A range of new compounds such as N1,N4-bis（diphenylmethlene）benzene-l,4-diamine zirconium （IV） chloride [{（Ar）2NC6HsN（Ar）z}ZrCl4] （Ar = C6H5） complex counting the chelating amine and chloride in position tra...A range of new compounds such as N1,N4-bis（diphenylmethlene）benzene-l,4-diamine zirconium （IV） chloride [{（Ar）2NC6HsN（Ar）z}ZrCl4] （Ar = C6H5） complex counting the chelating amine and chloride in position trans have been prepared. Well-defined NI,N4-bis（diphenylmethlene）benzene-l,4-diamine zirconium （IV） chloride [{（Ar）2NC6H5N（Ar）2}ZrCl4] （Ar = C6H5） was obtained by stoichiometric addition of {（Ar）2NC6H5N（Ar）2} （Ar = C6H5） and {ZrC14} in ethanol at reflex temperature. IR, 1H NMR, electronic properties using hyperchem program study has been improved for this compound such as bond distance, and this compound was also defined as electric conductivity which proves to be useful for conductively compound.展开更多
A new 3-D nickel（Ⅱ） metal-organic framework（MOFs） with formula [Ni（bib）_2（SO_4）]_n（1）, where bib = 1,4-bis（imidazol-1-yl）benzene, has been synthesized and characterized by single-crystal X-ray diffraction...A new 3-D nickel（Ⅱ） metal-organic framework（MOFs） with formula [Ni（bib）_2（SO_4）]_n（1）, where bib = 1,4-bis（imidazol-1-yl）benzene, has been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and surface photovoltage spectroscopy（SPS）. Complex 1 crystallizes in monoclinic system, space group C2/c with a = 19.5988（6）, b = 9.7531（3）, c = 11.8146（4） ？, β = 96.185（3）°, V = 2245.20（12） ？~3, C_（24）H_（20）N_8NiO_4S, M_r = 575.25, D_c = 1.702 g/cm^3, Z = 4, F（000） = 1184, μ = 1.011 mm-1, the final R = 0.0293 and w R = 0.0702. X-ray diffraction analyses indicated that the center Ni^（2＋） ion is six-coordinated with an O_2N_4 donor set of two μ_2-SO_4^（2–） and four bib ligands, resulting in an ideal octahedral geometry. Topological analysis on complex 1 considers each Ni^（2＋） as a 6-connected node, while bib and sulfate ion as linkers, giving an α-Po topology with short Schl？fli symbol 412·63. In the crystal packing, the components interact with pairs of intermolecular C–H×××O hydrogen bonds. The SPS of 1 indicates that there are positive response bands in the range of 300~600 nm showing photo-electric conversion properties.展开更多
The title coordination polymer 1,{[Cu8（btb）2（CN）8].3H2O}n（btb = 1,4-bis（1,2,4-triazol-1-yl）butane）,has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex...The title coordination polymer 1,{[Cu8（btb）2（CN）8].3H2O}n（btb = 1,4-bis（1,2,4-triazol-1-yl）butane）,has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group C2/c with a = 1.2938（3）,b = 1.9422（5）,c = 0.9406（2） nm,β = 121.891（4）°,V = 2.0066（9） nm3,C24H30Cu8N20O3,Mr = 1155.00,Dc = 1.912 g/cm3,μ（MoKα） = 4.209 mm？1,F（000） = 1140,GOF = 1.184,Z = 2,the final R = 0.0634 and wR = 0.1503 for I 2σ（I）.In complex 1,one-dimensional CuCN zigzag chains are linked by triazolyl groups of btb ligands to form two-dimensional networks,which are further bridged by 1,4-butyl moieties of btb ligands to fabricate a three-dimensional order framework,in which one-dimensional ellipsoid-like channels are observed.展开更多
A correlation equation between the UV absorption wavenumbers of 1,4-disubstituted benzenes and the excited-state substituent constant was obtained. For 80 sorts of 1,4- disubstituted benzenes, the correlation coeffici...A correlation equation between the UV absorption wavenumbers of 1,4-disubstituted benzenes and the excited-state substituent constant was obtained. For 80 sorts of 1,4- disubstituted benzenes, the correlation coefficient was 0.9805, and the standard deviation was only 672.27 cm^-1. The results imply that the excited-state substituent constant can be used productively for research on UV energy of 1,4-disubstituted benzenes. The present method provides a new avenue to study the UV absorption spectra of aromatic systems with the excited-state substituent constant, and it is helpful to understand the effect of substituent electrostatic effects on the chemical and physical properties of conjugated compounds with multiple substituents in excited state.展开更多
An energetic salt of bis（l,5-diamino-lH-tetrazolium）3,3＂-bis（nitramino）-4, 4x-azo- furazan （C6H10N2206） was synthesized with the total yield of 61.7% by using 3,4-diaminofurazan （DAF） as the starting material...An energetic salt of bis（l,5-diamino-lH-tetrazolium）3,3＂-bis（nitramino）-4, 4x-azo- furazan （C6H10N2206） was synthesized with the total yield of 61.7% by using 3,4-diaminofurazan （DAF） as the starting material. The structure of the title compound was confirmed by NMR, IR, elemental analysis and single-crystal X-ray diffraction. It crystallizes in orthorhombic, space group P21/c with a = 10.739（2）, b = 6.4765（12）, c = 14.138（3） A, fl= 108.787（3）°, V= 930.9（3） A3, Z = 1, Mr= 486.36, Dc = 1.735 g.cm3, μ= 0.15 mm-1, F（000） = 496, R = 0.042 and wR = 0.121. The thermal stability was analyzed by subsequently differential scanning calorimetry （DSC）. And the enthalpy of formation and detonation was calculated theoretically, showing the first decomposition temperature was 142.1℃, the enthalpy of formation was 1614.23 kJ.mol1 and the detonation velocity and detonation pressure were 8.781 km.s-1 and 30.7 GPa, respectively.展开更多
The solid-liquid equilibria of musk ketone + musk xylene, musk xylene +l,3-dimethyl-2,4-dinitro-5-tert-butyl benzene are measured by differential scanning calorimeter (DSC), these systems are proved to be simple eutec...The solid-liquid equilibria of musk ketone + musk xylene, musk xylene +l,3-dimethyl-2,4-dinitro-5-tert-butyl benzene are measured by differential scanning calorimeter (DSC), these systems are proved to be simple eutectics. Moreover the melting points and the fusion enthalpies of musk ketone, musk xylene and 1,3-dimethyl-2,4-dinitro-5-tert-butyl benzene are also measured by the DSC. These solid-liquid equilibrium data and the heats of fusion are reported for the first time. Then UNIFAC model is used to correlate the sofid-liquid equilibrium data. It is shown that the solid-liquid equilibria of musk systems can be predicted by the UNIFAC model.展开更多
A new complex [Cd（hba）2（bib）]n·nH2O（1,Hhba = 3-hydroxybenzoic acid,bib = 1,4-bis（imidazol-1-yl）-butane） has been hydrothermally synthesized and characterized by elemental analysis,IR spectrum,thermogravim...A new complex [Cd（hba）2（bib）]n·nH2O（1,Hhba = 3-hydroxybenzoic acid,bib = 1,4-bis（imidazol-1-yl）-butane） has been hydrothermally synthesized and characterized by elemental analysis,IR spectrum,thermogravimetric analysis,fluorescence spectrum,and singlecrystal X-ray diffraction.Yellow crystal crystallizes in the orthorhombic system,space group Pbca with a = 16.220（5）,b = 14.980（5）,c = 20.521（5） ？,V = 4986（3） ？~3,C（24）H（26）CdN4O7,Mr = 594.89,Dc = 1.585 g/cm^3,μ（Mo Kα） = 0.927 mm^（-1）,F（000） = 2416,Z = 8,the final R = 0.0242 and w R = 0.0589 for 4076 observed reflections（I 〉 2s（I））.In 1,the Cd（Ⅱ） ion takes a six-coordination mode,and bib ligand bridges adjacent Cd（Ⅱ） ions to generate 1D zigzag chains; these neighboring chains are connected by O–H···O hydrogen bonding interactions,producing a 2D folded layered structure.Furthermore,by O–H···O hydrogen bonding between layers and layers,a 3D supramolecular architecture is formed.In addition,we analyzed Natural Bond Orbital（NBO） in using the PBE0/LANL2 DZ method built in Gaussian 03 Program.The calculation results indicated obvious covalent interaction between the coordinated atoms and Cd（Ⅱ） ion.展开更多
The optical properties of N,N’-bis (Inaphthyl)N,N’-diphenyl-1,1’-biphenyl-4,4’-diamine (NPB) and tris (8-hydroxyquinolinato) aluminum (Alq3) organic materials used as hole transport and electron transport layers i...The optical properties of N,N’-bis (Inaphthyl)N,N’-diphenyl-1,1’-biphenyl-4,4’-diamine (NPB) and tris (8-hydroxyquinolinato) aluminum (Alq3) organic materials used as hole transport and electron transport layers in organic light-emitting devices (OLED) have been investigated. The NPB and Alq3 layers were prepared using thermal evaporation method. The results show that the energy band gap of Alq3 is thickness independence while the energy band gap of NPB decreases with the increasing of sample thickness. For the case of photoluminescence the Alq3 with thickness of 84 nm shows the highest relative intensity peak at 510 nm.展开更多
2,3-Bis（hydroxymethyl）-2,3-dinitro-1,4-butanediol（C6H12N2O8） was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the t...2,3-Bis（hydroxymethyl）-2,3-dinitro-1,4-butanediol（C6H12N2O8） was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the title compound was characterized by 1H NMR,13C NMR,FT-IR,elementary analysis,and X-ray single-crystal diffraction analysis,which reveals that the title compound crystallizes in triclinic,space group P with a = 0.6324（2）,b = 0.6454（3）,c = 0.7062（3） nm,α= 111.550（4）,β= 95.505（4）,γ= 113.395（4）°,V = 0.23595（16） nm3,Z = 1,Mr = 240.18,Dc = 1.690 g·cm-3,μ = 0.159 mm-1,F（000） = 126,R = 0.0304 and wR = 0.0907.展开更多
A new energetic complex,[Co（3,3？-Hbpt）（Htm）]·H_2O（1,3,3？-Hbpt = 3,5-bis（3-pyridyl）-1H-1,2,4-triazole and H_3tm = trimesic acid）,has been synthesized by hydrothermal reactions and characterized by single...A new energetic complex,[Co（3,3？-Hbpt）（Htm）]·H_2O（1,3,3？-Hbpt = 3,5-bis（3-pyridyl）-1H-1,2,4-triazole and H_3tm = 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 P 1 with a = 10.0911（1）,b = 10.2573（1）,c = 10.6393（1） ？,α = 103.793（2）,β = 101.041（2）,γ = 107.918（3）o,V = 974.9（2） ？~3,Z = 2,D_c = 1.732 g·cm-3,μ = 0.941 mm^（-1）,M_r = 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.展开更多
An efficient synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one is achieved via a reaction of acenaphthe-nequinone and indoles catalyzed by solid superacid SO4^2-/TiO2 under solvent-free conditions...An efficient synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one is achieved via a reaction of acenaphthe-nequinone and indoles catalyzed by solid superacid SO4^2-/TiO2 under solvent-free conditions at room temperature by grinding, which provides an efficient route to the synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one.This procedure offers several advantages including solvent-free conditions,excellent yields of products,simple work-up as well as reuse of catalysts which makes it a useful and attractive protocol for the synthesis of these compounds.展开更多
A new monomer of 4, 4-biphenyl-bis[4-phthalazin-1(2H)-one] was synthesized from biphenyl and phthalic anhydride, and a novel copoly(aryl ether ketone) (PPEK) was synthesized from 2, 2-bis(4-hydroxyphenyl)-propane (BPA...A new monomer of 4, 4-biphenyl-bis[4-phthalazin-1(2H)-one] was synthesized from biphenyl and phthalic anhydride, and a novel copoly(aryl ether ketone) (PPEK) was synthesized from 2, 2-bis(4-hydroxyphenyl)-propane (BPA), 4, 4'-biphenyl-bis-[4-phthalazin-1(2H)-one], 4, 4- difluorodiphenylketone (DFK). The monomer and copolymer were characterized by FT-IR and 1H-NMR. DSC and TGA were used to the novel polymer.展开更多
Our previous research showed that aliphatic amines were put in order of high reactivity as “ethylamine > ammonia > t-butylamine > diethylamine” on the aromatic nucleophilic substitution of 1-dimetylamino-2,...Our previous research showed that aliphatic amines were put in order of high reactivity as “ethylamine > ammonia > t-butylamine > diethylamine” on the aromatic nucleophilic substitution of 1-dimetylamino-2,4-bis(trifluoroacetyl)-naphthalene 1 in acetonitrile. The DFT calculation study (B3LYP/6-31G* with solvation model) for the reactions of 1 with above four amines rationally explained the difference of each amines reactivity based on the energies of their Meisenheimer complexes 3 which are assumed to formed as the reaction intermediates in the course of the reaction giving the corresponding N-N exchange products 2. Intramolecular hydrogen bond between amino proton in 1-amino group and carbonyl oxygen in 2-trifluoroacetyl group stabilizes Meisenheimer complexes 3 effectively, and accelerates the substitution reaction from 1 to 2. Our calculation results also predicted that the above order of amines is also true if less polar toluene is used as a solvent instead of acetonitrile even though more enhanced conditions are required.展开更多
A comparative thermal decomposition kinetic investigation on Fe(III) complexes of a antipyrine Schiff base ligand, 1,2-Bis(imino-4’-antipyrinyl)ethane (GA)), with varying counter anions viz. CIO4-, NO3-, SCN-, Cl-, a...A comparative thermal decomposition kinetic investigation on Fe(III) complexes of a antipyrine Schiff base ligand, 1,2-Bis(imino-4’-antipyrinyl)ethane (GA)), with varying counter anions viz. CIO4-, NO3-, SCN-, Cl-, and Br-, has been done by thermogravimetric analysis by using Coats-Redfern equation. The kinetic parameters like activation energy (E), pre-exponential factor (A) and entropy of activation (ΔS) were quantified. On comparing the various kinetic parameters, lower activation energy was observed in second stage as compared to first thermal decomposition stage. The same trend has been observed for pre-exponential factor (A) and entropy of activation (ΔS). The present results show that the starting materials having higher activation energy (E), are more stable than the intermediate products, however;the intermediate products possess well-ordered chemical structure due to their highly negative entropy of activation (ΔS) values. The present investigation proves that the counter anions play an important role on the thermal decomposition kinetics of the complexes.展开更多
Sodium 3,5-bis(hydroxyimino)-1-methyl-2,4,6-trioxocyclohexanide C7H5N2NaO5 (I) has been isolated as the only product of the reaction of nitrosation of methylphloroglucinol. The structure of the titled compound has bee...Sodium 3,5-bis(hydroxyimino)-1-methyl-2,4,6-trioxocyclohexanide C7H5N2NaO5 (I) has been isolated as the only product of the reaction of nitrosation of methylphloroglucinol. The structure of the titled compound has been determined from single crystal X-ray diffraction data. The hydrated C7H5N2NaO52.5H2O crystallizes in the monoclinic space group C2/c, with a(?) 16.408(3);b(?) 12.446(3);c(?) 13.716(3);(o) 126.34(3). The planar organic anion exists in a triketo-dihydroxyimino form with the C–O and C–N distances from 1.220(2) to 1.271(2)?? and from 1.292(2) to 1.293?? respectively. In the IR spectrum of I, the sharp absorption band occurred at 1681 cm-1 due to C=O stretching indicating the strong H-interactions. The correlations of theoretical (DFT-B3LYP/aug-cc-pVDZ) and experimental UV-vis absorption spectra in neutral and alkaline ethanolic solutions showed the existence of hydroxyimino-nitroso tautomerism while ionization of I.展开更多
A Zn（Ⅱ） supramolecular coordination polymer, {[Zn2（L）2（m-bix）（H20）]6H2O}n（1）, with an interesting 1D→2D polythreading array from a flexible and angular organic aromaticpolycarboxylate ligand 5-（4-hydroxyp...A Zn（Ⅱ） supramolecular coordination polymer, {[Zn2（L）2（m-bix）（H20）]6H2O}n（1）, with an interesting 1D→2D polythreading array from a flexible and angular organic aromaticpolycarboxylate ligand 5-（4-hydroxypyridinium-l-ylmethyl）isophthalic acid （H2L）, and N-donorligand 1,3-bis（imidazol-l-ylmethyl）benzene （m-bix）, has been obtained under hydrothermalconditions and characterized by elemental analysis, powder X-ray diffraction （PXRD）, IR, thermalgravimetric analyses （TGA） and single-crystal X-ray diffraction. In 1, the Zn（Ⅱ） center has twocoordination geometries. One exhibits a trigonal bipyramidal coordination sphere, and the other isa tetrahedral geometry; L2- has two different coordination modes, with one connecting three Zn（Ⅱ）ions through two monodentate carboxylate groups and the monodentate hydroxyl group, and theother bridging two Zn（Ⅱ） ions through two carboxylate groups. The L2- anions connect the Zn（Ⅱ）centers forming an infinite 1D tubular structure. These 1D tubes are interconnected by the m-bixspacers to form a 2D framework. Such 2D layers are further assembled into a 3D supramolecularnetwork via hydrogen bonds. Meanwhile, the luminescent property of 1 has also been investigatedin detail.展开更多
Hydrothermal reactions of three aromatic polycarboxylic acids and the transitional metal cations in the presence of phen and 1,4-bib afford three new coordination polymers： [Cd2（bpp）1.5（Hbpp）（phen）2]n （1）, [...Hydrothermal reactions of three aromatic polycarboxylic acids and the transitional metal cations in the presence of phen and 1,4-bib afford three new coordination polymers： [Cd2（bpp）1.5（Hbpp）（phen）2]n （1）, [Mn3（Htptc）2（phen）2（H2O）2]n （2）, and {[Cu（btc）0.5（1,4- bib）]·2H2O}n（3） （H2bpp = 2,6-bis（4＇-carboxyphenyl）-4-phenylpyridine, H4tptc = terphenyl-2,5,2＇,5＇-tetracar- boxylic acid, H4btc =biphenyl-2,2＇,4,4＇-tetracarboxylic acid, phen =1,10-phenanthroline, and 1,4-bib = 1,4-bis（1H-imidazol-1-yl）benzene）. Their structures have been determined by single- crystal X-ray diffraction analyses, elemental analyses, IR spectra, and powder X-ray diffraction （PXRD） analyses. In compound 1, the CdII cations are linked by bpp2- to form one ladder structure, based on which a 3D network is constructed with the help of non-covalent interactions. The topology of 2 is a 3D （3,4,5）-connected framework with the Point Schl？fli symbol of （42.6）2（43.62.8）（45.64.8）2. Compound 3 shows an unprecedented 3D （4,4）-connected framework with the Point Schl？fli symbol of （64.82）2（65.8）. Moreover, the luminescent property of 1 has been investigated.展开更多
文摘A range of new compounds such as N1,N4-bis（diphenylmethlene）benzene-l,4-diamine zirconium （IV） chloride [{（Ar）2NC6HsN（Ar）z}ZrCl4] （Ar = C6H5） complex counting the chelating amine and chloride in position trans have been prepared. Well-defined NI,N4-bis（diphenylmethlene）benzene-l,4-diamine zirconium （IV） chloride [{（Ar）2NC6H5N（Ar）2}ZrCl4] （Ar = C6H5） was obtained by stoichiometric addition of {（Ar）2NC6H5N（Ar）2} （Ar = C6H5） and {ZrC14} in ethanol at reflex temperature. IR, 1H NMR, electronic properties using hyperchem program study has been improved for this compound such as bond distance, and this compound was also defined as electric conductivity which proves to be useful for conductively compound.
基金supported by the Guangxi Provincial Department of Education(No.KY2015ZD130,YB2014414)the Natural Science Foundation of Guangxi Province(No.2014GXNSFBA118040)+2 种基金The supports of the National Natural Science Foundation of China(No.51402158)are gratefully acknowledgedthe financial support by the Opening Project of Guangxi Colleges and Universities Key Laboratory of Beibu Gulf Oil and Natural Gas Resource Effective Utilization(No.2015KLOG09)the financial support from the Natural Science Foundation of Qinzhou University(No.2014PY-GJ05)
文摘A new 3-D nickel（Ⅱ） metal-organic framework（MOFs） with formula [Ni（bib）_2（SO_4）]_n（1）, where bib = 1,4-bis（imidazol-1-yl）benzene, has been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and surface photovoltage spectroscopy（SPS）. Complex 1 crystallizes in monoclinic system, space group C2/c with a = 19.5988（6）, b = 9.7531（3）, c = 11.8146（4） ？, β = 96.185（3）°, V = 2245.20（12） ？~3, C_（24）H_（20）N_8NiO_4S, M_r = 575.25, D_c = 1.702 g/cm^3, Z = 4, F（000） = 1184, μ = 1.011 mm-1, the final R = 0.0293 and w R = 0.0702. X-ray diffraction analyses indicated that the center Ni^（2＋） ion is six-coordinated with an O_2N_4 donor set of two μ_2-SO_4^（2–） and four bib ligands, resulting in an ideal octahedral geometry. Topological analysis on complex 1 considers each Ni^（2＋） as a 6-connected node, while bib and sulfate ion as linkers, giving an α-Po topology with short Schl？fli symbol 412·63. In the crystal packing, the components interact with pairs of intermolecular C–H×××O hydrogen bonds. The SPS of 1 indicates that there are positive response bands in the range of 300~600 nm showing photo-electric conversion properties.
基金Supported by Nanjing University of Posts and Telecommunications (No. NY209032)the National Natural Science Foundation of China (No. 21001065)the Major State Basic Research Development Program of China (973 Program,No. 2009CB930600)
文摘The title coordination polymer 1,{[Cu8（btb）2（CN）8].3H2O}n（btb = 1,4-bis（1,2,4-triazol-1-yl）butane）,has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group C2/c with a = 1.2938（3）,b = 1.9422（5）,c = 0.9406（2） nm,β = 121.891（4）°,V = 2.0066（9） nm3,C24H30Cu8N20O3,Mr = 1155.00,Dc = 1.912 g/cm3,μ（MoKα） = 4.209 mm？1,F（000） = 1140,GOF = 1.184,Z = 2,the final R = 0.0634 and wR = 0.1503 for I 2σ（I）.In complex 1,one-dimensional CuCN zigzag chains are linked by triazolyl groups of btb ligands to form two-dimensional networks,which are further bridged by 1,4-butyl moieties of btb ligands to fabricate a three-dimensional order framework,in which one-dimensional ellipsoid-like channels are observed.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.20772028 and No.20472019）, the Natural Science Foundation of Hunan Province （No.06JJ2002）, and the Scientific Research Fund of Hunan Provincial Education Commission.
文摘A correlation equation between the UV absorption wavenumbers of 1,4-disubstituted benzenes and the excited-state substituent constant was obtained. For 80 sorts of 1,4- disubstituted benzenes, the correlation coefficient was 0.9805, and the standard deviation was only 672.27 cm^-1. The results imply that the excited-state substituent constant can be used productively for research on UV energy of 1,4-disubstituted benzenes. The present method provides a new avenue to study the UV absorption spectra of aromatic systems with the excited-state substituent constant, and it is helpful to understand the effect of substituent electrostatic effects on the chemical and physical properties of conjugated compounds with multiple substituents in excited state.
文摘An energetic salt of bis（l,5-diamino-lH-tetrazolium）3,3＂-bis（nitramino）-4, 4x-azo- furazan （C6H10N2206） was synthesized with the total yield of 61.7% by using 3,4-diaminofurazan （DAF） as the starting material. The structure of the title compound was confirmed by NMR, IR, elemental analysis and single-crystal X-ray diffraction. It crystallizes in orthorhombic, space group P21/c with a = 10.739（2）, b = 6.4765（12）, c = 14.138（3） A, fl= 108.787（3）°, V= 930.9（3） A3, Z = 1, Mr= 486.36, Dc = 1.735 g.cm3, μ= 0.15 mm-1, F（000） = 496, R = 0.042 and wR = 0.121. The thermal stability was analyzed by subsequently differential scanning calorimetry （DSC）. And the enthalpy of formation and detonation was calculated theoretically, showing the first decomposition temperature was 142.1℃, the enthalpy of formation was 1614.23 kJ.mol1 and the detonation velocity and detonation pressure were 8.781 km.s-1 and 30.7 GPa, respectively.
文摘The solid-liquid equilibria of musk ketone + musk xylene, musk xylene +l,3-dimethyl-2,4-dinitro-5-tert-butyl benzene are measured by differential scanning calorimeter (DSC), these systems are proved to be simple eutectics. Moreover the melting points and the fusion enthalpies of musk ketone, musk xylene and 1,3-dimethyl-2,4-dinitro-5-tert-butyl benzene are also measured by the DSC. These solid-liquid equilibrium data and the heats of fusion are reported for the first time. Then UNIFAC model is used to correlate the sofid-liquid equilibrium data. It is shown that the solid-liquid equilibria of musk systems can be predicted by the UNIFAC model.
基金supported by the Science and Technology Development Project of Jilin Provincial Science&Technology Department(201205080)the Science and Technology Research Projects of the Education Office of Jilin Province(No.2013.384)
文摘A new complex [Cd（hba）2（bib）]n·nH2O（1,Hhba = 3-hydroxybenzoic acid,bib = 1,4-bis（imidazol-1-yl）-butane） has been hydrothermally synthesized and characterized by elemental analysis,IR spectrum,thermogravimetric analysis,fluorescence spectrum,and singlecrystal X-ray diffraction.Yellow crystal crystallizes in the orthorhombic system,space group Pbca with a = 16.220（5）,b = 14.980（5）,c = 20.521（5） ？,V = 4986（3） ？~3,C（24）H（26）CdN4O7,Mr = 594.89,Dc = 1.585 g/cm^3,μ（Mo Kα） = 0.927 mm^（-1）,F（000） = 2416,Z = 8,the final R = 0.0242 and w R = 0.0589 for 4076 observed reflections（I 〉 2s（I））.In 1,the Cd（Ⅱ） ion takes a six-coordination mode,and bib ligand bridges adjacent Cd（Ⅱ） ions to generate 1D zigzag chains; these neighboring chains are connected by O–H···O hydrogen bonding interactions,producing a 2D folded layered structure.Furthermore,by O–H···O hydrogen bonding between layers and layers,a 3D supramolecular architecture is formed.In addition,we analyzed Natural Bond Orbital（NBO） in using the PBE0/LANL2 DZ method built in Gaussian 03 Program.The calculation results indicated obvious covalent interaction between the coordinated atoms and Cd（Ⅱ） ion.
文摘The optical properties of N,N’-bis (Inaphthyl)N,N’-diphenyl-1,1’-biphenyl-4,4’-diamine (NPB) and tris (8-hydroxyquinolinato) aluminum (Alq3) organic materials used as hole transport and electron transport layers in organic light-emitting devices (OLED) have been investigated. The NPB and Alq3 layers were prepared using thermal evaporation method. The results show that the energy band gap of Alq3 is thickness independence while the energy band gap of NPB decreases with the increasing of sample thickness. For the case of photoluminescence the Alq3 with thickness of 84 nm shows the highest relative intensity peak at 510 nm.
基金Supported by the National "973" project (No. 613740102)
文摘2,3-Bis（hydroxymethyl）-2,3-dinitro-1,4-butanediol（C6H12N2O8） was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the title compound was characterized by 1H NMR,13C NMR,FT-IR,elementary analysis,and X-ray single-crystal diffraction analysis,which reveals that the title compound crystallizes in triclinic,space group P with a = 0.6324（2）,b = 0.6454（3）,c = 0.7062（3） nm,α= 111.550（4）,β= 95.505（4）,γ= 113.395（4）°,V = 0.23595（16） nm3,Z = 1,Mr = 240.18,Dc = 1.690 g·cm-3,μ = 0.159 mm-1,F（000） = 126,R = 0.0304 and wR = 0.0907.
基金Supported by the National Natural Science Foundation of China(No.21263019 and 21467022)
文摘A new energetic complex,[Co（3,3？-Hbpt）（Htm）]·H_2O（1,3,3？-Hbpt = 3,5-bis（3-pyridyl）-1H-1,2,4-triazole and H_3tm = 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 P 1 with a = 10.0911（1）,b = 10.2573（1）,c = 10.6393（1） ？,α = 103.793（2）,β = 101.041（2）,γ = 107.918（3）o,V = 974.9（2） ？~3,Z = 2,D_c = 1.732 g·cm-3,μ = 0.941 mm^（-1）,M_r = 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.
基金supported by the research foundation of Hebei University of Science and Technology
文摘An efficient synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one is achieved via a reaction of acenaphthe-nequinone and indoles catalyzed by solid superacid SO4^2-/TiO2 under solvent-free conditions at room temperature by grinding, which provides an efficient route to the synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one.This procedure offers several advantages including solvent-free conditions,excellent yields of products,simple work-up as well as reuse of catalysts which makes it a useful and attractive protocol for the synthesis of these compounds.
基金This work is sponsored by the National Natural Science Foundation of China (No. 59473901).
文摘A new monomer of 4, 4-biphenyl-bis[4-phthalazin-1(2H)-one] was synthesized from biphenyl and phthalic anhydride, and a novel copoly(aryl ether ketone) (PPEK) was synthesized from 2, 2-bis(4-hydroxyphenyl)-propane (BPA), 4, 4'-biphenyl-bis-[4-phthalazin-1(2H)-one], 4, 4- difluorodiphenylketone (DFK). The monomer and copolymer were characterized by FT-IR and 1H-NMR. DSC and TGA were used to the novel polymer.
文摘Our previous research showed that aliphatic amines were put in order of high reactivity as “ethylamine > ammonia > t-butylamine > diethylamine” on the aromatic nucleophilic substitution of 1-dimetylamino-2,4-bis(trifluoroacetyl)-naphthalene 1 in acetonitrile. The DFT calculation study (B3LYP/6-31G* with solvation model) for the reactions of 1 with above four amines rationally explained the difference of each amines reactivity based on the energies of their Meisenheimer complexes 3 which are assumed to formed as the reaction intermediates in the course of the reaction giving the corresponding N-N exchange products 2. Intramolecular hydrogen bond between amino proton in 1-amino group and carbonyl oxygen in 2-trifluoroacetyl group stabilizes Meisenheimer complexes 3 effectively, and accelerates the substitution reaction from 1 to 2. Our calculation results also predicted that the above order of amines is also true if less polar toluene is used as a solvent instead of acetonitrile even though more enhanced conditions are required.
文摘A comparative thermal decomposition kinetic investigation on Fe(III) complexes of a antipyrine Schiff base ligand, 1,2-Bis(imino-4’-antipyrinyl)ethane (GA)), with varying counter anions viz. CIO4-, NO3-, SCN-, Cl-, and Br-, has been done by thermogravimetric analysis by using Coats-Redfern equation. The kinetic parameters like activation energy (E), pre-exponential factor (A) and entropy of activation (ΔS) were quantified. On comparing the various kinetic parameters, lower activation energy was observed in second stage as compared to first thermal decomposition stage. The same trend has been observed for pre-exponential factor (A) and entropy of activation (ΔS). The present results show that the starting materials having higher activation energy (E), are more stable than the intermediate products, however;the intermediate products possess well-ordered chemical structure due to their highly negative entropy of activation (ΔS) values. The present investigation proves that the counter anions play an important role on the thermal decomposition kinetics of the complexes.
文摘Sodium 3,5-bis(hydroxyimino)-1-methyl-2,4,6-trioxocyclohexanide C7H5N2NaO5 (I) has been isolated as the only product of the reaction of nitrosation of methylphloroglucinol. The structure of the titled compound has been determined from single crystal X-ray diffraction data. The hydrated C7H5N2NaO52.5H2O crystallizes in the monoclinic space group C2/c, with a(?) 16.408(3);b(?) 12.446(3);c(?) 13.716(3);(o) 126.34(3). The planar organic anion exists in a triketo-dihydroxyimino form with the C–O and C–N distances from 1.220(2) to 1.271(2)?? and from 1.292(2) to 1.293?? respectively. In the IR spectrum of I, the sharp absorption band occurred at 1681 cm-1 due to C=O stretching indicating the strong H-interactions. The correlations of theoretical (DFT-B3LYP/aug-cc-pVDZ) and experimental UV-vis absorption spectra in neutral and alkaline ethanolic solutions showed the existence of hydroxyimino-nitroso tautomerism while ionization of I.
基金supported by Education Chamber of Henan Province(No.15A150068)
文摘A Zn（Ⅱ） supramolecular coordination polymer, {[Zn2（L）2（m-bix）（H20）]6H2O}n（1）, with an interesting 1D→2D polythreading array from a flexible and angular organic aromaticpolycarboxylate ligand 5-（4-hydroxypyridinium-l-ylmethyl）isophthalic acid （H2L）, and N-donorligand 1,3-bis（imidazol-l-ylmethyl）benzene （m-bix）, has been obtained under hydrothermalconditions and characterized by elemental analysis, powder X-ray diffraction （PXRD）, IR, thermalgravimetric analyses （TGA） and single-crystal X-ray diffraction. In 1, the Zn（Ⅱ） center has twocoordination geometries. One exhibits a trigonal bipyramidal coordination sphere, and the other isa tetrahedral geometry; L2- has two different coordination modes, with one connecting three Zn（Ⅱ）ions through two monodentate carboxylate groups and the monodentate hydroxyl group, and theother bridging two Zn（Ⅱ） ions through two carboxylate groups. The L2- anions connect the Zn（Ⅱ）centers forming an infinite 1D tubular structure. These 1D tubes are interconnected by the m-bixspacers to form a 2D framework. Such 2D layers are further assembled into a 3D supramolecularnetwork via hydrogen bonds. Meanwhile, the luminescent property of 1 has also been investigatedin detail.
基金supported by the National Natural Science Foundation of China(20873150)the Natural Science Foundation of Shandong Province(ZR2010BL012,ZR2010BQ023)
文摘Hydrothermal reactions of three aromatic polycarboxylic acids and the transitional metal cations in the presence of phen and 1,4-bib afford three new coordination polymers： [Cd2（bpp）1.5（Hbpp）（phen）2]n （1）, [Mn3（Htptc）2（phen）2（H2O）2]n （2）, and {[Cu（btc）0.5（1,4- bib）]·2H2O}n（3） （H2bpp = 2,6-bis（4＇-carboxyphenyl）-4-phenylpyridine, H4tptc = terphenyl-2,5,2＇,5＇-tetracar- boxylic acid, H4btc =biphenyl-2,2＇,4,4＇-tetracarboxylic acid, phen =1,10-phenanthroline, and 1,4-bib = 1,4-bis（1H-imidazol-1-yl）benzene）. Their structures have been determined by single- crystal X-ray diffraction analyses, elemental analyses, IR spectra, and powder X-ray diffraction （PXRD） analyses. In compound 1, the CdII cations are linked by bpp2- to form one ladder structure, based on which a 3D network is constructed with the help of non-covalent interactions. The topology of 2 is a 3D （3,4,5）-connected framework with the Point Schl？fli symbol of （42.6）2（43.62.8）（45.64.8）2. Compound 3 shows an unprecedented 3D （4,4）-connected framework with the Point Schl？fli symbol of （64.82）2（65.8）. Moreover, the luminescent property of 1 has been investigated.
