两种具有三维孔道结构有机模板稀土硫酸盐的合成、表征及性质研究

本文分别采用水热和溶剂热的方法,以乙二胺和哌嗪为有机模板剂分别合成了两种新的三维孔道结构的稀土硫酸盐[Gd2(SO4)5(H2O)2][C2N2H10]2(1),[Eu2(SO4)5(H2O)2][C4N2H12]2(2),并且通过单晶X射线衍射、元素分析、红外、热重对两种化合物进行了表征。化合物1和2都属于单斜晶系,P21/c空间群。化合物1:a=0.652 1(4)nm,b=1.692 0(9)nm,c=2.023 3(11)nm,β=95.168(7)°,Z=4。化合物2:a=1.972 1(2)nm,b=1.927 1(2)nm,c=1.323 20(14)nm,β=92.307 0(10)°,Z=8。单晶结构分析表明,这两种化合物的无机骨架都是由SO4连接具有交替十六元环与八元环二维层形成的三维孔道结构。化合物2的固体荧光分析表明,在396 nm的激发波长下表现出Eu3+的特有发光性质。     

A New 3-D Lanthanide Porphyrin: Synthesis,Structure and Photophysical Properties

A new lanthanide porphyrin, [Sm III(H3TPPSIII)]n·n H2O(1, H6 TPPS = tetra(4-sulfonatophenyl)porphyrin), has been synthesized through a hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the P4/mcc space group of tetragonal system: a = 15.3683(12), c = 9.895(2) A, V = 2337.0(5) A3, C44H29N4O13S4 Sm, Mr =1100.30, Z = 2, Dc = 1.564 g/cm3, S = 1.063, μ(Mo Kα) = 1.502 mm–1, F(000) = 1102, R = 0.0583 and w R = 0.1666. Compound 1 is characteristic of a three-dimensional(3-D) framework with a slightly distorted square-antiprism eight-coordinated Sm3+ ion. Fluorescent study revealed that compound 1exhibits an emission in the red region. The fluorescence quantum yield and lifetime of 1 were determined to be 3.5% and 9.1 ns, respectively. UV-vis absorption spectra were also investigated.     

Hydrothermal Synthesis and Crystal Structure of a New 3-D Open-framework Zincophosphate

An open-framework zincophosphate, [C4N3H16][Zn4.5（PO4）4] 1, has been hydro- thermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in the tetragonal space group P4 with a = 14.512（5）, c = 8.914（3）A, V = 1877.3（11）A3, C4H16NaO16P4Zn4.50, Mr = 780 24： Z = 4, Dc = 2.761 g/cm^3,μ= 6.103 mm^-1, F（000） = 1536, T = 298（2） K, R = 0.0416 and wR = 0.0816. In the structure, ZnO4 and PO4 tetrahedra are linked to each other, forming four-membered rings which are connected variably to form two secondary building units （SBUs）. The SBUs are connected so as to generate two chains along the c axis, which are further linked together alternatively via common oxygen atoms （Zn-O-P） giving rise to 8-ring-channels in the [001] direction, and the protonated guest diethylenetriamine （DETA） molecules sit in the middle of these channels. Other characterizations are also described by elemental analysis, thermal analysis and IR and fluorescent spectra.     

Synthesis,Structural Characterization,and Optical Properties of Benzene-Fused Tetracyclic and Pentacyclic Stiboles

The expectation that antimony (Sb) compounds should display phosphorescence emissions based on the “heavy element effect” prompted our interest in the introduction of antimony to a biaryl as the bridging atom in a fused heterole system. Herein, the synthesis, molecular structures, and optical properties of novel benzene-fused heteroacenes containing antimony or arsenic atoms are described. The stiboles and arsole were prepared by the condensation of dibromo(phenyl)stibane or dichloro(phenyl)arsine with dilithium intermediates derived from the corresponding dibromo compounds. Nuclear magnetic resonance (NMR) spectroscopy and X-ray crystal analysis revealed that the linear pentacyclic stibole was highly symmetric in both the solution and crystal states. In contrast, the curved pentacyclic stibole adopted a helical structure in solution, and surprisingly, only M helical molecules were crystallized from the racemate. All synthesized compounds produced very weak or no emissions at room temperature or in the solid state. In contrast, the linear penta- and tetracyclic stiboles exhibited clear phosphorescence emissions in the CHCl₃ frozen matrix at 77 K under aerobic conditions.     

Hydrothermal Synthesis, Crystal Structure and Luminescent Properties of an Organically Templated 2-D Uranyl Sulfate

An organically templated 2-D uranyl sulfate, {（C2H8N）[（UO2）Cl（SO4）（H2O）] }n 1, has been hydrothermally synthesized. The crystal and molecular structures have been determined by X-ray crystallography method and spectral techniques. 1 belongs to monoclinic, space group P21/c with a = 8.3545（17）, b = 10.550（2）, c = 12.370（3）A, β = 102.64（3）°, V = 1063.9（4）A3, Mr = 464.64, De= 2.901 g/cm^3, F（000） = 836,μ = 15.710 mm^-1, Z= 4, the final R = 0.0286 and wR = 0.0685 for 10164 observed reflections with Ⅰ 〉 2σ（Ⅰ）. 1 presents a two-dimensional layer-like structure constructed from infinite anionic [（UO2）Cl（H2O）（SO4）]^- layers with [C2H8N]^＋ cations balancing the charge and a number of intermoleeular hydrogen bonds （C-H…O and O-H…Cl） existing in the solid state. The fluorescence properties of 1 have also been discussed.     

Synthesis,Structure Characterization,and Optical Properties of the Aluminosilicate Li2Na3AlSi2O8

The aluminosilicate Li₂Na₃AlSi₂O₈ was crystallized from the Li₂CO₃–H₃BO₃ flux system. It crystallizes in the orthorhombic space group Cmca, with cell dimensions a = 14.1045 (19) Å, b = 14.7054 (19) Å, c = 7.0635 (9) Å, and Z = 8. The crystal structure consists of a two‐dimensional infinite layer, which is composed of [Al₂Si₂O₁₂] groups and [SiO₄] tetrahedra. The lithium and sodium atoms filling in the interlayer and intralayer link the layers together and balance the charge. IR spectroscopy and BVS calculations were used to verify the validity of the structure. The calculated band structures and the density of states of Li₂Na₃AlSi₂O₈ suggest that its direct gap is 4.28 eV.     

Hydrothermal Synthesis and Crystal Structure of a Novel 3-D Porous Lanthanum Sulfate

A new lanthanum compound with three-dimensional channels, La₂(H₂O)(SO₄)₃ has been synthesized hydrothermally by using 1,2-dizminiopnopane as a structure-directing agent (SDA). The colorless block crystals were characterized by IR, TGA, ICP and XRD. The structure was determined by single-crystal diffraction. The title compound crystallizes in the orthorhombic, P2₁2₁2₁(No. 19) with cell parameters, a = 17.095(3) ?, b = 17.331(3) ?, c = 6.8633(12) ?, V = 1659.0(8) ?³, Z = 4, R = 0.0545, wR = 0.1246. The open framework of title compound is built up by LaO₁₀, LaO₉ polyhedra and SO₄ tetrahedra, connected to form interesting eight-membered ring channels along crystallographic a axis.     

基于金纳米棒的核壳纳米结构及其光学性质研究

以金纳米棒为核的核壳结构纳米粒子由于它独特的光学性质、结构特点以及在催化、表面增强拉曼散射方面的应用前景,成为目前纳米材料研究的热点之一。本文重点介绍以金纳米棒为核,包覆其他无机材料的核/壳结构之合成方法,同时阐述其结构特征、光学性质以及外界条件对结构和性质的影响。其中,由于金银纳米核壳结构的研究开始最早,研究最为深入,故对其进行重点阐述。最后对以金纳米棒为核的核壳结构未来研究进行了展望。     

Synthesis,Optical Properties,and Electronic Structures of Fully Core‐Modified Porphyrin Dications and Isophlorins

The synthesis, structures, optical properties, and electronic structures of the tetraphenyltetrathiaporphyrin dication (S₄TPP²⁺, 6 ) and tetrakis(pentafluorophenyl)tetrathiaisophlorin (S₄F₂₀TPP, 7 ) are reported. S₄TPP²⁺ ( 6 ) and S₄F₂₀TPP ( 7 ) were synthesized by acid‐catalyzed condensation of the corresponding hydroxylmethylthiophene, followed by oxidation. The electronic structures of S₄TPP²⁺ ( 6 ) and S₄F₂₀TPP ( 7 ) were analyzed by using UV/Vis‐absorption spectroscopy and by magnetic circular dichroism (MCD) spectroscopy and the bands were assigned by using time‐dependent density functional theory (TD‐DFT) and ZINDO/s calculations. A red‐shift of the Q bands of S₄TPP²⁺ ( 6 ) is observed relative to the spectra of tetraphenylporphyrins because a destabilization of the HOMO leads to a narrower HOMO–LUMO band‐gap. Michl′s perimeter model was used to assign the absorption bands and MCD spectra of S₄F₂₀TPP ( 7 ). Current‐density maps and nucleus‐independent chemical‐shift (NICS) calculations of S₄TPP²⁺ ( 6 ) and of a model compound predict marked modification to the diamagnetic ring current, whilst nonaromatic character is predicted for S₄F₂₀TPP ( 7 ).     

Synthesis, Crystal Structure and Magnetic Properties of a New 3D Cobalt Vanadate

A new cobalt vanadate compound 1 [Co^Ⅱ(H2O)2V2^VO6] has been hydrothermally synthesized and characterized by the elemental analyses and the single crystal X-ray diffraction analysis. Compound 1 crystallizes in the orthorhombic system, space group Pinna, with a=0.55646, b=1.06900, c=1.18452 nm, and Z=4. The magnetic susceptibility of the cobalt vanadate has been measured and indicates possible antiferromagnetic coupling between adjacent cobalt (Ⅱ) (0.5432—0.5697 nm) through bond or space.     

钛酸钠纳米带的合成、表征与气敏性能

通过钛酸丁酯与氢氧化钠浓溶液的两步水热反应合成出宽度为20～240 nm、厚度为10～40 nm、长度达几十微米的单一物相的Na₂Ti₃O₇纳米带。用X-射线衍射和电子显微镜分别表征了它们的结构和形貌。这些纳米带被加工成化学电阻型传感器以测量气敏特性。测试表明在350～400 ℃之间对丙酮、乙醇和二硫化碳具有明显感应,而对一氧化碳、苯、氨气和30%的甲醛水溶液几乎不敏感。用化学吸附模型解释其气敏机理。     

四元硫属化合物 La2CuBiS5 的合成、结构及光学性能研究

通过高温固相反应合成了首例镧系-过渡金属-铋-四元硫属化合物:La2CuBiS5。该化合物属于正交晶系,空间群:Pnma。其结构含有沿b方向的一维[BiCuS56-]∞带,带与带之间被La3+离子隔开。一维[BiCuS56-]∞带由[CuS4]四面体双链与BiS6八面体单链通过公顶点连接而成。漫反射光谱研究表明该化合物为半导体,能隙1.30 eV。理论研究表明其为直接半导体,光学能隙跃迁来源于S3p到La5d轨道的电子迁移。     

两个新的Dowson结构硫钼多酸盐合成，表征以及催化性质

通过水热技术合成了两种新的Dowson结构硫钼多酸盐[C5N2H14]2[S2MoⅥ18O62].8H2O(1)和[C5N2H14]8(H3O)2[S2MoⅤ2MoⅥ16O62]3.(C5H5N)2(2),并通过X射线分析、红外光谱和元素分析其进行了表征。X射线晶体结果分析,化合物1结晶于正交晶系,Pmmn空间群,a=1.79929(17)nm,b=1.35804(13)nm,c=1.41926(13)nm,V=3.4680(6)nm3,Z=2。化合物2结晶于单斜晶系,C2/m空间群,a=2.266 5(3)nm,b=1.374 9(2)nm,c=3.291 2(5)nm,β=104.31(0)°,V=9.938(2)nm3,Z=4。化合物1和2都含有Dawson结构的硫钼多酸阴离子和质子化的N-甲基哌嗪阳离子。并且由苯乙烯的氧化催化结果中看出混价钼的化合物2的催化活性要比化合物1略高。     

系列三核钼硫簇合物的合成、结构表征和性质研究

系统地报道了9个三核钼硫簇合物的合成和结构表征. 晶体结构分析表明, 其中化合物1和6具有[Mo₃(μ₃-S)(μ-S)₃]簇芯, 化合物2和3具有不对称的簇芯[Mo₃(μ₃-S)(μ-O)(μ-S)₂], 化合物4, 5, 7和8具有少见的[Mo₃(μ₃-O)(μ-S)₃]簇芯, 而化合物9则具有[Mo₃(μ₃-S)(μ-S₂)₃]簇芯. 这一系列不同的簇芯以及桥配体和“松散”配位的端配体造成了不同的堆积结构. 讨论了前三种簇芯的电子结构, 并根据它们的立体构型和电子结构对某些重要的谱学表征结果做了合理的诠释. 测定了化合物4的变温电导率, 表明其具有半导体导电性能.     

Ba2SbGaS5: Solid-state Synthesis, Crystal and Electronic Structures, and Property Characterization

Single crystal of Ba2SbGaS5 has been synthesized by the high temperature solidstate reaction method. The compound crystallizes in the orthorhombic space group Pnma with a = 12.177(4), b = 8.880(3), c = 8.982(3), V = 971.4(6)3 , Z = 4, Dc = 4.284 g/cm3 , = 14.487 mm-1 , F(000) = 1096, the final R = 0.0171 and wR = 0.0384 for all data. The structure comprises an infinite one-dimensional 1∞SbGaS54- anionic chain constructed from the GaS4 tetrahedra and the SbS5 polyhedra via sharing edge alternately. The paralleled 1∞SbGaS54- anionic chains engage with each other and form the two-dimensional Sb-Ga-S layer perpendicular to a-axis with the isolated Ba2+ cations arranged between layers. The IR spectrum and the UV-Vis spectrum have been investigated. Also, the first-principles band structure and density of states calculations indicate that the compound belongs to indirect semiconductor with the band gap of 2.1 eV, which is supported by the UV-Vis diffuse reflectance results.     

一种多钒氧酸有机铵盐的水热合成、晶体结构及催化性质研究

本文采用水热技术合成了一种多钒氧酸盐[NH3(CH2)4NH3][H2pip]2[V10O28].6H2O(1,pip=哌嗪),并且通过元素分析、红外、热重、单晶X-射线衍射对化合物1进行了表征。化合物1为单斜晶系,空间群为P21/n,晶胞参数为a=1.229 85(10)nm,b=1.075 10(9)nm,c=1.496 71(12)nm,β=93.947 0(10)°,V=1.974 3(3)nm3,Z=2。晶体结构分析表明,化合物1是由[V10O28]6-阴离子簇、质子化的1,4-丁二胺和哌嗪阳离子以及结晶水构成。有机阳离子和结晶水通过O-H…O和N-H…O氢键相互作用将阴离子连接形成三维结构。     

Synthesis,Structural Characterization,Electronic Structure,and Magnetic Properties of the Zintl Phase Eu10Cd6Bi12

A new transition‐metal‐containing Zintl phase, Eu₁₀Cd₆Bi₁₂, was synthesized by combining the elements in excess molten Cd. Single‐crystal X‐ray diffraction studies indicated that this compound crystallizes in the orthorhombic space group Cmmm (No. 65) with a=7.840(2), b=24.060(7), and c=4.7809(14) Å. The crystal structure of Eu₁₀Cd₆Bi₁₂ can be viewed as a stacking of a series of [Cd₆Bi₁₂] double layers, which are arranged alternately along the b axial direction. The layers are composed of corner‐ and edge‐shared CdBi₄ tetrahedra, a common feature in the crystal chemistry of many transition‐metal Zintl phases. Electronic‐band‐structure calculations confirm the closed‐shell configuration of all constituent elements and corroborate the electron count inferred by the Zintl formalism, that is, [Eu²⁺]₁₀[Cd²⁺]₆[Bi^3?]₈[Bi^2?]₄. Magnetic‐susceptibility measurements confirm the divalency of europium and show the existence of a long‐range antiferromagnetic order of the Eu spins below 12.3 K.     

Synthesis,Characterization, and Properties of [4]Cyclo‐2,7‐pyrenylene: Effects of Cyclic Structure on the Electronic Properties of Pyrene Oligomers

A cyclic tetramer of pyrene, [4]cyclo‐2,7‐pyrenylene ([4]CPY), was synthesized from pyrene in six steps and 18 % overall yield by the platinum‐mediated assembly of pyrene units and subsequent reductive elimination of platinum. The structures of the two key intermediates were unambiguously determined by X‐ray crystallographic analysis. DFT calculations showed that the topology of the frontier orbitals in [4]CPY was essentially the same as those in [8]cycloparaphenylene ([8]CPP), and that all the pyrene units were fully conjugated. The electrochemical analyses proved the electronic properties of [4]CPY to be similar to those of [8]CPP. The results are in sharp contrast to those obtained for the corresponding linear oligomers of pyrene in which each pyrene unit was electronically isolated. The results clearly show a novel effect of the cyclic structure on cyclic π‐conjugated molecules.     

Mild Hydrothermal Synthesis and Optical Properties of the Complex Fluoride KMgF_3 Doped with Eu

Perovskite complex fluorides have attracted great interests due to their particular physical properties such as antiferromagnetic characteristics1, photoluminescence behavior2. Complex fluorides are usually prepared by solid state reactions at high-temperature. In spite of inert atmosphere, it is inevitable to contain a bit of oxygen. This has great effect on the luminescent character of rare earth ions. There are also reports about synthesizing some binary fluorides by high-temperature hy…     

Synthesis and Properties of 4,5,6-Triphospha[3]radialene

[3]Radialenes: 4,5,6-Tris(2,4,6-tri-tert-butylphenyl)phospha[3]radialene has been synthesized. The compound can be easily handled in air under ambient conditions, despite the [3]radialene moiety containing P?C bonds, and exhibits red-shifted absorption as well as high electron-accepting ability. The unique electronic properties are brought about by the synergistic effect of the [3]radialene framework and the phosphorus substitution.