(H_2en)_2[Se_2Mo_5O_(21)]2H_2O的水热合成、晶体结构与光谱研究

在水热条件下, 以SeO2、V2O5、MoO3、K2CO3、en(乙二胺)作为起始原料, 得到了标题化合物(H2en)2[Se2Mo5O21]2H2O, 利用IR、UV、荧光光谱、单晶-X射线衍射等方法对其进行了表征。结构测定表明, 该化合物属于正交晶系, 空间群: P212121, 化学式: C4H24- Mo5N4O23Se2, 晶胞参数: a = 12.1386(7), b = 17.7118(8), c =11.7092(5) ? V = 2517.4(2) ?, Z = 4, Dc = 2.987 g/cm3, Mr = 1133.89, m = 5.419 mm-1, F(000) = 2144, 最终结构偏离因子R = 0.0285, wR = 0.0400, S = 0.904。该化合物由2个双质子化的en、2个H2O分子以及杂多阴离子[Se2Mo5O21]4-组成。其中,杂多阴离子由5个畸变的MoO6八面体以共边或共顶点形式连接构成一个平面骨架; 2个畸变的SeO3四面体和MoO6八面体以共顶点形式连接, 且位于平面的两侧;质子化的en位于4个[Se2Mo5O21]4-离子围成的四面体空位中, 与杂多阴离子和水分子通过氢键连接成无限三维结构。最后我们用B3LYP方法研究了阴离子簇的电子结构。     

新颖有机/无机杂化配位聚合物[(DBU-H)(PbI3)]n的合成、晶体结构和量子化学研究

The coordination polymer [（DBU-H）（PbI3）]n（DBU=catena-（1,8-diazabicyclo[5,4,0]-undec-7-ene） was synthesized by self-assembly reaction of DBU and PbI2 at room temperature with pH=6.0 and structurally characterized by means of X-ray single crystal diffraction. It crystallizes in monoclinic system with space group P21/c and crystal parameters a = 1.1940（2） nm, b = 1.7409（4） nm, c = 0.81347（16） nm, β= 100.32（3）°, chemical formula C9H17N213Pb and Mr=741.15, V= 1.6635（6） nm^3, Z=4, Dc=2.959 g/cm^3, F（000）= 1304,μ（Mo Kα）= 15.687 mm^-1, the final R=0.0389 and wR=0.0635 for 2279 observed reflections with 1〉2σ（I）. Structure analysis shows that the inorganic anion chain consists of distorted PbI6 octahedra, which shares the same faces with adjacent PbI6 units to form one-dimensional infinite chains along the c-axis. Anion chains are surrounded by protonated （DBU-H）^＋ cations. Anion chains and cations are in combination with each other by static attracting forces in the crystal to form so-called organic-inorganic hybrid structure. According to the crystal structure data, quantum chemical calculation with DFT at B3LYP level was used to reveal the electronic structure of title compound.     

Synthesis, Crystal Structure and Quantum Chemistry Calculation of a Bis（dafone） Di（dmf） Copper（Ⅱ） Complex

1 INTRODUCTION 4,5-Diazafluoren-9-one (dafone, scheme 1), a deri- vative of 1,10-phenanthroline (phen) with an exocyclic keto function group[1], has attracted much attention of researchers perhaps due to its DNA intercalation properties[2]. The reactive exocyclic keto function in dafone offers distinct advantages for further derivati- zation to yield multinuclear metal complexes having in- teresting catalytic and biological properties. In addi- tion, ruthenium complexes of dafone are fo…     

一种新颖一维铅碘聚合物[(Pb2I5)(L-H+)·2DMF]n (L=Piperazine)的自组装合成和晶体结构(英)

The lead iodide adduct [(Pb₂I₅)(L-H⁺)·2DMF]_n(L=piperazine) has been prepared by self-assembly and structurally characterized. It presents one dimensional structure and crystallizes in Triclinic, P1 space group with the crystal cell parameter: a=0.922 06(18) nm, b=1.237 5(3) nm, c=1.297 2(3) nm, α=99.05(3)°, β=102.98(3)°, γ=105.30(3)°, and V=1.353 8(6) nm³, Z=2, D_c=3.078 Mg·m^-3, μ(Mo Kα)=18.127 mm^-1, F(000)=1 085, chemical formula C₁₆H₄₃N₈O₄Pb₄I₁₀ and M_r=2 509.39, the final R=0.053 3 and wR=0.146 4 for 3 889 observed reflections with I>2σ(I). CCDC: 250760.     

Hydrothermal Synthesis and Structure of a New Molybdenum Phosphate: (NH_3CH_2CH_2NH_3)_(2.5)[Mo_5O_(15)(PO_4) (HPO_4)]·7.5H_2O

1 INTRODUCTION A new class of materials of metal oxide clusters based on anionic molybdenum phosphate frameworks has received much attention as a consequence of their potential applications in catalysis and materials science [1]. As a result, some molybdenum phosphates have been studied [2,3]. Recently we have studied the structure of NaPMO material[4] and the spectrum of multicomponent compound with Keggin struc- ture [5]. Here we report the synthesis and crystal structure of a new…     

Structure and Two-dimensional Correlation Infrared Spectroscopy Study of a New One-dimensional Chain Compound: (4,4’-Hbpy)_3[NaMo_8O_(26)](4,4’- bpy)_2(H_2O)_4 (bpy = Bipydine)

1 INTRODUCTION Owing to their unusual topological properties and economically important applications in many fields, such as catalysis, biology, materials science and mag- netochemistry[1～3], polyoxometalates (POMs) have aroused particular interest for a long time[4～6]. But the investigation in their capability and application are relatively less carried on. Even though some POMs have been put into practice, the mechanism of the function of POMs remains incompletely understood. Thus,…     

两种含铋的杂多化合物的光谱研究

在水热条件下合成了两个含铋的杂多化合物：Co₅[Bi₂Co₂W₂₀O₇₀(H2O)₆]·44H₂O(Ⅰ)和Na₃H₂[Ce₃(H₂O)₁₈Bi₂W₂₂O₇₆]·23H₂O(Ⅱ),通过用FTIR, NIR FT-Raman和UV-Vis DRS光谱研究了它们的结构和性能的关系。ν_as(MO_d)和ν_s(M—Ob—M)的特征振动频率和材料的结构相关。ν_as(M—O_b—M)振动频率可说明当W原子被Co原子取代时氧化活性增强。在化合物Ⅰ和Ⅱ的UV-Vis DRS谱中,分别存在254,319和220,310 nm的(O_d→W),(O_b, c→W)的荷移跃迁特征峰,化合物Ⅰ还在529 nm处出现宽而弱的Co2+的d-d跃迁吸收谱带。最后,文章还对化合物Ⅰ进行了量子化学计算,用于说明其结构特征。     

含对苯氧基联接链的羧酸盐Gemini表面活性剂合成及胶团化特性

合成了含对苯氧基联接链的羧酸盐Gemini表面活性剂,研究了其胶团化特性.结果表明,该羧酸盐Gemini表面活性剂具有很低的cmc值,给出了cmc-T(温度)以及lncmc-(m+1)(烷烃链长)的回归方程.计算了胶团化的热力学函数变化,证实胶团化过程来自熵驱动,并表现出焓/熵补偿现象,在所考察的系列中,以(m+1)=11的胶团最为稳定.     

Synthesis and Single-crystal Structure of a One-dimensional Zinc（Ⅱ） Phosphonate： [Zn3（PhPO3）2（PhPO3H）2（Phen）2]n

A new Zn（II） phosphonate complex, [Zn3（PhPO3）2（PhPO3H）2（Phen）2]n （Phen = 1,10-phenanthroline）, has been synthesized and structurally determined by X-ray single-crystal diffraction. The complex crystallizes in the monoclinic system, space group C2/c with a = 14.997（3）, b = 18.108（4）, c = 17.237（3） A, β = 96.61（3）°, V = 4649.9（16） A3, Z = 4, C48H38N4O12P4Zn3, Mr = 1182.87, Dc = 1.690 g/cm3^,μ = 1.743 mm^-1, F（000） = 2400, the final R = 0.0363 and wR = 0.0963. In the structure, the connectivity between two 5-coordinated Zn（II） atoms and four phosphonates as well as two Phen ligands form a Zn2（PhPO3H）2（PhPO3）2（Phen）2 unit, and such a neighboring unit is bridged by 4-coordinated Zn（II） to give rise to a 1D chain along the c axis. The π-π stacking interactions between Phen rings assemble adjacent chains packed together to form a 3D supermolecular architecture.     

三元杂多酸-甲基紫超分子化合物的合成及光谱研究

在水溶液条件下合成了一系列具有Keggin结构的PWxV12 -x MV(x =2 ,4 ,6 ,8,10 )超分子化合物 (PWxV12 -x为具有不同配比的磷钨矾三元杂多酸 ,MV为甲基紫 ) ,并对其紫外光谱 ,红外光谱和荧光光谱进行了研究。结果表明 ,杂多酸阴离子上的端氧与甲基紫阳离子上的N 间通过配合作用相互连结而形成超分子化合物。超分子化合物中仍保持有杂多阴离子的Keggin结构以及甲基紫的基本结构。且随着V的含量增加 ,杂多阴离子的氧化能力增强 ,阴离子PWxV12 -x和阳离子MV的相互作用增强 ,νas(M =Ot) ,νas(M Ob M )和νas(M Oc M )的FTIR吸收峰分别从 96 6 ,886和 80 4cm-1变化至 95 5 ,875和 786cm-1;紫外吸收峰也从 5 19nm移至 5 0 6nm ;用 5 30nm的光激发的荧光发射峰也从 6 92移至 6 4 4nm ,与PWxV12 -x和MV间配合作用的强弱呈现了很好的对应关系。