苯并咪唑修饰的2个Keggin型多酸基化合物的合成与晶体结构

利用水热合成方法合成了2个新的苯并咪唑修饰的Keggin型多酸基化合物[(C_7H_6N_2)_3(H_3PMo_(12)O_(40))]·H_2O(1)和[KNa_2(C_7H_5N_2)_2(H_(2.5)Si W_(12)O_(40))_2]·6(C_7H_6N_2)(2)(C_7H_6N_2=苯并咪唑).化合物1为超分子结构,化合物2为2种碱金属钾和钠与多酸配位形成链状多酸基化合物,并通过元素分析和X-射线单晶衍射方法确定了2种化合物的晶体结构.单晶结构分析表明化合物1属于三斜晶系,P-1空间群,晶胞参数a=1.1580(7)nm,b=1.3159(8)nm,c=1.8254(12)nm,α=84.418(10)°,β=88.958(10)°,γ=65.852(10)°,V=2.5255(3)nm3,Z=2;化合物2也属于三斜晶系,P-1空间群,晶胞参数a=1.3586(9)nm,b=1.4403(10)nm,c=1.8365(13)nm,α=109.509(10)°,β=90.755(10)°,γ=114.864(10)°,V=3.0236(4)nm3,Z=1.     

Synthesis, Characterization and Crystal Structure of an Inorganic-organic Composite Metatungstate: [Co(4,4'-bipy)2(H2O)4](4,4'-H2bipy)2[H2W12O40]·5.5H2O

A novel hybrid compound [Co(4,4'-bipy)2(H2O)4](4,4'- H2bipy)2[H2W12O40]·5.5H2Ohas been synthesized from an acidified aqueous solution and characterized by elemental and thermal analyses, IR and UV spectroscopy, and single-crystal X-ray structure determination. Structure analysis indicates that the title compound is of monoclinic, space group C2/c, with a = 21.315(9), b = 15.303 (7), c = 24.139(10) (A), β = 105.170(5)o, V = 7599(6) (A)3, Mr = 3706.99, Z = 4, F(000) = 6616, Dc = 3.231, μ = 18.395 mm-1, R = 0.0652 and wR = 0.1594. X-ray crystallographic study shows that the title compound consists of one [Co(4,4'-bipy)2(H2O)4]2 cation, two diprotonated 4,4'-bipyridine molecules, 5.5 water molecules of crystallization, and one metatungstate polyoxoanion [H2W12O40]6-, which approaches an effective Td point symmetry. TG-DTA analysis indicates that the framework of the metatungstate polyoxoanion is collapsed at 587.0 ℃.     

Polyoxometalate immobilization in Cu/Ag-pz porous coordination polymers: The influences of them on the structural properties of frameworks

Three new high dimensional Cu^I/Ag-pz porous coordination polymers (PCPs) with different Keggin polyoxometalate templates have been hydrothermally synthesized: [Cu^I₅(pz)₆Cl][HPMo^VI₁₀Mo^V₂O₄₀] (1) [Ag₅(pz)₇(BW₁₂O₄₀)] (2) and [Cu^I₅(pz)₆H(H₂W₁₂O₄₀)]·4H₂O (3) (pz=pyrazine). The choice of the particular Keggin POM templates is shown to influence the structural properties of the Cu/Ag PCPs. Compound 1 shows a Cl-bridged Cu-pz-Cl double layer, between which two kinds of [HPMo^VI₁₀Mo^V₂O₄₀]⁴⁻(PMo₁₂) polyanions are located. Compound 2 presents a 3D Ag-pz framework with parallelogram-like voids, into which BW₁₂O₄₀⁵⁻ (BW₁₂) Keggin ions are incorporated. Compound 3 contains a Cu-pz cationic layer framework, between which are located [H(H₂W₁₂O₄₀)]⁵⁻ (W₁₂) Keggin ions. Primary photocatalytic experiment indicates that compound 1 presents excellent photocatalytic activity. The photoluminescence properties and electrochemistry properties of the compounds are also discussed.     

单取代多金属氧酸盐有机亚胺衍生物（N-Bu4N）2[Mo6O18（=NAr）]（Ar=o-CH3OC6H4）的合成

采用N,N′-二环已基碳酰亚胺（DCC）脱水法，以（N-Bu4N）2[Mo6O19]：DCC：邻甲氧基苯胺=1．5：1．1：1．0的摩尔比，无水乙腈中加热回流12h，通过丙酮／乙醇溶液重结晶两次，得到橘红色片状晶体．探讨了最佳反应条件：DCC的量在1．0～1．1mmol，反应时间12h．通过元素分析，UV／Vis光谱和^1H NMR谱的研究表明，该晶体是一种新的六钼酸盐的有机亚胺衍生物（N-Bu4N）2[Mo6O18（=NAr）]（Ar=o-CH3OC6H4）.     

多金属氧酸盐的合成化学研究新进展

介绍了近几年来多金属氧酸盐(polyoxometalate,缩写为POM)在合成化学研究方面的新进展,内容包括:由水热合成方法得到的Keggin型[SiNb12O40]16-及其与[Ti2O2]4 连接构成的一维链状结构及[H2Si4Nb16O56]14-簇;Silverton型多阴离子[GdMo12O40]9-及三维网络结构;POM和过渡金属簇通过有机π共轭体系形成的杂化材料;一步法自组装合成的四核轮状的多金属钨酸盐;控制合成得到具有蛋白质尺寸的Mo368氧簇和开普勒环形山结构的多钼氧簇;用{P2W12}杂多阴离子作为建筑块合成出的含有20个Cu中心的大轮型POM;用常规方法突破“氧墙”效应,获得的第一例稳定的含有第三过渡金属元素的多金属氧酸盐;通过逐步合成法用[SiW9O34]10-作为建筑单元合成出二聚和四聚的POM化合物;合成带有均匀孔道结构,具有选择性吸附和分离混合低碳脂肪醇和低碳氰分子的三维网络结构等.     

Hydrothermal Synthesis, Crystal Structure and Fluorescent Property of a Keggin Polyoxometalate [Cu~I(2,2'-bipy)_2]_3[PW~(Ⅵ)_(12)O_(40)]

1 INTRODUCTION Polyoxometalates (POMs) have become a focus of contemporary chemical research due to their structure diversity and potential applications in many areas, such as catalysis[1], photochemistry[2], magnetism[3], etc. In this field, POMs containing Keggin moieties have received considerable attention. A large num- ber of efforts have been given to the decoration of POMs with various transition metal complexes and organic moieties[4]. To date, several compounds con- taining …     

Synthesis and characterization of new organic–inorganic nanohybrid film (TBA)PWFe/PVA/CTS as an efficient and reusable amphiphilic catalyst for ODS of real fuel

In this work, we report a new catalytic oxidative desulfurization (CODS) system based on (TBA)PWFe/PVA/CTS nanohybrid film as a highly active catalyst. The nanohybrid material was successfully fabricated by the composition of tetra (n‐butyl) ammonium salt of Fe‐substituted phosphotungstate, ((n‐C₄H₉)₄N)₄[PW₁₁Fe(H₂O)O₃₉] abbreviated as (TBA)PWFe, polyvinyl alcohol (PVA), and chitosan (CTS). The composite was characterized using various analytical techniques including FT‐IR, UV–vis, XRD, and SEM. The results revealed the hydrogen‐bonding interaction between inorganic (TBA)PWFe clusters and organic polymers. The catalytic activity of (TBA)PWFe/PVA/CTS was evaluated in the CODS of real gas oil. Also, the solutions of heterocyclic thiophenic compounds (HTCs) in n‐heptane were tasted as simulated fuels. It was found that the removal efficiency of HTCs in the presence of (TBA)PWFe/PVA/CTS catalyst reached as high as 95% at 60 °C after 2 h. The significant catalytic performance of the nanohybrid film might be attributed to its amphiphilicity and multifunctional active sites, which enhances adsorption and oxidation of sulfur compounds. Moreover, the (TBA)PWFe/PVA/CTS composite can be easily recovered and reused by simple filtration, making it a suitable catalyst for cleaner processing.     

铜配合物[Cu_2(L)_2(SiW_(12)O_(40))(H_2O)_8]·H_2O的合成、结构与性质研究

利用水热合成技术制备了基于半刚性双吡啶双酰胺配体L(N,N′-双(4-吡啶甲酰胺)-1,2-环己烷)和Keggin型多金属氧酸盐的铜功能配合物[Cu_2(L)_2(Si W_(12)O_(40))(H_2O)_8]·H_2O,并通过元素分析、红外光谱和X-射线单晶衍射方法确定了该配合物的晶体结构.结构分析表明该化合物属于三斜晶系,P1-空间群,晶胞参数a=1.153 10(10)nm,b=1.339 10(12)nm,c=1.429 40(12)nm,α=71.514 0(10)°,β=66.926 0(10)°,γ=68.111 0(10)°,V=1.846 0(3)nm~3,Z=1,R_1=0.067 3,w R_2=0.181 1.配合物由离散的[Si W_(12)O_(40)]~(4-)杂多阴离子和[Cu_2(L)2(H_2O)_8]~(4+)阳离子组成,2种结构单元间通过氢键作用形成二维超分子层结构.标题配合物修饰的碳糊电极对NO~(2-)还原有较好的电催化活性,而且该配合物对降解亚甲蓝分子有显著的光催化效率.     

用于合成新型1,3,5-三芳基吡唑啉衍生物的磷钨酸铯盐的纳米塑形、模板合成及结构研究(英文)

The elimination of the silica matrix of composites by HF occurred by a two-step reaction deposition of a Cs2.5H0.5PW12O40(CsHPW) salt nanocrystal.We used 2D hexagonal SBA-15 silica as a template for the nanofabrication of CsHPW nanoparticles.Nanocast CsHPW materials are stable against leaching and colloidization in polar solvents.The catalytic performance of the nanocast CsHPW materi-als exceeded that of bulk Cs2.5H0.5PW12O40,which is the most active among the acidic HPW salts.A series of novel 1,3,5-triaryl-pyrazoline derivatives were synthesized by the reaction between chalcone and phenylhydrazine in high yield in the presence of CsHPW salt nanocrystals.     

Photocatalytic Synthesis of Gold Nanoparticles Using Preyssler Acid and Their Photocatalytic Activity

Preyssler acid H14[NaP5W30O110] was used as reducing agent and stabilizer for the synthesis of gold nanoparticles by photolysis of Au(III)/Preyssler acid/propan-2-ol solution.Preyssler acid plays both the role of transferring electrons from propan-2-ol to Au(III) and stabilizing the nanoparticles.Propan-2-ol was used as sacrificial reagent for the photoformation of reduced Preyssler acid.Gold nanoparticles (Au NPs) were characterized by UV-Vis spectroscopy,transmission electron microscopy (TEM),and particle size distribution (PSD) measurements.The synthesized Au NPs had a uniform hexagonal morphology and their size was about 17 nm.The catalytic performance of these NPs for photodegradation of methyl orange (MeO) was investigated in aqueous solution.UV-Vis studies showed that Au NPs can catalyze photodegradation of this azo dye.The pseudo-first-order rate constants were also calculated for this reaction.