首页 > 期刊 > Chinese Journal of Structural Chemistry

  

其它
Rational Design of Star-shaped Molecules with Benzene Core and Naphthalimide Derivatives End Groups as Organic Light-emitting Materials
Li-Ping ZHANG, Wan-Dong CHAI, Rui-Fa JIN
2016, 35(12): 1811-1818  doi: 10.14102/j.cnki.0254-5861.2011-1319
[摘要]  (813) [HTML全文] (813) [PDF 0KB] (0)
摘要:
A series of star-shaped molecules with benzene core and naphthalimides derivatives end groups have been designed to explore their optical, electronic, and charge transport properties as charge transport and/or luminescent materials for organic light-emitting diodes (OLEDs). The frontier molecular orbitals (FMOs) analysis has turned out that the vertical electronic transitions of absorption and emission are characterized as intramolecular charge transfer (ICT). The calculated results show that the optical and electronic properties of star-shaped molecules are affected by the substituent groups in N-position of 1,8-naphthalimide ring. Our results suggest that star-shaped molecules with n-butyl (1), benzene (2), thiophene (3), thiophene S',S'-dioxide (4), benzo[c][1,2,5]thiadiazole (5), and 2,7a-dihydrobenzo[d]thiazole (6) fragments are expected to be promising candidates for luminescent and electron transport materials for OLEDs. This study should be helpful in further theoretical investigations on such kind of systems and also to the experimental study for charge transport and/or luminescent materials for OLEDs.
Theoretical Investigation for Two-state Reactivity of CO2 Hydrogenation Catalyzed by Ru in Gas Phase
Yong-Cheng WANG, Yi-Ming JIA, Wen-Xue WANG, Pan-Pan MA
2016, 35(12): 1819-1828  doi: 10.14102/j.cnki.0254-5861.2011-1119
[摘要]  (946) [HTML全文] (946) [PDF 0KB] (0)
摘要:
Gas-phase CO2 catalyzed activation hydrogenation by Ru atoms was studied with density functional theory. Based on the structure optimization of different potential energy surfaces, there are two crossing points between singlet and triplet potential energy surfaces and there is a crossing point between quintet and triplet potential energy surfaces in the whole catalytic cycle. Spin transition probabilities in the vicinity of the intersections have been calculated by the Landau-Zener model theory. There are three minimum energy crossing points (MECPs) with strong spin-orbital coupling effect and higher spin transition probability, and all spin inversion occurred in s orbital and different d orbitals of ruthenium, indicating this is a typical two-state reactivity (TSR) reaction. Finally, the lowest energy reaction path is ensured.
Electrochemical and Theoretical Studies of 1-Alkyl-2-substituted Benzimidazoles as Corrosion Inhibitors for Carbon Steel Surface in HCl Medium
Hong SHI, Bin XU, Hong-Jun ZHU
2016, 35(12): 1829-1839  doi: 10.14102/j.cnki.0254-5861.2011-1099
[摘要]  (695) [HTML全文] (695) [PDF 0KB] (0)
摘要:
The inhibition efficiencies of newly synthesized four 1-alkyl-2-substituted benzimidazole compounds (a~d) have been studied for the corrosion of carbon steel in 1.0 M HCl by using potentiodynamic polarization measurement. The four inhibitors act as mixed-type inhibitors, which mainly inhibit cathodes. The inhibition efficiency of these compounds enhanced when the concentration of the inhibitors increased. A theoretical study of the corrosion inhibition efficiency of these compounds was carried out by using the B3LYP level with the 6-31+G* basis set. Considering the solvent effect, the IEFPCM model was selected. Furthermore, the adsorption energies of the inhibitors with the iron (001) surface were studied by using molecular dynamic (MD) simulations. The theoretical results show that these inhibitors all exhibit several adsorption active-centers. Meanwhile, the MD simulations indicate that the adsorption occurs mostly through benzene ring and the lone pair electrons of the nitro atoms. These results demonstrated that the theoretical studies and MD simulations are reliable and promising methods for analyzing the inhibition efficiency of organic inhibitors.
Computer Simulation and Experimental Investigations of Phenobarbital Molecular Imprinting System
Jun-Bo LIU, Shan-Shan TANG, Zheng-Qiang DAI, Yan WANG, Qian GAO, Rui-Fa JIN
2016, 35(12): 1840-1848  doi: 10.14102/j.cnki.0254-5861.2011-1238
[摘要]  (620) [HTML全文] (620) [PDF 0KB] (0)
摘要:
The interaction process between the phenobarbital (PHN) and acrylamide (AM) was studied using the M062X/6-31G(d,p) method. The PHN and AM were used as the template and functional monomer, respectively. The molecular electrostatic potential (MEP) was simulated for predicting the reactive sites. The atoms in molecules theory helped to reveal the imprinting mechanism and optimize the molar ratios for PHN and AM. The molecular imprinted polymers (MIPs) containing PHN were synthesized through the precipitation polymerization. The diameter range of the obtained MIPs was from 150 to 390 nm. According to the computational results, MIPs with the molar ratio of PHN and AM equal to 1:6 showed high selective adsorption for PHN. The apparent maximum adsorption quantity (Qmax) of MIPs toward PHN was 7.9 mg/g, and the Qmax of nonimprinted polymer microspheres (NIPs) was 3.2 mg/g. Herein, the studies can provide theoretical and experimental references for the controllable fabrication of MIPs.
Synthesis, Structure and Antimicrobial Activity of 9,9-Dimethyl-9,10-dihydrospiro[benzo[a]-xanthene-12,3'-indoline]-2',11(8H)-dione
Du-Lin KONG, Jie JIANG, Lu-Yong WU, Xiang-Hui WANG, Zai-Feng SHI, Ming-Shu WU, Xin WANG, Qiang LIN
2016, 35(12): 1849-1854  doi: 10.14102/j.cnki.0254-5861.2011-1249
[摘要]  (736) [HTML全文] (736) [PDF 0KB] (0)
摘要:
One novel spiro-compound (C26H21NO3) has been synthesized and characterized by means of NMR spectroscopy, elemental analyses and X-ray diffraction. The single crystal belongs to the monoclinic system, space group P21/c with a=8.8039(7), b=24.123(2), c=10.0751(9)Å, β=108.403(3)°, Mr=395.44, V=2030.3(3)Å3, Z=4, Dc=1.294 g/cm3, F(000)=832.0, μ=0.085 mm-1, R=0.0801 and wR=0.2228. The title compound shows good activities against Micrococcus tetragenus, Bacillus cereus, Bacillus subtilis, Staphylococcus aureus, S. albus and Escherichia coli.
Synthesis, Crystal Structure and Antifungal Activity of 2-((2-Fluorobenzyl)thio)-5-(pyridin-4-yl)-1,3,4-oxadiazole
Guo-Xiang SUN, Yan-Xia SHI, Zhi-Wen ZHAI, Zhao-Hui SUN, Jian-Quan WENG, Cheng-Xia TAN, Xing-Hai LIU, Bao-Ju LI
2016, 35(12): 1855-1859  doi: 10.14102/j.cnki.0254-5861.2011-1352
[摘要]  (578) [HTML全文] (578) [PDF 0KB] (0)
摘要:
The title compound 2-((2-fluorobenzyl)thio)-5-(pyridin-4-yl)-1,3,4-oxadiazole (C14H10FN3OS) was synthesized, and its structure was confirmed by 1H NMR, MS, elemental analyses and X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a=11.541(16), b=8.226(12), c=13.683(19)Å, β=94.872(17)°, V=1294(3)Å3, Z=4 and R=0.0648 for 2198 observed reflections with I>2σ(I). The preliminary biological test shows that the title compound has good activity against Pythium ultimum with inhibitory to be 100%.
Synthesis, Crystal Structure, and Optical Property of Zero-dimensional Quaternary Thioborate: Ba9B3GaS15
Jin-Qiu WANG, Peng-Fei LIU, Yan-Yan LI, Li-Ming WU
2016, 35(12): 1860-1867  doi: 10.14102/j.cnki.0254-5861.2011-1236
[摘要]  (678) [HTML全文] (678) [PDF 0KB] (0)
摘要:
A new zero-dimensional (0D) thioborate Ba9B3GaS15 has been discovered by conventional high-temperature solid-state reaction. The compound crystallizes in orthorhombic space group Pbca with a=8.4759(8), b=22.266(2), c=31.426(3)Å, V=5931(2)Å3, Z=8, Mr=1819.11, Dc=4.075 g/cm3, μ=13.684 mm-1, F(000)=6320, S=1.034, (Δρ)max=5.039, (Δρ)min=-5.409 e/Å3, the final R=0.0362 and wR=0.1053 for 19243 observed reflections with I>2σ(I). The structure is constructed by discrete [BS3]3- trigonal planes and isolated [GaS4]5- tetrahedra with Ba2+ and isolated S2- filled among them. The UV-Vis-near-IR spectrum reveals a wide band gap of 3.15 eV that agrees with the electronic structure calculation.
Thermoelectric Properties of Ag-doped In4Se2.95 Polycrystalline Compounds
Yan-Chun CHEN, Peng-Fei LIU, Ling CHEN, Li-Ming WU
2016, 35(12): 1868-1875  doi: 10.14102/j.cnki.0254-5861.2011-1224
[摘要]  (585) [HTML全文] (585) [PDF 0KB] (0)
摘要:
In4Se3-based materials are noticeable n-type thermoelectric materials because of lead-free and intrinsically low lattice thermal conductivity, but the In4Se3-δ crystals (with Se-deficiency, δ) suffer strong anisotropy and cleavage habit. Thus the researches on polycrystalline In4Se3-based materials are of great importance. Herein, we experimentally and theoretically investigated the thermoelectric properties of In4-xSe2.95Agx polycrystalline compounds. Ag occupying the intercalation or In4 site is energetically most favorable in light of the density functional theory calculation. The maximum solubility of Ag (xm) is very low (xm<0.03) and the experimental result indicates that the electrical transport behavior of In4-xSe2.95Agx compounds is not significantly optimized by Ag-dopant. Consequently, a maximum ZT of 0.92 at 723 K is obtained by In3.98Se2.95Ag0.02 compound that represents 15% enhancement over that of the un-doped one which benefits from the slightly enhanced power factor and the reduced total thermal conductivity.
Hydrothermal Synthesis, Crystal structure, DFT and Application of a Dinuclear Cadmium(II) Complex Based on NPHSNPAB
Jin-Long DONG, Zhen SONG, Rui-Tao ZHU, Ting-Ting ZHAO, Hao-Yang LI, Jian-Guo REN
2016, 35(12): 1876-1884  doi: 10.14102/j.cnki.0254-5861.2011-1164
[摘要]  (527) [HTML全文] (527) [PDF 0KB] (0)
摘要:
A new dinuclear cadmium(II) complex,[Cd(NPHSNPAB)(H2O)2(CH3CH2OH)]2 (1), was synthesized by the hydrothermal reaction of N-phenyl-2-[2-hydroxyl-3-sulfo-5-nitrophenylazo] butadiene-1,3 (NPHSNPAB) and Cd(NO3)2·4H2O, and characterized by elemental analysis, infrared, UV-visible, fluorescence, thermal behavior and single-crystal X-ray diffraction. For this complex:C36H42Cd2N8O22S2, Mr=1227.74, triclinic system, space group 1, a=7.555(9), b=12.006(14), c=13.943(16)Å, α=67.955(2), β=88.573(2), γ=77.550(2)°, V=1142.5(2)Å3, Z=2, Dc=1.784 g/cm3, λ=0.71073Å, F(000)=620, S=1.125, R=0.0460 and wR=0.1159 for 3949 observed reflections with I>2(I). X-ray diffraction analysis reveals that the central Cd(II) ion is bound by six oxygen atoms, forming a slightly distorted octahedral geometry. Density functional theory of complex 1 was studied. Noticeably, the application of 1 on metallic yarn got good effect.
Syntheses, Crystal Structures and Fluorescence Properties of Two Mononuclear Copper(II) Compounds
Yan-Guo CHEN, Qi-Ying WANG, Qiang TANG, Peng HONG, Chuan-Qun HU
2016, 35(12): 1885-1893  doi: 10.14102/j.cnki.0254-5861.2011-1142
[摘要]  (578) [HTML全文] (578) [PDF 0KB] (0)
摘要:
Two new compounds, 1 ([Cu(IDB)2]Cl2·2CH3CH2OH·2H2O (IDB=N,N-di(2-benzimidazolylmethyl)imine]) and 2 ([Cu(EDTB)]·2[C6H4(OH)COO]·6H2O (EDTB=N,N,N',N'-tetrakis-[(2-benzimidazolyl)methyl]-1,2-ethanediamine]), have been synthesized and their crystal structures were determined by single-crystal X-ray diffraction. Crystal 1 belongs to the triclinic system, space group P>1 with a=9.565(2), b=9.863(2), c=10.252(3)Å, α=81.915, β=88.330, γ=87.347°, V=956.28(40)Å3, Z=1, F(000)=427, Dc=1.419 g/cm3, Mr=817.27 and μ(Mo)=0.764 mm-1. The final R indices (I>2σ(I)):R=0.0505, wR=0.1417; R indices (all data):R=0.0591, wR=0.1525. Crystal 2 is of triclinic system, space group P>1 with a=11.487(3), b=13.396(4), c=17.977(5)Å, α=73.899(5), β=86.629(5), γ=65.018(4)°, V=2403.8(12)Å3, Z=2, F(000)=1072, Dc=1.417 g/cm3, Mr=1025.54, μ(Mo)=0.528 mm-1. The final R indices (I>2σ(I)):R=0.0769, wR=0.163 2; R indices (all data):R=0.0769, wR=0.1632. The two compounds exhibit mononuclear structures. The copper(II) atom of crystal 1 is six-coordinated by four nitrogen atoms of benzimidazole groups and two amine nitrogen atoms from the ligand IDB to adopt a distorted octahedral coordination geometry. The copper(II) atom of crystal 2 is six-coordinated by four nitrogen atoms of benzimidazole groups and two amine nitrogen atoms from the ligand EDTB to show a distorted octahedral coordination geometry. Particularly, the two compounds exhibit fluorescent properties at room temperature in ethanol.
Syntheses and Crystal Structures of Two New Complexes Generated from 2-((Pyridin-3-ylmethyl)thio)-5-(6-quinolinyl)-1,3,4-oxadiazole and AgI Salts
Xiang-Wen WU, Shi YIN, Jian-Ping MA
2016, 35(12): 1894-1901  doi: 10.14102/j.cnki.0254-5861.2011-1148
[摘要]  (640) [HTML全文] (640) [PDF 0KB] (0)
摘要:
Two new AgI-complexes have been synthesized based on the semi-rigid ligand 2-((pyridin-3-ylmethyl)thio)-5-(6-quinolinyl)-1,3,4-oxadiazole (L), obtained by the condensation reaction of 5-(6-quinolinyl)-1,3,4-oxadiazole-2-thiol and 3-chloromethyl pyridine hydrochloride. Crystallization of L with AgOTf and AgPF6 in a CH2Cl2/MeOH mixed solvent system at room temperature affords a novel supramolecular[Ag2L2(CF3SO3)2] (I) and a coordination polymer[AgL(PF6)]n (II), respectively. Two complexes were characterized by TGA, X-ray powder and single-crystal diffraction.
Catalytic Kinetic on the Thermal Decomposition of Ammonium Perchlorate with a New Energetic Complex Based on 3,5-Bis(3-pyridyl)-1H-1,2,4-triazole
Hui GAO, Bing LI, Xiao-Dong JIN, Shu-Xian BI, Xiao-Yan TIAN, Wan-Yi LIU
2016, 35(12): 1902-1911  doi: 10.14102/j.cnki.0254-5861.2011-1165
[摘要]  (747) [HTML全文] (747) [PDF 0KB] (0)
摘要:
A new energetic complex,[Co(3,3'-Hbpt)(Htm)]·H2O (1, 3,3'-Hbpt=3,5-bis(3-pyridyl)-1H-1,2,4-triazole and H3tm=trimesic acid), has been synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction, elementary analysis, IR spectroscopy, thermogravimetric analysis and X-ray powder diffraction. Single-crystal X-ray diffraction indicates that the complex belongs to triclinic system, space group P1 with a=10.0911(1), b=10.2573(1), c=10.6393(1)Å, α=103.793(2), β=101.041(2), γ=107.918(3)°, V=974.9(2)Å3, Z=2, Dc=1.732 g·cm-3, μ=0.941 mm-1, Mr=508.31, F(000)=518, the final R=0.0523 and wR=0.0935 with I>2σ(I). In the title complex, Co(II) ions are connected by Htm2- anions generating 1D ladder-like chains which are linked by 3,3'-Hbpt to form 1D cages. In addition, the thermal decomposition of ammonium perchlorate (AP) with complex 1 was explored by differential scanning calorimetry (DSC). AP is completely decomposed in a shorter time in the presence of complex 1, and the decomposition heat of the mixture is 2.531 kJ·g-1, significantly higher than that of pure AP. By Kissinger's method, the ratio of Ea/ln(A) is 11.05 for the mixture, which indicates that complex 1 shows good catalytic activity toward the AP decomposition.
A Chain Cadmium(II) Coordination Polymer with Diacylhydrazide: Synthesis, Crystal Structure and Luminescent Property
Kai WANG, Xu-Ke HUANG, Li ZHU, Zi-Lu CHEN, Fu-Pei LIANG
2016, 35(12): 1912-1919  doi: 10.14102/j.cnki.0254-5861.2011-1230
[摘要]  (501) [HTML全文] (501) [PDF 0KB] (0)
摘要:
A novel Cd(II) coordination polymer with diacylhydrazide ligand N,N'-bis(3-methoxysalicyl)-2,6-pyridinedicarbohydrazide (H6msphz),[Cd2(H2msphz)(Py)4]n (1, Py=pyridine) has been synthesized through solvothermal reaction and structurally characterized by single-crystal X-ray diffraction, IR, TGA and PXRD investigations. It crystallizes in triclinic system, space group P1, with a=11.0230(11), b=11.7264(15), c=17.3395(14)Å, α=70.520(9), β=84.806(7), γ=81.965(9)°, V=2089.9(4)Å3, Dc=1.638 g cm-3, μ=1.083 mm-1, F(000)=1032, Z=2 and S=1.040. In complex 1, the H2msphz4- ligand uses not only its coordinated pocket to catch one Cd(II) ion, but also its two terminal groups to chelate other two Cd(II) ions, leading to the formation of a chain structure. The adjacent chains are further assembled together by two kinds of π-π interactions between the Py rings, resulting in the finial double layered supramolecular structure. In addition, complex 1 is found to show photoluminescence in the solid state at room temperature, which can be ascribed to the intraligand ππ* transitions.
A Novel Three-dimensional Mn(II) Coordination Polymer Constructed from Biphenyl-3,3',5,5'-tetracarboxylic Acid and Water
Shao-Dong LI, Li-Ping LU, Feng SU
2016, 35(12): 1920-1928  doi: 10.14102/j.cnki.0254-5861.2011-1180
[摘要]  (472) [HTML全文] (472) [PDF 0KB] (0)
摘要:
The title Mn(II) coordination polymer, poly{[heptaaqua-(μ4-bi-phenyl-3,3',5,5'-tetracarboxylate)-bimanganese(II)] pentahydrate},[Mn2(bpta)(H2O)7]n·5nH2O (I), is crystallized from a mixture of biphenyl-3,3',5,5'-tetracarboxylic acid (H4bpta) and MnCl2·4H2O in waterethanol under room temperature. Its asymmetric unit consists of one and two halves of crystallographically independent Mn(II) cations, one fully deprotonated H4bpta ligand, seven coordinated water molecules and five solvent water as guest molecules. In I, each Mn(II) atom is octahedrally coordinated by six oxygen atoms from bpta4- anions and coordinated water molecules. In the Mn(II) cations, one half Mn(II) ion of them located at a 2-fold axis generating a trinuclear[Mn3(H2O)2(RCOO)2] linker by μ1,1-O(water) and μ1,3-O,O'(carboxylate) bridges and another half Mn(II) ion with an inversion is a mononuclear linker. These neighbouring trinuclear and mononuclear Mn(II) cations are linked together by biphenyl-3,3',5,5'-tetracarboxylates to form a three-dimensional framework with a (42.84) topology of a (4,4)-connected net, in which the positions of the trinuclear[Mn3(H2O)2(R-COO)2] linker as a 4-connector linking four bpta4- ligands in I reproduce an eagle-shaped arrangement. The polymeric structure exhibits a water channel with an accessible void of 797.1Å3, amounting to 15.7% of the total unit-cell volume. Each of the cavities in the network is occupied by solvent water molecules.
Synthesis and Characterization of a Water-stable Metal-organic Framework Based on Mixed Ligands
Lei ZHANG, Xiao-Yuan WU, Can-Zhong LU, Wen-Zhe CHEN
2016, 35(12): 1929-1935  doi: 10.14102/j.cnki.0254-5861.2011-1226
[摘要]  (1252) [HTML全文] (1252) [PDF 0KB] (0)
摘要:
A new water-stable metal-organic framework,[Cu2(bdc)2(tpt)3]·2H2O (1, H2bdc=terephthalic acid, tpt=2,4,6-tri(4-pyridinyl)-1,3,5-triazine), has been synthesized and characterized by elemental analysis, infrared (IR) spectrum, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. Compund 1 crystalizes in monoclinic, space group C2/c with a=30.147(5), b=11.0548(17), c=20.867(4)Å, β=115.035(2)°, C70H48Cu2N18O10, Mr=1428.34, V=6301.0(18)Å3, Z=8, Dc=1.506 g/cm3, μ=0.754 mm-1, F(000)=2928, GOOF=1.058, λ(Mo)=0.71073Å, the final R=0.0387 and wR=0.1091 for 6230 observed reflections with I>2σ(I). In compound 1, the half metallacycles[Cu2(tpt)3] are linked by the bdc2- ligands to form a 1D bent ladder-like chain featured with a nano-sized channel, and these chains link each other via intermolecular hydrogen bonds and π-π stacking interactions to form a 3D supramolecular architecture with the voids filled with free water molecules. In addition, the water stability of 1 was investigated by PXRD patterns, which indicate that compound 1 keeps its structural integrity in boiling water for at least three days.
A (3,4)-Connected 3D Heteronuclear Framework with Three Kinds of Discrete Cadmium(II) Ions: Synthesis, Crystal Structure and Luminescence Property
Rong-Fang LI, Xin-Fang LIU, Yu-Fang WANG, Xun FENG, Lu-Fang MA
2016, 35(12): 1936-1943  doi: 10.14102/j.cnki.0254-5861.2011-1225
[摘要]  (570) [HTML全文] (570) [PDF 0KB] (0)
摘要:
A novel 3D hetero-nuclear framework, namely[K2Cd5(Hbptc)4(H2O)12·12H2O]n (1, H4bptc=biphenyl-2,3,3',5'-tetracarboxylic acid), was obtained by hydrothermal reaction. X-ray singlecrystal structure analysis reveals that polymer 1 crystallizes in orthorhombic, space group Pbcn with a=26.6152(13), b=11.7449(5), c=29.5923(14)Å, V=9250.3(7)Å3, C64H76Cd5K2O56, Mr=2381.44, Dc=1.710 g/cm3, μ(Mo)=1.323 mm-1, F(000)=4744, Z=4, the final R=0.0668 and wR=0.1135 for 10613 observed reflections (I>2σ(I)). Polymer 1 displays a 3D network that is built on the unprecedented heterobimetallic[Cd3Cd2K] molecular building block with a (3, 4)-connected (6·8·8)2(6·6·82·82·126·126) topology which represents a rare 2-fold interpenetrating 3D framework topology network. The luminescence analyses reveal that polymer 1 shows obvious emission at room temperature in the solid state. In addition, it was also characterized by elemental, IR spectra and TG analyses.
Syntheses, Crystal Structures and Luminescent Properties of Two New Zinc(II) Complexes Based on Bifunctional Ligand
Ying-Xiang YE, Jian-Hong ZHENG, Yan-Ting ZENG, Yan-Li LIN, Liu-Qin ZHANG, Li-Hua WANG, Zhang-Jing ZHANG, Sheng-Chang XIANG
2016, 35(12): 1944-1952  doi: 10.14102/j.cnki.0254-5861.2011-1217
[摘要]  (615) [HTML全文] (615) [PDF 0KB] (0)
摘要:
By using solvothermal method, two novel coordination polymers based on 4-(4-carboxyphen-yl)-1,2,4-triazole (Hcpt) and Zn(II) cations,[Zn(cpt)(OH)]n·nH2O (FJU-32) and[Zn(cpt)(atrz)]n (FJU-33) (Hatrz=3-amino-1,2,4-triazolate), were synthesized and characterized by single-crystal X-ray diffraction analyses, elemental analyses, FT-IR and powder X-ray diffraction. FJU-32 crystallizes in monoclinic, space group P21/c with a=3.7441(3), b=23.0384(19), c=11.8562(10)Å, β=99.069(8)°, V=1009.91(15)Å3, Dc=1.898 g/cm3, C9H9N3O4Zn, Mr=288.57, F(000)=916, μ(Mo)=2.439 mm-1, Z=4, R=0.0600 and wR=0.1306 for 2412 observed reflections (I>2σ(I)), and R=0.0704 and wR=0.1349 for all data. FJU-33 crystallizes in monoclinic space group P21/c with a=12.7483(5), b=9.9922(3), c=9.8403(3)Å, β=100.756(4)°, V=1231.47(7)Å3, Dc=1.816 g/cm3, C11H9N7O2Zn, Mr=336.62, F(000)=680, μ(CuKα)=2.957 mm-1, Z=4, R=0.0478 and wR=0.1184 for 2466 observed reflections (I>2σ(I)), and R=0.0687 and wR=0.1309 for all data. In FJU-32, Zn(II) is coordinated to three μ3-OH groups forming an unprecedented 1D zigzag-like double chain, and the 1D double chains are connected to four neighbouring double chains by the cpt ligands to form an extended 3D porous coordination polymer. In FJU-33, the adjacent[Zn(atrz)] 2D layers are further connected by the cpt ligands via Zn-O coordinated bonds and neighboring interlayer hydrogen-bonding interactions to give rise to an overall 3D pillared layer structure. The neutron triazole group of the cpt ligand has weaker coordination ability than the triazolate anion of atrz ligand. Furthermore, FJU-32 and FJU-33 display high thermal stability up to 300℃, and the solid state fluorescence reveals that two new complexes are potential optical materials.
Syntheses, Structures and Properties for ZnII Coordination Polymers Based on a Functional 4'-(3-Pyridyl)-3,2': 6',3"-terpyridine Ligand
Yue CHENG, Xiao-Fang WANG, Bei LV, Huai-Ming HU
2016, 35(12): 1953-1959  doi: 10.14102/j.cnki.0254-5861.2011-1215
[摘要]  (432) [HTML全文] (432) [PDF 0KB] (0)
摘要:
Two new ZnII coordination polymers, namely,[ZnL(o-bdc)]n (1) and [ZnL(m-bdc)]n·nH2O (2) (L=4'-(3-pyridyl)-3,2':6',3"-terpyridine, H2(o-bdc)=benzene-1,2-dicarboxylic acid, H2(m-bdc)=benzene-1,3-dicarboxylic acid), were synthesized by hydrothermal methods. The crystal structures have been determined by single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic C2/c space group, with a=28.016(2), b=11.3815(11), c=19.8071(17)Å, β=133.961(2)°, V=4546.2(7)Å3, Z=8, Mr=539.83, Dc=1.577 Mg/m3, μ=1.127 mm-1, F(000)=2208, the final R=0.0426 and wR=0.0986 for 2875 observed reflections with I>2σ(I) and displays a 1D coordination chain. While compound 2 crystallizes in monoclinic C2/c space group, with a=15.6003(14), b=11.9152(11), c=26.633(3)Å, β=94.320(2)°, V=4936.5(8)Å3, Z=4, Mr=1115.67, Dc=1.496 Mg/m3, μ=1.043 mm-1, F(000)=2272, the final R=0.0499 and wR=0.1342 for 2659 observed reflections with I>2σ(I) and shows a classical 3D cds topological network with point symbol of {65.8}. Furthermore, thermal stability and luminescent properties of 1 and 2 have also been investigated.
A New 3-Fold Interpenetrating 3D Zn(II) Metal-organic Framework: Synthesis, Structure and Luminescent Property
Shao-Bin MIAO, Zhao-Hao LI, Chun-Yin XU, Bao-Ming JI
2016, 35(12): 1960-1966  doi: 10.14102/j.cnki.0254-5861.2011-1209
[摘要]  (529) [HTML全文] (529) [PDF 0KB] (0)
摘要:
A new Zn(II) coordination polymer, namely {[Zn1.5(1,3,5-btc3-)(dtb)(H2O)](H2O)2}n (1) (1,3,5-H3btc=1,3,5-benzenetricarboxylic acid, dtb=1,3-di-(1,2,4-triazole-4-yl)benzene), has been hydrothermally synthesized and structurally characterized. X-ray single-crystal diffraction determination reveals that 1 crystallizes in the monoclinic C2/c space group with a=33.811(12), b=8.406(2), c=17.296(4)Å, β=120.593(2)°, V=4232(2)Å3, Z=4, Mr=1142.88, Dc=1.794 Mg/m3, μ=1.783 mm-1, F(000)=2320, the final R=0.0338 and wR=0.0827 for 3043 observed reflections with I>2σ(I). Compound 1 exhibits 1D Zn(II)-carboxylate chains, which are connected into a 3D porous framework with large channels by dtb, and then three identical 3D networks are interpenetrated with each other. In addition, the luminescence property of the complex has also been investigated.
Hydrothermal Synthesis, Crystal Structure and Properties of a 1D Chain Copper(II) Polymer with 3-(2-Pyridiyl)-1H-1,2,4-triazole(Hpt)
Xiong-Wen TAN, Chang-Hong LI, Zhi-Hui CHEN, Heng-Feng LI, Wei LI
2016, 35(12): 1967-1971  doi: 10.14102/j.cnki.0254-5861.2011-1407
[摘要]  (389) [HTML全文] (389) [PDF 0KB] (0)
摘要:
A new 1D copper(II) polymer[Cu(Hpt)(3,5-DMBA)]n has been hydrothermally synthesized with copper acetate, 3-(pyridin-2-yl)-1,2,4-triazole(Hpt) and 3,5-dimethylbenzoic acid (3,5-DMBA). It crystallizes in triclinic space group P1, with a=8.1974(6), b=8.3280(6), c=12.5021(9)Å, α=84.3320(10), β=71.8870(10), γ=65.4560(10)°, V=737.44(9)Å3, Dc=1.612 g/cm3, Z=2, F(000)=366, GOOF=1.035, R=0.0298 and wR=0.0855. The crystal structure is a one-dimensional (1-D) chain in which the Cu(II) is five-coordinated with square pyramidal geometry. The crystal structure shows that the whole molecule consists of two copper ions bridged by two μ2-η1:η0-3,5-dimethylbenzoic acid anions and two 3-(pyridin-2-yl)-1,2,4-triazole molecules. The coordination environment of Cu(II) ion is CuO2N3. The luminescence and thermal properties of the complex were investigated.
Five-heterocyclic-biphosphinesubstituted Fe-only Hydrogenase Mimic: Synthesis, Characterization and Properties
Qing WANG, Cheng-Bing MA, Hui CHEN, De-Guang HUANG, Chang-Neng CHEN
2016, 35(12): 1972-1979  doi: 10.14102/j.cnki.0254-5861.2011-1211
[摘要]  (439) [HTML全文] (439) [PDF 0KB] (0)
摘要:
A new five-heterocyclic-biphosphine-substituted Fe-only hydrogenase mimic,[(μ-pdt)Fe2(CO)5]2(PTP) (1), has been synthesized at room temperature. 1·H2O crystallizes in triclinic system, space group P1, with a=11.5897(4), b=13.6156(4), c=18.0333(6)Å, α=76.306(3), β=72.742(3), γ=68.939(3)°, V=2508.84(14)Å3, Dc=1.570 g/cm3, Z=2, Mr=1186.37, F(000)=1204, the final R=0.0748, and wR=0.2012. In the tetranuclear complex 1·H2O, each[2Fe2S] butterfly unit is attached to one P atom of the diphosphine bridge and exhibits a square-pyramidal geometry. Complex 1 was characterized by elemental analysis, IR spectra, UV-vis absorption spectra, 1H-NMR and 31P-NMR. The cyclic voltammetry behavior of compound 1 was investigated as well.
Synthesis, Crystal Structure and Photoluminescent Property of a Novel Dy3+ Coordination Compound Containing Rare (H2O)22 Clusters
Yan-Zhu YE, Xin-Jian WU, Xian-Jin ZHANG, A-Lian WANG
2016, 35(12): 1980-1986  doi: 10.14102/j.cnki.0254-5861.2011-1418
[摘要]  (707) [HTML全文] (707) [PDF 0KB] (0)
摘要:
A novel Dy3+ coordination compound, (H2pipz)(H3O)[Dy(pydc)3]·11H2O (1, pipz=piperazine and H2pydc=pyridine-2,6-dicarboxylic acid), has been hydrothermally synthesized and characterized by X-ray single-crystal diffraction, elemental analysis. It is interesting that the packing structure of compound 1 contains 22-core water clusters. Compound 1 is extended into a threedimensional supramolecular structure via O…H…O hydrogen bonding interactions. Furthermore, the luminescent property of compound 1 was also investigated.
theoretical chemistry
Structural, Electronic and Optical Properties of Te-Doped GaAs Nanowires: the First Principles Study
Zi-Ping LAN, Xiang-Hai WEI, Hai-Feng WANG, Quan LI, Tao GAO
2016, 35(7): 993-1001  doi: 10.14102/j.cnki.0254-5861.2011-1062
[摘要]  (128) [HTML全文] (128) [PDF 760KB] (128)
摘要:
The first-principles calculations have been performed to determine the effects of Te doping to the structural, electronic, and optical properties of GaAs NWs. The calculated formation energies show that the single Te energetically prefers to substitute the core Ga (Ef=0.4111 eV) under As-rich conditions of GaAs nanowires, while on surface, the single Te tends to substitute the surface As site. With increasing the Te concentration, the favorable substitution sites are 2Te-Ga-A and 3Te-Ga-D. Thus, the stability of the structure of the electronic structure and optical properties are discussed.
medicinal structural chemistry
Syntheses, Crystal Structures and Antibacterial Activities of Cobalt(Ⅱ) and Manganese(Ⅱ) Complexes with Schiff Base Ligand Derived from Tryptamine
Chao LIU, Jun-Feng NIU, Yang LI, Ji-Gui XU, Xin-Hua LIU
2016, 35(7): 1002-1010  doi: 10.14102/j.cnki.0254-5861.2011-1049
[摘要]  (120) [HTML全文] (120) [PDF 0KB] (120)
摘要:
Two new mononuclear complexes, namely[Co(L)2] (1) and [Mn(L)2] (2) (HL=N-(3-methylsalicylidene)tryptamine), have been synthesized by the reactions of the ligand with cobalt acetate or manganese acetate in anhydrous ethanol. The crystal structures of the complexes were characterized by IR spectrum, elemental analysis, PXRD and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group C2/c, with a=23.146(2), b=9.4864(10), c=13.9261(15)Å, β=102.898(2)°, V=2980.6(5)Å3, Z=4, Dc=1.367 g/cm3, F(000)=1284 and μ=0.616 mm-1. Complex 2 crystallizes in monoclinic, space group P21/n, with a=14.807(11), b=13.118(10), c=16.663(13)Å, β=111.237(14)°, V=3017(4)Å3, Z=4, Dc=1.342 g/cm3, F(000)=1276 and μ=0.477 mm-1. The units of complex 1 are linked by intermolecular N-H…π hydrogen bonds into infinite 1D chains, which are further extended into a 3D supramolecular structure by a series of π…π stacking interactions. The units of complex 2 are linked by intermolecular N-H…π hydrogen bonds and C-H…π hydrogen bonds into an infinite 3D supramolecular structure. Meanwhile, the antibacterial activities of the ligand and its complexes have been tested against four kinds of bacteria. The results show that the three compounds all have excellent antibacterial activities and that 1 and 2 possess stronger inhibiting effects against the bacteria than the Schiff base.
Synthesis, Crystal Structure and Biological Activity of 2-((2, 2-Dimethyl-2, 3-dihydrobenzofuran-7-yl)oxy)-N-(3-(furan-2-yl)-1-phenyl-1H-pyrazol-5-yl)acetamide
Jing-Qian HUO, Liu-Yong MA, Zhe ZHANG, Zhi-Jin FAN, Jin-Lin ZHANG, Beryozkina Tetyan, A. Bakulev Vasiliy
2016, 35(7): 1011-1018  doi: 10.14102/j.cnki.0254-5861.2011-1221
[摘要]  (132) [HTML全文] (132) [PDF 0KB] (132)
摘要:
The title compound 2-((2, 2-dimethyl-2, 3-dihydrobenzofuran-7-yl)oxy)-N-(3-(furan-2-yl)-1-phenyl-1H-pyrazol-5-yl) acetamide (C25H23N3O4, Mr=429.46) has been synthesized, and its structure was characterized by 1H-NMR, 13C-NMR, H RMS, and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a=20.6205(18), b=5.2930(5), c=18.9282(17)Å, β=94.089(2)°, V=2060.6(3)Å3, Z=4, Dc=1.384 g/cm3, μ(Mo)=0.71073 mm-1, F(000)=904, R=0.0345 and wR=0.0930. The intramolecular hydrogen bond at N(1)-H(1)…O(2), intermolecular weak interactions at O(3)…H(4) and weak π-π interactions connected the molecules to lead to one-dimensional tapes. Bioassay results indicated that the title compound had moderate herbicidal and fungicidal activities.
A Novel 3-D Zn(II) Coordination Polymer for Inhibiting the Human Osteosarcoma Cells Growth
Fan ZHANG, Hao PENG, Zheng-Hui SHANG, Jie LIANG, Neng RU
2016, 35(7): 1019-1023  doi: 10.14102/j.cnki.0254-5861.2011-1059
[摘要]  (107) [HTML全文] (107) [PDF 0KB] (107)
摘要:
A new three-dimensional Zn(II) coordination polymer, namely[Zn4(bpydb)3(tz)2(H2O)2]n (1), has been synthesized by the self-assembly reactions of Zn(NO3)2·6H2O, bpydbH2, Htz and DMF. Single-crystal X-ray structural analysis reveals that compound 1 features a three-dimensional framework structure and is the first example of Zn-containing coordination polymers based on two kinds of ligands bpydbH2 and Htz. It crystallizes in triclinic, space group P1 with a=14.9953(12), b=17.5335(17), c=20.2381(11)Å, α=115.225(7), β=92.329(5), γ=105.606(8)°, V=4561.9(7)Å3, Z=2, F(000)=1644, Dc=1.177 Mg/m3, Mr=1616.76 and μ=1.098 mm-1. The antitumor activities of compound 1 and its corresponding organic ligands (bpydbH2 and Htz) were investigated for inhibiting human osteosarcoma cells (MG-63 and U-2 OS) growth by MTT assay. It was found that compared with the two ligands, compound 1 exerted rather potent activities against all of these cell lines.
Isolation, Crystal Structure and Na+/K+-ATPase Inhibitory Activity of 1β-Hydroxydigitoxigenin
Yun-Hui XU, Jian XU, Xue-Yang JIANG, Zhi-Hua CHEN, Zi-Jian XIE, Ren-Wang JIANG, Feng FENG
2016, 35(7): 1024-1030  doi: 10.14102/j.cnki.0254-5861.2011-1073
[摘要]  (114) [HTML全文] (114) [PDF 394KB] (114)
摘要:
The title compound 1β-hydroxydigitoxigenin (1) was isolated from the ethanol extract of the roots of Streptocaulon juventas. The crystal structure of 1, C23H34O5·H2O, was determined by Synchrotron X-ray diffraction analysis due to small crystal size (0.14mm×0.04mm×0.01 mm). The crystal belongs to monoclinic, space group P21, with a=7.6624(15), b=13.460(3), c=10.370(2)Å, β=92.40(3)°, V=1068.6(4)Å3, Z=2, Mr=406.50, Dx=1.263 g/cm3, λ(synchrotron)=1.2399Å, μ(synchrotron 1.23990)=0.333 cm-1, F(000)=550, S=1.059, R=0.0625 and wR=0.1687 for 4247 unique reflections, of which 3687 were observed (I>2σ(I)). The asymmetric unit contains one independent molecule of 1 and one water molecule which are connected through hydrogen bonds. The conformation of 1 in crystalline state is in good agreement with the solution structure in methanol as indicated by 1H-NMR analysis. The absolute configuration of 1 could be assigned by referring to the known configuration of the lactone ring at C(17β). In the solid state, intermolecular hydrogen bonds involving carbonyl group in the lactone moiety and the hydroxyl groups in the steroid moiety ester linked adjacent molecules into a three-dimensional network. Compound 1 showed significant inhibition on Na+/K+-ATPase with an IC50 of 2.46 μM, which is stronger thiocarbonylbufalin but weaker than a close analog digitoxigenin, suggesting that a lactone ring is important and the substitution of a hydroxyl group at C(1) is not favored for the inhibition of Na+/K+-ATPase.
organic and inorganic structural chemistry
pH Dependent Supramolecules Based on Co-crystallization of Pyrazine-2,3,5,6-tetracarboxylic Acid with 4,4'-Bipyridine through Intermolecular Hydrogen Bonds
Ying-Xuan MEI, Feng XU, Zhen-Hong WEI, Hu CAI
2016, 35(7): 1031-1037  doi: 10.14102/j.cnki.0254-5861.2011-1005
[摘要]  (147) [HTML全文] (147) [PDF 453KB] (147)
摘要:
Co-crystallization of pztcH4 with 4,4'-bipyridine (4,4'-bipy) in pH=3~4 and 1~2 gave two new binary molecular adducts:[(4,4'-bipyH2)(pztcH2)] (1) and [(4,4'-bipyH2)(pztcH3)(Cl)]·4H2O (2), respectively. Compounds 1 and 2 have been characterized by IR, elemental analysis, NMR and X-ray single-crystal diffraction. Compound 1 crystallizes in triclinic, space group P1 with a=5.7752(12), b=7.9126(16), c=9.4492(19)Å, α=97.49(3), β=107.71(3), γ=94.52(3)°, V=404.62(14)Å3, Z=1, μ=0.137 mm-1, Dc=1.692 Mg/m3, C18H12N4O8, Mr=412.32, F(000)=212, S=1.025, R=0.0360 and wR=0.0973. Compound 2 crystallizes in monoclinic, space group C2/c with a=17.093(3), b=7.7665(16), c=18.414(4)Å, β=113.36(3)°, V=2244.1(8)Å3, Z=4, μ=0.244 mm-1, Dc=1.542 Mg/m3, C18H21ClN4O12, Mr=520.84, F(000)=1080, S=1.021, R=0.0343 and wR=0.0978. In compound 1, pztcH22- anions self-formed 2-D sheets by strong Oacid-H…Oacid hydrogen bonds, which are further extended to form a 3-D supramolecular network bridged with 4,4'-bipy via N-H…Oacid interactions. In compound 2, besides the 1-D chain constructed by pztcH3- itself through strong H-bond Oacid-H…Oacid, the other chain is constructed with 4,4'-bipyH22+, Cl-anion and water molecules by moderate H-bonds and Ow-H…Cl and N-H…Ow. The two chains are linked with μ3-connected water molecules resulting from the combination of strong synthon-assisted H-bonding Oacid-H…Ow to afford an interlaced 3-D network.
Synthesis and Characterization of 8-Chloro-7-(4-(3-chloropropanoyl)piperazin-1-yl)-1-cyclopropyl-6-fluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic Acid
Jian-Yong WEI, Zheng-Hong REN, Yu CHEN, Li FAN, Xing-Ran XU, Da-Cheng YANG
2016, 35(7): 1038-1046  doi: 10.14102/j.cnki.0254-5861.2011-1157
[摘要]  (465) [HTML全文] (465) [PDF 597KB] (465)
摘要:
A new compound 8-chloro-7-(4-(3-chloropropanoyl)piperazin-1-yl)-1-cyclopropyl-6-fluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic acid (II, C20H20Cl2FN3O4, Mr=456.08) was synthesized and characterized by 1H NMR, 13C NMR, HR MS and single-crystal X-ray diffraction. X-ray powder diffraction (XRPD), thermal stabilities, UV-Vis spectrum, photoluminescent properties and absolute quantum yield of compound II were also investigated. The structure demonstrates that the crystal belongs to the triclinic system, space group P1 with a=7.7339(3), b=10.2396(5), c=15.9076(8)Å, α=76.517(4), β=77.609(4), γ=80.320(4)°, V=1187.22(9)Å3, Z=2, Dc=1.514 g/mm3, μ=4.901 mm-1, F(000)=556.0, R=0.0534 and wR=0.1447(I>2σ(I)). The result reveals that fluoroquionolone moiety in this structure stacks with π…π interactions to generate an infinite 1D chain, which can stabilize the whole framework of compound II. Delightfully, preliminary antibacterial activity in vitro against 4 cell strains uncovers that compound II has almost equal strong activity in comparison with Clinafloxacin, but stronger than Norfloxacin. These outcomes provide important information for further exploration of the structure-activity relationship (SAR) of compound II derivatives or analogs.
Synthesis and Crystal Structure of N1-(2-(4-Bromo-2-nitrophenoxy)-2-dimethyl acyloxymethyl)-5-fluorouracil
Zhong JIA, Jing LI, Yang ZHANG, Jing-Si ZHAO, Na XI, Chun-Hong HU, Min-Min HU, Dian HE
2016, 35(7): 1047-1053  doi: 10.14102/j.cnki.0254-5861.2011-1068
[摘要]  (118) [HTML全文] (118) [PDF 380KB] (118)
摘要:
The title compound N1-(2-(4-bromo-2-nitrophenoxy)-2-dimethyl acyloxymethyl)-5-fluorouracil (C15H13BrFN3O7, Mr=446.19) was synthesized and structurally characterized by 1H-NMR, 13C-NMR, ESI-MS and single-crystal X-ray diffraction. The compound crystallizes in triclinic, space group P1, with a=8.3325(6), b=10.1808(13), c=11.8194(16)Å, α=73.194(12), β=72.351(9), γ=89.509(8)°, V=911.2(2)Å3, Z=2, T=300.79(10) K, μ(Cu)=3.578 mm-1, Dc=1.626 g/cm3, F(000)=448.0, GOF=1.060, 5723 reflections measured (8.232≤2θ≤139.592°), 3339 unique (Rint=0.0184, Rsigma=0.0254) which were used in all calculations. The final R=0.0517 (I>2σ(I)) and wR=0.1494 (all data). Hydrogen bonds and π-π interactions together stabilize the structure of the molecule. The preliminary biological test shows that the title compound has good antitumor activity against A549 in vitro and lower toxicity to normal cells.
Synthesis and Crystal Structure of 7-((7S)-7-Aminospiro[2.4]heptan-5-yl)-8-chloro-6-fluoro-1-((1R,2S)-cis-2-fluorocyclopropyl)-4-oxo-1,4-dihydroqun-oline-3-carboxylic Acid Fumaric Acid Monohydra
Hai-Yan SUN, Neng-Fang SHE
2016, 35(7): 1054-1058  doi: 10.14102/j.cnki.0254-5861.2011-1032
[摘要]  (172) [HTML全文] (172) [PDF 415KB] (172)
摘要:
A new compound[C19H19N3O3F2Cl·C4H3O4·H2O] (I), (7-((7S)-7-aminospiro[2.4]heptan-5-yl)-8-chloro-6-fluoro-1-((1R,2S)-2-fluorocyclopropyl)-4-oxo-1,4-dihydroquinoline-3-carboxylic acid fumaric acid monohydrate), was synthesized and structurally characterized by single-crystal X-ray diffraction, 1H NMR, 14C spectra and mass spectra. I crystallizes in monoclinic, space group P21/c with a=8.495(2), b=12.545(3), c=11.832(3)Å, β=103.37(1)°, V=1226.8(5)Å3, Z=2, Mr=543.90, Dc=1.472 g/cm3, F(000)=564, μ=0.225 mm-1, the final R=0.0307 and wR=0.0892 for 6886 observed reflections with I>2σ(I). X-ray diffraction analysis reveals that the quinolinone ring is almost coplanar, and the pyrrole ring adopts an envelope form. Packing of crystal I is constructed and stabilized by the N-H…O, O-H…O and N-H…Cl hydrogen bonds together with C-H…π interations.
materials structural chemistry
Design of Cadmium Hydroxyapatite Hierarchical Structures with Adjustable Morphology by a Template-free Hydrothermal Route
Wen-Fei GUAN, Ting-Jiang YAN, Ying XIAO, Jun TIAN, Wen-Juan LI, Jin-Mao YOU
2016, 35(7): 1059-1069  doi: 10.14102/j.cnki.0254-5861.2011-1063
[摘要]  (106) [HTML全文] (106) [PDF 1429KB] (106)
摘要:
Cadmium hydroxyapatite (Cd-Hap) hierarchical structures with novel morphologies were successfully synthesized via a simple template-free and mild hydrothermal method. By properly monitoring the initial pH value of the reaction solutions, the morphology of the Cd-Hap crystals could be tuned to be bunch-like (consist of nanosized cuboids), quasi peanut-like (consist of nanoparticles) and flower-like (consist of assembled bundles units). On the basis of a series of contrast experiments over time, the probable growth mechanism and fabrication process of the products were proposed. The optical and photocatalytic properties of the obtained Cd-Hap hierarchical structures were firstly investigated. The results showed that pure Cd-Hap could only absorb UV light with wavelength shorter than ~350 nm while hydroxyapatite supported Ag3PO4 composites showed a pronounced photocatalytic activity upon decomposition of methyl orange dye in aqueous solution under visible light irradiation. The support of hydroxyapatite can also greatly reduce the cost of expensive Ag3PO4 photocatalysts in practical applications.
organometallic structural chemistry
Synthesis, Crystal Structure and Fluorescent Property of a Zn(II) Complex with 1,3-Bis(imidazol-1-yl)benzene and 1,3-Benzenedicarboxylate
Chun-Li ZHANG, He-Gen ZHENG
2016, 35(7): 1070-1076  doi: 10.14102/j.cnki.0254-5861.2011-1003
[摘要]  (152) [HTML全文] (152) [PDF 484KB] (152)
摘要:
A novel zinc complex[Zn(BIB)(bdc)]n (1, BIB=1,3-bis(imidazol-1-yl)benzene, bdc=1,3-benzenedicarboxylate) has been synthesized in solvothermal conditions. The title complex was characterized by elemental analysis, IR spectra, thermal analysis, single-crystal and powder X-ray diffraction. The result proved that the alliance of BIB and aromatic carboxylic acids is good for the diversity of getatable structure. Complex 1 crystallizes in the monoclinic system of P2/c space group with a=11.5591(10), b=9.6239(8), c=33.727(3)Å, β=103.816(3)°, V=3643.4(5)Å3, Z=8, μ=1.385 mm-1, F(000)=1792, Dc=1.603 g/cm3 and Mr=439.72 g/mol. Additionally, luminescent properties of complex 1 are also investigated and it shows good fluorescence.
Two Near-infrared Emissive Lanthanide-based Metal-organic Complexes Constructed from Efficient Energy Transfer Ligand
Shu-Zhi ZOU, Shao-Wu DU
2016, 35(7): 1077-1084  doi: 10.14102/j.cnki.0254-5861.2011-0709
[摘要]  (266) [HTML全文] (266) [PDF 574KB] (266)
摘要:
Utilizing two polycarboxylic acids as primary ligands and 1, 10-phenanthrolion as an auxiliary ligand in the existence of lanthanide nitrates, two lanthanide-based complexes formulated as[Nd4(2, 6-pydcOH)6(Phen)4(H2O)2](H2O)2 (1) and [Yb2(m-BDC)3(Phen)2]n (2) (2, 6-H2pydcOH=4-hydroxypyridine-2, 6-dicarboxylic acid, m-H2BDC=isophthalic acid, Phen=1, 10-phenanthroline) have been solvothermally synthesized. They have been fully characterized by satisfactory elemental analysis, FT-IR spectra, TGA and single-crystal X-ray diffraction. Single-crystal X-ray diffraction study reveals that 1 has a zero-dimensional structure and 2 exhibits a rare cds topological net structure. Compounds 1 and 2 exhibit strong characteristic emissions of Nd(III) and Yb(III) ions in the near-infrared (NIR) region.
Mononuclear and Dinuclear Yttrium Complexes Supported by Pyrrolide Ligands: Syntheses, Structures and Catalytic Behaviors towards the Ring-opening Polymerization of ε-Caprolactone
Hao PEI, Ning LU, Wei LIU, Yan-Mei CHEN, Bing WU, Hai-Yan LI, Ya-Hong LI, Wu LI
2016, 35(7): 1085-1092  doi: 10.14102/j.cnki.0254-5861.2011-0980
[摘要]  (136) [HTML全文] (136) [PDF 536KB] (136)
摘要:
The syntheses, structures and catalytic activities of two yttrium complexes supported by pyrrolide ligands are reported. Treatment of Y(N(SiMe3)2)3 with one equivalent of H3bptd (H3bptd=1,9-bis(2-pyrrolyl)-2,5,8-triazanona-1,8-diene) in THF gave a complex of composition[Y(bptd)(THF)]2 (1). Reaction of Y(N(SiMe3)2)3 with one equivalent of H3tpa (H3tpa=tris(pyrrolyl-α-methyl)amine) in THF generated[Y(tpa)(THF)3] (2) in good yield. Complexes 1 and 2 have been characterized by single-crystal X-ray diffraction, elemental analyses and NMR spectroscopy. Complex 1 is dinuclear. The two metal centers are doubly bridged by two amine nitrogen atoms to form a Y-N-Y-N four-membered rhombus ring. The geometries of Y3+ ions in 1 and 2 are well described as pentagonal bipyramid and capped octahedron, respectively. The ring-opening polymerization reactions of ε-caprolactone initiated by 1 and 2, respectively, were investigated. They both exhibited good catalytic activity for the polymerization of ε-caprolactone. All of the obtained polymers have high molecular weights and relatively narrower PDIs. The polymers generated by 2 possessed polydispersity close to 1.1. The good catalytic activities of 1 and 2 reveal their potential applications in polymer industry.
Crystal Structure, Spectroscopic Characterization, and Electrochemical and Thermal Stability Properties of a Dinuclear Nickel(II) Complex
Chang-Hong LI, Zhi-Hui CHEN, Heng-Feng LI, Wei LI
2016, 35(7): 1093-1098  doi: 10.14102/j.cnki.0254-5861.2011-1244
[摘要]  (290) [HTML全文] (290) [PDF 423KB] (290)
摘要:
A new nickel(II) complex Ni2(L)2(2,2'-bipy)2·5.5H2O with methy-bicycle[2.2.1]hept-5-ene-2,3-dicarboxylic acid (H2L) and 2,2'-bipyridine (2,2'-bipy) as ligands has been synthesized in the mixed solvent DMF and water (v:v=5:2). It crystallizes in the triclinic space group P1 with a=10.414(2), b=12.884(3), c=16.176(4)Å, α=70.715(5), β=80.599(5), γ=77.383(6)°, V=1989.4(8)Å3, Dc=1.531 g/cm3, Z=2, F(000)=958, GOOF=1.028, the final R=0.0808 and wR=0.2036. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two nickel ions are bridged by two μ2-η1:η0 3-carboxylate groups of L2- anions. The coordination environment of Ni(II) ion is NiN2O3, giving a distorted square pyramidal geometry. The thermal stability and electrochemical properties of the complex were investigated.
[Au(η2-Sn2Sb2)2]3-: a Mixed Group 14/15 Tetrahedral Dimer Bridged by Au
Fu-Xing PAN, Lei-Jiao LI, Zhong-Ming SUN
2016, 35(7): 1099-1106  doi: 10.14102/j.cnki.0254-5861.2011-1125
[摘要]  (259) [HTML全文] (259) [PDF 597KB] (259)
摘要:
A new ternary cluster anion [Au(η2-Sn2Sb2)2]3- was synthesized and identified. The electronic structure of [Au(η2-Sn2Sb2)2]3- was analyzed by means of DFT calculations. The electronic energy and energy gap indicate that [Au(η2-Sn2Sb2)2]3- features coplanar faces AuSn2 in which gold is directly coordinated by four tin atoms. Molecule orbital composition analysis indicates that d-orbital in Au atom contributes to bonding. Charge decomposition analysis (CDA) shows that electron donation and back donation are the key factors forming planar conformation of Au atom in [Au(η2-Sn2Sb2)2]3-. Meanwhile, the calculated Mayer bond order indicates relatively weaker interactions between Au and coordinated tetrahedral [Sn2Sb2]2-.
Structures and Photoluminescent Properties of Two Complexes Based on Dipyrido[3,2-a: 2',3'-c]phenazine and 2,4'-Biphenyldicarboxylic Acid
Da-Yu JIANG, Bo WANG, Bo FENG, Xiu-Ying LI, Yu QIAO, Zhan-Lin XU, Guang-Bo CHE
2016, 35(7): 1107-1114  doi: 10.14102/j.cnki.0254-5861.2011-1038
[摘要]  (141) [HTML全文] (141) [PDF 613KB] (141)
摘要:
Two new complexes[Cd(2,4'-bpdc)(DPPZ)]2n·nH2O (1) and [Zn(2,4'-Hbpdc)2(DPPZ)]·H2O (DPPZ=dipyrido[3,2-a:2',3'-c]phenazine, 2,4'-H2bpdc=2,4'-biphenyldicarboxylic acid) have been hydrothermally synthesized. The structure of complex 1 was determined by single-crystal X-ray diffraction diffraction and further characterized by elemental analysis, IR spectrum, powder X-ray diffraction (XRD) and single-crystal X-ray diffraction. Complex 1 has 1D chains, which are further connected by π-π stacking interactions of neighbouring chains, generating a steady 3D supramolecular structure. Complex 2 shows the isolated mononuclear units, which are further extended to a 2D supramolecular layered structure through π-π stacking interactions and hydrogen bonds. Furthermore, complexes 1 and 2 exhibit green photoluminescent properties at room temperature.
A New Vanadium Phosphate Incorporating Copper-organonitrogen Ligand: Synthesis, Crystal Structure and Electrochemical Property
Xin-Fang ZHENG, Zhan-Gang HAN
2016, 35(7): 1115-1121  doi: 10.14102/j.cnki.0254-5861.2011-1010
[摘要]  (289) [HTML全文] (289) [PDF 577KB] (289)
摘要:
A new phosphovanadate metal-organic complex Cu(mbpy)(VO2)(PO4) (1, mbpy=5,5'-dimethyl-2,2'-dipyridyl) has been hydrothermally synthesized and structurally characterized. Single-crystal structure analysis reveals that compound 1 crystallizes in the monoclinic space group P21/c with a=7.6640(4), b=18.8832(10), c=10.1893(5)Å, β=94.782(1)°, V=1469.47(13)Å3, Z=4, Mr=425.69, Dc=1.924 g/cm3, F(000)=852, μ(Mo)=2.224 mm-1, R=0.0291 and wR=0.0980. The crystal structure of 1 features a one-dimensional framework constructed by inorganic {Cu(VO2)(PO4)} neutral chain and organic mbpy ligands. The electrochemical property of compound 1 modified carbon paste electrode has also been investigated.
Synthesis, Crystal Structure and Luminescent Property of Ladder-shaped Zinc Coordination Polymer with Mixed Polyfunctional Ligands
Tian ZHANG, Rong-Fang LI, Ai-Qin TIAN, Xun FENG, Pan-Hao TIAN
2016, 35(7): 1122-1128  doi: 10.14102/j.cnki.0254-5861.2011-1019
[摘要]  (141) [HTML全文] (141) [PDF 1092KB] (141)
摘要:
One new Zn(II) complex[Zn2(cptpy)2(tzba)(H2O)]·H2O (1, Hcptpy=4-(4-carboxyphenyl)-2,2':4',4"-terpyridine (Hcptpy), H2tzba=4-(tetrazol-5-yl)benzenecarboxylic acid) has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction techniques. It is formulated as C52H36O8N10Zn2, crystallizes in monoclinic system, space group P21/c with α=15.1599(13), b=28.083(2), c=10.9039(9)Å, β=97.517(8)°. V=4602.3(6)Å3, Z=4, Mr=1059.68, Dc=1.529 g/cm3, F(000)=2168 and μ=1.112 mm-1. The final R=0.0831 and wR=0.2143 for 8458 observed reflections with I>2σ(I). The assembly of polyfunctional organic ligands Hcptpy and H2tzba with Zn(II) atoms resulting in a rare example of double-edge ladders, which is further extended into a 3D supramolecular network via O-H…O/N hydrogen bonds. In addition, thermal gravimetric analysis (TGA) and PXRD patterns for 1 were studied. Photo luminescent property of 1 was also investigated.
Synthesis, Crystal Structure, Fluorescent Property and DFT Calculations of a New Zn(II) Complex Based on 3-(2-Pyridyl)-5-(4-pyridyl)-1H-1,2,4-triazole
Xiao-Dong JIN, Bing LI, Hui GAO, Xia ZHANG, Wan-Yi LIU
2016, 35(7): 1129-1136  doi: 10.14102/j.cnki.0254-5861.2011-1030
[摘要]  (125) [HTML全文] (125) [PDF 521KB] (125)
摘要:
A new coordination compound Zn(2,4'-bpt)2(H2O) (1) based on the versatile ligand 2,4'-Hbpt (2,4'-Hbpt=3-(2-pyridyl)-5-(4-pyridyl)-1H-1,2,4-triazole) was prepared by hydrothermal reactions. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis indicates that the complex belongs to monoclinic system, space group C2/c with a=23.877(3), b=0.7483(9), c=1.2492(2)Å, β=92.681(2)°, V=2230.6(4)Å3, Z=4, Dc=1.572 g/cm3, μ=1.143 mm-1, Mr=527.85 and F(000)=1080. The final R=0.0581 and wR=0.0898 with I>2σ(I). 1 is a 0D motif which is connected by hydrogen bonds to form a corrugated 1D pattern. In addition, 1 shows strong photoluminescent emissions in the solid state at room temperature which can be used as potential optical materials. Theoretical calculations based on density functional theory (DFT) were employed in order to explicate the stability and chemical reactivity of 2,4'-Hbpt with different conformations. The results indicated that conformation I is more stable and prior to coordination in the reactions.
Two Novel Mercury(II) and Copper(II) Complexes Based on (5-Chloro-quinolin-8-yloxy)acetic Acid
Teng ZHAO, Yu-Hong WANG, Rui-Feng SONG
2016, 35(7): 1137-1144  doi: 10.14102/j.cnki.0254-5861.2011-1034
[摘要]  (191) [HTML全文] (191) [PDF 506KB] (191)
摘要:
Two novel mononuclear complexes with 5-chloro-8-(methoxycarbonylmethoxy)quinoline ligand (L), namely, HgLBr2 1 and CuL2Cl2 2, have been prepared by solvothermal reaction of (5-chloro-quinolin-8-yloxy)acetic acid with HgBr2 and CuCl2, respectively. Their structures were characterized by IR, elemental analysis, UV-Vis-NIR spectra, TG and single-crystal X-ray diffraction analysis. Interestingly, (5-chloro-quinolin-8-yloxy)acetic acid is changed as 5-chloro-8-(methoxycarbonylmethoxy)quinoline ligand (L) in complexes 1 and 2. Crystal data for 1:C12H10Br2ClHgNO3, Mr=612.07, triclinic, space group P1 with a=8.5983(7), b=9.7726(6), c=10.1549(6)Å, α=66.355(6), β=77.067(8), γ=78.803(8)°, V=756.6(9)Å3, Z=2, Dc=2.687 g/cm3, F(000)=560, μ=15.633 mm-1, R=0.0351 and wR=0.0504. Crystal data for 2:C24H20Cl4CuN2O6, Mr=637.76, triclinic, space group P1 with a=10.5324(9), b=11.2377(16), c=12.0143(12)Å, α=83.413(11), β=64.475(9), γ=83.144(11)°, V=1270.9(2)Å3, Z=2, Dc=1.667 g/cm3, F(000)=646, μ=1.324 mm-1, R=0.0408 and wR=0.0922. In 1, the HgII centre is a distorted trigonal planar geometry comprised of two Br atoms and one quinoline N atom of L. Intermolecular π-π, C-H…π stacking interactions and intermolecular C-H…Br hydrogen bonds are observed in the molecular packing of 1. In complex 2, each CuII center has a distorted octahedral geometry comprised of two chloride ions, two quinoline N atoms and two O atoms of two L ligands. Intermolecular C-H…Cl hydrogen bonds exist in the molecular packing of 2. The fluorescence emission peak of complexes 1 and 2 appears near 406 and 410 nm, respectively. Optical diffuse-reflection spectral results suggest complex 1 has the property of semiconductor.
A Zn(II) Coordination Polymer with 4-Connected bbf Topology: Synthesis, Crystal Structure and Luminescent Property
Xin ZHANG, Ye-Yan QIN, Ming-Ling SUN, Yuan-Gen YAO
2016, 35(7): 1145-1150  doi: 10.14102/j.cnki.0254-5861.2011-1013
[摘要]  (323) [HTML全文] (323) [PDF 430KB] (323)
摘要:
A new Zn(II) compound, namely {Zn(BTA)(pdc)0.5}n (1, HBTA=1,2,3-benzotriazole, H2pdc=terephthalic acid), has been hydrothermally synthesized and characterized by elemental analysis, infrared analysis, powder X-ray diffraction analysis and single-crystal X-ray structural analysis. The crystal structure is of monoclinic system, space group P21/c with a=10.751(3), b=9.792(3), c=9.292(3)Å, β=95.391(4)°, V=973.9(5)Å3, C10H6N3O2Zn, Mr=265.57, Z=4, Dc=1.811 g/cm3, F(000)=532, μ=2.506 mm-1, R=0.0221 and wR=0.0605 for 2075 observed reflections (I>2σ(I)). Single-crystal X-ray structural analysis reveals that compound 1 features a three-dimensional (3D) framework with 4-connected bbf topology. Moreover, the thermogravimetric (TG) analysis and photoluminescent property of 1 were also discussed.