussed.
2016, 35(8): 1245-1252
doi: 10.14102/j.cnki.0254-5861.2011-1043
Abstract:
Three new 2D metal-organic frameworks,[M(BIDPE)2(bdc)2]n (M=Co for 1, Ni for 2) and [Ni(PIDPE)2(H2O)2(bdc)]n (3) (BIDPE=4,4'-bis(imidazol-1-yl) diphenyl ether, PIDPE=4-(pyridyl)-4'-(imidazol-1-yl) diphenyl ether, bdc2-=1,3-benzenedicarboxylate), were characterized by single-crystal X-ray diffraction, elemental analysis, PXRD, IR spectroscopy and TGA analysis. Complex 1 crystallizes in monoclinic, space group P21/n, with a=9.1568(12), b=16.943(2), c=15.441(2)Å, β=104.049(2)°, V=2323.9(5)Å3, Dc=1.420 g/cm3, Mr=993.83, F(000)=1026, μ=0.440 mm-1 and Z=2. Complex 2 crystallizes in monoclinic, space group P21/n, with a=9.1395(17), b=17.019 (3), c=15.473(3)Å, β=104.651(2)°, V=2328.5(7)Å3, Dc=1.414 g/cm3, Mr=991.58, F(000)=1024, μ=0.487 mm-1, Z=2. Complex 3 also belongs to the monoclinic system, space group P21/n, with a=11.4365(16), b=18.346(3), c=11.7068(17)Å, β=91.022(2)°, V=2455.9(6)Å3, Dc=1.422 g/cm3, Mr=1051.66, F(000)=1092, μ=0.468 mm-1, Z=2. All complexes 1, 2 and 3 are 2D layer structures constructed from intermolecular hydrogen bonds. In addition, the solid UV-vis properties of complexes 1, 2 and 3 were also studied.
Three new 2D metal-organic frameworks,[M(BIDPE)2(bdc)2]n (M=Co for 1, Ni for 2) and [Ni(PIDPE)2(H2O)2(bdc)]n (3) (BIDPE=4,4'-bis(imidazol-1-yl) diphenyl ether, PIDPE=4-(pyridyl)-4'-(imidazol-1-yl) diphenyl ether, bdc2-=1,3-benzenedicarboxylate), were characterized by single-crystal X-ray diffraction, elemental analysis, PXRD, IR spectroscopy and TGA analysis. Complex 1 crystallizes in monoclinic, space group P21/n, with a=9.1568(12), b=16.943(2), c=15.441(2)Å, β=104.049(2)°, V=2323.9(5)Å3, Dc=1.420 g/cm3, Mr=993.83, F(000)=1026, μ=0.440 mm-1 and Z=2. Complex 2 crystallizes in monoclinic, space group P21/n, with a=9.1395(17), b=17.019 (3), c=15.473(3)Å, β=104.651(2)°, V=2328.5(7)Å3, Dc=1.414 g/cm3, Mr=991.58, F(000)=1024, μ=0.487 mm-1, Z=2. Complex 3 also belongs to the monoclinic system, space group P21/n, with a=11.4365(16), b=18.346(3), c=11.7068(17)Å, β=91.022(2)°, V=2455.9(6)Å3, Dc=1.422 g/cm3, Mr=1051.66, F(000)=1092, μ=0.468 mm-1, Z=2. All complexes 1, 2 and 3 are 2D layer structures constructed from intermolecular hydrogen bonds. In addition, the solid UV-vis properties of complexes 1, 2 and 3 were also studied.
2016, 35(8): 1253-1259
doi: 10.14102/j.cnki.0254-5861.2011-1088
Abstract:
The interaction of Hg2+ with polyphenyl quinoxaline ligand 2,3,6,7,10,11-hexaphenyldipyrazino[2,3-f:2',3'-h]quinoxaline (HPQ) was investigated, and a new complex (C49H32N6Br2Cl2Hg) has been synthesized and characterized. It exhibits a 0D single-core structure, and adopts triclinic P1 space group with a=11.139(2), b=13.429(3), c=14.488(3)Å, α=76.10(3), β=83.16(3), γ=87.36(3)°, V=2088.4(7)Å3, Z=2, S=1.056, F(000)=1104, R=0.0417 and wR=0.0931 (I>2σ(I)). Furthermore, the behavior of HPQ with Hg2+ in the solution was also investigated, and the result shows that HPQ was found to have excellent fluorescent selectivity for Hg2+ over many other metal ions (Li+, K+, Na+, Sr+, Ca2+, Mg2+, Mn2+, Fe3+, Ni2+, Co2+, Cu2+, Zn2+, Cd2+, Pb2+, Al3+ and Cr3+) based on the intermolecular charge-transfer mechanism, which makes HPQ a potential fluorescence sensor or probe for Hg2+.
The interaction of Hg2+ with polyphenyl quinoxaline ligand 2,3,6,7,10,11-hexaphenyldipyrazino[2,3-f:2',3'-h]quinoxaline (HPQ) was investigated, and a new complex (C49H32N6Br2Cl2Hg) has been synthesized and characterized. It exhibits a 0D single-core structure, and adopts triclinic P1 space group with a=11.139(2), b=13.429(3), c=14.488(3)Å, α=76.10(3), β=83.16(3), γ=87.36(3)°, V=2088.4(7)Å3, Z=2, S=1.056, F(000)=1104, R=0.0417 and wR=0.0931 (I>2σ(I)). Furthermore, the behavior of HPQ with Hg2+ in the solution was also investigated, and the result shows that HPQ was found to have excellent fluorescent selectivity for Hg2+ over many other metal ions (Li+, K+, Na+, Sr+, Ca2+, Mg2+, Mn2+, Fe3+, Ni2+, Co2+, Cu2+, Zn2+, Cd2+, Pb2+, Al3+ and Cr3+) based on the intermolecular charge-transfer mechanism, which makes HPQ a potential fluorescence sensor or probe for Hg2+.
2016, 35(8): 1260-1268
doi: 10.14102/j.cnki.0254-5861.2011-1174
Abstract:
Two manganese(II) coordination polymers, namely, {[Mn(PIP)(BIBP)]·(BIBP)0.5}n (1) and {[Mn(PTA)(BIMBP)(H2O)]·H2O0.69}n (2) (H2PIP=5-(4-pyridyl)-isophthalic acid, H2PTA=6-(4-pyridyl)-terephthalic acid, BIBP=4,4'-bis(imidazol-1-yl)biphenyl, and BIMBP=4,4'-bis(imidazol-1-ylmethyl)biphenyl), have been synthesized by using the bifunctional pyrinde-benzene carboxylic acids and bis(imidazole) linkers as mixed ligands to react with MnSO4, and further characterized by elemental analysis, IR, and PXRD. Compound 1 is in the triclicnic system, space group P1 with a=10.1089(8), b=13.1927(12), c=14.0638(12)Å, α=69.437(2), β=73.2890(10), γ=78.5320(10)°, V=1671.9(2)Å3, Z=2, Dc=1.449 g/cm3, F(000)=705, μ(MoKα)=0.453 mm-1, S=1.053, R=0.0491 and wR=0.1367 for 5837 unique reflections (Rint=0.0208) with I>2σ(I). Compound 2 belongs to the monoclicnic system, space group C2/c with a=15.199(3), b=19.731(3), c=21.537(5)Å, β=105.228(3)°, V=6232(2)Å3, Z=8, Dc=1.363 g/cm3, F(000)=2648, μ(MoKα)=0.475 mm-1, S=1.048, R=0.0489 and wR=0.1151 for 7414 unique reflections (Rint=0.0425) with I>2σ(I). Structural analyses reveal that complex 1 is a 4-connected (44.62)-sql bilayer structure with binuclear[Mn2(COO)2] SBU, while complex 2 is a normally (3,5)-connected (42.67.8)(42.6)-3,5L2 monolayer. And the sheets interacted with the adjacent sheets through weak interactions, finally giving a stable three-dimensional (3D) supramolecule. Besides, the variable-temperature magnetic susceptibility measurement of complex 1 was investigated.
Two manganese(II) coordination polymers, namely, {[Mn(PIP)(BIBP)]·(BIBP)0.5}n (1) and {[Mn(PTA)(BIMBP)(H2O)]·H2O0.69}n (2) (H2PIP=5-(4-pyridyl)-isophthalic acid, H2PTA=6-(4-pyridyl)-terephthalic acid, BIBP=4,4'-bis(imidazol-1-yl)biphenyl, and BIMBP=4,4'-bis(imidazol-1-ylmethyl)biphenyl), have been synthesized by using the bifunctional pyrinde-benzene carboxylic acids and bis(imidazole) linkers as mixed ligands to react with MnSO4, and further characterized by elemental analysis, IR, and PXRD. Compound 1 is in the triclicnic system, space group P1 with a=10.1089(8), b=13.1927(12), c=14.0638(12)Å, α=69.437(2), β=73.2890(10), γ=78.5320(10)°, V=1671.9(2)Å3, Z=2, Dc=1.449 g/cm3, F(000)=705, μ(MoKα)=0.453 mm-1, S=1.053, R=0.0491 and wR=0.1367 for 5837 unique reflections (Rint=0.0208) with I>2σ(I). Compound 2 belongs to the monoclicnic system, space group C2/c with a=15.199(3), b=19.731(3), c=21.537(5)Å, β=105.228(3)°, V=6232(2)Å3, Z=8, Dc=1.363 g/cm3, F(000)=2648, μ(MoKα)=0.475 mm-1, S=1.048, R=0.0489 and wR=0.1151 for 7414 unique reflections (Rint=0.0425) with I>2σ(I). Structural analyses reveal that complex 1 is a 4-connected (44.62)-sql bilayer structure with binuclear[Mn2(COO)2] SBU, while complex 2 is a normally (3,5)-connected (42.67.8)(42.6)-3,5L2 monolayer. And the sheets interacted with the adjacent sheets through weak interactions, finally giving a stable three-dimensional (3D) supramolecule. Besides, the variable-temperature magnetic susceptibility measurement of complex 1 was investigated.
2016, 35(8): 1269-1276
doi: 10.14102/j.cnki.0254-5861.2011-1143
Abstract:
A new boroantimonate K2SbB3O8 has been synthesized by high-temperature solidstate reactions, and its crystals have been obtained by the flux method. The crystal structure has been determined from single-crystal X-ray diffraction analysis. The compound crystallizes in the monoclinic space group P21/c with a=5.8890(2), b=11.0512(4), c=10.8951(4)Å, β=103.200(4)°, V=690.32(4)Å3, Z=4, F(000)=672, ρc=3.467 g/cm3, Mr=360.38 and μ=5.215 mm-1. Its structure feature is a three-dimensional framework composed of SbO6 octahedra and isolated [B3O8]7- groups with K+ cations residing in the one-dimensional tunnels along the a-axis. Interestingly, the isolated [B3O8]7- groups are distinct from the known [B3O8]7- groups, which always connect to each other. The UV-vis-NIR absorption, thermal stability and infrared spectrum are also discussed in this paper.
A new boroantimonate K2SbB3O8 has been synthesized by high-temperature solidstate reactions, and its crystals have been obtained by the flux method. The crystal structure has been determined from single-crystal X-ray diffraction analysis. The compound crystallizes in the monoclinic space group P21/c with a=5.8890(2), b=11.0512(4), c=10.8951(4)Å, β=103.200(4)°, V=690.32(4)Å3, Z=4, F(000)=672, ρc=3.467 g/cm3, Mr=360.38 and μ=5.215 mm-1. Its structure feature is a three-dimensional framework composed of SbO6 octahedra and isolated [B3O8]7- groups with K+ cations residing in the one-dimensional tunnels along the a-axis. Interestingly, the isolated [B3O8]7- groups are distinct from the known [B3O8]7- groups, which always connect to each other. The UV-vis-NIR absorption, thermal stability and infrared spectrum are also discussed in this paper.
2016, 35(8): 1277-1282
doi: 10.14102/j.cnki.0254-5861.2011-1069
Abstract:
The bicyclic product containing a chromene skeleton and a propargylamine skeleton (C22H22N2O2) was synthesized from the double sites of terminal alkyne, piperazine derivative and formaldehyde via one-pot procedure. Its structure was characterized by 1H NMR, 13C NMR, IR and H RMS, and further confirmed by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a=12.6571(14), b=11.3249(12), c=12.6571(14)Å, β=105.22°, V=1750.6(3)Å3, Z=4, R=0.0568 and wR=0.1444. The fluorescence of the product was discussed.
The bicyclic product containing a chromene skeleton and a propargylamine skeleton (C22H22N2O2) was synthesized from the double sites of terminal alkyne, piperazine derivative and formaldehyde via one-pot procedure. Its structure was characterized by 1H NMR, 13C NMR, IR and H RMS, and further confirmed by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a=12.6571(14), b=11.3249(12), c=12.6571(14)Å, β=105.22°, V=1750.6(3)Å3, Z=4, R=0.0568 and wR=0.1444. The fluorescence of the product was discussed.
2016, 35(8): 1283-1288
doi: 10.14102/j.cnki.0254-5861.2011-1083
Abstract:
Two crystals of receptor 1, C42H52N10O4S2 (anthracene-9,10-dicarbaldehyde bis-(phenyl-semithiocarbazone)) and 1-H2PO4-, C68H114N10O10P2S2 were obtained at room temperature successfully, and their structures were characterized by X-ray crystallography diffraction. X-ray diffraction reveals that, receptor 1 crystallizes in monoclinic, space group P21/c, with a=9.487(3), b=20.674(6), c=11.821(4)Å, β=113.416(8)°, Mr=825.06, V=2127.5(12)Å3, Z=2, Dc=1.288 g/cm3, μ=0.18 mm-1, F(000)=876, MoKα radiation (λ=0.71073Å), the final R=0.0472 and wR=0.0930. A total of 3758 unique reflections were collected, of which 3313 with I>2σ(I) were observed. Compound 1-H2PO4- crystallizes in triclinic, space group P21/n, with a=8.767(1), b=13.6190(15), c=16.615(2)Å, α=98.727(14), β=103.061(14), γ=91.382(16)°, Mr=1357.75, V=1906.6 (4)Å3, Z=1, Dc=1.183 g/cm3, μ=0.17 mm-1, F(000)=734, MoKα radiation (λ=0.71073Å), the final R=0.0769 and wR=0.1884. A total of 6699 unique reflections were collected, of which 2989 with I>2σ(I) were observed. As it was observed in the crystal structure of 1-H2PO4-, 1 bound H2PO4- at a 1:2 ratio by intermolecular interaction of N-H…O hydrogen bond obviously. Another interesting feature was that H2PO4- groups assembled chains themselves via intramolecular hydrogen bond O-H…O and connected the 1 molecules together through the interaction of H-bonds, which improved the planarity of 1 and increased the stability of the entire structure.
Two crystals of receptor 1, C42H52N10O4S2 (anthracene-9,10-dicarbaldehyde bis-(phenyl-semithiocarbazone)) and 1-H2PO4-, C68H114N10O10P2S2 were obtained at room temperature successfully, and their structures were characterized by X-ray crystallography diffraction. X-ray diffraction reveals that, receptor 1 crystallizes in monoclinic, space group P21/c, with a=9.487(3), b=20.674(6), c=11.821(4)Å, β=113.416(8)°, Mr=825.06, V=2127.5(12)Å3, Z=2, Dc=1.288 g/cm3, μ=0.18 mm-1, F(000)=876, MoKα radiation (λ=0.71073Å), the final R=0.0472 and wR=0.0930. A total of 3758 unique reflections were collected, of which 3313 with I>2σ(I) were observed. Compound 1-H2PO4- crystallizes in triclinic, space group P21/n, with a=8.767(1), b=13.6190(15), c=16.615(2)Å, α=98.727(14), β=103.061(14), γ=91.382(16)°, Mr=1357.75, V=1906.6 (4)Å3, Z=1, Dc=1.183 g/cm3, μ=0.17 mm-1, F(000)=734, MoKα radiation (λ=0.71073Å), the final R=0.0769 and wR=0.1884. A total of 6699 unique reflections were collected, of which 2989 with I>2σ(I) were observed. As it was observed in the crystal structure of 1-H2PO4-, 1 bound H2PO4- at a 1:2 ratio by intermolecular interaction of N-H…O hydrogen bond obviously. Another interesting feature was that H2PO4- groups assembled chains themselves via intramolecular hydrogen bond O-H…O and connected the 1 molecules together through the interaction of H-bonds, which improved the planarity of 1 and increased the stability of the entire structure.
Size Effect on the Raman Spectra and Electronic Structure of the Glycine-alanine Oligopeptide Chains
2016, 35(8): 1289-1296
doi: 10.14102/j.cnki.0254-5861.2011-1065
Abstract:
A theoretical study on oligopeptide chains of glycine-alanine by density functional theory (DFT) is given in this paper. Raman spectra of the oligopeptide chains are examined. The geometric structures, frontier orbital, energy gap, atomic charge distribution, density of states and chemical activity of the side chain are studied at the B3LYP/6-31G (d) level. Results show that, with the number of residues increasing, vibrations of typical functional groups present Raman frequency shift, and the energy gap is gradually reduced. The HOMO and LUMO focus on the amino and carboxyl at the ends of oligopeptides. It is helpful for oligopeptides to self-assemble into chains. In addition, different residues (glycine or alanine) at the ends of chains result in the even-odd effect of orbital energy in the growth process. The size effects of physical and chemical properties only exist when the oligopeptides are shorter, and the phenomenon disappeared as the chain continues to grow.
A theoretical study on oligopeptide chains of glycine-alanine by density functional theory (DFT) is given in this paper. Raman spectra of the oligopeptide chains are examined. The geometric structures, frontier orbital, energy gap, atomic charge distribution, density of states and chemical activity of the side chain are studied at the B3LYP/6-31G (d) level. Results show that, with the number of residues increasing, vibrations of typical functional groups present Raman frequency shift, and the energy gap is gradually reduced. The HOMO and LUMO focus on the amino and carboxyl at the ends of oligopeptides. It is helpful for oligopeptides to self-assemble into chains. In addition, different residues (glycine or alanine) at the ends of chains result in the even-odd effect of orbital energy in the growth process. The size effects of physical and chemical properties only exist when the oligopeptides are shorter, and the phenomenon disappeared as the chain continues to grow.
2016, 35(8): 1297-1305
doi: 10.14102/j.cnki.0254-5861.2011-1076
Abstract:
The effect of the distribution of organic cations CH3NH3+(MA+) on the stability, electronic structures and optical properties of CH3NH3PbI3 perovskite have been investigated using the plane-wave ultrasoft pseuudopotentials. Generalized gradient approximation and local density approximation are used to optimize the geometries of six models, which are different in the orientation of organic cations. The results show that model C is more stable than others, and the main contribution to the top of valence band is from I 5p states. In the bottom of conduction bands, the main components are Pb 6s states with an overlapping of I 5p states. When the orientation of organic group is transforming, the PbI6 octahedra will distort and the band structure will alter with it, which affect the generation and migration of photon-generated carriers and optical properties.
The effect of the distribution of organic cations CH3NH3+(MA+) on the stability, electronic structures and optical properties of CH3NH3PbI3 perovskite have been investigated using the plane-wave ultrasoft pseuudopotentials. Generalized gradient approximation and local density approximation are used to optimize the geometries of six models, which are different in the orientation of organic cations. The results show that model C is more stable than others, and the main contribution to the top of valence band is from I 5p states. In the bottom of conduction bands, the main components are Pb 6s states with an overlapping of I 5p states. When the orientation of organic group is transforming, the PbI6 octahedra will distort and the band structure will alter with it, which affect the generation and migration of photon-generated carriers and optical properties.
2016, 35(8): 1306-1312
doi: 10.14102/j.cnki.0254-5861.2011-1186
Abstract:
The nitrate ester substitution derivatives of prismane were studied at the B3LYP/6-311G** level. The sublimation enthalpies and heats of formation in gas phase and solid state were calculated. The detonation performances were also predicted by using the famous Kamlet-Jacbos equation. Our calculated results show that introducing nitrate ester group into prismane is helpful to enhance its detonation properties. Stabilities were evaluated through the bond dissociation energies, bond order, characteristic heights (H50) and band gap calculations. The trigger bonds in the pyrolysis process of prismane derivatives were confirmed as O-ON2 bond. The BDEs of all compounds were large, so these prismane derivatives have excellent stability consistent with the results of H50 and band gap.
The nitrate ester substitution derivatives of prismane were studied at the B3LYP/6-311G** level. The sublimation enthalpies and heats of formation in gas phase and solid state were calculated. The detonation performances were also predicted by using the famous Kamlet-Jacbos equation. Our calculated results show that introducing nitrate ester group into prismane is helpful to enhance its detonation properties. Stabilities were evaluated through the bond dissociation energies, bond order, characteristic heights (H50) and band gap calculations. The trigger bonds in the pyrolysis process of prismane derivatives were confirmed as O-ON2 bond. The BDEs of all compounds were large, so these prismane derivatives have excellent stability consistent with the results of H50 and band gap.
