The one-pot synthesis of dimethyl carbonate（DMC） with co-production of propy-lene carbonate（PC） and propylene glycol（PG） from propylene oxide（ PO）, carbon dioxide and methanol as the starting materials was inv...The one-pot synthesis of dimethyl carbonate（DMC） with co-production of propy-lene carbonate（PC） and propylene glycol（PG） from propylene oxide（ PO）, carbon dioxide and methanol as the starting materials was investigated. The catalyst adopted here was a mixture of tetrabutyl ammonium bromide and sodium methoxide. It was found that un- der the reaction conditions of t = 150 ℃, p =3-4 MPa and 2 h, the PO conversion could reach 100%, the DMC, PC and the PG selectivities were 49. 7%, 42. 7% and 49. 8%, respectively, and the selectivity of by-products was below 10%.展开更多
A new three-dimensional supramolecule composed of copper-Schiff base complex, [Cu（naphdien）]Cl·H2O, where naphdien is Schiff base of 2-hydroxy-1-naphthaldehyde and diethylenetriamine, has been synthesized and d...A new three-dimensional supramolecule composed of copper-Schiff base complex, [Cu（naphdien）]Cl·H2O, where naphdien is Schiff base of 2-hydroxy-1-naphthaldehyde and diethylenetriamine, has been synthesized and determined by single-crystal X-ray diffraction. It belongs to the monoclinic system, space group P21/c, with a = 7.3490（15）, b = 7.0847（16）, c = 30.845（3）A, β= 95.33（3）°, V = 1599.0（5）A3, Z = 4, C15 H20ClCuN3O2, Mr = 373.33, De = 1.551 g/cm3, μ = 1.543 mm^-1, F（000） = 772, R = 0.0536 and wR = 0.0927 for 2788 unique reflections with 1659 observed ones （I 〉2σ（I））. In the crystal structure, mononuclear units [Cu（naphdien）]Cl·H2O are linked into a two-dimensional framework via strong hydrogen bonds, and extended into a three-dimensional supramolecular structure through π-π stacking interactions.展开更多
Preparation method of photocatalyst, using TiCl4 and SnCl2 as raw material and photocatalytic activity of nano-scaled core-shell Sn^2＋ -doped titania photocatalyst was studied in this paper. The as-prepared samples w...Preparation method of photocatalyst, using TiCl4 and SnCl2 as raw material and photocatalytic activity of nano-scaled core-shell Sn^2＋ -doped titania photocatalyst was studied in this paper. The as-prepared samples were studied by UV-Vis, XRD, XPS, TEM. The particles of Sn^2＋-doped TiO2 photocatalyst, calcined from 150 to 600 ℃ for 5 h, possesses narrow particle size distribution and the sample was composed of anatase phase. Its photocatalytic efficiency was investigated by UV irradiation.展开更多
The title complex {[AgL]ClO4}n（L=2,5-bis（3-pyridinylmethylthio）-1,3,4-thiadiazole） was synthesized by the reaction of Ag（I） salt and a novel flexible ligand L.Its structure was determined by X-ray crystallograph...The title complex {[AgL]ClO4}n（L=2,5-bis（3-pyridinylmethylthio）-1,3,4-thiadiazole） was synthesized by the reaction of Ag（I） salt and a novel flexible ligand L.Its structure was determined by X-ray crystallography with the following data：monoclinic,space group P21/n,a=16.5068（13）,b=7.6548（4）,c=16.5521（13）A,β=115.119（3）o,V=1893.7（2）A^3,Z=4,Dc=1.893 g/cm^3,μ=1.565 mm^-1,F（000）=1072,C14H12AgClN4O4S3,Mr=539.78,T=293（2） K,S=1.067,the final R=0.0342 and wR=0.0870.The silver ion in the complex is in a trigonal coordination geometry to link three different L.Meanwhile,each L connects three different silver ions by its N coordination sites to form a two-dimensional layer structure.展开更多
A novel three-dimensional（3D） supramolecular architecture, {[Nd（OH-BDC）（OH-HBDC）（H2O）2]·2HaO）n（1） （OH-H2BDC=5-hydroxyisophthalic acid）, which was formed through hydrogen bonds and π-π stacking betw...A novel three-dimensional（3D） supramolecular architecture, {[Nd（OH-BDC）（OH-HBDC）（H2O）2]·2HaO）n（1） （OH-H2BDC=5-hydroxyisophthalic acid）, which was formed through hydrogen bonds and π-π stacking between two-dimensional（2D） layers, was hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Windmill building blocks, which consist of two nine-coordinated metal centers and four OH-H2BDC groups are connected through two carboxyl groups, to lead to a one-dimensional infinite inorganic chain（… M--O--C--O--M…） along the [100] direction. An observed intense blue luminescence with an emission band peaked at 390 nm for compound 1 may results from ligand-to-metal charge transfer（LMCT）. Variable-temperature magnetic susceptibility of compound 1 was investigated and the value was deviated from the Curie-Weiss law.展开更多
CPDT-TCNQ and its derivatives are good candidates for charge-transfer acceptors. In this work, the electronic ground and excited states of CPDT-TCNQ as well as its difluoro and dimethyl derivatives are studied. The gr...CPDT-TCNQ and its derivatives are good candidates for charge-transfer acceptors. In this work, the electronic ground and excited states of CPDT-TCNQ as well as its difluoro and dimethyl derivatives are studied. The ground state optimized structures and energies were obtained using a restricted （closed-shell） density functional theory （DFT） as approximated by the various hybrid functionals （RB3LYP, RB3P86, RB3PW91）. The 6-31G＊＊ and 6-31＋G＊＊ basis sets were employed in calculations. All derivatives are planar and exhibit a quinoid structure in their electronic ground states. The energy and oscillator strength of the first 15 singlet-singlet electronic transitions have been investigated by applying the dine-dependent density functional theory （TD-DFT） approximations to the correspondingly optimized ground state geometries. The results show the strongest absorption in electronic spectra of molecules due to the HOMO-LUMO electronic transition of the thiophene backbone.展开更多
Two complexes, [ Cu （salpn） ] · NH （ CH3 ）2 （ 1 ） and [Ni （ salpn ）·H20] （ 2 ） （ H2 salpn = N, N-bis（salicylidene）-propane-1,3-diamine） were characterized by IR, element analysis and single cry...Two complexes, [ Cu （salpn） ] · NH （ CH3 ）2 （ 1 ） and [Ni （ salpn ）·H20] （ 2 ） （ H2 salpn = N, N-bis（salicylidene）-propane-1,3-diamine） were characterized by IR, element analysis and single crystal X-ray diffraction analysis. Crystal data for complex 1 ： monoclinic, P21/C, a = 1. 097 4×10^-7 cm, b=1.4806x10-7 cm, c=1.0315×10^-7 cm, β=94.43（3）°. The Cu （II） ion in complex 1 is four coordinated with distorted square planar coordination geometry. The crystal structure of com- plex 1 consists of [ Cu（salpn）] coordination complex and a vip molecule NH（ CH3 ）2 that can act as both H-bonding donor and acceptor and plays an important role in constructing supramolecular ar- chitecture. Crystal structure data for complex 2： orthorhombic, Pnma, a = 8. 676 3 ×10^-8 cm, b = 2. 414 5 ×10^-7 cm, c = 7. 538 8×10^-8 cm. The Ni（II） ion in complex 2 is five-coordinated with a but- terfly coordination geometry. The coordinated water molecule plays a key role in hydrogen-bonded networks.展开更多
We study the interaction between a single-mode quantized field and a quantum system composed of two qubits. We suppose that two qubits initially be prepared in the mixed and separable state, and study how entanglement...We study the interaction between a single-mode quantized field and a quantum system composed of two qubits. We suppose that two qubits initially be prepared in the mixed and separable state, and study how entanglement between two qubits arises in the course of evolution according to the Jaynes-Cummings type interaction with nonclassical radiation field. We also investigate the relation between entanglement and purity of qubit subsystem. We show that different photon statistics have different effects on the dynamical behavior of the qubit subsystem. When the qubits are initially prepared in the maximally mixed and separable state, for coherent state field we cannot find entanglement between two qubits; for squeezed state field entanglement between two qubits exists in several short period of time; for even and odd coherent state fields of large photon number, the dynamical behavior of the entanglement between two qubits shows collapse and revival phenomenon. For odd coherent state field of small photon number, the entanglement with both qubits initially prepared in maximally mixed state can be stronger than that with both qubits initially prepared in pure states. For fields of small photon number, the entanglement strongly depends on the states they are initially prepared in. For coherent state field, and odd and even coherent state fields of large photon number, the entanglement only depends on the purity of the initial state of qubit subsystem. We also show that during the evolution the unentangled state may be purer than the entangled state, and the maximum degree of entanglement may not occur at the time when the qubit subsystem is in the purist state.展开更多
A novel 2D coordination polymer [Zn2（bim）4]n（1）（Hbim=benzimidazole） based on dihydrated- [N,N＇-bis（2-aminophenl）-oxalamide]（L1·2H2O） with zinc nitrate has been synthesized. Previously we have synthesiz...A novel 2D coordination polymer [Zn2（bim）4]n（1）（Hbim=benzimidazole） based on dihydrated- [N,N＇-bis（2-aminophenl）-oxalamide]（L1·2H2O） with zinc nitrate has been synthesized. Previously we have synthesized complexes [In：Zn3（im）12]n（2）（Him= imidazole） and [Zn（im）2]n（3） successfully. In complex 1, each Zn（Ⅱ） coordinated with four ligands adopts a distorted tetrahedron coordination mode, and the 2D grid structure is built by the Zn（bim）4 as the secondary building unit（SBU）. The luminescence properties of the three complexes were investigated for the first time. The emissions with maxima for complexes 1, 2 and 3 are at 379, 469 and 392 nm, respectively.展开更多
1-（1-Adamantylamino）-2,4,6-trinitrobenzene （1） as a potential energy material has been synthesized in excellent yield and characterized by FT-IR, 1H NMR and single crystallographic methods, and is thermally stable...1-（1-Adamantylamino）-2,4,6-trinitrobenzene （1） as a potential energy material has been synthesized in excellent yield and characterized by FT-IR, 1H NMR and single crystallographic methods, and is thermally stable, decomposed in the range of 215- 72℃.展开更多
New amphiphilic[60]fullerene monoadduct TPF and bisadducts BTPF were synthesized and well-characterized. Their aggregation properties in aqueous solution was investigated by UV-vis and TEM methods. In aqueous solution...New amphiphilic[60]fullerene monoadduct TPF and bisadducts BTPF were synthesized and well-characterized. Their aggregation properties in aqueous solution was investigated by UV-vis and TEM methods. In aqueous solution, monoadduct TPF forms irregularly shaped and some rod-like aggregates, whereas bisadducts BTPF gives sphadcal aggregates with diameters of 50-150 rim. It indicated that the aggregation properties of amphiphilic fullerene derivatives depend on the number of hydrophilic展开更多
Rational design and simple synthesis of one-dimensional nanofibers with high specific surface areas and hierarchically porous structures are still challenging. In the present work, a novel strategy utilizing a thermal...Rational design and simple synthesis of one-dimensional nanofibers with high specific surface areas and hierarchically porous structures are still challenging. In the present work, a novel strategy utilizing a thermally removable template was developed to synthesize hierarchically porous N-doped carbon nanofibers （HP-NCNFs） through the use of simple electrospinning technology coupled with subsequent pyrolysis. During the pyrolysis process, ZnO nanoparticles can be formed in situ and act as a thermally removable template due to their decomposition and sublimation under high-temperature conditions. The resulting HP-NCNFs have lengths of up to hundreds of micrometers with an average diameter of 300 nm and possess a hierarchically porous structure throughout. Such unique structures endow HP-NCNFs with a high specific surface area of up to 829.5 m2-g 1, which is 2.6 times higher than that （323.2 m2.g 1） of conventional N-doped carbon nanofibers （NCNFs）. Compared with conventional NCNFs, the HP-NCNF catalyst exhibited greatly enhanced catalytic performance and improved kinetics for the oxygen reduction reaction （ORR） in alkaline media. Moreover, the HP-NCNFs even showed better stability and stronger methanol crossover effect tolerance than the commerdal Pt-C catalyst. The optimized ORR performance can be attributed to the synergetic contribution of continuous and three-dimensional （3D） cross-linked structures, graphene-like structure on the edge of the HP- NCNFs, high specific surface area, and a hierarchically porous structure.展开更多
A novel and efficient photocatalyst, CdIn2S4, was simply prepared by a programmed temperature hydrothermal method. The product had a nanometer size （10-15 nm） and strong absorption in the range of 200 to 580 nm, and...A novel and efficient photocatalyst, CdIn2S4, was simply prepared by a programmed temperature hydrothermal method. The product had a nanometer size （10-15 nm） and strong absorption in the range of 200 to 580 nm, and it exhibited visible-light photocatalytic activity to decompose dye methyl orange in aqueous system.展开更多
Two novel complexes based on 2-aminopyridine and polyoxometalates （POMs） formulated as （C5H7N2）6- [PMo11^ⅤMo^ⅥO40（V^ⅥO）4]·H2O （1） and （C5H7N2）16[P2W18O61.5]2 （2） were hydrothermally synthesized and...Two novel complexes based on 2-aminopyridine and polyoxometalates （POMs） formulated as （C5H7N2）6- [PMo11^ⅤMo^ⅥO40（V^ⅥO）4]·H2O （1） and （C5H7N2）16[P2W18O61.5]2 （2） were hydrothermally synthesized and structurally characterized by elemental analysis, ICP, IR, UV-Vis, TG, ESR and single crystal X-ray diffraction methods. Complex 1 consists of a novel tetra-capped Keggin POMs, [PMo11^ⅤMo^ⅥO40（V^ⅣO）4]^6-, in which four [V^ⅣO5] square pyramids cap the equatorial positions of Keggin core [PMo11^ⅤMo^ⅥO40]^14-, linked together with six protohated 2-aminopyridine via hydrogen bonding interactions. Dawson and lacunary Dawson POMs, [P2W18O62]^6- and [P2W17O61]^10- coexist in complex 2, they link together with sixteen protonated 2-aminopyridine via hydrogen bonding interactions. Complex 2 exhibits photochromic property.展开更多
Three new compounds, namely, [Zn（mtpo）2（H2O）4]（l）, [Cd（mtpo）2-CH3CH2OH].（2） and [Mn（mtpo）2·CH3CH2OH]n（3）（Hmtpo=4,7-dihydro-5-methyl-7-oxo-[1,2,4]triazolo[1,5-a]pyrimidine）, have been synthesized v...Three new compounds, namely, [Zn（mtpo）2（H2O）4]（l）, [Cd（mtpo）2-CH3CH2OH].（2） and [Mn（mtpo）2·CH3CH2OH]n（3）（Hmtpo=4,7-dihydro-5-methyl-7-oxo-[1,2,4]triazolo[1,5-a]pyrimidine）, have been synthesized via hydrothermal or solvothermal methods and characterized by means of elemental analyses, Fourier transform infrared（FYIR） spectroscopy, powder X-ray diffraction（PXRD）, thermogravimetric analysis（TGA） and single-crystal X-ray diffraction. The results obtained from the single-crystal X-ray diffraction indicate that compound 1 has a mononuclear structure, and crystallizes in a monoclinic crystal system with P21/c space group, which exhibits a 2D supramolecular network constructed by hydrogen bonds and π-π interactions. Compounds 2 and 3 are isomorphous and crystallize in a tetragonal system with space group of I41/a. The M^2＋（M=Cd, Mn） ions in compounds 2 and 3 have the octahedral coordination geometry. Hmtpo acts as a bridging ligand linking the metal ions to form an infinite 3D framework with 4-connected {4^2·8^4} topology. There are hydrogen bonds between the vip ethanol molecules and the mtpo ligands, which make the ethanol molecules exist in a 3D framework. In addition, luminescent properties of compounds 1 and 2 as well as magnetic property of compound 3 were investigated and water vapor adsorption and nitrogen sorption for compounds 2 and 3 were researched at 298 and 77 K, respectively.展开更多
A three-dimensional complex [Cu（3-ampy）（HEO）4]（SO4）·（H2O） （3-ampy = 3-amino- pyridine） has been synthesized. Crystallographic data： C5H16CuN2O9S, Mr = 343.80, triclinic, space group P1, a = 7.675（2）,...A three-dimensional complex [Cu（3-ampy）（HEO）4]（SO4）·（H2O） （3-ampy = 3-amino- pyridine） has been synthesized. Crystallographic data： C5H16CuN2O9S, Mr = 343.80, triclinic, space group P1, a = 7.675（2）, b = 8.225（3）, c = 10.845（3）A, α= 86.996（4）, β = 76.292（4）, γ= 68.890（4）°, V = 620.0（3）A^3, Z = 2, Dc = 1.841 g/cm^3, F（000） = 354 and μ = 1.971 mm^-1. The structure was refined to R = 0.0269 and wR = 0.0659 for 1838 observed reflections （I 〉 2a（/））. The structure consists of [Cu（3-ampy）（H2O）4]^2＋ cations, SO4^2- anions and lattice water molecules. 3-Ampy acting as a bidentate bridging ligand generates a 1D covalent chain. A supramolecular 2D framework is formed through π-π stacking of pyridine rings. The lattice water molecules and SO4^2- anions are located between the adjacent 2D frameworks. The hydrogen bonding interactions from lattice water molecules and SO4^2- anions to coordinate water extend the 2D framework into a 3D network.展开更多
Three new Keggin polyoxometalates, [Zn（phen）3]2[SiW12O40]＇5H2O（1）, [Co（phen）3]2[SiW12O40]（2） and [Ni（phen）3]2[SiW12O40].2H2O（3）（phen=1,10＇-phenanthroline） have been hydrothermally synthesized and chara...Three new Keggin polyoxometalates, [Zn（phen）3]2[SiW12O40]＇5H2O（1）, [Co（phen）3]2[SiW12O40]（2） and [Ni（phen）3]2[SiW12O40].2H2O（3）（phen=1,10＇-phenanthroline） have been hydrothermally synthesized and characterized by elemental analysis, IR, crystal X-ray diffraction, thermogravimetric analyses（TGA） and fluorescence tech- niques. Complex 1, crystallized in the triclinic space group Pi, consists of one [SiW12O40]4 anion, two discrete [Zn（phen）3]^2＋ cations and five crystal water molecules. Complexes 2 and 3 have the similar configuration to complex 1, but they crystallized in the monoclinic space group C2/c. Variable-temperature magnetic susceptibilities of complexess 2 and 3 reveal antiferromagnetism and ferromagnetism, respectively.展开更多
Three novel isostructural complexes M（gatx）2（H2O）2·4H2O [gatx=gatifloxacin, M = Zn （1）, Ni （2） and Co （3）] were synthesized at room temperature and structurally characterized by elemental analysis, IR a...Three novel isostructural complexes M（gatx）2（H2O）2·4H2O [gatx=gatifloxacin, M = Zn （1）, Ni （2） and Co （3）] were synthesized at room temperature and structurally characterized by elemental analysis, IR and single crystal X-ray diffraction, which exhibit a similar mononuclear structure, in which the metal ion is coordinated by two gatifloxacin and two aqua ligands to furnish a distorted octahedral geometry, and show different activities against staphylococcus due to the different metal ions in the structures.展开更多
Cu2O nanocubes and Cu nanoparticles were prepared by reducing Cu（ Ⅱ ） salt with ethanol as the reducing agent and solvent in the presence of multidentate ligand poly（vinylpyrrolidone） （PVP） under different cond...Cu2O nanocubes and Cu nanoparticles were prepared by reducing Cu（ Ⅱ ） salt with ethanol as the reducing agent and solvent in the presence of multidentate ligand poly（vinylpyrrolidone） （PVP） under different conditions. The morphologies and the crystalline structures of the products were characterized by using scanning electron microscopy （SEM）, transmission electron microscopy（TEM）, selected-area electron diffraction（ SAED）, and powder X-ray diffraction（XRD）. In particular, the influences of the solvothennal reaction temperature and alkalinity on the products were investigated. A lower temperature and a lower alkali concentration favor the formation of the Cu2O phase, whereas a higher temperature and a higher alkali concentration generally lead to the formation of the Cu phase.展开更多
文摘The one-pot synthesis of dimethyl carbonate（DMC） with co-production of propy-lene carbonate（PC） and propylene glycol（PG） from propylene oxide（ PO）, carbon dioxide and methanol as the starting materials was investigated. The catalyst adopted here was a mixture of tetrabutyl ammonium bromide and sodium methoxide. It was found that un- der the reaction conditions of t = 150 ℃, p =3-4 MPa and 2 h, the PO conversion could reach 100%, the DMC, PC and the PG selectivities were 49. 7%, 42. 7% and 49. 8%, respectively, and the selectivity of by-products was below 10%.
基金This work was supported by the National Natural Science Foundation of China (Nos. 20671011, 20331010, 90406002 and 90406024)the 111 Project (B07012) and Key Laboratory of Structural Chemistry Foundation (No. 060017)
文摘A new three-dimensional supramolecule composed of copper-Schiff base complex, [Cu（naphdien）]Cl·H2O, where naphdien is Schiff base of 2-hydroxy-1-naphthaldehyde and diethylenetriamine, has been synthesized and determined by single-crystal X-ray diffraction. It belongs to the monoclinic system, space group P21/c, with a = 7.3490（15）, b = 7.0847（16）, c = 30.845（3）A, β= 95.33（3）°, V = 1599.0（5）A3, Z = 4, C15 H20ClCuN3O2, Mr = 373.33, De = 1.551 g/cm3, μ = 1.543 mm^-1, F（000） = 772, R = 0.0536 and wR = 0.0927 for 2788 unique reflections with 1659 observed ones （I 〉2σ（I））. In the crystal structure, mononuclear units [Cu（naphdien）]Cl·H2O are linked into a two-dimensional framework via strong hydrogen bonds, and extended into a three-dimensional supramolecular structure through π-π stacking interactions.
基金The National Natural Science Foundation of China(No.20271007 and 20331010)Specialized Research Fund for the Doctoral Program of Higher Education(No.20030007014)are acknowledged for financial support.
文摘Preparation method of photocatalyst, using TiCl4 and SnCl2 as raw material and photocatalytic activity of nano-scaled core-shell Sn^2＋ -doped titania photocatalyst was studied in this paper. The as-prepared samples were studied by UV-Vis, XRD, XPS, TEM. The particles of Sn^2＋-doped TiO2 photocatalyst, calcined from 150 to 600 ℃ for 5 h, possesses narrow particle size distribution and the sample was composed of anatase phase. Its photocatalytic efficiency was investigated by UV irradiation.
基金Supported by the National Natural Science Foundation of China (Nos 20801004/B01, 20871016/B0101, 10876002/A06)the 111 Project (B07012)Excellent Young Scholars Research Fund of Beijing Institute of Technology (No 2006Y0715)
文摘The title complex {[AgL]ClO4}n（L=2,5-bis（3-pyridinylmethylthio）-1,3,4-thiadiazole） was synthesized by the reaction of Ag（I） salt and a novel flexible ligand L.Its structure was determined by X-ray crystallography with the following data：monoclinic,space group P21/n,a=16.5068（13）,b=7.6548（4）,c=16.5521（13）A,β=115.119（3）o,V=1893.7（2）A^3,Z=4,Dc=1.893 g/cm^3,μ=1.565 mm^-1,F（000）=1072,C14H12AgClN4O4S3,Mr=539.78,T=293（2） K,S=1.067,the final R=0.0342 and wR=0.0870.The silver ion in the complex is in a trigonal coordination geometry to link three different L.Meanwhile,each L connects three different silver ions by its N coordination sites to form a two-dimensional layer structure.
基金the National Natural Science Foundation of China(Nos.20371007 and 20476011)
文摘A novel three-dimensional（3D） supramolecular architecture, {[Nd（OH-BDC）（OH-HBDC）（H2O）2]·2HaO）n（1） （OH-H2BDC=5-hydroxyisophthalic acid）, which was formed through hydrogen bonds and π-π stacking between two-dimensional（2D） layers, was hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Windmill building blocks, which consist of two nine-coordinated metal centers and four OH-H2BDC groups are connected through two carboxyl groups, to lead to a one-dimensional infinite inorganic chain（… M--O--C--O--M…） along the [100] direction. An observed intense blue luminescence with an emission band peaked at 390 nm for compound 1 may results from ligand-to-metal charge transfer（LMCT）. Variable-temperature magnetic susceptibility of compound 1 was investigated and the value was deviated from the Curie-Weiss law.
基金This work was supported by the Science Research Foundation of Yangtze University
文摘CPDT-TCNQ and its derivatives are good candidates for charge-transfer acceptors. In this work, the electronic ground and excited states of CPDT-TCNQ as well as its difluoro and dimethyl derivatives are studied. The ground state optimized structures and energies were obtained using a restricted （closed-shell） density functional theory （DFT） as approximated by the various hybrid functionals （RB3LYP, RB3P86, RB3PW91）. The 6-31G＊＊ and 6-31＋G＊＊ basis sets were employed in calculations. All derivatives are planar and exhibit a quinoid structure in their electronic ground states. The energy and oscillator strength of the first 15 singlet-singlet electronic transitions have been investigated by applying the dine-dependent density functional theory （TD-DFT） approximations to the correspondingly optimized ground state geometries. The results show the strongest absorption in electronic spectra of molecules due to the HOMO-LUMO electronic transition of the thiophene backbone.
基金Supported by the National Natural Science Fundation of China(20771014,21071018)the Specialized Research Fund for the Doctoral Program of Higher Education,State Education Ministry of China(20091101110038)
文摘Two complexes, [ Cu （salpn） ] · NH （ CH3 ）2 （ 1 ） and [Ni （ salpn ）·H20] （ 2 ） （ H2 salpn = N, N-bis（salicylidene）-propane-1,3-diamine） were characterized by IR, element analysis and single crystal X-ray diffraction analysis. Crystal data for complex 1 ： monoclinic, P21/C, a = 1. 097 4×10^-7 cm, b=1.4806x10-7 cm, c=1.0315×10^-7 cm, β=94.43（3）°. The Cu （II） ion in complex 1 is four coordinated with distorted square planar coordination geometry. The crystal structure of com- plex 1 consists of [ Cu（salpn）] coordination complex and a vip molecule NH（ CH3 ）2 that can act as both H-bonding donor and acceptor and plays an important role in constructing supramolecular ar- chitecture. Crystal structure data for complex 2： orthorhombic, Pnma, a = 8. 676 3 ×10^-8 cm, b = 2. 414 5 ×10^-7 cm, c = 7. 538 8×10^-8 cm. The Ni（II） ion in complex 2 is five-coordinated with a but- terfly coordination geometry. The coordinated water molecule plays a key role in hydrogen-bonded networks.
文摘We study the interaction between a single-mode quantized field and a quantum system composed of two qubits. We suppose that two qubits initially be prepared in the mixed and separable state, and study how entanglement between two qubits arises in the course of evolution according to the Jaynes-Cummings type interaction with nonclassical radiation field. We also investigate the relation between entanglement and purity of qubit subsystem. We show that different photon statistics have different effects on the dynamical behavior of the qubit subsystem. When the qubits are initially prepared in the maximally mixed and separable state, for coherent state field we cannot find entanglement between two qubits; for squeezed state field entanglement between two qubits exists in several short period of time; for even and odd coherent state fields of large photon number, the dynamical behavior of the entanglement between two qubits shows collapse and revival phenomenon. For odd coherent state field of small photon number, the entanglement with both qubits initially prepared in maximally mixed state can be stronger than that with both qubits initially prepared in pure states. For fields of small photon number, the entanglement strongly depends on the states they are initially prepared in. For coherent state field, and odd and even coherent state fields of large photon number, the entanglement only depends on the purity of the initial state of qubit subsystem. We also show that during the evolution the unentangled state may be purer than the entangled state, and the maximum degree of entanglement may not occur at the time when the qubit subsystem is in the purist state.
基金Supported by the National Natural Science Foundation of China(Nos. 20771013/B0101, 20476011).
文摘A novel 2D coordination polymer [Zn2（bim）4]n（1）（Hbim=benzimidazole） based on dihydrated- [N,N＇-bis（2-aminophenl）-oxalamide]（L1·2H2O） with zinc nitrate has been synthesized. Previously we have synthesized complexes [In：Zn3（im）12]n（2）（Him= imidazole） and [Zn（im）2]n（3） successfully. In complex 1, each Zn（Ⅱ） coordinated with four ligands adopts a distorted tetrahedron coordination mode, and the 2D grid structure is built by the Zn（bim）4 as the secondary building unit（SBU）. The luminescence properties of the three complexes were investigated for the first time. The emissions with maxima for complexes 1, 2 and 3 are at 379, 469 and 392 nm, respectively.
基金the Natural Science Fund Council of China(Nos.20671011 and 20731002)the 111 Project(B07012),Key Laboratory of Structural Chemistry Foundation(No.060017)+1 种基金Excellent Young Scholars Research Fund of Beijing Institute of Technology(No.2006Y0715)Basic Research Fund of Beijing Institute of Technology(Nos.20060742022 and 20070742010).
文摘1-（1-Adamantylamino）-2,4,6-trinitrobenzene （1） as a potential energy material has been synthesized in excellent yield and characterized by FT-IR, 1H NMR and single crystallographic methods, and is thermally stable, decomposed in the range of 215- 72℃.
基金the National Natural Science Foundation of China(No.20503039)the Scientinc Research Starting Foundation of Department of Chemistry,Renmin University of China.
文摘New amphiphilic[60]fullerene monoadduct TPF and bisadducts BTPF were synthesized and well-characterized. Their aggregation properties in aqueous solution was investigated by UV-vis and TEM methods. In aqueous solution, monoadduct TPF forms irregularly shaped and some rod-like aggregates, whereas bisadducts BTPF gives sphadcal aggregates with diameters of 50-150 rim. It indicated that the aggregation properties of amphiphilic fullerene derivatives depend on the number of hydrophilic
基金This work wassupported by the Natural Science Foundation Council of China （No.20271007 and 20331010）and Specialized Research Fund for the Doctoral Program of Higher Education （No.20030007014）
基金This work was financially supported by the National Natural Science Foundation of China （Nos. 21471016 and 21271023） and the 111 Project （No. B07012）.
文摘Rational design and simple synthesis of one-dimensional nanofibers with high specific surface areas and hierarchically porous structures are still challenging. In the present work, a novel strategy utilizing a thermally removable template was developed to synthesize hierarchically porous N-doped carbon nanofibers （HP-NCNFs） through the use of simple electrospinning technology coupled with subsequent pyrolysis. During the pyrolysis process, ZnO nanoparticles can be formed in situ and act as a thermally removable template due to their decomposition and sublimation under high-temperature conditions. The resulting HP-NCNFs have lengths of up to hundreds of micrometers with an average diameter of 300 nm and possess a hierarchically porous structure throughout. Such unique structures endow HP-NCNFs with a high specific surface area of up to 829.5 m2-g 1, which is 2.6 times higher than that （323.2 m2.g 1） of conventional N-doped carbon nanofibers （NCNFs）. Compared with conventional NCNFs, the HP-NCNF catalyst exhibited greatly enhanced catalytic performance and improved kinetics for the oxygen reduction reaction （ORR） in alkaline media. Moreover, the HP-NCNFs even showed better stability and stronger methanol crossover effect tolerance than the commerdal Pt-C catalyst. The optimized ORR performance can be attributed to the synergetic contribution of continuous and three-dimensional （3D） cross-linked structures, graphene-like structure on the edge of the HP- NCNFs, high specific surface area, and a hierarchically porous structure.
基金This work was financially supported by NNSFC(No.20271007).
文摘A novel and efficient photocatalyst, CdIn2S4, was simply prepared by a programmed temperature hydrothermal method. The product had a nanometer size （10-15 nm） and strong absorption in the range of 200 to 580 nm, and it exhibited visible-light photocatalytic activity to decompose dye methyl orange in aqueous system.
基金Project supported by the National Natural Science Foundation of China （Nos. 20271007. 20331010 and 90406002） and the Specialized Research Fund for the Doctoral Program of Higher Education of China （No. 20030007014）. Dedicated to Professor Xikui Jiang on the occasion of his 80th birthday.
文摘Two novel complexes based on 2-aminopyridine and polyoxometalates （POMs） formulated as （C5H7N2）6- [PMo11^ⅤMo^ⅥO40（V^ⅥO）4]·H2O （1） and （C5H7N2）16[P2W18O61.5]2 （2） were hydrothermally synthesized and structurally characterized by elemental analysis, ICP, IR, UV-Vis, TG, ESR and single crystal X-ray diffraction methods. Complex 1 consists of a novel tetra-capped Keggin POMs, [PMo11^ⅤMo^ⅥO40（V^ⅣO）4]^6-, in which four [V^ⅣO5] square pyramids cap the equatorial positions of Keggin core [PMo11^ⅤMo^ⅥO40]^14-, linked together with six protohated 2-aminopyridine via hydrogen bonding interactions. Dawson and lacunary Dawson POMs, [P2W18O62]^6- and [P2W17O61]^10- coexist in complex 2, they link together with sixteen protonated 2-aminopyridine via hydrogen bonding interactions. Complex 2 exhibits photochromic property.
基金Supported by the National Natural Science Foundation of China（Nos.21271024, 20971014） and the Natural Science Foundation of Beijing City, China（No.2112037）.
文摘Three new compounds, namely, [Zn（mtpo）2（H2O）4]（l）, [Cd（mtpo）2-CH3CH2OH].（2） and [Mn（mtpo）2·CH3CH2OH]n（3）（Hmtpo=4,7-dihydro-5-methyl-7-oxo-[1,2,4]triazolo[1,5-a]pyrimidine）, have been synthesized via hydrothermal or solvothermal methods and characterized by means of elemental analyses, Fourier transform infrared（FYIR） spectroscopy, powder X-ray diffraction（PXRD）, thermogravimetric analysis（TGA） and single-crystal X-ray diffraction. The results obtained from the single-crystal X-ray diffraction indicate that compound 1 has a mononuclear structure, and crystallizes in a monoclinic crystal system with P21/c space group, which exhibits a 2D supramolecular network constructed by hydrogen bonds and π-π interactions. Compounds 2 and 3 are isomorphous and crystallize in a tetragonal system with space group of I41/a. The M^2＋（M=Cd, Mn） ions in compounds 2 and 3 have the octahedral coordination geometry. Hmtpo acts as a bridging ligand linking the metal ions to form an infinite 3D framework with 4-connected {4^2·8^4} topology. There are hydrogen bonds between the vip ethanol molecules and the mtpo ligands, which make the ethanol molecules exist in a 3D framework. In addition, luminescent properties of compounds 1 and 2 as well as magnetic property of compound 3 were investigated and water vapor adsorption and nitrogen sorption for compounds 2 and 3 were researched at 298 and 77 K, respectively.
基金the Natural Science Found Council of China (Nos. 20671011, 20331010, 90406002 and 90406024) the Key Laboratory of Structural Chemistry Foundation (No. 060017)
文摘A three-dimensional complex [Cu（3-ampy）（HEO）4]（SO4）·（H2O） （3-ampy = 3-amino- pyridine） has been synthesized. Crystallographic data： C5H16CuN2O9S, Mr = 343.80, triclinic, space group P1, a = 7.675（2）, b = 8.225（3）, c = 10.845（3）A, α= 86.996（4）, β = 76.292（4）, γ= 68.890（4）°, V = 620.0（3）A^3, Z = 2, Dc = 1.841 g/cm^3, F（000） = 354 and μ = 1.971 mm^-1. The structure was refined to R = 0.0269 and wR = 0.0659 for 1838 observed reflections （I 〉 2a（/））. The structure consists of [Cu（3-ampy）（H2O）4]^2＋ cations, SO4^2- anions and lattice water molecules. 3-Ampy acting as a bidentate bridging ligand generates a 1D covalent chain. A supramolecular 2D framework is formed through π-π stacking of pyridine rings. The lattice water molecules and SO4^2- anions are located between the adjacent 2D frameworks. The hydrogen bonding interactions from lattice water molecules and SO4^2- anions to coordinate water extend the 2D framework into a 3D network.
基金Supported by the National Natural Science Foundation of China(Nos.20771013, 20476011 and 20371007)
文摘Three new Keggin polyoxometalates, [Zn（phen）3]2[SiW12O40]＇5H2O（1）, [Co（phen）3]2[SiW12O40]（2） and [Ni（phen）3]2[SiW12O40].2H2O（3）（phen=1,10＇-phenanthroline） have been hydrothermally synthesized and characterized by elemental analysis, IR, crystal X-ray diffraction, thermogravimetric analyses（TGA） and fluorescence tech- niques. Complex 1, crystallized in the triclinic space group Pi, consists of one [SiW12O40]4 anion, two discrete [Zn（phen）3]^2＋ cations and five crystal water molecules. Complexes 2 and 3 have the similar configuration to complex 1, but they crystallized in the monoclinic space group C2/c. Variable-temperature magnetic susceptibilities of complexess 2 and 3 reveal antiferromagnetism and ferromagnetism, respectively.
基金Project supported by the Natural Science Young Scholars Foundation of Chongqing University, the National Natural Science Foundation of China （No. 20331010） and Chongqing University Postgraduates＇ Science and Innovation Fund.
文摘Three novel isostructural complexes M（gatx）2（H2O）2·4H2O [gatx=gatifloxacin, M = Zn （1）, Ni （2） and Co （3）] were synthesized at room temperature and structurally characterized by elemental analysis, IR and single crystal X-ray diffraction, which exhibit a similar mononuclear structure, in which the metal ion is coordinated by two gatifloxacin and two aqua ligands to furnish a distorted octahedral geometry, and show different activities against staphylococcus due to the different metal ions in the structures.
基金Supported by the National Natural Science Foundation of China(Nos. 20331010 and 90406002) and Specialized ResearchFund for the Doctoral Program of Higher Education(No. 20030007014).
文摘Cu2O nanocubes and Cu nanoparticles were prepared by reducing Cu（ Ⅱ ） salt with ethanol as the reducing agent and solvent in the presence of multidentate ligand poly（vinylpyrrolidone） （PVP） under different conditions. The morphologies and the crystalline structures of the products were characterized by using scanning electron microscopy （SEM）, transmission electron microscopy（TEM）, selected-area electron diffraction（ SAED）, and powder X-ray diffraction（XRD）. In particular, the influences of the solvothennal reaction temperature and alkalinity on the products were investigated. A lower temperature and a lower alkali concentration favor the formation of the Cu2O phase, whereas a higher temperature and a higher alkali concentration generally lead to the formation of the Cu phase.
